Organization - Unicampliqcqits/publications/other_files/ICG2010_boo… · Solid state nmr of...

Organization

The 22nd International Congress on Glass was organized by Associação Técnica Brasileira das Indústrias

Automáticas de Vidro (ABIVIDRO) in close collaboration with the International Commission on Glass (ICG).

www.adeventosbrasil.com.br

www.editoracubo.com.br

www.abividro.org.br

Summary

Associação Técnica Brasileira das Indústrias Automáticas de Vidro (ABIVIDRO) ........................... IV

International Commission on Glass (ICG) ................................... V

Opening ............................................................................... VII

ICG Awards .......................................................................... VIII

Scientific Committee ............................................................... X

Invited Speakers .................................................................... XI

Sponsors and support ............................................................ XII

Program ............................................................................. XIII

Opening talk ......................................................................... XIV

Weyl Award talk .................................................................... XV

Invited and Oral Presentations

Tuesday, Sept. 21 ............................................................. 3

Wednesday, Sept. 22 ....................................................... 11

Thursday, Sept. 23 .......................................................... 37

Friday, Sept. 24 .............................................................. 55

Saturday, Sept. 25 .......................................................... 82

Poster Presentations

Tuesday, Sept. 21 ........................................................... 91 Posters #0016-0200

Wednesday, Sept. 22 ..................................................... 117 Posters #0201-0359

Friday, Sept. 24 ............................................................ 145 Posters #0368-0487

Author Index ....................................................................... 171

- IV - Salvador, BA, Brazil – September 20-25, 2010

Associação Técnica Brasileira das Indústrias Automáticas de Vidro (ABIVIDRO)

www.abividro.org.br

ABIVIDRO gathers sixteen of the most important companies located in Brazil, which work closely with the construction market, domestic products, packaging, automobile industries, furniture, etc. Founded on April 11th of 1962, this institution aims to promote and enhance the use of glass, systematize information from all sectors of the glass productive chain, to stimulate the continuous improvement of techniques of this industrial activity and to represent it on everything that is of common interest. Modern and competitive, the Brazilian glass industry works in concert with the demands of the society and actively encourages increased recycling of glass.

Salvador, BA, Brazil – September 20-25, 2010 - V -

- VI - Salvador, BA, Brazil – September 20-25, 2010

Officers

Participating national organisations are represented by two national members on the ICG Council.

The Council elects the administration of the ICG, that is the members of the Management Board (President, Vice-President, Executive Secretary, Honorary Treasurer and Chair of CTC), Steering Committee and Coordinating Technical Committee (CTC).

The CTC supervises and coordinates the activities of the various Technical Committees (TCs) which carry out applied scientific investigations.

The TCs report to the CTC which in turn is responsible to the Steering Committee.

Management Board

President Dr Fabiano Nicoletti Stevanato Group, Piombino Deve, ItalyStazione Sperimentale del Vetro, Italy

Vice-President Mr Peng Shou China Triumph Int Eng Consultation Co, China Chinese Ceramic Society, China

Executive Secretary Prof Peter SimurkaNábrežná 5, 911 01 Trenčín, SlovakiaSlovak Glass Society, Slovakia

Honorary Treasurer Dr Alicia Durán CarreraInstituto de Ceramica y Vidrio, Madrid, SpainSociedad Espanola de Ceramica y Vidrio, Spain

Chair of CTC Prof Renè Vacher Montpellier University, FranceInstitute du Verre, France

Salvador, BA, Brazil – September 20-25, 2010 - VII -

Executive Secretary of theICG 2010

Lucien BelmonteABIVIDRO

ICG President Fabiano NicolettiStevanato Group, Italy

President of theICG2010

Prof. Edgar Dutra ZanottoVitreous Materials Lab (LaMaV)Federal University of São Carlos, Brazilwww.lamav.ufscar.br

Opening Ceremony

Weyl AwardJohn Mauro (USA)

Gottardi PrizeMaria Jesus Pascual (Spain)

President´s awardGünter Frischat (Germany), David Pye (USA) and Helmut Schaeffer (Germany)

Turner AwardKlaus Bange (Germany)

2010 Awards

Round Table

“Glass, energy and environment”

Moderator: Klaus Bange

Speakers: R. Beerkens, TNO (Netherlands) “Energy efficiency improvement potentials in glass manufacturing”

R. Langfeld, Schott (Germany) “Glass - A Key Material for Renewable Energy”

D. Roux, St-Gobain (France) “Flat glass for buildings: energy efficiency and opportunities”

- VIII - Salvador, BA, Brazil – September 20-25, 2010

ICG Awards

The ICG offers four awards for advancement of glass science and technology.

WOLDEMAR A. WEYL INTERNATIONAL GLASS SCIENCE AWARD

Was established in 1976 by Pennsylvania State University in collaboration with the ICG in memory of Prof. W.A. Weyl*. It is awarded once every three years to an outstanding young scientist working in glass research.

*formerly affiliated with the Kaiser Wilhelm Institute for Silicate Research, Berlin, and with the Pennsylvania State University.

1977 P. Schulze (US)1980 D. Ravaine (FR)1983 B. Smets (NL)1986 G. Scherrer (US)1989 T. Michalske (US)1992 Y. Watanabe (JP)1995 E. Pope (US)1998 S. Sen (UK)2001 H. Ebendorff-Heidepriem (DE)2004 M. Dejneka (US)2007 A. Hayashi (JP)

THE GOTTARDI PRIZE

Initiated in 1987 in memory of Prof. V. Gottardi* is awarded annually to young people with outstanding achievements in the field of glass in research and development, teaching, writing...

*former ICG president and affiliated with the University of Padua.

1987 P. Fournier (FR) and ex aequo F. Geotti-Bianchini (IT)1988 A. Duran Carrera (ES)1989 H. J. Barklage-Hilgefort (DE)1990 K.Hirao (JP)1991 D. M. Krol (NL)1992 M. Guglielmi (IT)1993 E. D. Zanotto (BR)1994 R. G. C. Beerkens (NL)1995 M. Tatsumisago (JP)1996 R. K. Brow (US)1997 M. Mennig (DE)1998 X. Zhao (CN)1999 K. Nakanishi (JP)2000 A. Clare (US)2001 T. Uchino (JP)2002 J. Deubener (DE)2003 M. Mika (CZ)2004 B. Hehlen (FR)2005 S. Jiang (CN)2006 K. Tadanaga (JP)2007 L. Cormier (FR)2008 K. Fujita (JP)2009 R. Kedding (DE)

Salvador, BA, Brazil – September 20-25, 2010 - IX -

THE TURNER AWARD

Inaugurated in 2002 in memory of Prof. W.E.S. Turner*, rewards those who have made a noteworthy contribution to the ICG Technical Committees.

* first ICG president and founder of the Department of Glass Technology at Sheffield University.

2002 O. Corumluoglu (TR)

2003 P. Polato (IT)

2004 R. M. Brill (US) J. M. Parker (UK)

2005 H. de Waal (NL)

2006 U. Kircher (DE) I. Smith (UK)

2007 E. Guadagnino (IT)

2008 R. Beerkens (NL)

2009 W. Höland (LI)

THE ICG PRESIDENT’S AWARD

Was established in 1995 to recognise outstanding lifetime contributions to the international glass community in areas such as scientific discoveries, engineering developments, artistic accomplishments leadership and communications.

1995 A.R. Cooper (US) N. J. Kreidl (US) J. Stanek (CZ)

1998 M. Cable (UK) H. Rawson (UK) J. Petzoldt (DE)

2001 G. Fuxi (CN) P. Gilard (BE) O. Mazurin (RU)

2004 C. Guillemet (FR) F. Nicoletti (IT) N. Soga (JP)

2007 J. Barton (FR) A. Varshneya (US) A. Yaraman (TR)

- X - Salvador, BA, Brazil – September 20-25, 2010

ICG 2010 PresidentProf. Edgar Dutra Zanotto

Federal University of São Carloswww.lamav.ufscar.br

Prof. Alicia DuránICV, Spain

Dr. Antonio TucciSSV, Italy

Prof. Carlo PantanoPenn State, USA

Carlos SolierINTI, Argentina

Prof. Christian RusselOSI, Germany

Dr. D. KoepselSchott, Germany

Dr. Dusan GalusekInstitute of Inorganic Chemistry, Slovak Republic

Dr. Fabiano NicolettiESV, Italy

Dr. Hervé ArribartSaint Gobain, France

Dr. Iván A. CornejoCorning, USA

Prof. Jianrong QiuZhejiang University, China

Prof. Jun MatsuokaUniversity of Shiga, Japan

Dr. J. C. MarraSNRL, USA

Prof. J. M. ParkerSheffield University, UK

Prof. J.R. VarnerAlfred University, USA

Prof. Kazuyuki HiraoKyoto University, Japan

Dr. Michael DunklSchott, Germany

Prof. René VacherUniversité de Montpellier, France

Prof. Rui AlmeidaIST, Portugal

Prof. Ruud BeerkensTNO, Netherlands

Dr. W. LinzSchott, Germany

International Advisory Board

Edison ToporcovWheaton

Fábio dos Santos BernardoSaint-Gobain Glass

Marcelo GuerraSaint-Gobain SEFpro

Mauro AkermanEscola do Vidro

Samuel M. ToffoliPoli-USP

Prof. Alicia DuranICG

Dr. Klaus BangeICG

Prof. K. HiraoICG

Prof. René VacherICG

José Roberto MartinelliPhD, IPEN, São Paulo

Luis Carlos BarbosaDr., IF-UNICAMP, Campinas

Mauro Luciano BaessoDr., DF-UEM, Maringá

Samuel M. ToffoliPhD, Poli-USP, São Paulo

Valmor Roberto MastelaroPhD, IFSC-USP, São Carlos

Younes MessaddeqPhD, IQ-UNESP, Araraquara

Conference Executive SecretaryLucien Belmonte

Abividro, Brazil www.abividro.org.br

Local Technical Committee

Scientific Committee

Salvador, BA, Brazil – September 20-25, 2010 - XI -

Invited speakers

R. Conradt, Germany Thermodynamic modeling of the initial and final stages of glass corrosion

C. Enss, Germany Glasses at ultra-low temperatures: interplay of atomic tunneling systems and nuclear magnetic moments

L. Galoisy, France The environment of transition elements in oxide glasses

L. Cormier, FranceStructural role of nucleating elements (Zr, Ti and Ni) during glass nucleation: influence on physical properties

N. Greaves, UK Low poisson ratio perfect glasses formed by amorphising zeolites

P. Gupta, USA The landscape view of sub-tg relaxation in liquids and glasses

R. Hand, UK Improving practical glass strength: myths and realities

J. Jones, UK Bioactive glass and hybrid scaffolds for bone regeneration

D. Krol, USA New functionalities in glass via femtosecond laser writing of micro and nano structures

A. Martucci, Italy Luminescence and amplified stimulated emission in quantum dot doped sol-gel waveguides

Y. Ohishi, Japan New photonics glasses and waveguides for lightwave processing

S. Ribeiro, Brazil Multifuncionality on silica glass. Advanced nanostructured coating

W. Schirmacher, Germany Theory of vibrational excitations in glass

M. Smith, UK Solid state nmr of bioglasses – new techniques and applications

S. Tanabe, Japan Active glass and ceramic materials for green photonics

A. Varshneya, USA Review of chemical strengthening of glass: lessons learned and yet to be learned

T. Kamihori, JapanProgress and prospect of float process technology

C. Pantano, USAAdsorption reactions and polymer interfaces with multicomponent glass surfaces

J. Parker, USAThe future of glass education

W. Hoeland, LiechtensteinSurface or internal nucleation and crystallization of glass-ceramics

K. Oda, JapanMathematical model of sulfate fining in a glass tank furnace

J. Marra, USAEvaluating the solubility and homogeneity of plutonium in an alkali borosilicate glass

- XII - Salvador, BA, Brazil – September 20-25, 2010

- XIV - Salvador, BA, Brazil – September 20-25, 2010

Welcome

Method to organize an international conference

Edgar Dutra

scar.br

In this talk I will address an empirical method I have used in organizing several conferences in the past three decades. This method has been updated continuously over the years and the last version has been applied to the present conference: the XXII International Congress on Glass.

Once a conference is approved by the executive board, the chairman and his closest advisors decide on the main objectives, which in the present case were: “to produce a high-level, attention-grabbing, perfectly crystallized scientific program in a pleasant venue at a reasonable cost.” Then the organizational procedure starts with the establishment of the scientific committee and the international advisory board, which proposes a list of topics and designate invited speakers. This is followed by contacts with potential sponsors, creation of a web site, setup of a local (working) team, visits to and negotiations with hotels and conference centers in different venues, compilation of a mailing list (in the present case, we created one containing about 3000 valid e-mails of “glass” researchers), open pre-registration to estimate the number of attendees, a decision about the vehicle to be used for publication of selected papers and negotiation with the editorial office, launch of the call for abstracts, and receipt and selection of abstracts for a preliminary version of the oral and poster programs. These programs must be constantly corrected and updated (in the present case we produced seven versions). Proposals then must be sent to potential sponsors, the registration fees estimated (a delicate matter), the potential conference attendees have to be kept informed about all the conference details – including Visa requirements - sound and video infrastructure must be rented; the opening ceremony, decoration, dinners and excursions must be organized; the call for (full) papers launched, and finally the book of abstracts, badges, banners, certificates, etc. must be prepared. We will show highlights of these activities and interesting statistics about the number of e-mails sent and received, abstracts submitted, cancellations, participation per country, etc. We will also summarize the scientific program.

Although this “brute-force” method relies heavily on the intensive use of Internet facilities, it also requires some highly motivated people, from whom it demands considerable energy and dedication. However, in an analogy with thermodynamics – which always pushes point defects and dislocations in crystals – I have found that, regardless of the methods used, last minute cancellations are practically unavoidable. Hence, the resulting scientific program is like a real “crystal” – mostly organized but still containing defects –, and this chairman has learned once more that he can’t beat thermodynamics!

I dedicate this opening talk to the pioneers who organized the previous ICG, and hope that it may be of some help to anyone who is naive enough to contemplate organizing future conferences. I would like to extend my sincere thanks to all the sponsors; the students, post-docs and colleagues at LaMaV (Vitreous Materials Lab – Federal University of São Carlos), especially professors Ana C.M. Rodrigues and Valmor Mastelaro - who submitted proposals to Fapesp and CNPq - and the members of the scientific committee and the international advisory board not only for lending their names – which has raised the prestige of this twin conference to a very high level – but also for their help and invaluable suggestions. Special thanks are due to Luciana Zanotto, Laurie Leonardo, Dr. José Martinelli, the ABIVIDRO team and the AD eventos team for the many hours we spent hashing out all the above listed details and several non-listed ones over the last 12 months. Last, but not least, I extend my deepest thanks to all the attendees; it is you, who have traveled from all the corners of the world, that have made this conference possible!

Salvador, BA, Brazil – September 20-25, 2010 - XV -

Weyl Award talk

Recent advances in liquid and glassy dynamics

John C. MauroScience and Technology Division, Corning Incorporated, Corning, NY 14831, USA

[email protected]

The low temperature dynamics of ultraviscous liquids and glasses have posed an especial challenge from both experimental and theoretical perspectives, owing to the long dynamical time scales involved at and below the glass transition. Nevertheless, accurate modeling of these dynamics is of crucial technological importance for the glass industry, since precise knowledge of the temperature and thermal history dependence of viscosity is vital for glass composition research, glass manufacturing processes, and prediction of the aging/relaxation behavior of the final glass products. Unfortunately, existing models of liquid and glassy dynam-ics fail to capture essential details of either state. In this presentation, I revisit the problem of supercooled liquid and glassy dynamics from a fundamental physical perspective, employing temperature-dependent constraint theory and the energy landscape formalism to derive new models for both equilibrium liquid dynamics and the nonequilibrium dynamics of glass. Through comprehensive experimental validation using Corning glass compositions, I show that the new models offer significant improvements over previous approaches. In addition to the practical technological value of these models, there are also important physical implications, including: (a) clear evidence against the notion of a Kauzmann entropy catastrophe and dynamic diver-gence at finite temperature; (b) treatment of the glass transition as a continuous breakdown of ergodicity with an associated loss of configurational entropy; (c) the physical origin of liquid fragility as a tradeoff between enthalpic and entropic effects; (d) the relationship between liquid and glassy viscosities as governed by fragility; and (e) the universality of the fragile-to-strong transition as interpreted through topological constraint and energy landscape theories.

Keywords: Dynamics; viscosity, glass transition, relaxation, topology, configurational entropy, energy landscapes, modeling, nonequilibrium viscosity.

Invited and Oral PresentationsTuesday, Sept. 21

14:00-16:00 h - Room A: Structure . . . . . . . . . . . . . . . . . .3Chairman: J. Shackelford

14:00-16:00 h - Room B: Non-oxide & sol-gel . . . . . . . . . . .6Chairwoman: K. Richardson

14:00-16:00 h - Room Tech.: Education in glass . . . . . . . . .9Chairman: J. Parker

Wednesday, Sept. 228:00-9:45 h - Room A: Structure & Cryst: TC3 & TC7 . . . .11Chairman: R. Müller

10:00-12:00 - h Room A: Structure & Properties TC 22 . . .14Chairman: G. Callas

14:00-16:15 - Room A: Structure & Vibrations TC 26 . . . .17Chairman: B. Hehlen

8:00-9:45 h - Room B: Optically active glasses . . . . . . . .21Chairman: L.C. Barbosa

10:00-12:15 h - Room B: Optically active glasses . . . . . . .23Chairman: D. Krol

14:00-16:15 h - Room B: Nastructured sol-gel TC 16 . . . .26Chairman: R. Almeida

8:00-09:45 h - Room Tech.: Fracture resistant glasses . . .29Chairman: C. Kurkjian

10:00-12:15 h - Room Tech.: Waste management TC 5 . .31Chairman: J. Marra

14:00-16:15 h - Room Tech.: Raw materials & Refract. . . .34Chairman: D. Koepsel

Thursday, Sept. 238:00-9:45 h - Room A: Tg & Relaxation . . . . . . . . . . . . . .37Chairman: J. Mauro

10:00-12:15 h - Room A: Thermo & Optical Properties . . .39Chairman: R. Brow

8:00-9:45 h - Room B: Glass-Ceramics TC 7 . . . . . . . . . .42Chairman: C. Russel

10:00-12:15 h - Room B: Glass-Ceramics TC7 . . . . . . . . .45Chairman: J. Deubener

8:00-9:45 h - Room Tech.: Optical Properties . . . . . . . . . .48Chairman: Y. Messaddeq

10:00-12:15 h - Room Tech.: Bubbles TC14 & 21 . . . . . . .52Chairman: D. Koepsel

Friday, Sept. 248:00-9:45 h - Room A: Glass Formation . . . . . . . . . . . . .55Chairman: J. Schmelzer

10:00-12:15 h - Room A: New Functional . . . . . . . . . . . 57Chairman: B. Aitken

14:00-16:15 h - Room A: Crystallization . . . . . . . . . . . . 60Chairman: E. D. Zanotto

8:00-9:45 h - Room B: Bio Glasses TC 4 . . . . . . . . . . . 63Chairman: J. Jones

10:00-12:15 h - Room B: Bio Glasses TC 4 . . . . . . . . . . . .66Chairman: E. Vernè

14:00-16:15 h - Room B: Miscellaneous Properties . . . . . .69Chairman: M. Baesso

8:00-9:45 h - Room Tech.: New Applications of glass . . . .73Chairman: J. Martinelli

10:00-12:00 h - Room Tech.: Glass Meeting and Forming .75Chairman: R. Beerkens

14:00-16:15 h - Room Tech.: Environment and Sust. . . . . .79Chairman: F. Nicoletti

Saturday, Sept. 258:00-9:45 h - Room A: Glass Surfaces . . . . . . . . . . . . . .82Chairman: C. Pantano

8:00-9:45 h - Room B: Electrical Conductors . . . . . . . . . .84Chairman: J.L. Souquet

8:00-9:45 h - Room Tech.: New Glasses/Blisters TC14 . . .87Chairman: S. Toffoli

Salvador, BA, Brazil – September 20-25, 2010 - 3 -

Invited and oral Presentations

Sept. 21 – 14:00-16:00 h – Room A

Structure (Chairman: J. Shackelford)

0364 | Statistical descriptors for glass structureJames F. Shackelford

University of California, Davis, CA 95616 USA, e-mail: [email protected]

Various probability distribution functions (PDF) have been used to describe various structural features of glass. For example, the lognormal PDF has provided a good description of the distribution of interstitial site sizes in non-crystalline solids, both metallic and nonmetallic, using both experimental measurements and computer simulations. A normal (Gaussian) PDF has been found to be a good description of ring statistics of vitreous silica under a wide range of pressures, serving as a sensitive indicator of the onset of plastic deformation under high pressure. These and other distributions will be reviewed for the purpose of defining general statistical descriptors for glass structure.

Keywords: vitreous, silica, descriptor.

0385 | Statistical description of glass network interconnectivity in calcium alumosilcate glasses

Ralf Keding1*, Mette Moesgaard1, Jørgen Skibsted2, Yuanzeng Yue1

1Section of Chemistry, Aalborg University, DK-9000 Aalborg Denmark, e-mail: [email protected] 2Instrument Centre for Solid-State NMR Spectroscopy and Interdisciplinary Nanoscience Center (iNANO)

Department of Chemistry, Aarhus University, DK-8000 AARHUS C, Denmark

Two series of peralkaline glasses with a composition close to the eutectic compositons of anorthite-wollatsonite-gehlenite and amnorthite-wollasonite-tridymite were synthesized and investigated using 29Si and 27Al MAS-NMR. The structure of the glass is described by a network of SiO4/2 and AlO4/2- tetrahedrons as network former and Ca2+ ions as charge compensation for AlO4/2

– or as network modifier. Beside the separation into bridging oxygen and non-bridging oxygen the 2. coordination sphere is described by a combinatorial statistic continuous random network or by a hierarchic random network. The description of the network is used to calculate the molar fraction of Si with different first (O) and second (Si or Al) coordination sphere. The ratio of the areas of the 29Si NMR resonances of the different coordinated Si specimens is assumed to be proportional to the molar fraction obtained from the structural models. The other parameters for the peaks attributed to different 29Si specimens is calculated by fitting the measured spectra. The quasi heterogeneous modeling approach with a hierarchy in the intermediate range order results in the best description of the NMR spectra while the intensities obtained from combinatorial statistic continuous random network do not result is a proper fit. This procedure of analysing common 29Si MAS-NMR gives hints, that the investigated Ca-alumosilicate glasses are best described by a quasi-heterogeneous intermediate range order.

Keywords: hierarchic random network, Intermediate range order, 29Si MAS NMR, Calcium alumosilicate, peralcaline.

0117 | Static and dynamic volume fluctuations in silicate glass – MD studyOndrej Gedeon1*, Marek Liska2, Alexander Dubcek3

1*Institute of Chemical Technology, Technicka 5, CZ-166 28 Prague, Czech Republic, e-mail: [email protected]

2Vitrum Laugaricio – Joint Glass Center of Institute of Inorganic Chemistry SAS, 3University of Trencin and RONA Lednicke Rovne, Studentska 2, Trencin, Slovak Republic

Potassium-silicate glass was prepared by molecular dynamics under three different regimes (cooling rates, simulating box sizes) to study their influence to temperature regimes of volume fluctuations. Partial volume fluctuations were introduced with help of Voronoi polyhedra tessellation. Dynamic and static fluctuations were suggested as a measure for time- and space-related fluctuations. The glass transition was preceded by the parting of the dynamic and static volume fluctuations. The glass transition was identified with the change of the temperature cause of the static fluctuations. The dynamic fluctuations changed their temperature regimes well below the glass transition and the transition temperature was identified with the change of the

- 4 - Salvador, BA, Brazil – September 20-25, 2010


mobility. Glass transition cages the atoms in similar surroundings and Voronoi polyhedra are definitely shaped well below the glass transition temperature. Anharmonic contribution was found to be present even at the lowest-temperature.

Keywords: molecular dynamics, voronoi polyhedra, volume fluctuations.

0101 | Spectroscopic phenomenon of IR (0.7-2 μm) emission of post-transition elements in different glasses

Evgeny F. Kustov1, Lenar I. Bulatov2, Vladislav V. Dvoyrin2, Valery M. Mashinsky2*1Moscow Power Institute (Technical University) – Moscow, Russia

2Fiber Optics Research Center, Russian Academy of Sciences – Moscow, Russia, e-mail: [email protected]

Active centers (ACs) of post-transition elements (PTEs) (Bi, Sb, Pb, Sn, In, Te, etc.) together with surrounding atoms of glass form a new class of optical centers in which spectral transitions occur between PTE states of p electrons participating in chemical bonds with atoms of glass environment.

The nature of various glasses (silicate, germanate, and other oxide ones) is reflected in spectral properties of PTEs which can serve as a probe for the research of glass network structure. This is based on the fitting of experimental optical spectra and theoretical spectra obtained by the developed method of simultaneous calculation of the energy of levels and the intensities of transitions between them.

It has been found that for various PTEs and for different, both cations and anions glass networks, the absorption and luminescence spectra of PTE ACs are of the same type because they are not determined by PTE atomic states, but by molecular orbits of a complex formed by PTE atom and ligands from the first coordination sphere, which, in their turn, are under the influence of the structure of the second coordination sphere.

Keywords: post-transition elements, active centers, spectra modeling, glass structure probe.

0269 | Structural analysis of bismuth zinc borate glasses using high energy x-ray diffraction and 11B MAS NMR measurements

Yasuhiko Benino1*, Kenji Ida1, Shinichi Sakida2, Tokuro Nanba1

1*Graduate School of Environmental Science, Okayama University 2Environmental Management Center, Okayama University, Tsushima-naka 3-1-1,

Okayama 700-8530, Japan, e-mail: [email protected]

Heavy metal oxide containing glasses have been attracted our interest because of their low melting character, linear and nonlinear optical functions and crystallization behavior for designing and fabricating functional glass and glass-ceramic materials. These properties are closely related to the glass structure, e.g. coordination number of network forming cation, and structural analysis is an important approach for understanding structural details of the glasses for all the difficulties due to containing heavy elements. In the present paper, glass structure of ternary Bi2O3-ZnO-B2O3 glasses was investigated, in which the coordination number of Bi and B atoms were estimated by high energy X-ray diffraction and 11B MAS NMR measurements, respectively. For the glass series with constant ZnO contents, the fraction of 4-fold boron atoms, N4, showed convex curves, while the average number of oxygen atoms around a Bi atom, nBi-O, decreased continuously with increasing Bi2O3 content. Reverse Monte Carlo (RMC) simulations were successfully performed using constraints based on the experimental results, and the validity of structural units or groups found in the RMC glass model were discussed by comparing with those in conventional borate glasses.

Keywords: glass structure, bismuth borate glass, coordination number, high energy X-ray diffraction, 11B MAS NMR, reverse Monte Carlo modeling.

0049 | Cation distribution in mixed-alkali phosphate glassesJefferson Tscuchida1, José Schneider1*, Hellmut Eckert2

1*Instituto de Física de São Carlos, Universidade de São Paulo, São Carlos-SP, e-mail: [email protected] 2Institut für Physikalische Chemie, Westfälische Wilhelms-Universität Münster, Germany

The local order and distribution of alkali was analyzed in mixed-alkali metaphosphate glasses AxB1-xPO3, with A-B pairs Li-Rb, Na-Rb, Li-Na and Li-Cs, with the aim to identify segregation or random mixture of both cation species. These glasses exhibit some degree of mixed-alkali effect in dc conductivity and glass transition temperature. A broad set of Nuclear Magnetic Resonance (NMR) techniques were applied: 31P, 23Na, 7Li and 133Cs high-resolution NMR, 23Na Triple-Quantum-MAS NMR, REDOR between 31P, 23Na, 7Li and



133Cs, 87Rb quadrupolar Carr-Purcel-Meiboom-Gill, and 23Na-NMR spin-echo decay. The structural picture emerging from these results reveals the similarity in local environments of each kind of alkali, irrespective of the substitution ratio, but also a common subtle structural adjustment: the compression of the oxygen environment around the smaller cation of the pair. The linear behavior observed for the chemical shift of alkalis indicates mixture of species at atomic scale. However, the 23Na-23Na magnetic coupling reveals that this mixing is not statistical, existing a detectable like-cation preference at short range. These structural properties are consistent with the so-called Random Ion Distribution Model, indicating that the origin of the mixed-alkali effect in the conductivity of these glasses may be explained by structurally blocked ion diffusion.

Keywords: mixed-alkali effect, glass structure, phosphate glasses, nuclear magnetic resonance, 87Rb NMR.

0104 | Combination of advanced solid-state NMR and numerical simulation for the study of phosphate glass alteration

Nina Forler, Lionel Montagne*, Laurent Delevoye, Grégory Tricot, Filipe VasconcelosUniversité Lille Nord de France F-59000 Lille – France, Unité de Catalyse et de

Chimie du Solide, UMR-CNRS 8181, USTL F-59652, e-mail: [email protected]

Glasses need to be highly durable for practical applications. In the case of phosphate glasses, most applications require indeed high durability. However, other applications would need low durability glasses, e.g. for water treatment, resorbable biomaterials, soil nutrients. Hence, a better knowledge of phosphate glass alterations is important to improve their applicability.

We used advanced NMR methods to obtain new information on the alteration mechanism of phosphate glasses. Their degradation by water is indeed closely related to the connectivity of their network, which can now be probed using homo- and heteronuclear correlation NMR methods. They were applied to simple binary glass compositions and also to aluminophosphate compositions.

In a second step, we chose to monitor the glass alteration using 17O NMR in order to obtain complementary information. Using this isotope, we were able to label and to reveal the specific sites of attack by the 17O-enriched water molecules. As only part of the data was available for 17O NMR of hydroxylated phosphates, we prepared 17O labeled crystalline references of these compounds. In a complementary fashion, we performed ab-initio DFT calculations to confirm the measured values of the NMR parameters for these compounds. With this knowledge, we are now able to predict NMR parameters for unlabelled compounds. Finally, the simulation of 17O MQ-NMR spectra enabled to obtain quantitative data and to evaluate the kinetics of alteration.

Keywords: glass, phosphate, alteration, NMR, DFT.

0312 | Application of atmospheric microwave plasma to glass surface analysis, surface conditioning and coating

Monika Willert-Porada*, Zahra Negahdari, Zeljko Pajkic, Andreas Rosin, Daniel Leykam, Thorsten Gerdes

Universität Bayreuth, Lehrstuhl für Werkstoffverarbeitung, 95440 Bayreuth

Atmospheric pressure microwave plasma is a versatile tool for surface analysis as well as for coating of glass. When glass surfaces are subjected to microwave plasma, a “fingerprint” of volatile oxides is obtained. The composition of the volatile materials is analyzed with the help of optical emission spectroscopy, OES. Significant differences are found when our new, atmospheric microwave induced plasma method AMIP-OES is compared with LIPS, Laser Induced Plasma Spectroscopy. In the paper the set-up developed for the AMIP-OES is described and OES analysis results for different glasses are presented along with a discussion on the influence of substrate temperature and total gas pressure on the AMIP-OES signals.

In the second part of the paper, utilisation of atmospheric microwave plasma for glass processing will be presented. One example will be an atmospheric chemical vapor deposition process (APCVD), again with application of OES as a tool to monitor the progress of the glass coating process. In addition, the role of the microwave plasma for conditioning of the glass surface in air and in nitrogen as well as for reduction of the precursor deposition temperature and for an increase of deposition rates will be discussed.



Sept. 21 – 14:00-16:00 h – Room B

Non-oxide & sol-gel (Chairwoman: K. Richardson)

0116 | Luminescence and amplified stimulated emission in quantum dot doped sol-gel waveguides

Alessandro Martucci1*, Paul Mulvaney2

1Università di Padova, Dipartimento di Ingegneria Meccanica Settore Materiali, Italy 2University of Melbourne, Chemistry School & Bio21, Australia

Highly luminescent waveguides have been obtained by doping different kind of sol-gel films (ZrO2-SiO2 hybrid organic-inorganic, TiO2 and ZrO2) with semiconductor quantum dots (CdSe, CdSe@CdS and CdSe@ZnS). The nanoparticles have been prepared separately by colloidal chemistry and than mixed with the sol-gel matrix solution after surface ligand exchange. The influence of the different sol-gel matrix on the active optical properties have been studied. Titania based composites were seen to be inherently photo-unstable due to photoelectron injection into the bulk matrix and subsequent nanocrystals oxidation. In comparison, zirconia composites were significantly more robust with high photoluminescence retained for annealing temperatures up to 300 °C. Both titania and zirconia composite waveguides exhibited amplified stimulated emission (ASE) with one-photon optical pumping, however only zirconia based waveguides exhibited long term photostability (loss of less than 30% ASE intensity after more than 40 minutes continuous excitation). These waveguides showed also ASE with two-photon infrared optical pumping. We conclude that the low electron affinity of zirconia and its inherent high refractive index makes it an ideal candidate for nanocrystals based optical waveguides.

Keywords: sol-gel, quantum dots, waveguides, photoluminescence, amplified stimulated emission, nanoparticles.

0356 | Writing of lithium niobate patterns on sol-gel derived Li2O-Nb2O5-SiO2 film surface by laser irradiation

Tsuyoshi Honma*, Takayuki KomatsuDepartment of Materials Science and Technology –

Nagaoka University of Technology, Japan, e-mail: [email protected]

Laser writing of lithium niobate (LiNbO3) crystal was fabricated on the amorphous thin film surface of sol-gel derived Li2O-Nb2O5-SiO2. At first, to make heater layer that absorb laser light and convert thermal energy, transition metal ion doped silica film was coated on fused silica substrate by dip coat method. After annealing Li2O-Nb2O5-SiO2 amorphous layer was fabricated by lithium niobium silicon ethoxide solution coating and annealing process. By irradiation of ytterbium fiber laser (l = 1080 nm), laser focal point was crystallized immediately. By means of micro Raman spectroscopy, it is cleared that laser induced point consists of LiNbO3 single phase. Comparing with laser-induced crystallization in bulk Li2O-Nb2O5-SiO2 glass we also discussed about crystal orientation and second harmonic generations.

Keywords: lithium niobate, laser irradiation, crystallization, micro Raman spectroscopy.

0128 | Structural chemistry of meso-macroporous functional hexagonal tungsten oxide based electrochromic (EC) devices

Yahia Djaoued1*, Subramanian Balaji1, Ralf Brüning2

1Laboratoire de Micro-spectroscopies Raman et FTIR, Université de Moncton – Campus de Shippagan, 218, boul. J.-D. Gauthier, Shippagan, New-Brunswick, E8S 1P6, Canada, e-mail: [email protected]

2Physics Department, Mount Allison University, Sackville, NB, E4L 1E4, Canada

Tungsten oxide exists in 3 types of crystal structures: i) ReO3 type, ii) metastable hexagonal WO3 (h-WO3), and iii) pyrochlore structures. h-WO3 has a very interesting structure, as it can accommodate more Li ions when compared with the ReO3 type WO3 structures. This feature of h-WO3 has generated lot of interest in their synthesis for applications as host in lithium ion (Li+) batteries. But not many studies have demonstrated their applicability in the construction of an EC device. Hence we developed a method to synthesis transparent, crack-free, meso-macroporous h-WO3 films up to ~850 nm with a single dipping. Also we have constructed EC devices using thus prepared films. As of today, Li+ intercalation mechanism in the h-WO3 has been proposed based on the electrochemical methods and XRD. Although, electrochemical methods quantify the amount of Li inserted, and XRD reveals the corresponding lattice parameter changes in the h-WO3, both techniques falls

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short of explaining the Li+ insertion sites in the hexagonal framework. In order to overcome this obstacle, we employed Raman and XRD to study h-WO3 and the structural changes observed due to the Li+ insertion. This work has provided a new insight into the ion intercalation mechanism into the h-WO3 structure, and a first hand experimental evidence for the Li+ occupancy of square windows in the h-WO3 structure. We proved that the coloration process in the EC device based h-WO3 is mainly due to Li+ that occupy hexagonal and square windows sites of the h-WO3. This study will potentially influence the characterization methods that have been conventionally used to study the Li ion host materials for so many applications as it provides a quick and reliable signature of the structural modifications occurring in the ion host materials.

Keywords: meso-macroporous hexagonal tungsten oxide, electrochromic device, lithium intercalation, micro-raman spectroscopy, X-ray diffraction, coloration in hexagonal tungsten oxide.

0058 | Progress on the fabrication of on-chip, integrated chalcogenide glass (ChG)-based sensors

Kathleen Richardson1*, Laeticia Petit1, Nathan Carlie1, Bodgan Zdyrko1, Igor Luzinov1, Juejun Hu1, Anu Agarwal1, Lionel Kimerling1, Troy Anderson1, Martin Richardson1

1*Clemson University, School of Materials Science and Engineering/COMSET, e-mail: [email protected] 2Massachusetts Institute of Technology, Microphotonics Lab 3University of Central Florida, College of Optics/CREOL/FPCE

To address the issues of existing chemical sensor technologies, including high cost; large footprint; and low sensitivity, we review ongoing progress on the material design, fabrication and performance of chalcogenide glass resonators utilizing cavity-enhancement for high sensitivity MIR chemical sensing. Ultra-high-Q optical resonance enables sensitive detection of even tiny optical property perturbations (optical absorption and/or refractive index change) in the environment of the sensors; allowing improvement of detection limits by an order of magnitude over commercial surface plasmonic resonance sensors. The use of CMOS-compatible fabrication techniques and incorporation of microfluidcs for analyte delivery, offer a solution which is highly robust. We report the results of our recent efforts to optimize device optical performance through glass chemistry selection and deposition process optimization, as well as enhancement of structure selectivity to fluid- and vapor-based chemical species via composition tailoring of polymer cladding layers, The results of recent efforts to translate NIR performance to MIR platform/device geometries are discussed.

Keywords: Chalcogenide glass, infrared, lithography, microfluidics, sensors.

0390 | Effect of CdS in bulk GeS2-Ga2S3-CdS chalcogenide glasses to third-order nonlinear optical properties by Z-scan method

Xuan He, Qiming Liu*, Xiujian ZhaoKey Laboratory of Silicate Materials Science and Engneering (Wuhan University of Technology),

Ministry of Education, Wuhan, Hubei 430070, e-mail: [email protected]

The third-order optical nonlinearity of GeS2-Ga2S3-CdS chalcogenide glasses was inverstigated using the Z-scan technique. The results indicated that the addition of CdS in the glass has obviously impact on the value of the third-order nonlinear susceptibility. The largest third-order nonlinear susceptibility of the glass containing 15% CdS (in mol) has been obtained as 9.17×10-13 esu. The third-order nonlinear response was dominantly due to the distortion of electron clouds in the samples.

Keywords: chalcogenide glasses, third-order nonlinearity, Z-scan.

0352 | Low-temperature extrusion molding of oxygen-free fluoride glassesPeter B. Baskov*, Vadim A. Perezhilin, Vyacheslav V. Sakharov, Valentin V. Shatalov

Scientific – Research Institute of Chemical Technology

Fluoride glasses’ tendency to crystallization seriously limits opportunities of casting methods for efficient fabrication of glass ware with high optical and operational properties. The alternative of fluoride glasses production is low-temperature glass formation by extrusion molding. High pressure ensures the process at temperatures of the lower border of vitrification area (near to vitrification temperatures Tg), far from dangerous Tamman zones of crystals’ nucleation and growth.

Low-temperature processes of viscous flow of fluorozirconate, fluorohafnate and fluoroaluminate glasses have been studied. The two-level nano-inhomogeneous structure of extruded fluoride glasses was established – the bottom level 2-8 nm and the top one 30-150 nm. The technology of forced cold molding at high pressures (FCMP) was used for fabrication of thin (1-4 mm) long (0.5-1 m) rods with the polished



external surface, two-layer performs and other products. Optical losses in a wide spectral range – from UV up to middle IR areas – are less than 0.2-0.5 dB/m. Implementation of FCMP deformation processes in vacuum provides minimal content of O2- and OH- in glasses, and also prevents the processes of nano- and microcrystallization.

Profiled glasses produced by FCMP method expand the nomenclature of optical elements for lens optics, laser and measuring optics for UV-IR range. Low-temperature extrusion procedures, such as FCMP, certainly increase the possibility of practical use of some other easily crystallized glasses with remarkable but not realizable at present properties.

Keywords: fluoride glass, ware, molding at vitrification temperature.

0063 | The square-well model in mean spherical approximation as a reference system in variational calculations

Nikolay E. Dubinin1*, Vladimir V. Filippov2

1*Institute of Metallurgyof theUral Division of the Russian Academy of Sciences Amundsen 101,Ekaterinburg-RUS, e-mail: [email protected]

2Ekaterinburg High ArtillerySchool – Shcherbakov 145, Ekaterinburg-RUS

The variational method is widely used for thermodynamic calculations of liquid and amorphous metals. Recently, the square-well model (SW) was suggested as a reference system in the thermodynamic variational calculations for simple liquid metals for the first time [1]. It was found that the SW-variational procedure gives a lower upper bound of the Helmholtz free energy than the hard-sphere-variational procedure. In [1] the SW system is taken within the random phase approximation (RPA). It is a shortcoming of the work [1] since the SW-RPA solution leads to unphysical behavior of the structure factor at some sets of the SW parameters. Progress in this area of investigations can be achieved by using more accurate theories of liquids than the RPA, such as the mean spherical approximation (MSA).

Here, we apply the SW-MSA reference system. The semi-analytical solution of the SW obtained in the MSA [2, 3] is used. Thermodynamics and structure of pure liquid alkali metals are studied. The local Animalu-Heine model pseudopotential, the Vashishta-Singwi exchange-correlation function, and the Nozieres-Pines exchange-correlation energy are taken for the calculations.

This work is supported by the grant 08-03-00992 of RFBR and the grant 02.740.11.0152 of Russia Science.1. N.E. Dubinin et al., J. Non-Equilibr. Therm., in print (2010).2. N.E. Dubinin et al., J. Non-Crystal. Solids, 353 (2007) 1798.3. N.E. Dubinin et al., Cent. Eur. J. Phys., 7 (2009) 584.

Keywords: variational method, square-well reference system, mean spherical approximation.



Sept. 21 – 14:00-16:00 h – Room Tech.

Education in glass (Chairman: J. Parker)

0465 | The future of glass educationJohn M. Parker

Departament of Engineering Materials, University of Sheffield, Hadfield Building, Mappin St., Sheffield, S1 3JD, UK, e-mail: [email protected]

The earlier part of the last century saw the rapid growth of universities and technical schools offering courses in glass science and technology. More recently in the developed world the demand from industry for glass technologists has declined, and other engineering/scientific skills have been perceived as more important. This paper will examine some of the actual and potential responses of our community to such pressures, with the goal of ensuring that our knowledge base is maintained and indeed that we can continue to be a hothouse for new developments. Various ways of cementing the links between industry, professional societies and academia have been tried in the UK and elsewhere; the effectiveness of key examples of such approaches will be analysed. Finally some recent developments such as the ICG Summer Schools, now in their second year and ICG roadmapping exercises will be outlined.

Keywords: education, ICG, workshops, road maps.

0493 | Glass education without boundariesWilliam R Heffner1, Himanshu Jain1, Carlo G. Pantano2*

1Lehigh University and 2Penn State University, Pennsylvania, USA 2NSF International Materials Institute on New Functionality in Glasses

One of the missions of the NSF International Materials Institute on New Functionality in Glasses is to promote and facilitate glass education for K-12, undergraduate and graduate students in science and engineering, glass engineers and scientists, and the general public. With a goal of making information on glass available freely to anyone, anywhere with access to the Internet, a collection of 180 videos has been produced. These video lectures were generated through a variety of Invited Lectures, International Conferences, Workshops and Schools. A series of demonstrations using ‘candy glass’ is also developed to engage young students in the science, engineering and applications of glass through familiar materials, with a hands-on focus, real-science experience, and within the resources of a typical public school. Precollege teachers have expressed strong interest in adopting these curricular demonstrations for enhancing the learning of chemistry and physics. To help draw undergraduates into the field of glass, an international contest was held to generate ideas for new glass products and technologies that could be enabled by the development of stronger glass. Also underway is a novel concept of cooperative International multi institution team teaching-learning (MITT) at the graduate level whereby advanced topics of glass science are taught over the Internet by pooling faculty expertise at several universities to teach students at other universities. Finally, glass science is introduced to the general public via three unusual programs: ‘Pennsylvania Glass Trail’, ‘New Glass Technology for Artists’, and various group events at the local science museum – ‘Da Vinci Science Center’. Selected programs and outcomes will be described with the goal of expanding our International glass education and research network.

0386 | Brazilian ceramic society’s glass schoolMauro Akerman1*, Samuel M. Toffoli2

1Consultor Independente 2 Universidadel de São Paulo – USP, São Paulo – SP

Brazil is a continental country and exhibits a large glass manufacturing sector. ABIVIDRO (Brazilian Technical Association of the Automated Glass Producers) congregates 16 associates, among domestic and international companies, representing, in 2008, almost 2.3 billion USD, and 12000 direct jobs. In Brazil, there is no formal training of technicians or engineers with a solid background in glass technology. Because of that, the larger industries usually train their own technical people, whereas the smaller size companies have difficulties in putting together adequately formed teams. One of the basic missions of the Brazilian Ceramic Society (ABC) is to offer technical training and information exchange. Therefore, to fill the workforce gap, ABC started, in 2009, a short-term training program entitled “Glass School”, inviting specialists formed within the factories, academic people, and independent consultants, as well as suppliers of materials, equipments, and

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services to be the instructors. The “Glass School” offered 3 different courses in 2009, repeating them (and adding 3 more) in 2010, focusing their programs on the most relevant points for the glass manufacturing process, what covers since the basic scientific contents to much more technological issues, like furnace operation, for example. This paper presents and discusses the structure, contents, and results of the first year of existence of the “ABC’s Glass School”.

Keywords: glass school, training, glass technology.

0337 | Lecture on knowledge management on the floor of the glass industry plantEdison José Toporcov1*, Jorge Muniz Junior2, Carlos Donizetti3, Walter Minutti Santalucia Junior4, Edgard Dias Batista Junior5

1Wheaton Brasil Vidros – São Bernardo do Campo – SP 2Universidade Estadual Paulista – UNESP, Campus de Guaratinguetá – SP

3Faculdade de Engenharia Industrial – São Paulo 4Wheaton Brasil Vidros – São Bernardo do Campo – SP

5Universidade Estadual Paulista – UNESP – Campus de Guaratinguetá – SP

The lecture purposes to expose experiences, methodologies and techniques for knowledge sharing, specifically involving the knowledge of the professional glassmaker in the “shop floor”.

Will be presented lessons learned from the evaluation process based on knowledge (PAI-C), for the diagnosis of the needs of professionals in order to aim at Knowledge Management, Production and Labor Organization.

Highlights discusses the experiences of the Technical and Operational Training Center (CTTO), using techniques that promote meetings of skilled and not skilled glassmakers, “silver hairs”, to share knowledge, discuss quality deviation, process improvement and labor glass training.

Tools such as “storytelling,” integration with the “silver hairs”, implementation of the “SECI”, application of Andragogy, not classical Pedagogy in operational training, are part of the creation of favorable environment that will be addressed in this work.

Keywords: andragogy, glassmaker, knowledge management, SECI, silver hairs, storytelling.

0490 | Glass research and education in BrazilAna Candida M. Rodrigues*, Edgar Dutra Zanotto

Universidade Federal de São Carlos – Departamento de Engenharia de Materiais, São Carlos – SP, Brazil, e-mail: [email protected]

We present an overview about glass research and education in Brazil. We list the active research groups in Brazil focused on glasses, and especially which research topics are presently covered by these groups. Besides, we describe which glass related topics are currently being taught at Brazilian universities at undergraduate and graduate levels. The steady evolution of the number of academic papers related to glasses published by Brazilian researchers will also be discussed. Finally, we propose that it is important to improve the interaction between academic research groups and industry.

Keywords: glass education, glass research, research and industry.



0442 | The school of glass implementation: the tool to develop employeesFlávio Cavalcanti de Oliveira Lopes*, Catarina Maria Câmara Uchoa,

Tereza Helena S. Cavalcanti TaraziukCompanhia Industrial de Vidros – CIV – Engenho São João, S/N – Recife – PE

The Industrial Glass Company – CIV, is a Brazilian company with over 50 years, 100% national capital, and installed capacity of 1000 tons of glass for day.

The School of Glass was created to develop in the employees a deeper awareness of the process of glass production. We aim at covering 100% of the employees in the period of four years, having everyone share the same level of knowledge with a focus on quality of production.

The program also exists to meet the needs of training centers for this factoring process in the region, since it is no mean feat to find a glass worker in our market. Besides that, the school aims at unifying the technical jargon among the different departments of the company. The pedagogical method was structured in four levels of training.

• Module–NotionsofGlass Technology–Basicoverview for threehours for employeeswhohavenoexperience/knowledge in glass companies.

• Module–Glasstechnician–Trainingaimedatglasstechnicians,whodonotyetholdabachelor’sdegreebut are involved in the production process, even though they do not have deeper experience/knowledge in the area. It is a 20-hour course and the syllabus content includes the History of glass, structure and properties, raw materials, preparation of the composition, fusion, conformation, quality and recycling, besides presenting an overview of the glass industry in Brazil and in the World.

• Glass TechnicianSeminar – Programdeveloped for employeeswho have practical knowledge in theprocess of glass production, lasting up to four days and with themes that are selected according to a needs analysis.

• Technician-focusedModule–Taughtaccordingtothespecificneedsofeacharea,focusedontechnicalemployees who already have wide experience and extensive knowledge in the area.

In the three training areas, the pedagogical guidance team will be in change of facilitators who are selected from inside CIV (the company) itself, as well as hired consultants.

Keywords: school, glass, technology, CIV, knowledge, seminar, company.

Discussion of previous talks and synopsis.

Sept. 22 – 8:00-9:45 h – Room A

Structure & Crystallization TC3 & TC7 (Chairman: R. Müller)

0496 | Structural Role of Nucleating Elements (Zr, Ti and Ni) During Glass Nucleation: Influence on Physical Properties

Laurent Cormier*, Olivier Dargaud, Nicolas Menguy, Aymeric Dugué, Marie Guignard, Laurence Galoisy, Georges Calas

Institut de Minéralogie et de Physique des Milieux Condensés, Universités Paris 6 et 7, IPGP and CNRS, 140 Rue de Lourmel, 75015 Paris, France; [email protected]

Glass–ceramics are commonly made by forming glasses and applying a controlled heat treatment, to cause crystalline nucleation in the glassy matrix. Zirconium, titanium or nickel may act as an efficient nucleating agent, which promotes controlled bulk nucleation. We present a review of some recent results obtained on the structural modifications induced by the introduction of ZrO2, TiO2 or NiO in MgO–Al2O3–SiO2 glasses and their changes during nucleation. Original information on the local structure of the pristine glasses has been obtained by a combination of X-ray and neutron wide-angle scattering coupled to Reverse Monte Carlo simulations, EXAFS and XANES spectroscopy, providing detailed structural information on the initial glass at atom-level details. They show unusual coordination and/or site sharing of the nucleating agents and structural

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fluctuations characteristic of the medium range structure of the pristine glass. These fluctuations may play a major role in the nucleation process, by minimizing the energy barrier of the glass to crystal transformation. The formation of crystallites has been observed with Transmission Electron Microscopy, and in-situ XRD has also been used to monitor the kinetics of appearance of crystals in Zr-bearing glasses. Eventually, the change in the coloring role of Ni during the nucleation process has been investigated by diffuse reflectance spectroscopy. All thesse data show that original processes at short and medium range scales govern the glass-to crystal transformation, in the pristine glass as well as during crystalline nucleation.

Keywords: glass structure, glass nucleation, structure/property relationships, EXAFS, XANES, transmission electron microscopy, optical absorption spectroscopy

0219 | Atomistic modeling of crystallization processAkira Takada

Research Center, Asahi Glass Co., Ltd, 1150Hazawa-cho, Yokohama, Kanagawa 221-8755 Japan, University College London, Gower Street, London WC1E6BT, UK, Institute of Industrial Science,

University of Tokyo, Meguro, Tokyo 153-8505, Japan, e-mail: [email protected]

Computer simulations such as molecular dynamics and reverse Monte Carlo methods have been revealing new insights into medium range order, surface structures, and dynamical changes in local structures. However, it is still a great challenge to develop a new atomic modeling technique that enables investigation of the crystallization process. A major obstacle is that it is very difficult to crystallize glass materials through quenching by ordinary molecular dynamics and Monte Carlo methods except the crystallization of very simple structures. To overcome this problem new techniques for investigating crystallization process are developed and applied to silica and silicate glasses in this study. First, homogeneous and heterogeneous nucleation is discussed in terms of the sequentially irreversible change of atomic structures. Next, cooperative atomic motions and their structural orderings are interpreted in terms of thermodynamics, that is, focused on the change of internal energy and entropy. Finally, the future prospect of atomic modeling of crystallization is discussed.

Keywords: glass structure, crystallization, computer simulation, silica glass, silicate glass.

0073 | Effect of neodymium and molybdenum addition on the structure and crystallization tendency of a SiO2-Na2O-CaO-Al2O3-B2O3 glass

N. Chouard1,2*, D. Caurant1, O. Majérus1, J-L. Dussossoy2, R. Baddour-Hadjean3, J-P. Pereira-Ramos3

1Laboratoire de Chimie de la Matière Condensée de Paris (UMR CNRS 7574), ENSCP Chimie-Paristech, 11 rue Pierre et Marie Curie 75231 Paris, France, e-mail: [email protected]

2CEA, DEN, DTCD, SECM, Laboratoire d’Etude et Développement des Matrices de Conditionnement, Marcoule, 30207 Bagnols-sur-cèze, France

3Groupe Electrochimie et Spectroscopie des Matériaux (UMR CNRS 7182), Institut de Chimie et des Matériaux Paris-Est, 2-8 rue Henry Dunant 94320 Thiais, France

Neodymium and molybdenum are two chemical elements of big interest in nuclear glasses since they both present high concentrations in fission products coming from high discharge burn-up nuclear spent fuel. Consequently, during glass melt cooling, they may induce liquid-liquid phase separation and crystallization of apatite Ca2Nd8(SiO4)6O2 and powellite CaMoO4 phases that may lead to a modification of the expected glassy matrix properties (chemical durability, self-irradiation resistance…).

This work is an attempt to rely glass structure and crystallization tendency, by studying, for a simplified aluminoborosilicate glass belonging to the system SiO2-Na2O-CaO-Al2O3-B2O3, the effect of neodymium (from 0 to 16 wt% Nd2O3) and molybdenum (from 0 to 7 wt% MoO3) addition on the competition between the crystallization of apatite and powellite (both phases contain calcium and powellite can incorporate neodymium). In this paper, we present the main results, on one hand on the crystallization tendency of this glass, obtained by XRD (at room temperature and at high temperature) and SEM, after two kinds of thermal treatments: a controlled cooling from the melt and a thermal treatment of nucleation and growth. On the other hand, the structure of the same samples before and after crystallization is studied by Raman and neodymium optical spectroscopies.

Keywords: nuclear glasses, nucleation and growth, apatite, powellite, rare earth, molybdenum, glass structure.



0057 | Multispectroscopic study of a rare-earth rich aluminoborosilicate glass with relationship to its crystallization propertiesDaniel Caurant1, Odile Majérus1*, Arnaud Quintas1, Isabelle Bardez1,2, Pascal Loiseau1,

Thibault Charpentier3, Philippe Vermaut4, Jean-Luc Dussossoy2

1Laboratoire de Chimie de la Matière Condensée de Paris (UMR-CNRS 7574) – ENSCP (Chimie-ParisTech) – 75231 Paris, France, e-mail: [email protected]

2Laboratoire d’Etudes et Développement de Matrices de Conditionnement – DEN/DTCD/SECM, CEA Marcoule – Bagnols-sur-Cèze, 30207, France

3CEA, IRAMIS, Service Interdisciplinaire sur les Systèmes Moléculaires et Matériaux - CEA Saclay – 91191 Gif-sur-Yvette, France

4Groupe de Métallurgie Structurale, Laboratoire de Physico-Chimie des Surfaces (UMR CNRS 7045) – ENSCP (Chimie ParisTech) – 75231 Paris, France

In order to increase the nuclear waste load in containment glasses, new glass formulations are studied with respect to their physical properties, thermal stability and chemical durability. The chemical complexity of these multicomponent glasses has to be taken into account in order to get an appropriate understanding of the crystallization properties. In this work we studied the structure of a SiO2-B2O3-Al2O3-Na2O-CaO-ZrO2-RE2O3 glass derived from a new nuclear glass composition (RE2O3 with RE = Nd or La is taken as a structural simulant of minor actinides and lanthanides from the wastes), by using a multispectroscopic approach on systematic glass series with a varying chemical parameter. For instance, the RE2O3 content, the Na2O/Al2O3 ratio, the Na2O/CaO ratio and the B2O3 contents were varied in order to get insight into the structural role of the RE ions, the distribution of Na+ ions and charge compensation mechanisms in the glass. MAS NMR 11B, 29Si, 27Al and 23Na spectroscopy as well as Raman and Nd LIII- or K-edge EXAFS were the complementary structural tools. The crystallization tendency of the glasses was systematically assessed by the mean of a slow cooling from the melt followed by XRD, TEM or SEM and correlation with structural features can be drawn.

Keywords: glass structure, aluminoborosilicate, rare-earths, MAS NMR, EXAFS, crystallization.

0127 | 10B NMR studies of borate glasses and crystalsSteve Feller*1, Jack Berkowitz1, Michael McConnell1, Kevin Tholen1, Mario Affatigato1, Steve

Singleton1, Tiffany Myers1 , Steve W. Martin2, Diane Holland3, Mark Smith3, Tom Kemp3

1Coe College, Cedar Rapids, Iowa, USA, e-mail: [email protected] 2Iowa State University, Ames, Iowa, USA

3University of Warwick, Coventry, England, UK

Pulsed experiments were used with a field sweep magnet (main field at 7 T) to obtain the full 10B NMR spectra from a series of borate glasses and related crystals. These spectra then were fitted using the quadruple interaction extended to third order perturbation theory. Distributions of the quadruple coupling constant (CQ) and asymmetry parameter (η) were also found . Experimental data for vitreous boron oxide (both slow and rapidly cooled), vitreous and crystalline cesium triborate, vitreous cesium diborate, crystalline potassium diborate, crystalline lithium metaborate, crystalline lithium orthoborate, and vitreous cesium enneaborate have been fitted to yield their quadrupole parameters. The asymmetry parameter (h) is particularly sensitive to differences in the environments of three-coordinated borons placed in differing intermediate range order positions.

Keywords: NMR, structure, 10B, distributed quadrupole parameters.

0034 | Structural order parameters, relaxation and crystallizationJuern W. P. Schmelzer1*, Ivan Gutzow2

1Institute of Physics, University of Rostock, 18051 Rostock, Germany, e-mail: [email protected] 2Institute of Physical Chemistry, Bulgarian Academy of Sciences, Sofia 1113, Bulgaria

Crystallization processes in glass-forming melts occur most frequently in a range of temperature and pressure overlapping the glass transition interval. Here the characteristic times of change of the external parameters are of the same order of magnitude as the relaxation times of the glass-forming melts. In this range of thermodynamic control parameters, employing the thermodynamics of irreversible processes, additional structural order parameters like fictive temperature and fictive pressure have to be introduced into the description. These parameters describe the current structure of the melt and, in this way, its effect on crystallization. In the present contribution, first, a general thermodynamic definition of fictive pressure and fictive temperature is presented. Second, an explanation of relaxation behavior proportional to the square root of time and the origin of the Kohlrausch relaxation law is developed. Finally, it is discussed how differences in the structure of the glass-forming melt – described by a set of structural order parameters –



may affect crystallization processes via their effect on the thermodynamic (bulk and surface) properties (both of the ambient and newly evolving crystal phases) and the kinetic parameters (like relaxation times, diffusion coefficients or viscosity) of the glass-forming melt.

Keywords: relaxation, structural order parameters, fictive pressure, fictive temperature, crystallization.

Sept. 22 – 10:00-12:00 h – Room A

Structure & Properties TC 22 (Chairman: G. Callas)

0311 | The environment of transition elements in oxide glassesLaurence Galoisy*, Georges Calas, Laurent Cormier

Institut de Minéralogie et de Physique des Milieux Condensés (IMPMC), Université Paris VI and Paris VII, IPGP and IRD, 140 rue de lourmel 75015 Paris, FRANCE

The compositional dependence of the glass coloration and the local environment of transition elements is followed using various spectroscopic techniques. Ni, Zn, Zr and Mo, present a good illustration of the diversity of local structures in oxide glasses. The coordination numbers of transition elements in glasses are often lower than those in crystalline compounds. 4-fold sites correspond to a network-forming position in Ni and Zn, but also indicate the presence of polyanions, structurally independent of the network. The charge compensation of the tetrahedral cation by alkalis and/or alkaline-earths is important for rationalizing glass stability. Original 5-fold site for Ni, may explain the origin of the peculiar coloration of most Ni-bearing glasses. 6-fold site may be encountered in some compositions, in relation with the presence of B. Ni-bearing, low-alkali borate and borosilicate glasses exhibit colors ranging from green to yellow, related to the presence distorted [6]Ni, indicating the presence of defective NiO clusters. Zr, is generally encountered in regular octahedra, an unusual coordination seldom encountered in anhydrous minerals. A molecular scale approach helps understand the origin of the peculiar physicochemical properties provided by the presence of Zr in glasses, e.g. the resistance to alteration or the formation of glass ceramics. All these examples will show how transition elements illustrate the structure-property relationships in oxide glasses.

Keywords: UV-visible, X-ray absorption spectroscopy, transition elements, local structure, oxide glasses.

0218 | Prediction of structure-property relationship in glasses based on numerical simulation

Akira TakadaResearch Center, Asahi Glass Co., Ltd, 1150Hazawa-cho, Yokohama, Kanagawa 221-8755 Japan,

University College London, Gower Street, London WC1E6BT, UK, Institute of Industrial Science, University of Tokyo, Meguro, Tokyo 153-8505, Japan, e-mail: [email protected]

Numerical simulation is more and more growing as a very powerful tool to explain the structure-property relationship in glasses. The key factor lies in constructing a bridge between microscopically estimated atomic configurations and macroscopically observed properties. Each property of interest has to be analyzed with its own proper recipe for simulation techniques. In this paper a variety of properties such as thermal, transport, spectroscopic, thermodynamic, and optical properties are estimated based on simulated structure in silica glass, silicate glass or B2O3 glass employing various simulation techniques. Finally, the future prospect of structure-property relationship by numerical simulation is discussed.

Keywords: glass structure, glass property, computer simulation, silica glass, B2O3 glass, silicate glass.

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0415 | Structural role of Zr as a nucleating agent in silicate glassesOlivier Dargaud1,2*, Laurent Cormier1, Laurence Galoisy1, Nicolas Menguy1,

Georges Calas1, Cécile Jousseaume2, Gilles Querel31Insitut de Minéralogie et de physisque de la Matière Condensée,

140 Rue De Lourmel, Paris 75015, France, e-mail: [email protected] 2Saint-Gobain Recherche, 39 Quai Lucien Lefranc, Aubervillier 93303, France

3Saint-Gobain Northboro Research and Development Centre, Goddard Road, Northborough 01532-512 MA, USA

The nucleation control of a glass matrix is mainly achieved using nucleating agents such as ZrO2 or TiO2, that precipitates promptly upon heating. From a fundamental point of view nucleation is still poorly described by theory [1] and little is known about the evolution of the structural environment of the nucleating elements in the parent glass and its modification during nucleation. A major property of Zr is that it adopts a peculiar coordination of 7-fold in MgO-Al2O3-SiO2 glasses [2] by contrast to alkali glasses in which it occurs in a regular 6-fold coordination [3]. The peculiar organization around Zr relative to Zr and Si next nearest neighbors explains the role of this element as a precursor of further structural transformations leading to crystal nucleation [4].

The local structure of Zr will be analysed in various glasses of general composition XnO-Al2O3-SiO2 and YnO-Al2O3-SiO2, where X is Li or Na and Y, Mg, Zn or Ca. Structural properties are obtained using X-ray absorption spectroscopy (XAS) at both Zr-K and -L edges. They will be compared to the nucleating ability of Zr in each system and more generally to the thermal evolution of the glass followed by high performance DSC. Establishing structure-property relationships will help in the prediction of the nucleating role of Zr in new matrices.1. Fokin, et al. JNCS, 352, p. 2686, 20062. Dargaud, et al. J. Am. Ceram. Soc., 93, 2, p. 342, 20103. Ferlat, et al., Physical review B, vol. 73, no. 214207, p. 1, 20064. Dargaud, et al. Submitted, 2010

Keywords: nucleation, structure-property relationships, XAS, HRTEM.

0191 | Network topology and diffusion in soda lime borate glass systemsMorten M. Smedskjaer1*, John C. Mauro2, Sabyasachi Sen3, Yuanzheng Yue1

1*Section of Chemistry, Aalborg University, Denmark, e-mail: [email protected] 2Science and Technology Division, Corning Incorporated, Corning, NY 14831, USA

3Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, USA

In this paper, we have investigated the structure, transport properties, and network topology of the borate glass series (in mol%): (89-x)B2O3− xNa2O−10CaO−1Fe2O3 with x = 5, 10, 15, 20, 25, 30, and 35. By using a temperature-dependent topological constraint model, we have predicted the scaling of the glass transition temperature, fragility, and boron speciation with composition (x). Experimental results are in good agreement with the predicted ones, and this provides insights into the correlation between the glassy dynamics and the structure of soda lime borate glasses. Through this correlation, we attempt to clarify the origin of the correlation between the inward cationic diffusion and the glass composition. The inward cationic diffusion is induced by reducing ferric ions to ferrous ions in the glasses near the glass transition temperature. The extent of inward diffusion varies with composition and this variation depends on the boron speciation and the electrostatic environments of the involved modifying ions. This work also provides information on the microstructural origin of fragility of oxide liquids.

Keywords: borate glasses, diffusion, network topology, topological constraint model, boron speciation, fragility, glass transition.

0287 | New raman scattering investigations in silica: relaxation monitoring at high temperatures

Maggy Dutreilh-Colas1,2,3 Miriam Chligui,1,2 A. Canizarès,1,2 N. Raimboux,1,2 Y. Vaills,1,2 P. Simon1,2*1C.N.R.S UPR 3079 C.E.M.H.T.I, 45071 Orléans Cedex 2-F

2*Université d’Orléans, 45067 Orléans Cedex 2- F, e-mail: [email protected] 3now at SPCTS, CNRS UMR 6638, Université de Limoges, 123 rue A. Thomas, 87060 Limoges Cedex-F

The topology of the silica network is rather simple, allowing to probe small structural effects, as those due to relaxation under annealing in the vicinity of the glass transition temperature, i.e. change of fictive temperature. Direct investigations are difficult due to the considered temperature range (1000-1400 °C). For Raman scattering the main problem is thermal emission, which masks the vibrational information. A time-resolved Raman device was used to reject this black body-like contribution. The time dependence at constant



temperature was then obtained, for temperatures from 1400 °C down to 1100 °C, during relatively long times (some days for the lowest temperatures). A continuous monitoring of the Raman spectrum was done (1spectrum/minute). The great number of collected spectra gives a very good statistics, allowing to display the smooth structural changes due to relaxation and change of fictive temperature, and to measure the relaxation times. These relaxation times are somewhat longer than expected through existing models or estimations.

Besides this, new detailed room-temperature Raman measurements on silica will be reported, which could help to a better understanding of the low-frequency dynamics.

Keywords: raman, silica, relaxation, high temperature.

0289 | Brillouin and raman investigations in binary heavy alkali silcate glasses (Rb2O-SiO2 and Cs2O-SiO2)M. Chligui*, A. Canizarès, N.Raimboux, Y. Vaills, P. Simon

C.N.R.S UPR 3079 C.EM.H.T.I, 45071 Orléans Cedex 2-F, Université d’Orléans, 45067 Orléans Cedex 2-F, e-mail: [email protected]

In this study, we are interested in heavy binary alkali glasses, Rb2O-SiO2 and Cs2O-SiO2, for a better understanding of the specificities of the heavy cations on the silicate network.

Twenty compositions R2O-SiO2 (R = Cs, Rb) between 5 and 36 % have been elaborated and analyzed by Raman and Brillouin spectroscopies. The hygroscopic character of the high alkali compositions needs some precautions but does not preclude vibrational studies.

The Raman spectra deconvolutions show some specific features for these glasses. At low wavenumbers, a Voigt function must be added in the spectral range of the boson peak region in cesium glasses, and two such Voigt functions for rubidium glasses, denoting some localized vibrations of heavy ions in their oxygen surrounding. This has still not been observed in other binary alkali glasses of silicates. In the immediately subsequent spectral range (50-650 cm-1) dominated by SiO4 bending modes, the ratio of Cs over Rb Raman spectra is practically wavenumber-independent for x compositions lower than 10% : this shows that then the silicate networks and the connections between tetrahedral are practically identical in Cs and Rb glasses.

Besides this, more macroscopic investigations have been undertaken by Brillouin scattering, to probe the elastic properties of these glasses from room temperature up to the Tg range. We have observed relaxation phenomena in the glasses blow the glass transition.

Keywords: raman, billouin, relaxation.

0329 | Infrared emission spectroscopy of silicate and borate glasses up to 1500 °CCristiane N. Santos1*, Domingos de S. Meneses1,2, Patrick Echegut1

1CNRS, UPR3079 CEMHTI, 1D Avenue de la Recherche Scientifique, 45071, Orléans cedex 2, France, e-mail: [email protected]

2Université d’Orléans, Polytech-Orléans, Avenue du Parc Floral, BP 6749, 45067 Orléans cedex 2, France

Silicate and borate glass compositions are among the most studied systems due to their optical and physicochemical properties, with applications varying from industrial use to scientific development. The optical properties at ambient conditions have been largely investigated when compared to their features at elevated temperatures. In emissivity measurements, high-precision spectrometers and the accurate knowledge of the surface temperature are some of the key aspects to be taken into account when developing such challenging experiments. We have performed reliable in-situ emissivity measurements using a home-made apparatus composed of two spectrometers, a black-body reference and a CO2 laser as the heat source. The laser ensures a homogeneous heating and melt stability up to 1500 °C during the data acquisition while maintaining a relatively cold environment. The optical complex functions of the studied compositions were obtained from 25 to 20000 cm–1 by applying a dielectric function model [1]. All emissivity spectra were compared to the ones at ambient temperature obtained by the indirect method using the reflectivity and transmission data. In this context we carefully analyze the role of glass composition on the vibration of internal and external modes and the emissivity properties. Structural dynamics with temperature and vibrations due to remaining water bonded molecules are reported.1. De Sousa Meneses, M. Malki and P. Echegut, J. Non-Cryst. Solids 352, 769 (2006).

Keywords: glasses, emissivity.



0313 | Spectroscopy of chromium in oxide glasses: local structure, redox states and thermal expansion

Georges Calas*, Laurence Galoisy, Laurent Cormier, Odile MajerusInstitut de Minéralogie et de Physique des Milieux Condensés, Universités Paris 6 et 7,

IPGP and CNRS 140 Rue de Lourmel, 75015 Paris, France, e-mail: [email protected]

We present a comparative spectroscopic study of chromium in oxide glasses, using EXAFS, XANES and optical absorption spectroscopy. Coexisting octahedral Cr3+ and chromate groups may be detected by XANES and optical absorption data. In all investigated glasses, EXAFS and optical absorption spectra indicate that Cr3+ is located in preferential environments, as shown in borosilicate or mixed alkali/alkaline earth glasses. High temperature crystal field spectra have been obtained in the range 10-800K. In all glasses, the Cr3+ crystal field band exhibits a red shift with increasing temperature, and the glass color is modified consequently. This implies a modification in the relative position of the Fano antiresonances located on this crystal field band. Optical absorption spectra are strongly sensitive to temperature effects, even over small temperature intervals. Crystal field splitting energy as well as red shift amplitude are not the same for the different glasses investigated. Using the dependence of crystal field splitting energy on cation-oxygen distances, local thermal expansion coefficients (TEC) can be extracted from these spectroscopic in-situ measurements. Local TEC values obtained in glasses are lower than bulk TEC’s, and are similar to those observed for octahedral Cr3+ in crystals. These local TEC’s vary by as much as 50% as a function of glass composition, the local and bulk TEC’s varying in a similar way.

Keywords: structure/property relationships, glass structure, glass coloration, redox states, EXAFS, XANES, optical absorption spectroscopy.

Sept. 22 – 14:00-16:15 – Room A

Structure & Vibrations TC 26 (Chairman: B. Hehlen)

0037 | Theory of vibrational excitations in glassWalter Schirmacher

Institut für Physik, Universität Mainz, D-55099 Mainz, Germany Physik-Department E13, Technische Unviersität München, D-85747 Garching, Germany

A theoretical description of vibrational excitations in disordered solids, especially glassy materials is presented. It is based on a generalization of elasticity theory allowing for spatially fluctuating elastic constants (elastic disorder). The enhancement of the spectrum in comparison with the Debye theory, which is observed in many glasses in the THz regime (boson peak) is explained as a consequence of the elastic disorder. This anomaly marks the lower frequency boundary of a frequency band in which random-matrix-type excitations prevail. Explicit expressions are given for the inelastic neutron- X-ray and Raman spectra. The theory can be used as a means to reconcile the anomalous spectra obtained with different spectroscopic methods. Explicit model calculations are in good agreement with experiments.

Keywords: boson peak, vibrational anomalies, neutron scattering, X-ray scattering, raman scattering.

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0193 | Nature of vibrational modes in simple silicate glassesSimona Ispas*, Masahiko Matsubara, Walter Kob

Laboratoire des Colloïdes, Verres et Nanomaétriaux, CNRS UMR 5587 Université Montpellier 2,34095 Montpellier CEDEX 5, France, e-mail: [email protected]

The vibrational properties of silica glass have been intensively studied experimentally and theoretically during the last four decades. However, only few investigations have explored the evolution of the vibrational features of simple alkali glasses or silica under compression. In this contribution, we will present a detailed mode analysis of two simple (Li/Na) alkali glass models as well as for silica glass models obtained by combined classical and Car-Parrinello molecular dynamics.

In particular we will discuss how the presence of the network modifier influences the relevant vibrational parameters: positions, shapes and intensities of the main peaks in the vibrational density of states (VDOS) and IR spectra. We will also show the decomposition of the VDOS on symmetry-adapted modes of the basic structural units of our models networks: SiO4 tetrahedra and SiOSi bridges. The same analysis will be carried out in the case of few silica glass models at normal density as well as at higher density.

Keywords: alkali silicate glass, vibrations, Molecular dynamics, DFT.

0060 | Equivalence of the boson peak in glasses to the Transverse acoustic singularity of crystals

Aleksand I. Chumakov1*, Andrea Monaco1, Giulio Monaco1, Wilson Crichton1, Alexey Bosak1, Rudolf Rüffer1, Andreas Meyer2, Florian Kargl2, Lucia Comez3,4, Daniele Fioretto3,4, Hubertus Giefers5,

Stefan Roitsch5, Gerhard Wortmann5, Murli H. Manghnani6, Anwar WushurHushur6, John Balogh6, Quentin Williams7, Krzysztof Parliński8,9, Paweł T. Jochym8, Przemysław Piekarz8

1European Synchrotron Radiation Facility, BP 220, F-38043 Grenoble, France, e-mail: [email protected] 2Physics Department E13, Technische Universität München, D-85747 Garching, Germany

3INFM CRS-SOFT, c/o Universitá di Roma “la Sapienza”, I-00185 Roma, Italy 4Dipartimento di Fisica, Universitá di Perugia, I-06123 Perugia, Italy

5Department of Physics, University of Paderborn, D-33095 Paderborn, Germany 6School of Ocean and Earth Science and Technology, University of Hawaii, Honolulu, Hawaii 96822, USA

7University of California at Santa Cruz, Department of Earth Sciences, Santa Cruz, CA 95064, USA 8Institute of Nuclear Physics, Polish Academy of Science, 31-342 Kraków, Poland

9Institute of Techniques, Pedagogical University, 30-084 Kraków, Poland

We studied the pressure dependence of vibrational dynamics of sodium silicate glass. The density of vibrational states (DOS) was measured using a diamond anvil cell. The DOS of a crystalline counterpart of the glass was measured at ambient conditions.

The increase of pressure causes a shift of the boson peak to higher energy and a decrease of its height. The reduced DOS of the crystalline phase shows a peak at yet higher energy and with still lower height. Ab-initio calculations show that this peak arises from the van Hove singularity of a transverse acoustic (TA) branch.

The changes in elastic medium of the glass with pressure were characterized by the pressure dependence of Debye energy. When the DOS data are plotted in Debye energy units, the boson peak of the glass matches the energy and the height of the TA singularity of the crystalline phase. Furthermore, it has the same absolute number of vibrational states. The results suggest that the boson peak originates from flattening of the TA modes in glasses around the pseudo-Brillouin zone boundary.

Keywords: glass dynamics, density of states, boson peak.

0154 | The boson peak of silica and its relation with elastic propertiesB. Rufflé1*, S. Ayrinhac1, E. Courtens1, R. Vacher1, M. Foret1, A. Wischnewski2, U. Buchenau2

1Laboratoire des Colloïdes, Verres et Nanomatériaux, UMR 5587 CNRS, Université Montpellier II, F-34095 Montpellier Cedex 5, France

2Institut für Feskörperforschung, Forschungszentrum Jülich, Postfach 1913, D-52425 Jülich, Germany, e-mail: [email protected]

The nature of collective vibrations in glasses and their relation to structural disorder are topics of active discussion and considerable interest. The reduced density of vibrational states generally shows an excess over the Debye level known as the boson peak. Tetrahedrally coordinated glasses have unusual thermomechanical properties related to their structure, among which decreasing elastic moduli under pressure and hardening with increasing temperature. Simulations of silica have shown that these properties relate to a progressive



polyamorphic transformation owing to reorientations of the --Si--O--Si-- bonds forming the ring structures, this without bond breaking or reconstruction. It is conceivable that a measure of the degree of transformation can be found in a suitably determined elastic modulus. Recent quantitative analysis of the elastic properties of silica has allowed extracting bare velocities. It is found that unrelaxed moduli increase considerably with temperature. The unrelaxed bulk modulus should provide a measure of the average rigidity of the structure at short distances. We show that indeed the boson peak of silica, which is a strong function of the temperature, successfully scales unto a single master curve with the use of unrelaxed bulk modulus, this with exponents that are non-trivial. Conversely, the scaling largely fails when plotted in Debye units.

Keywords: low frequency vibrations, boson peak.

0345 | Infrared spectroscopy by emission measurement to investigate structure and dynamics of glasses

Domingos De Sousa Meneses1,2, Cristiane Nascimento Santos1, Leire Del Campo1, Patrick Echegut1,*1CNRS, UPR3079 CEMHTI, 1D Avenue de la Recherche Scientifique, 45071 Orléans cedex 2, France

2Université d’Orléans, Polytech’Orléans, Avenue du Parc Floral, BP 6749, 45067 Orléans cedex 2, France, e-mail: [email protected]

The temperature dependence of the infrared spectra of some silica and silicate glasses is reported up to high temperature over the solid state and above the glass transition in the melt state. It is not so trivial to record reflectivity or transmissivity of samples at high temperature and particularly in a quasi liquid state. In our laboratory, this is possible within a homemade device coupling two Bruker spectrometers working from far infrared to visible ranges. The experimental method is based on the spectral emissivity measurement of CO2 power laser heated glass samples. From around 500 to 2500 K, measurements were performed by using a so called direct method consisting in the comparison of the flux emitted by the heated sample to those of a black body reference. Following Kirchhoff’s law, the spectral emissivity of semi-transparent compounds is the combination of reflection and transmission spectra so it is another way to reach the dielectric function. The analysis of the recorded spectra is obtained from their best fits with the appropriate dielectric function model. The retrieval of the optical functions on a very wide range of temperature allows to probe in a quantitative way several changes of the glass structure and dynamics related to the stretching motion of the SiO4 tetrahedra.

Keywords: silica, infrared spectroscopy, emissivity, optical function, high temperature, glass transition.

0065 | Hyper-Raman scattering: a powerful tool to probe structure in glassesGuilhem Simon1, Bernard Hehlen2*, René Vacher2, Eric Courtens2

1Université Pierre et Marie Curie, Paris, France-LAboratoire Dynamique Interaction Réactivité LADIR UMR 7075 2Université Montpellier II, France- Laboratoire des Colloïdes, Verres et

Nanomatériaux LCVN UMR 5587, e-mail: [email protected]

Hyper-Raman scattering (HRS) is a non-linear optic process in which two incident photons of frequency wi scatter a photon of frequency ws after interaction with a vibrational excitation σ of frequency wσ = ws – 2wi in the media. The main interest of HRS is that the selection rules are different from those of Raman and Infrared absorption.

The Hyper-Raman spectroscopy of various silicate and borate glasses has been performed. The selection rule analysis is based on a simple structural model considering a randomly connected network of well defined elementary structural units (ESUs). In silica the ESUs are the SiO4 tetrahedra while in borate glasses those are the BO3 triangles, the B3O3 rings, and the BO4 tetrahedra. The results show that the main HRS spectral components can be assigned to internal vibrations of ESUs, except for the boson peak which is associated to –quasi local- librations of rigid structural units, that is external-like motions.

Keywords: hyper Raman, oxide glasses, vibrations, boson peak, spectroscopy.



0286 | Amorphous-to-amorphous transitions in germanate glasses by thermal poling-induced proton injection

Guillaume Guimbretiere1*, E.I. Kamitsos2

1Centre National de la Recherche Scientifique, UPR3079 CEMHTI, 1D avenue de la recherche Scientifique, France e-mail: [email protected]

2Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, Greece, e-mail: [email protected]

Restructuring in germanate glasses, either chemically by addition of alkali oxides [1] or mechanically by application of pressure, is an old and still debated issue. We report here structure modifications in amorphous germanates induced by thermal poling (when a constant voltage is applied during heating and subsequent cooling down under the electric field), and monitored by polarized µ-Raman spectroscopy. The germanate structures are characterized by the usual deconvolution/assignment procedure and the use of an Effective Force Constant (EFC) model. This links the spectroscopic data with the average angle θ and the effective stretching force constant, kr, of the Ge-O-Ge bridges. It was found for xNa2O-(1-x)GeO2 glasses that thermal poling induces migration of Na+ ions, coupled with the injection of protons (H+) from the atmosphere. Depending of the poling parameters, two modes of germanate restructuring were observed in terms of the H+ injection rate. The two restructuring mechanisms (compactions) are illustrated in Figure 1 by correlating the Ge-OH content with kr. The compaction level is pictured by arrows and is estimated from the Raman data (θ value and its distribution and population of small rings).1. E.I. Kamitsos et al., J. Phys. Chem. 100 (1996) 11755.

Keywords: raman spectroscopy, germanate glasses, amorphous transition, thermal poling.




Sept. 22 – 8:00-9:45 h – Room B

Optically active glasses (Chairman: L.C. Barbosa)

0204 | New photonics glasses and waveguides for lightwave processing

Yasutake OhishiResearch Center for Advanced Photon Technology, Graduate School of Engineering, Toyota Technological Institute,

2-12-1 Hisakata, Tempaku, Nagoya 468-8511, Japan, e-mail: [email protected]

Many efforts have been devoted to material and waveguide device developments to meet the demands of future telecommunication systems and other data transmitting services. Silica fibers are currently used as major waveguide materials in telecom technologies. However, they have limited performance if they are applied to active fiber devices. Among non-silica glasses, such as heavy metal oxide and non-oxide glasses, are promising materials for photonic applications, as they combine (i) a wide transmission window, (ii) good glass stability, (iii) increased nonlinear optical properties, and (iv) relatively low phonon energies. We have studied the potential of tellurite and chalcogenide fibers including microstructured fibers as optical signal processing and coherent light generation media. We have succeeded in chromatic dispersion control using microstructured fibers and opened a new prospect for lightwave processing and coherent light generation using nonlinear phenomena. The specific properties of tellurite and chalcogenide glasses are applicable to not only optical amplifications and multi-wavelength lasers, wavelength conversion, THG, SHG and supercontinuum generation from visible to mid-infrared region but also efficient slow light generation. I will present a new prospect of lightwave processing and coherent light generation using new high nonlinear waveguides.

Keywords: Tellurite glasses, chalcogenide glasses, microstructured fibers, high nonlinear, optical signal processing, coherent light.

0175 | Near infrared broadband luminescence in bIsmuth doped chalco-halide glasses

Yannick Ledemi1*, Danilo Manzani1, Sidney J. L. Ribeiro1, Younés Messaddeq1, Cid B. De Araújo2

1*Laboratorio dos Materiais Fotônicos, Insituto de Química, Universidade Estadual Paulista (UNESP), Campus de Araraquara, Araraquara-SP, Brazil

2Departamento de Física, Universidade Federal de Pernambuco (UFPE), Recife-PE, Brazil, e-mail: [email protected]

Since the past decade, bismuth doped glasses have attracted a great attention for glass researchers due to their potential as broadband amplifiers and tunable lasers in the near infrared range. Most of the Bi containing glasses investigated up to now for such application are based on silicates, germanates or phosphates systems. Few studies dealing with Bi infrared luminescence in chalcogenide glass hosts have been reported in the literature.

In the present work, we report the luminescence from Bi doped Ga2S3-GeS2-CsCl chalco halide glasses in the 1000-1700 nm range under excitation at 980 nm wavelength with diode laser. The near infrared luminescence of Bi in the Ga2S3-GeS2-CsCl glass has been measured in function of the Bi concentration, the glass thermal history (temperature and rate quenching), and the heat treatments performed above glass transition temperature. A wide and complex emission band with a full width of half maximum (FWHM) of about 600 nm was observed upon excitation at 980 nm. The obtained results will be discussed and compared to the published models of Bi emission in glasses.

Keywords: chalco halide glass, bismuth, broadband luminescence, near infrared.

0236 | Barium doping effect on the local structure around erbium ions in silica glass prepared by containerless processing

Atsunobu Masuno1*, Hiroyuki Inoue1, Junji Iihara2, Yoshihiro Saito2

1Institute of Industrial Science, the University of Tokyo – 4-6-1, Komaba, Meguro, Tokyo, Japan, e-mail: [email protected]

2Sumitomo Electric Industries, Ltd., – 1, Taya-cho, Sakae, Yokohama, 244-8588 Japan

Ba2+ doping effect on the local structure around Er3+ in silica glass was investigated. The glasses with the composition of BaxSi(0.999-x)Er0.001Oy were fabricated in the range of 0 < x < 0.4 by using containerless processing. The optical and the structural properties were varied depend on Ba2+ concentration. With increase

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of Ba2+ concentration, the infrared luminescence at around 1.54 mm excited by 980 nm light was broadening and the oxygen coordination number of Er3+ from the results of X-ray absorption fine structure measurements increased. These characteristic changes were occurred in quite low x value and were saturated at x = 0.05. This x region corresponds to where the temperature of the immiscibility boundary in the BaO-SiO2 system increases. The correlation between the local structure around Er3+ with a direct effect on physical properties and the phase separation induced by BaO was discussed.

Keywords: silica glass, containerless processing, infrared luminescence, Er3+.

0242 | TB3+ and CE3+ doped soda-zinc-aluminosilicate glasses for white light generation

Adolfo Speghini1,Simone Berneschi2, Massimo Brenci2, Marco Bettinelli1, Ulises Caldino3, Alessandro Chiasera4, Maurizio Ferrari4, and Giancarlo C. Righini2*

1Laboratorio di Chimica dello Stato Solido, Università di Verona & INSTM, UdR Verona, 37134 Verona, Italy 2*MDF Lab, Nello Carrara Institute of Applied Physics, CNR, 50019,

Sesto Fiorentino (Firenze), Italy, e-mail: [email protected] 3Departamento de Fisica, Universidad Autonoma Metropolitana, 09340 Iztapalapa (Mexico D.F.), Mexico

4CSMFO Lab, Institute of Photonics & Nanotechnology, CNR, 38123 Povo-Trento, Italy

Among the different materials being investigated for white-light-emitting devices, oxide glasses doped with two (Ce3+ and Tb3+) or three (Ce3+, Tb3+ and Mn2+) luminescent ions have attracted some interest.

We intend to exploit soda-zinc-aluminosilicate glasses as hosts for the three above mentioned ions, and we have prepared glasses singly doped with Tb3+ or Ce3+ ions or codoped with Tb3+ and Ce3+, in order to carefully test their suitability for this application.

In this communication we present the characterization of some glass samples of composition x SiO2 – y Na2O – z K2O – w ZnO – 5 Al2O3, with (x, y, z) equal to (70, 20, 0), (60, 30, 0), and (60, 18, 12), respectively. The value of w was changed according to dopant concentration (0.05 or 0.1) in order to keep their sum equal to 5 (all figures are mol% ).

Optical properties (refractive index and chromatic dispersion) were first measured by dark-line spectroscopy. Afterwards, waveguides were produced in the samples by Ag+ and K+ ion exchange; different exchange temperatures and diffusion times were tested.

Finally, absorption, emission, and Raman spectroscopic measurements were performed both on as-produced glasses and on ion-exchanged samples. The results will be reported in detail at the conference.

Keywords: rare earths, luminescence, white-light generation.



Sept. 22 – 10:00-12:15 h – Room B

Optically active glasses (Chairman: D. Krol)

0206 | Active glass and ceramic materials for green photonicsSetsuhisa Tanabe

Graduate School of Human and Environmental Studies, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan

Facing the present global crisis against human survival, various kinds of technologies have been proposed and under trials for realization. Among many controversial technologies that are stated to be “sustainable”, there seems little room for discussion in the statement that increased installation of photovoltaic systems and adoption of energy-efficient LEDs in many lighting fields are no doubt the trend toward sustainability. Even overcoming cost-related issues, the optimism has bright prospect on these “green technologies”, which we see is not a kind of those fading away, at least, in the next several decades.

We now recognize that cost have dropped to the point where LEDs are the way to go in general lighting and backlighting of displays and more. Rare-earth doped phosphors are playing crucially important roles in the phosphor-converting white LED (pc-wLED), where they convert blue light from an InGaN-based LED into white spectra with good color-rendering and without any UV and infrared light, unlike incandescent light bulbs, being on its way out after 130-years run due to government restrictions or efficiency regulations.

Since 2004, we have developed glass ceramic phosphors based on Ce3+:YAG or various Eu2+ silicate crystals, proposing “all inorganic solution” for the solid-state lighting, especially high-power illumination. The broadband photoluminescence by the Laporte-allowed 5dà4f transitions in the lanthanide (Ln) enables efficient and reasonable conversion of near-UV or blue light into visible white in the pc-wLEDs. Device forms of glass ceramics in the pc-wLED have many advantages of formability, thermal resistance and no need of packaging powder phosphors.

Recently, we are also developing “quantum-cutting” (QC) phosphors for photovoltaic (PV) applications to improve solar cell efficiency by modifying solar spectrum. Since the sun is regarded as a black-body radiator with temperature around 6000K, the solar spectrum is very broad having a peak around 500nm (2.4eV). Solar cells, on the other hand, create one electron-hole pair most effectively with a photon of energy just above the semiconductor band gap, i.e., 1.1eV for the c-Si. The mismatch between the incident solar spectrum and the spectral response of semiconductors is one of the main reasons to limit the efficiency of single-junction cells. The efficiency limit of the c-Si has been estimated to be 29% by Shockley and Queisser [1]. However, this limit is estimated to be improved up to 38.4% by modifying the solar spectrum by a QC down-converting phosphor that converts one photon of high energy into two photons of lower energy [2]. Among thirteen lanthanide elements, the Yb3+ ion has a simple energy-level structure having only one excited level, 2F5/2 at 1.2eV. There are several combinations of Ln and Yb in glass and ceramics, by which Ln3+ ions can sensitize the Yb3+ emission at 1mm. Some of the combinations exhibit the QC after optical absorption of uv and blue photon. Since the Yb3+ :2F5/2®

2F7/2 emission and sensitivity peak of the c-Si solar cell overlap each other, the QC materials which convert one UV or blue photon into two 1.2eV photons would be an ideal phosphor for the PV generation.

In this talk, I will review the glass ceramic phosphors for solid-state lighting and also discuss recent studies on the QC phosphors of Ln3+ and Yb3+ ions codoped ceramics and glasses [3,4] for efficient PV generation.1. W. Shockley and H. J. Queisser, J. Appl. Phys. 32, 510 (1961).2. T. Trupke, M. A. Green, and P. Wurfel, J. Appl. Phys. 92, 1668 (2002).3. J.Ueda, S.Tanabe, J. Appl. Phys. 106, 043101 (2009).4. Y.Katayama, S.Tanabe, Materials (2010) in press.

Keyword: LED, green technology, luminescence, photonics, photovoltaics, quantum-cutting, solar cell.

0176 | Correlation between the refractive index change and the crystallization kinetics in photo-thermo-refractive glass

Julien Lumeau*, Leonid B. GlebovCREOL, The College of Optics and Photonics, University of Central Florida, 4000, Central Florida Blvd, ORLANDO, FL 32816-2700, e-mail: [email protected]

Photo-thermo-refractive (PTR) glass is a photosensitive multi-component silicate glass that exhibits refractive index change after successive UV-exposure and thermal treatment. The refractive index change was recently demonstrated to be due to stresses that appear after precipitation of NaF nano-crystals in the glass matrix. Therefore understanding the mutual relations between the refractive index change and the crystallization kinetics is a key point for fabricating any holographic elements based on PTR glass. In this paper

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we present the data on the dependence of the refractive index change versus thermal treatment duration and temperature in already UV-exposed and nucleated samples. Using Avrami plots, we show that the slope of the linear fit is equal to 1.5, demonstrating that the refractive index change is based on a diffusion-controlled growth of particles from pre-existing nuclei. We demonstrate that such findings are relevant as refractive index change is expected to be directly proportional to the size and volume fraction of NaF crystals in the glass. The effect of thermal treatment temperature on maximum refractive index change is studied and a conclusion about the basic mechanisms of refractive index change in PTR glasses is proposed.

Keywords: crystallization, growth, photosensitivity, optical glasses, refractive index, avrami plot.

0326 | Effect of dosage and thermal treatment on photo-thermo-refractive glass crystallization propertiesKarima Chamma, Julien Lumeau, Larissa Glebova, Leonid B. Glebov

CREOL, The College of Optics and Photonics, University of Central Florida, 4000, Central Florida Blvd, ORLANDO, FL 32816-2700, e-mail: [email protected]

Photo-Thermo-Refractive (PTR) glass is a photosensitive multicomponent silicate glass and is extensively used for the fabrication of diffractive optical elements (DOE). The refractive index change is the result of photo-thermo-induced precipitation of sodium fluoride (NaF) nanocrystals inside the glass matrix, following exposure to UV radiation and thermal development. The aim of this study is to reveal the correlation between the volume fraction of NaF nanocrystalline phase and the refractive index change in PTR glass by means of X-ray diffraction and differential scanning calorimetry (DSC). In order to achieve this, we studied the evolution of the intensity and positions of the X-ray diffraction lines as a function of UV-dosage and heat treatment duration and temperature. DSC measurements performed on the same samples also are presented and compared to the previous results. In conclusion the influence of the volume fraction of NaF crystal on the refractive index change and losses in PTR glass is established and the data used for designing optimal thermal treatments that will allow improving the properties of DOEs.

Keywords: photosensitivity, optical glasses, crystallization, nanoparticles, X-ray diffraction, differential scanning calorimetry.

0108 | Precious metal functionalized soda-lime silicate glassesA. Simo*, K. Rademann

Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany, e-mail: [email protected]

Since ion-exchanged glasses turned out to be excellently suited as host matrix for nanoparticles due to their outstanding stabilizing properties, metal functionalized surfaces of glass can play an important role in future bioanalytics especially in the field of chemical and biological sensing, drug design and catalysis. In the present contribution we report on precious metal functionalized soda-lime silicate glasses, namely Au, Ag and Cu nanoparticles in the sub-surface region of glass. We developed an optimised technique consisting of a combined ion-exchange method under isothermal and isochronal conditions and a subsequent reactive diffusion process in hydrogen atmosphere, that permits to introduce efficiently very high metal concentrations spatial localized in a thin sub-surface layer of the glass. By taking advantage of the electromagnetic near field enhancement of noble metal clusters those plasmonic structures are promising e.g. as long-term stable SERS (surface enhanced raman scattering) substrates due to the well stabilizing properties of glass. In our investigations the enhancement factor can be quoted in the range of 106-107. Moreover we like to point out that those glass substrates were found to be long-term stable over a course of one year without any signal intensity decrease. For a directed and controlled particle design a constitutive understanding of mechanistic details is essential. Recently, it could be shown that Small Angle X-ray Scattering (SAXS) is a powerful tool to investigate the nucleation and growth processes of nanoparticles.

In this contribution we focus on systematic investigations of metal nanoparticle formation in soda-lime silicate glass using a coupling of methods such as Electron Paramagnetic Resonance Spectroscopy (EPR), Small Angle X-Ray Scattering (SAXS), Transmission Electron Microscopy (TEM) and UV/VIS. New insights can be achieved using these methods providing information about the chemical state as well as the size, number and polydispersity of formed particles at one time. From the data the different phases of particle formation, nucleation and growth mechanism will be discussed.

Keywords: noble metal nanoparticles, nucleation and growth, small angle X-ray scattering.



0381 | Thermo-optical properties of soda lime silicate glasses doped with erbium and silver

Maria José Valenzuela Bell1*, Virgilio de Carvalho dos Anjos1, Zélia Maria Da Costa1, Alysson Freitas 1, Luiz Carlos Barbosa2, Walter Maigon Pontuschka3, Enver Fernandez Chillcce2, Júlia Maria Giehl3

1Universidade Federal de Juiz de Fora, Juiz de Fora – MG, Brazil, e-mail: [email protected] 2Instituto de Física Gleb Wataghin – UNICAMP, Campinas, Brazil

3Instituto de Física – USP, São Paulo, Brazil

Glasses containing metallic nanoparticles are attracting great interest because they may present enhanced optical properties. In particular, glasses doped with rare earth ions containing metallic nanoparticles have been exploited because the rare earth luminescence may be intensified due to the presence of nanoparticles.

Soda-lime silicate glasses are attractive materials for the fabrication of low cost integrated optical amplifiers and lasers by using the ion exchange technique due to their good chemical durability and adaptability. Nevertheless, concerning their thermal properties, namely thermal diffusivity, thermal conductivity and heat capacity there is a lack of data. Moreover, the influence of nanoparticles is still a matter of debate in the literature.

In this work the thermal properties of Soda-lime silicate glasses co-doped with silver and Er3+, were measured by using the thermal lens and heat capacity techniques. Focus was given to the role of Ag for the host properties. It was shown that the presence of silver aggregates increase the thermal diffusivity and thermal conductivity of the glasses.

Keywords: glasses, nanoparticles, soda lime aluminosilicate, thermal diffusivity.

0411 | Photo-thermo-refractive glass co-doped with Nd3+ as a new laser mediumLarissa Glebova1,2*, Julien Lumeau2, and Leonid B. Glebov2

1OptiGrate Corp. 3267 Progress Dr. Orlando, FL 32826 2CREOL, The College of Optics and Photonics, University of Central Florida,

4000 Central Florida Blvd, ORLANDO, FL 32816-2700, e-mail: [email protected]

The use of volume holographic elements recorded in photo-thermo-refractive (PTR) for different types of lasers enabled dramatic increase of spectral and spatial brightness. These elements work as output couplers, selectors of resonator modes, short pulses stretchers and compressors, and spectral beam combiners. PTR glass is a multicomponent silicate glass doped with Ce and Ag which provide refractive index change after exposure to UV radiation followed by thermal development. This work is directed to the study of PTR glass co-doped with Nd3+ as well. The glass samples with different concentration of Nd and Ce were prepared and investigated. Absorption and luminescence spectra of such glasses have shown features typical for all multicomponent silicate glasses. It was found that co-doping of PTR glass with Nd does not eliminate its photosensitivity. Therefore this glass could be used as a complex gain medium enabling creation of an all-solid-state laser where a gain medium and a resonator are incorporated in the same piece glass.

Keywords: photo-thermo-refractive glass, laser glass, photosensitivity.



Sept. 22 – 14:00-16:15 h – Room B

Nastructured sol-gel TC 16 (Chairman: R. Almeida)

0467 | Multifuncionality on silica glass. Advanced nanostructured coating

Sidney J.L. RibeiroInstitute of Chemistry- São Paulo State University- UNESP,

CP 355, Araraquara- SP- 14801-970, Brazil, e-mail: [email protected]

Photochromic windows, IR and/or UV pumped white light emitting films and luminescent mesoporous sensing materials are the main functional activities we have considering to add to silica glass substrates through nanostructured coatings.

Photochromicity is being achieved by the utilization of the well known redox pairs W6+/W5+, Mo6+/ Mo5+ and Ti4+/Ti3+. Hosts considered in the films fabrication include cellulose derivatives and vegetable oils based organic-inorganic hybrids and polyurethanes. The light activated redox phenomena is studied as a function of the films and metal containing nanoparticles chemical nature

IR and/or UV pumped white light emission is being achieved by the deposition of nanoparticulate films based on rare earth compounds, mainly vanadates and tellurites. The triads Eu3+-Tb3+-Tm3+ and Yb3+-Ho3+-Tm3+ have been considered for UV and IR pumping respectively, with the emitting colors being tuned by the rare earth relative compositions and also the chemical nature of the nanoparticles.

Finally, mesoporous silica films have been obtained by dip-coating together with Evaporation Induced Self Assembly (EISA). Mesoporous thin films constitute a platform for special luminescent/raman sensors and luminophors by incorporating rare earth compounds and colloidal metal particles in the ordered porous structure.

Keywords: photochromic, white light emission, mesoporous films, raman sensors, luminescence.

0150 | Nanostructured SiO2 – TiO2 functional glass coating with low emissivity prepared by sol-gel

M. Clara Gonçalves*, Rui M. AlmeidaDepartamento de Engenharia de Materiais, ICEMS, Instituto Superior Técnico, TULisbon,

Av. Rovisco Pais, 1000 Lisboa, Portugal, e-mail: [email protected]

A low-emissivity (low-E) coating transmits short-wavelength visible light, while absorbing ultra-violet (UV) and short-wavelength infrared (IR) and reflecting long-wavelength thermal radiation. Such coatings are normally deposited by spray pyrolysis or by sputtering. The sol-gel method is another possible low-cost alternative technology to be investigated for this purpose. In particular, sol-gel derived Bragg mirrors have been investigated as possible coating structures for such application.

Multilayer quarter-wave Bragg mirrors were modelled by the Transfer Matrix method, designed to have either UV or near-IR reflectivity (but visible transparency), based on alternating silica/titania quarter-wave stacks. Composite multilayer structures consisting of the two types of Bragg mirrors overlapped on a common substrate have been deposited by sol-gel processing on selected glass substrates and their optical properties have been measured by optical absorption and reflection spectroscopies, as well as spectroscopic ellipsometry.

The UV-visible-IR absorption and reflection characteristics of these multilayer coatings revealed low-E behavior. The combination of multiple types of Bragg mirrors on a common substrate offers an interesting possibility for obtaining functional optical coatings with low-E properties, while the sol-gel technique is a potential low-cost method to deposit such coatings on large area glass substrates.

Keywords: film, sol-gel, silica/titania, low-emissivity, Bragg mirror, ellipsometry, near IR-reflectivity.

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0199 | Transition metal oxide nanocomposite thin films on glassNathan P. Mellott1*, Betul Akkopru1,2, Brian Adams1, Caner Durucan2, Scott T. Misture1

1*Alfred University, Inamori School of Engineering, Alfred, NY 14802, USA, e-mail: [email protected] 2Middle East Technical University, Department of Metallurgical and Materials Engineering, Ankara, Turkey 06531

Transition metal oxide thin films and nanocomposites are functional structures that have current or potential application as transparent conducting oxides, chromogenics, photocatalysts, and bactericidal agents. In this study several binary transition metal oxide nanocomposite systems were synthesized via sol-gel processing. Their structure, chemistry, and morphology were determined using a wide range of in-situ and ex-situ surface-sensitive techniques including; in-situ x-ray diffraction and x-ray reflectivity, x-ray photoelectron spectroscopy, and atomic force microscopy. Particular attention was focused on the transformation(s) occurring throughout the amorphous to nanocrystalline transition with post-coating heat treatment. A variety of functionality measurements including surface resistivity, photocatalytic activity, and bactericidal activity were measured on selected thin films.

Keywords: nanocomposites, thin films, sol-gel, surface characterization.

0210 | Multifunctional nanocomposite coating from titanate nanosheets and semiconductor quantum dots

Alessandro Antonello1*, Massimo Guglielmi1, Alessandro Martucci1, Alessandro Chiasera1, Maurizio Ferrari2

1Università di Padova, Dipartimento di Ingegneria Meccanica Settore Materiali, Italy 2CNR-IFN Istituto di Fotonica e Nanotecnologie, CSMFO group, Povo (Trento) Italy

A powerful tool for the realization of multifunctional materials is represented by nanocomposites, where the incorporation of nanoparticles in suitable hosts allows for materials with combined properties. TiO2 nanoparticles have been widely used due to high refractive index and transparency in the visible. An interesting alternative to TiO2 colloids is represented by layered titanates consisting of crystalline sheets of titanium oxide.

In this work titanates have been used as the high refractive index component. A colloidal solution of exfoliated titanate sheets has been developed employing sol-gel precursors and an aminoalcohol. This material could be introduced in specifically designed hybrid organic-inorganic material derived from silane functionalized polyethylene glycol short chains, obtaining nanocomposites with improved processing behavior.

Transparent materials with refractive index up to about 1.8 are obtained which can be used for planar waveguides fabrication by spin coating technique. Beyond refractive index enhancement, the chemical environment of titanates allowed the incorporation of properly functionalized highly luminescent CdSe@ZnS semiconductor Quantum Dots, obtaining a nanocomposite with both high refractive index and stable photoluminescence.

In addition to spin casting, this material could be processed using aerosol-based deposition techniques that allows for almost defect-free structure in the sub-millimeter range.

Keywords: nanocomposites, titanate nanosheets, semiconductor quantum dots, waveguides, sol-gel.

0367 | Preparation of layered double hydroxide nano-crystals precipiTated coatings by the sol-gel method with hot water treatment

Kiyoharu Tadanaga*, Naoko Yamaguchi, Takaaki Tamura, Ryoya Suezawa, and Masahiro TatsumisagoDeparment of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University,

Sakai, Osaka 599-8531, Japan, e-mail: [email protected]

Layered double hydroxides (LDHs) have been studied for their potential application to anion-exchangers, catalysts, electrochemical sensors, and so on. LDHs are typically prepared using co-precipitation processing and are obtained as powder. However, for application of LDH to functional materials and for evaluation of their optical properties or intercalation reaction of LDH crystals, formation of LDH thin films on substrates is favorable. In the present study, Zn-Al layered double hydroxide (LDH) nano-crystals precipitated coatings intercalated with various organic anions were prepared on glass substrates by immersion of sol-gel derived amorphous Al2O3-ZnO thin films in hot water containing organic salts and organic dyes. We found that Zn-Al LDH thin films intercalated with various organic anions, such as dodecyl sulfate, p-toluenesulfonate, benzenecarboxylate and organic dyes such as sulfonated 1,3’,3’-trimethyl-6-nitrospiro[2H-chromene-2,2’-indoline], pyranine, Brilliant blue FCF, Fast green FCF, and Bordeaux S were easily prepared on glass substrates. These coatings can be applied to anti-reflective coatings, and colored coatings for glass substrates.

Keywords:. layered double hydroxide, sol-gel process, thin films, anionic organic dyes.



0283 | Meso-structured TiO2-P2O5 and SiO2-TiO2-P2O5 membranes prepared by EISA method for applications in PEMFC

Y. Castro, L. Peláez, M. Aparicio, A. Durán*Instituto de Cerámica y Vidrio (ICV), CSIC, Campus de Cantoblanco,

28049 Madrid, e-mail: e-mail: [email protected]

One important application of sol-gel process is the preparation of thin membranes for Proton Exchange Membrane Fuel Cells (PEMFC). NAFIONÒ membranes present several limitations such as high cost and low stability above 80 ºC, its maximum operation temperature. One important requirement for new membranes is the increase of working temperature up to T~ 150-200 ºC, permitting enhancing the thermal and chemical stability.

Inorganic mesoporous membranes constitute a clear option for producing fast proton conductors. Pore structure (pore size and pore orientation) and pore interconnectivity are essential issues for obtaining high proton conductivity.

The aim of this work has been to prepare mesostructured TiO2-P2O5 and SiO2-TiO2-P2O5 thin membranes by sol-gel and evaporation-induced self-assembly (EISA) method. The synthesis parameters such as type of precursor, RH, and concentration of reagents have been optimized to obtain stable sols. The membranes, deposited by dipping controlling the relative humidity and the withdrawal rate, and sintered at 350ºC, were characterized by GXRD, TEM and Spectral Ellipsometry. Conductivity measurements were performed at different RH (40-100%) and temperatures (40-100 ºC) to evaluate the behaviour of these membranes as a function of composition, temperature, RH, pore volume, pore size distribution and specific surface area.

Keywords: membranes, sol-gel, PEMFC, conductivity, mesostructure, mesoporous.

0405 | Growth of semiconductor nanoparticles network in sol-gel matrices using different laser irradiations

Odile Cristini1*, Christophe Kinoswki1, Katazyrna Raulin2, Sylvia Turrell2, Bruno Capoen1 and Mohamed Bouazaoui1

1PhLAM (CNRS, UMR 8523) and CERLA, Université Lille 1, 59650 Villeneuve d’Ascq, France 2LASIR (CNRS, UMR 8516) and CERLA, Université Lille 1, 59650

Villeneuve d’Ascq, France, e-mail: [email protected]

Nanostructured materials have many applications in the development of sub-wavelength optical components in the visible and near infrared. Up to now, the structuring of materials on a nano-scale has usually involved methods based on one of the following mechanisms: soft chemical processes for self-organization of nano-structures using the laws of hydrodynamics or random precipitation of nanocrystals during thermal treatment. On the contrary, the present work aims to master the in situ creation and the localized organization of CdS nanoparticules (NPs) in a sol-gel matrix by controlling the growth with an optical beam.

SiO2 and ZrO2–based glasses are of particular interest because of their excellent mechanical, thermal and optical properties. Our materials have been prepared using a sol–gel route which makes it possible to obtain porous host matrices with controlled pore-sizes and high quality planar waveguides.

In this communication, we present results on UV-irradiation of SiO2 monoliths and TPA-assisted organized growth of CdS semiconductor NPs in ZrO2 thin films and on their optical properties. The formation kinetics of the CdS NPs can be followed using time-resolved photoluminescence spectra. The systems obtained were also characterized using micro-Raman spectroscopy, a fully suitable tool for verifying the presence of CdS NPs in the matrices, even at low concentrations and to follow the structural modification of the sol-gel matrices.

Keywords: Nanostructured glasses, Sol-gel, Semiconductor nanoparticles, UV irradiation, TPA process, Raman spectroscopy.

0067 | Sol-gel preparation of hybrid electrolytes between glass and ionic liquidMasayuki Nogami*, Akihiro Kato, Masanobu Nakayama, Gandham LakshminarayanaNagoya Institute of Technology, Showa, Nagoya, 466-8555 Japan, e-mail: [email protected]

Sol-gel process was applied to prepare proton-conducting membranes between glass and ionic liquid. Ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI) was incorporated in P2O5-SiO2 glass using the sol-gel method and their proton conductivities were investigated. Proton conductivity of the fabricated membranes was measured within temperature range –30 °C to 150 °C, and high conductivity of 5 × 10–3 S/cm was obtained for 40 wt% EMITFSI ionic liquid-doped P2O5-SiO2 membrane, at 150 °C under non-humidified conditions. The effect of EMITFSI ionic liquid addition on the microstructure of the membranes



was examined by SEM, 1H-MAS-NMR, FT-IR, and TG-DTA analysis. The EMITFSI ionic liquid was also confined in the small pores formed in the P2O5-SiO2 glass, where it was found that the melting temperature of EMITFSI decreases to below the normal melting temperature of pure EMITFSI, which contributes to high conductivities at low temperatures.

Keywords: sol-gel, proton-conductor, ionic-liquid, electrolyte.

Sept. 22 – 08:00-09:45 h – Room Tech.

Fracture resistant glasses (Chairman: C. Kurkjian)

0142 | Improving practical glass strength: myths and realitiesRussell J. Hand

Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield, S1 3JD, UK, e-mail: [email protected]

It is well known that the strength of glass is controlled by small surface flaws and that fibre optics, which are prepared in an essentially flaw free state and then coated, achieve strength values approaching theoretical values. The coatings on fibre optics prevent mechanical damage but do not prevent some chemical and strength degradation over time. Currently there is much discussion concerning ways of improving the practical strength of other glass articles to increase the competitiveness of glass, whether this is by compositional change, coatings or induced residual stresses. Our work on relating mechanical properties and glass composition indicate that compositional gains are likely to be limited and that surface hydration leads to at least a local degradation of glass properties. Meanwhile our work on thin soft epoxy based coatings shows that damage can be overcome and strengths returned to values similar to those arising from initial production. Significant increases in the practical strength of glass articles must do more than this and must also be maintained with time whilst retaining other desirable properties. This presentation will review our compositions and coating related work with the aim of identifying both the myths and realities of improving practical glass strength.

Keywords: glass strength, mechanical strength, coatings.

0061 | Review of chemical strengthening of glass: lessons learned and yet to be learned

Arun K. VarshneyaSaxon Glass Technologies, Inc. Alfred NY, and NY State College of

Ceramics at Alfred University, Alfred NY 14802, e-mail: [email protected]

This paper reviews the progress that has been made in our understanding of the chemical strengthening of glass by ion exchange over its nearly five decades of history. Lessons learned are briefly discussed; more importantly, those which are yet to be learned are highlighted. It is recognized that the influence of chemical composition could be understood better; the science of stress generation and its concurrent relaxation are far from being clear despite the elegant analogy to thermal stresses invoked by Cooper. The need to understand plasticity of glass network during accommodation of a larger invading ion is emphasized. In turn, the influence of network topology on its yield strength in shear as well as hydrostatic modes is recognized. For expanded applications under extreme conditions of loading, damage evolution in chemically strengthened glass needs to be studied. Such study is linked to our understanding of the terms “strength”, “hardness”, “toughness”, and “brittleness” of glass.

Keywords: armor application, chemical strengthening, ion exchange, network plasticity,strength, surface compression, tempering.

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0331 | Two-point bend studies of the failure characteristics of glassZhongzhi Tang1, Nathan P. Lower1, Richard K. Brow1*, Charles R. Kurkjian2 and Prabhat K. Gupta3

1*Missouri University of Science and Technology, Dept. Materials Sci. & Engrg., Rolla, MO 65409 USA, e-mail: [email protected]

2University of Southern Maine, Dept. Engineering, Gorham, ME 04038 USA 3The Ohio State University, Dept. Materials Sci. & Engrg., Columbus, OH 43210 USA

The two-point bend (2pb) technique is a simple method to study the failure characteristics of glass fibers. With care in handling and testing under liquid nitrogen, the intrinsic failure behavior of pristine glasses can be evaluated. The 2pb technique measures the strain at failure (ef) and this can exceed 20% for some glasses when tested under liquid nitrogen to eliminate fatigue effects. In general, modified silicate glasses with greater numbers of non-bridging oxygens have greater ef than silicate or aluminosilicate glasses that possess more cross-linked structures. In addition, the failure strain of modified glasses increases with decreasing strain rates under liquid nitrogen, whereas the cross-linked glasses exhibit no strain-rate dependence, or a slight decrease in failure strain with decreasing strain rate. This strain rate dependence has been called the ‘inert delayed failure effect’ (IDFE).

In the present paper, the results from inert two-point bending studies of a variety of commercial and laboratory silicate glasses will be reviewed. In general, glasses with greater zero-strain elastic moduli have smaller inert failure strains and there is a correlation between IDFE and the way a glass responds to indentation loads. These results will be discussed in relation to the development of fracture-resistant glasses.

Keywords: failure strain, strength, glass structure, indentation.

0071 | Measurement of elastic and residual stresses at indents in glassesC. R. Kurkjian1*, S. Yoshida2, H. Aben3, A. Errapart3, R. Oldenbourg4, M. J. Matthewson5

1University of Southern Maine 2University of Shiga Prefecture, Japan

3Tallinn Technical University 4Woods Hole Marine Biology Laboratory

5Rutgers University

Indentation of a glass surface with a blunt indenter will initially result in the development of elastic stresses in the glass. If the glass surface contains flaws, the presence of tensile surface radial stresses will result in the development of a ring crack just outside the area of contact. Increased loading will allow circumferential stresses to propagate this ring crack into the body of the glass as a cone crack. As the ball becomes smaller (e.g., is less than 0.1 mm), yielding will occur with or without cracking, depending on the effective stresses and the perfection of the glass surface. All of these stresses may be conveniently imaged using photoelastic techniques and we have shown in principle that all of the three-dimensional stresses may be calculated from these data. To date almost no work has been done in this area despite its obvious importance to the understanding of processes involved in glass damage and the resulting catastrophic strength degradation. We show images and calculations of the elastic stresses under load and also present images of residual stress birefringence which develops as the yield point of the glass is exceeded. While completely satisfactory calculations of three-dimensional residual stresses from birefringence data have not yet been made, preliminary results as well as calculations using Yoffe’s equations have been carried out and illustrate the magnitudes expected and the value of such studies.

Keywords: birefringence, contact stresses, cracking, indentation, strength.

0194 | Effect of thermal history on indentation-induced densification of glassSatoshi Yoshida1*, Akiko Konno1, Toru Sugawara1, Yoshinari Miura1, Jun Matsuoka1

1*Center for Glass Science and Technology, The University of Shiga Prefecture, Hikone, Shiga, Japan, e-mail: [email protected]

It is known that brittle behaviors of glass are related with its mechanical response against foreign bodies. Indentation test is one of the simple and convenient tests for evaluating such a contact problem. At room temperature, deformation of conventional glass under a sharp diamond indenter can be classified into two different modes, shear flow and permanent densification. It was already reported that the ratio of densified volume to total indentation volume can be estimated from the change in indentation volume before and after annealing at around glass transition temperature. It has been also found out that the densification contribution to total indentation deformation of glass shows a distinct compositional dependence. In this study, effects of thermal history on the indentation-induced densification of soda-lime silicate glass were investigated by AFM observation of Vickers indents before and after annealing. The volume ratio of densified



region to total indentation deformation increases with increasing fictive temperature of glass. It is elucidated that the mechanism of inelastic deformation in glass under a sharp indenter changes not only with glass compositions but also with structures given by different heat treatments. It is expected that the deformation mechanism of glass surely affects cracking behaviors under the indenter.

Keywords: densification, indentation, thermal history, fictive temperature.

Sept. 22 – 10:00-12:15 h – Room Tech.

Waste management TC 5 (Chairman: J. Marra)

0169 | Evaluating the solubility and homogeneity of plutonium in an alkali borosilicate glass

James C. Marra1*, Charles L. Crawford1, Kevin M. Fox1, Sergey V. Stefanovsky2

1*Savannah River National Laboratory, Aiken, SC U.S.A., e-mail: [email protected] 2SIA Radon Institute, Moscow, Russia

Glass waste forms have been considered as candidate immobilization matrices for long-term Pu disposal. A disposition approach that involves immobilizing plutonium in alkali borosilicate high level radioactive waste (HLW) glass is now being considered. In typical HLW glasses, the concentration of plutonium is low (typically on the order of 0.01 wt % PuO2 in the glass). The behavior of plutonium in the glass at these low concentrations has been analyzed and determined not to impact processing, criticality safety or glass performance. If Pu levels in the glass are increased to significantly higher levels, an understanding of the behavior of Pu during processing and in the produced glass is needed. In this study, the behavior of plutonium in an HLW glass of nominal composition was evaluated at concentrations up to 2 wt % Pu in the glass. The homogeneity of Pu in the glass was assessed using scanning electron microscopy coupled with energy dispersive spectroscopy. X-ray diffraction analysis was used to assess crystallization within the glass. The results will be related to previous testing involving higher concentrations of plutonium in a lanthanide borosilicate (LaBS) glass.

Keywords: Waste vitrification, plutonium immobilization, glass crystallization, glass structure, glass homogeneity.

0151 | Durability of a simulant ilw glass in a high ph environmentClaire Utton1, Neil C. Hyatt1, Steve Swanton2, Steve Williams3, Russell J. Hand1*

1*ISL, Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street,Sheffield, S1 3JD, UK, e-mail: [email protected]

2Serco Technical Services, 150 Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0QB, UK 3NDA Harwell Office, Building 587, Curie Avenue, Harwell Science and

Innovation Campus, Didcot, Oxfordshire, OX11 0RH, UK

The current baseline for the conditioning of most UK intermediate-level radioactive waste (ILW) is immobilisation with cement. However, vitrification of some UK ILW is being considered as an alternative. If vitrified waste is deposited in the same part of a geological disposal facility as cement-based wasteforms then it will be subject to a highly alkaline environment. Very few long term durability experiments have been carried out on glasses in this sort of environment. Therefore we have been studying the performance of a simulant vitrified ILW glass in a Ca(OH)2-buffered, high pH environment using PCT and MCC-1 type tests over a range of temperatures. Initial results indicate relatively rapid alteration of the glass studied under these conditions coupled with formation of secondary products. These results will be discussed and presented within the context of our wider understanding of glass alteration mechanisms.

Keywords: waste vitrification, glass durability, alkaline environment.

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0149 | Redox control of nuclear glassOlivier Pinet*, Isabelle Hugon, Sylvain Mure

CEA, DEN, DTCD, SECM, LDMC, F-30207 Bagnols sur Cèze Cedex, France, e-mail: [email protected]

Vitrification is one of the recommended immobilization routes for nuclear waste, and is currently implemented at industrial scale in several countries, notably for high-level waste. To optimize and extend the scope of nuclear waste vitrification, research is conducted to specify suitable glass formulations and develop more effective processes. Vitrified nuclear waste often contains several multivalent species whose oxidation state can impact the properties of the melt and of the final glass. The redox control of nuclear glass is often advantageous: in many case it could improve the glass melting and increase the amount of waste in the final glass.

In the glassmaking industry, the oxidation state of glass is optimized in order to improve the glass properties, notably refinement and color. In this case the aimed redox state is obtained by a relevant choice of raw materials.

Redox control of nuclear glass is more complex because several redox species are contained in these glasses. Furthermore raw materials are partly imposed by the chemical and physical property of the waste that must be vitrified and specific constraints due to the active process. Different techniques of glass redox control developed by the CEA for nuclear waste vitrification are reviewed.

Keywords: foaming, nuclear glass, oxygen fugacity, redox, vitrification process.

0188 | Summary of cold crucible vitrification tests results with savannah river site high level waste surrogates

Sergey. V. Stefanovsky1*, Vladimir V. Lebedev1, Sergey Y. Shvetsov1, Dmitriy Y. Suntsov1, Oleg A. Knyazev1, James C. Marra2

1*State Unitary Enterprise of the City of Moscow – United Ecology, Technology and Research Center for RAW Management and Environmental Remediation (SIA Radon) – Moscow – Russia, e-mail: [email protected]

2Savannah River National Laboratory, Aiken – USA

Successful operation of the cold crucible based unit at SIA Radon for vitrification of low- and intermediate-level radioactive wastes facilitated consideration of the Cold Crucible Induction Melting (CCIM) technology for implementation in high level waste vitrification facilities. During the last eight years, SIA Radon researchers investigated the application of CCIM for vitrification of high level wastes (HLW) stored at the US DOE sites. In the framework of collaborations between Savannah River National Laboratory and SIA Radon, high-Fe (SB2) and high-Fe/Al (SB4) Savannah River Site HLW surrogates were combined with borosilicate frit in slurries with water contents varying from ~27 wt.% to ~70 wt.%. These feed slurries were successfully vitrified in crucibles up to 418 mm inner diameter. The maximum slurry feeding rate, melt pouring rate, specific productivity and melting ratio at ~50 wt.% water content in the slurry reached ~40 kg/hr, ~14 kg/hr, ~2400 kg/(m2d), and ~10 kW h/kg of glass, respectively. The maximum waste loading in the glass reached 55-60 wt.%. Spinel crystals with a magnetite/trevorite composition and a generalized formula (Fe,Ni,Mn,Mg)2+(Fe,Cr,Al)3+O4 (with trace of Cu2+ and Zn2+) were the only crystalline phases observed in all the glassy products at ~10-15 vol.% of the total bulk. The presence of the spinel crystals had no effect on product quality as demonstrated by the high leach resistance of the vitrified product.

Keywords: borosilicate glass, cold crucible inductive melting, radioactive waste, spinel, vitrification, waste loading.



0164 | Liquidus Temperature Round-Robin Testing for Waste GlassesBrian Riley1, James Marra2*, Fabienne Raszewski2, Andrew Buechele3, Jean-Luc Dussossoy4, Russell

Hand5, Rick Short6, Cristina Leonelli7, Martin Mika8, John Vienna1

1 Pacific Northwest National Laboratory, Richland, WA U.S.A. 2 Savannah River National Laboratory, Aiken, SC U.S.A - *[email protected]

3 Vitreous State Laboratory, Catholic University of America, Washington, DC, U.S.A. 4 Commissariat à l’Énergie Atomique, Marcoule, France

5 Immobilisation Science Laboratory, University of Sheffield, Sheffield, U.K. 6 National Nuclear Laboratory, Seascale, Cumbria, U.K.

7 University of Modena and Reggio Emilia, Modena, Italy 8 Institute of Chemical Technology, Prague, Czech Republic

In 2008, the International Commission on Glass (ICG) Technical Committee on Nuclear and Hazardous Waste Vitrification (TC05) identified a common need for test method development as it related to waste glass properties. Liquidus temperature (TL) was pinpointed as an important glass property for vitrification processing regardless of the melter technology being used or glass system being employed for waste immobilization and was, therefore, considered of world-wide interest. However, waste glasses are often opaque, making TL measurements by conventional means problematic. An isothermal TL determination technique was developed at Pacific Northwest National Laboratory (Richland, WA, U.S.A.) that appeared to be repeatable and accurate for waste glasses. Round-robin testing was needed to verify and validate the experimental technique for eventual adoption as an ASTM procedure. Two glasses were sent to 8 laboratories from 5 different countries for isothermal TL measurements. A procedure was sent to each laboratory for isothermal TL measurements using two test method variations. The data have been statistically analyzed to evaluate the accuracy and precision of the method. The results showed that the procedure provides accurate, reproducible results for the measurement of TL in these glasses.

Keywords: Liquidus temperature, waste vitrification, ASTM procedure, glass crystallization

0354 | Thermal Properties of Iron Phosphate Glasses for Nuclear Waste Applications

A.P. da Silva1, Z.M. da Costa Ludwig1, M.J.V. Bell1*, V. Anjos1, S.T. Reis2

1Departamento de Física, Universidade Federal de Juiz de Fora, Juiz de Fora-MG, Brazil *[email protected]

2Graduate Center for Materials Research, MST, Rolla, MO, EUA

Phosphate glasses are known to be useful for immobilization and disposal of nuclear waste. The combination of iron phosphate glasses with various types of simulated nuclear waste showed that it is possible to have nuclear wasteform with corrosion rate one thousand times less than that of borosilicate glasses. Moreover, iron phosphate presents better chemical durability than borosilicate glass.

Even though there can be found a large amount of data concerning Raman scattering, Mosbauer effect, DTA analysis and X-Ray diffraction, there is a lack of thermal data of iron phosphate. In this way, complementary investigations are necessary to complete the database of this compound, notably concerning the thermal diffusivity, thermal conductivity and heat capacity. Such properties are of importance for the proposed applications, since vitrified disposals may be submitted to elevated temperatures.

In the present work, Open Cell Photo-acoustic technique was used to obtain the thermal diffusivity. The thermal conductivity was obtained by volumetric heat capacity measurements. To our knowledge this is the first time the thermal properties of iron phosphate glasses are measured. It is shown that these glasses present high thermal conductivity, comparable with other materials used for nuclear waste. It is an advantage in order to limit the temperatures rising due to the thermal effects associated with the nuclear disintegration of radionuclides.

Keywords: waste disposal, glasses, thermal diffusivity, thermal conductivity, heat capacity.




Sept. 22 – 14:00-16:15 h – Room Tech.

Raw materials & Refractories (Chairman: D. Koepsel)

0013 | Melting kinetics of normal glass forming raw material batches and pretreated batchHans van Limpt*, Erwin Engelaar, Ruud Beerkens

TNO Glass Group, P.O.Box 6235, 5600 HE Eindhoven, The Netherlands, e-mail: [email protected]

This paper will show the different aspects of melting pelletized normal raw material batch, compared to non-pelletized batch. Experimental tests will be shown to visualize the melting of those batches and to compare the first formation of liquid (melt) phases and the batch free time.

Dry pellets compared to normal batch (poweder/grain batch) show lower energy consumption in industrial furnaces, due to faster melting rates. These faster rates are partly caused by the better heat transfer to and into the pellets and because of the better contact of the different raw material grains reacting with each other inside the pellets.

Results of modeling will show the expected increases in melting capacity when changing from a normal powder/grain batch to a pelletized (granulated) batch, and expected energy savings will be discussed.

The use of homogeneous pellets (all raw material ingredients included in each pellet) will have additional advantages compared to normal powder batch:

• obtainableglasshomogeneity;

• nobatchsegregation;

• improvedhandlingproperties;

• nodustingandlimitedcarry-overinthefurnace;

• possibilitytoeasilypreheatthepelletswiththeheatcontentsoffluegasesfromthefurnace.

Some results of TNO’s experimental investigations on the melting behavior will be presented and modeling of energy balances of glass furnaces using pellets (room temperature and preheated pellets) will be shown.

Keywords: melting kinetics, melting energy, normal batch, pelletized batch, melting observations, batch preheating.

0131 | Tin oxide electrodes with Enhanced corrosion resistanceJulien Fourcade* and Olivier Citti

Saint-Gobain SEFPRO – Northboro R&D Center – 9 Goddard Rd, Northborough, MA-01532 (USA), e-mail: [email protected]

Tin oxide electrodes have been used for many years for the electrical melting of lead crystal glasses, and more recently, to melt alkali free borosilicate glasses for electronic applications.

Solubility of tin oxide in silicate-rich melts is relatively low which makes this material a good refractory for glass melting. However at very high temperature (>1550 °C), the corrosion resistance of tin oxide decreases very significantly due to what the authors describe as a partial reduction of Sn+4 to Sn2+. In air, the reduction

of tin oxide is often described as : ( ) ( ) ( )gO21gSnOsSnO 22 +⇔

This reaction is function of pO2 and thus, remains limited up to 1400 °C in air and in oxidized melts. Nevertheless, when electrodes are used in reduced melts and/or at temperature above 1550 °C, reduction of tin dioxide starts to have a significant impact on the corrosion of the material: stannic oxide is reduced into the more soluble stannous oxide and, the corrosion resistance of tin oxide electrodes is significantly affected.

Authors have developed a new tin oxide material for electrode with enhanced corrosion resistance at very high temperature and high redox melts. The new material is doped so as to enhance its corrosion resistance and microstructure stability without decreasing its electrical conductivity.

Keywords: electrical melting, LCD glass, tin oxide electrode, corrosion.



0315 | Control of parasitic currents in electrically heated compact glass melting tanks

Thorsten Gerdes1*, Andreas Rosin1, Hannes Wolf1, Monika Willert-Porada1, Alexandra Füller2, Hermann Füller2

1Chair of Material Processing, University of Bayreuth, 95440 Bayreuth, Germany, e-mail: [email protected]

2Füller Glastechnologie Vertriebs-GmbH, Industriestr. 1, 92445 Spiegelau, Germany

Electrically heated compact glass melting units enable the production and development of new glass types as well as the continuous production of small quantities of high quality glasses independent from huge glass tanks.

Because of the small dimensions and the resulting unfavourable large contact area between glass melt and refractory material, the design of the melting tank and the arrangement of the electrodes is a crucial factor. Especially if the electrical resistance of the refractory compared to the glass melt is not sufficiently high, it leads to parasitic currents, caused by increased ion conductivity close to the glass-refractory phase boundary.

As a result the refractory material is infiltrated and corroded, and thus the life time of refractory material is reduced. Furthermore the glass quality is affected because of impurities of dissolved refractory components.

Therefore an important development goal is to define durable operation conditions by avoiding parasitic currents.

For different glass types and for model glasses with enrichment of dissolved compounds from refractory material the electrical impedance has been measured up to 1500 °C. Together with conductivity data from the refractories the results have been implemented into a FEM-Model to simulate the current distribution in an electrically heated compact melter.

Within the paper the modelling results will be compared with experimental data from a compact melter for different glass and refractory types.

Keywords: compact melter, refractory material, electrically heating, ion conductivity, parasitic currents.

0207 | Modifying of refractories – ways to increase the service lifeRolf Weigand*, Heiko Hessenkemper, Anne-Katrin Rössel, Michael Hubrich

University of Mining and Technology Freiberg- Institute of Ceramic, Glass and Construction Materials

Due to the rising prices of raw materials and energy it is necessary to minimize the investment and operating costs of a glass furnace. Refractories play an essential role in energy-intensive industries and stand for the main part of the investment costs of a typical plant. So the service life of the tank has a high economic relevance.

A new cost-effective alternative to traditional methods for refining refractory bricks in contact with glass melt is shown. By creating an oxygen depression in the pores of the refractory bricks, it is possible to increase the interfacial tension of the glass melt, thus counteracting the infiltration of pores with melt as well as the progress of corrosion.

This way of refining makes it possible to improve the corrosion resistance of every used refractory. The treatment technologies as well as the effect of refining are described. Different types of industrial used refractory bricks are tested by static and dynamic fingertests in diverse glass melts. Also the influences to the ceramic microstructure and to the glass melt as a result of the treatment are characterised.

Keywords: glass melt, refractories, corrosion, oxygen depression, fingertest.



0048 | New high zirconia fused cast material having a high electrical resistivity for alkali free glass melting

Isabelle Cabodi*, Michel Gaubil, Christel Morand1, Bruno Escaravage, Jeremy Poiret2

1Saint-Gobain C.R.E.E – Cavaillon, France, e-mail: [email protected], [email protected], [email protected]

2Saint-Gobain SEFPRO – Le Pontet, France, e-mail: [email protected], [email protected]

Melting alkali free glasses, due to their high electrical resistivity, could induce some problems with refractory blocks in electrical glass furnaces or in glass furnaces using electrical boosting. Indeed, current High Zirconia Fused Cast (HZFC) products, even with a quite high electrical resistivity, can reach their limit and do not allow the melting of higher resistive glasses or to use higher electrical power.

To improve the electrical resistivity of products, the common approach has been so far to improve the electrical resistivity of the glassy phase (alkali free) and/or to increase the glassy phase content.

Going further in this direction of increasing glassy phase content could become hazardous for the glass defects potential and corrosion resistance of the materials. Then we develop a new approach, combining a high resistivity glassy phase with a significant increase of the resistivity of the Zirconia network itself.

The electrical properties of this product are discussed through new electrical corrosion tests results. The glass contact properties remain in accordance with the glass quality level. Some data on the industrial manufacturing products are given.

Keywords: electrical resistivity, alkali free glass, High Zirconia fused cast products.

0126 | New refractory cruciform for improved energy efficiency of regenerative glass furnaceDavid Lechevalier1, Olivier Citti1*, Sebastien Bourdonnais2

1Saint-Gobain SEFPRO – Northboro R&D Center – 9 Goddard Rd, Northbrorough, MA-01532 (USA), e-mail: [email protected]

2Saint-Gobain SEFPRO – SEPR – route de Lyon BP 25 – 84131 Le Pontet Cedex (France)

SEPR has a 35 year experience of innovation in regenerator of glass furnaces. Special products like ER5312RX (fused alumina) have been developed for protecting top of the packing and increasing regenerator life. For improving fuel savings, Type 4, a corrugated surface product, has been used widely in the industry for a long time. Today a new solution, Type 8, is introduced for the glass furnace to reach even higher range of energy efficiency. Its development is the result of experimental trials obtained on half scale simulator equipment. A numerical model that reproduces the heat transfer regimes encountered in a regenerator is now in place and used to optimize the packing for each application.

This paper presents the technical benefit of this new solution: Type 8 has a higher specific surface area and a shape enhancing drastically the heat exchange. Due to these characteristics the type 8 product, dedicated to the top of the packing, makes the optimization of the regenerator design more versatile. First feedback from full scale industrial experience will be detailed.

Keywords: regeneration, checkerworks, cruciform, heat transfer, convection, numerical modeling.

0373 | Risks in testing and selection of fusion-cast AZS and alumina refractories for glass melting furnaces

Amul Gupta1*, Kevin Selkregg2, Roland Heidrich3

1*RHI Monofrax, Falconer, New York, USA 2RHI Monofrax, Falconer, New York, USA 3RHI Refel, San Vito al Tagliamento, Italy

Fusion-cast AZS and Alumina refractories have been used in the lining of glass melting furnaces for more than 60 years. The improvement in the quality of these refractories has enabled the glass industry to extend the life of their furnaces significantly, while at the same time producing high quality glass. However, furnace campaign life and glass quality are in doubt again as glass industry in the Americas and Europe has started using lower-cost AZS and Alumina refractories. Many companies producing lower-cost fusion-cast refractories reportedly do not adhere to the same strict standards for quality control as used by more established producers of fusion-cast refractories.

This paper will present the risks involved in testing and selction of lower-cost fusion-cast refractories. Results from commonly used test methods for corrosion resistance, exudation, and blister potential will be presented.

Keywords: fusion-cast, fused-cast, azs, alumina, testing, glass melting furnaces, lower-cost.



Sept. 23 – 8:00-9:45 h – Room A

Tg & Relaxation (Chairman: J. Mauro)

0130 | The landscape view of sub-tg relaxation in liquids and glasses

Prabhat K. Gupta*The Ohio State University,Columbus, OH, USA 43235, e-mail: [email protected]

Glass objects are frequently exposed to temperatures below the glass transition temperature (Tg) for a variety of reasons either during the forming stages of their manufacture or later during use. In such sub-Tg treatments, physical dimensions and properties change as a consequence of structural relaxation. The present understanding of sub-Tg relaxation remains poor. There exists a wide spread belief that such changes occurring in glasses at low temperatures are insignificant. However, there is evidence of measurable property changes taking place provided the temperatures and times are large enough. In this paper, we examine the phenomenology of sub-Tg relaxation using the energy landscape formalism. According to this landscape view, sub-Tg relaxation is composed of secondary and primary relaxation processes. The relaxation kineics of these thermally activated processes are analyzed by examining the rates of transition across the activated states.

Keywords: relaxation, glass transition, activation states.

0371 | Polyamorphism and the universallity of liquid-liquid critical points in the supercooled state

G.N. GreavesCentre for Advanced Functional Materials and Devicesm – Institute of Mathematics and

Physics, Aberystwyth University, Aberystwyth SY23 3BZ, UK, e-mail: [email protected]

The physics of critical phenomena is well-established in systems as diverse as molecular fluids, crystalline alloys, and magnetic materials. As the critical point is approached fluctuations of increasing correlation length give rise to dramatic opalescence. In the last decade evidence has emerged for the existence of a second critical point in the liquid state at supercooled temperatures, below which phases coexist differing in density but sharing the same composition – polyamorphism. Whilst much attention has been paid to supercooled water, polyamorphic phases have been observed in many elemental and oxide liquids offering routes to low entropy glasses. Our recent direct observation of a first-order liquid-liquid phase transition in levitated molten yttria-alumina offers the first opportunity to study the associated critical point in a real supercooled system. In situ small angle X-ray scattering records sharp changes in the average correlation length of fluctuations as the transition is approached. This approximates to the universal power law relation predicted by the 3D Ising model common to all critical point transitions. The observation brings the second critical point predicted in liquids into line with the liquid-gas critical point that has been familiar in water for well over a century. In so doing the experimental approach promises to unify polyamorphism in systems as chemically different as water, elemental liquids, silica and complex molten refractory oxides.

Keywords: polyamorphism, low entropy glasses, liquid-liquid transitions, universal critical point, density fluctuations.

0198 | Twinkling fractals and glass transition in amorphous oxidesMichael I. Ojovan

University of Sheffield, UK, e-mail: [email protected]

Recently Wool [1] suggested that transition of amorphous materials to glassy state is due to formation of dynamic percolating structures e.g. twinkling fractals. Fractals made of broken bonds – configurons were found at glass-liquid transition in amorphous SiO2 and GeO2[2]. These findings explain why material properties drastically change at glass transition as a result of structural reorganisations.

Whether a material is liquid or solid depends primarily on the connectivity between its elementary building blocks. Solids are characterised by a high degree of connectivity whereas structural blocks in fluids have lower connectivity. Melting of a material can be considered as a percolation via broken bonds – configurons [2]. The temperature of transition from glassy to liquid state depends on quasi-equilibrium thermodynamic parameters of bonds. The connectivity of a bond lattice is characterised by its geometry and corresponding

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Hausdorff dimensionality. The glass-liquid transition is a percolation-type phase transition associated with the reduction of the Hausdorff dimension of bonds from the 3-D Euclidean in the glassy state to the fractal Df = 2.55 ± 0.05-dimensional in the liquid state.1. R.P. Wool. J. Polymer Science B 46, 2765 (2008).2. M.I. Ojovan and W.E. Lee. J. Phys.: Condensed Matter 18, 11507 (2006).

Keywords: amorphous oxides, bond lattice, configuron, glass transition, connectivity, percolation, fractal structure.

0262 | New view to the glass transitionV.S. Minaev1,2*

1State Unitary Enterprise “Scientific-production center “Spurt “, Russia 2Moscow Institute of Electronics Engineering (Technical University), Russia, e-mail: e-mail: [email protected]

Differential Thermal Analysis (DTA) and Differential Scanning Calorimetry (DSC) are fixing exothermic effect below the generally accepted (despite to the Tamman – 1933) Tg in chalcogenide and oxide glass-forming As2Se3 (Ludwig – 1975), H2O (Johary – 1987), Se (Kasap – 1989) GeS2 (Liuchun Cai, Boolchand – 2002), Ca (Po3)2 (Yue – 2005), as well as pre-endo effect before exothermic effect in phosphate, silicate, metal glass, glassy water [1,2].

Thus, at heating glass (resulted in certain conditions) can be consistently observed:1) Pre-endo effect;2) Exo-effect (possible glass crystallization);3) Endo-effect with conventional Tg;4) Exo-effect of crystallization;5) Endo- effect of crystal melting.

Physicochemical nature of all these effects at the present time is not fully clear. According to the conception of polymer-polymorphoid structure of non-crystalline substance and glass-forming liquid for the individual chemical substance (ICS) [3,4], the glass is the copolymer of different structure fragments of crystal polymorph modifications (PMs) without translational symmetry (long-range order) but having intermediate- and short-range orders inherent in these PMs, interprets all these effects as a result of copolymerization-depolymerization process and interconversion of different PMs polymorphoids.1. Yohav G.P. J.Chem. Phys. 2003. V. 119, 2935.2. Y.Z.Yue, Phys. Chem. Glasses, 2005, V.46(4), 354-358).3. Minaev V.S., Elsevire Academic Press.4. Minaev V.S., J. Optoelectron. Adv. Mater. 2009, V.11, N.12, P.1946.

Keywords: pre-endo effect, exo-effect, endo-effect, glass transition, polymophoid.

0230 | Influence of residual stress on color generation of gold ruby glassTepiwan Jitwatcharakomol1*, Mateekul Jiarawattananon2, Sirithan Jiemsirilers3

1*Department of Science Service, Bangkok, Thailand, e-mail: [email protected] 2,3Research Unit of Advanced Ceramics, Department of Materials Science, Faculty of Science,

Chulalongkorn University, Bangkok,Thaila, e-mails: [email protected]; [email protected]

Self-striking ruby glass is always fascinating to scientist according to the difficulties of reproducibility. In this study, gold foils were used as the gold carrier in the glass composition of 72SiO2, 11CaO, 11Na2O, 1PbO, 6K2O (wt. %). The quantity of selenium, carbon and gold were varied. Dilatometric curves suggested the suitable annealing temperature, namely 570 °C. Some glasses shown self striking phenomenon meanwhile some appeared no color. Residual stresses in these glass samples were quantitatively measured by a Strain Viewer in order to clarify the significant of time and temperature in glass cooling step. In addition, regarding to PbO toxicity, Li2O3 and B2O3 were used in the selected formula. However the measured residual stress supported that among these, PbO is the most promising flux in gold ruby glass.

Keywords: self-striking, gold ruby glass, ruby glass, strain viewer, residual stress.



Sept. 23 – 10:00-12:15 h – Room A

Thermo & Optical Properties (Chairman: R. Brow)

0298 | Thermodynamic modeling of the initial and final stages of glass corrosion

Reinhard ConradtRWTH Aachen University, Germany, e-mail: [email protected]

Thermodynamics has been used for more than three decades as a tool to model the hydrolytic stability of glasses. Yet, until today, the prediction of the corrosion behavior of a specific glass in a given aqueous environment still is a great challenge. After giving a brief review of previous achievements, the present paper focuses on modeling both the initial and final stages of glass corrosion. It is true, thermodynamics alone is unable to model these processes on a time scale, but the stages towards which the processes move are readily predicted.

It is shown that the initial stages of glass corrosion, especially at high ratios of glass surface area to solution volume, are governed (1) by the formation of concentration gradients in the sub-surface zone of the glass – which is a well-know and well investigated fact – and (2) by a distinct lateral differentiation of the glass surface. It is pointed out that the formation of glass-specific “initiator crystals” plays the role of a key mechanisms during this early stage. This is confirmed by experiments. In modeling the initial stage of glass corrosion, it is essential to correctly asses the thermodynamic activities of individual oxides j in the glass matrix.

In contrast to the initial situation, the final stage of glass corrosion is modeled by a complete mineralization of the glass matrix. This stage is equivalent to the hydrolytic diagenesis of a crystalline matrix isochemical to the glass.

Keywords: glass corrosion, hydrolytic stability, solubility, thermodynamics.

0153 | Surface fluorination effect on chemical durability of phosphate glassYuki Kondo1*, Hiroyuki Ohkawa1, Jun Sasai1, Yuichi Iida2, Chikaya Tamitsuji1, Kunio Watanabe1

1*Research Center, Asahi Glass Co. Ltd., e-mail: [email protected] 2AGC Techno Glass Co. Ltd.

Phosphate glass can be utilized as optical glass for lenses, filters and laser media. Chemical durability of phosphate glass is not very high, so its application is limited for practical use. On the other hand, phosphate glass which contains fluorine ions, that means fluorophosphate glass, shows high chemical durability. In this study, we investigate surface fluorination effect on chemical durability of aluminophosphate glass. Surface fluorination is carried out in fluorine gas atmosphere at high pressure in autoclave chamber. We have found that chemical durability of fluorinated aluminophosphate glass becomes remarkably high and similar to that of fluorophosphate glass. Annealing after fluorination is effective to stabilize the fluorination. While as-fluorinated glass shows some deterioration on part of the surface, subsequent annealed glass shows no deterioration on the whole surface. By means of X-ray photoelectron spectroscopy, we have confirmed that concentration of phosphorous and oxygen ions decreases, and that of aluminum and fluorine ions increases at the surface. The depth of fluorinated layer is approximately 20 nm. Since the binding energy of network former ions such as phosphorous and aluminum ions becomes similar to that of fluorophosphate glass, it is considered that fluorinated aluminophosphate glass shows remarkable improvement of chemical durability.

Keywords: surface fluorination, fluorine gas, surface modification, phosphate glass, chemical durability.

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0275 | Roles of non-bridging oxygen and free volume on the milling-induced enthalpy increase in simple silicate glasses

Jun Matsuoka1*, Kouichi Muranaka1, Satoshi Yoshida1,2, Toru Sugawara2,1

1*Depart of Materials Science, School of Engineering, The University of Shiga Prefecture, Hikone, Shiga, Japan, e-mail: [email protected]

2Center for Glass Science and Technology, School of Engineering, The University of Shiga Prefecture, Hikone, Shiga, Japan

Milling process of glass is important in preparing glass powders which are used as bonding, coating or sintering agents in electronic device manufacturing. As the process forms large area of fractured surface, it can also be used for investigating the fracture phenomena of glass. In our previous studies, we measured the heat of solution of milled glass into hydrofluoric acid, and found that milling makes the densified layer at the fractured surface. The densification increases the enthalpy of glass. In this study, composition dependence of the enthalpy increase by milling, DHmill, was studied in R2O-R’O-SiO2 glasses. In the case of glasses having the same free volume and the different non-bridging oxygen to silicon ratio, increase of the non-bridging oxygen is found to increase DHmill in the composition range of 0.67 < [NBO]/[Si] < 1.00. However, the magnitude of DHmill in this case is smaller than the case of [NBO]/[Si]=0, i.e., the case of silica glass. In the case of same [NBO]/[Si] ratio of 0.67, increase of the free volume is found to increase DHmill. Very large DHmill was observed in silica glass, and should be due to its very large free volume.

Keywords: fracture, milling, densification, non-bridging oxygen, free volume, silicate.

0202 | Thermodynamic mixing properties of liquids in the system Na2O-SiO2

Toru Sugawara1*,2, Kentaro Shinoya2, Satoshi Yoshida1,2, Jun Matsuoka2

1*Center for Glass Science and Technology, The University of Shiga Prefecture, Hikone, Shiga, Japan 2Department of Materials Science, The University of Shiga Prefecture,

Hikone, Shiga, Japan, e-mail: [email protected]

Enthalpies of fusion have been measured by differential scanning calorimetry in the Na2O-SiO2 system at 50, 66.6 and 74.4 mol% SiO2. Enthalpies of mixing of liquids obtained from different calorimetry techniques are critically evaluated. Using the data of calorimetric enthalpy, activity of Na2O, cristobalite liquidus and immiscibility gap, the enthalpy and entropy of mixing of sodium-silicate liquids are determined as a functions of composition by a least squares method. The derived mixing properties are based only on the experimental data, and are independent of any assumption about the structure and chemical species in liquids. The enthalpy of mixing shows a minimum value of –120 kJ/mol at 35-40 mol% SiO2 and is convex upward around 80-90 mol% SiO2. The entropy of mixing shows a maximum value of + 6 J/K-mol at 75 mol% SiO2, and decreases with decreasing SiO2 content to –5 J/K-mol at 40 mol% SiO2. This decrease in entropy can be accounted for by ideal mixing of Q4, Q3 and Q0+1+2 (=Q0+Q1+Q2) species in the liquids, and is responsible for negative temperature dependence of the partial molar Gibbs energy of mixing of Na2O observed in activity measurements. Comparison of the present results with previous values suggests that Quasi-chemical model and Adam-Gibbs model overestimate the configrational entropy of mixing of liquids.

Keywords: enthalpy of mixing, entropy of mixing, thermodynamics, calorimetry, sodium silicate melts.

0231 | Mixed rare earth oxides in B2O3-La2O3 based glassesSatoru Tomeno*, Kenji Kitaoka, Kazutaka Hayashi, and Yuki KondoResearch Center, Asahi Glass Co., Ltd., 1150 Hazawacho, Kanagawa-ku,

Yokohama 221-8755, Japan, e-mail: [email protected]

B2O3-La2O3 based glasses are applied to optical lenses with high refractive index and low dispersion. Viscosity at liquidus temperature (LT) is important issue which should be adjusted to appropriate value for mass production. The author previously demonstrated that mixed rare earth oxides in B2O3-La2O3 based glasses can control the LT.

In this study, liquidus temperature change was investigated in detail by changing the ratio and kind of mixed rare earth oxides. The total amount of rare earth oxides is fixed. Mixed rare earth oxides ratio is substituted Ln2O3 (ex. Ln = Pr, Gd, Er, Yb) for La2O3. Liquidus temperatures of samples depend on the rare earth elements; ‘light rare earth’ or ‘heavy rare earth’. Combination of La2O3 and heavy rare earth elements



shows a minimum of LT. On the other hand, combination of La2O3 and light rare earth elements maintains a constant LT. These results can be explained by the crystalline phases of mixed rare earth elements. The LT can be controlled by the mixing ratio of Aragonite type crystal and Vaterite type crystal.

Effect of mixed rare earth oxides on thermal properties is discussed in terms of glass structure.

Keywords: optical lens, B2O3-La2O3 based glass, liquidus temperature, rare earth element, crystalline phase, viscosity.

0256 | Thermal dependance of sheet resistance of FTO-coated films on glassAneta Flejszar*, Gundula Helsch, Joachim Deubener

Institute of Non-Metallic Materials, Clausthal University of Technology, Zehntnerstraße 2a, 38678 Clausthal-Zellerfeld (Germany), e-mail: [email protected]

Thermal stability of FTO-coats is important for lifetime of functional glass products for domestic appliances with service temperatures up to 800 K. Process temperature is needed to crystallise amorphous deposits to become electrically conductive, while during service thermal cycling can cause degradation due to ion diffusion and changes in microstructure. In a multi method approach using 2 point probe head, SEM, AFM, XRD, SNMS we investigated the resistivity, microstructure, topography, and diffusivity of FTO-coated glasses subsequent to prolonged heat treatments. The results show that glass cations, such as Na+ and Ca2+ move towards the coat while tin ions of the coat were detected in the glass substrate. Depending on the crystallisation temperature of different deposition techniques studied these effects led to changes in the microstructure (crystal growth) and sheet resistance. Using simple temperature-time approximates lifetime predictions are presented.

Keywords: FTO-films, thermal stability, interface diffusivity, sheet resistance.

0084 | Properties of zinc silicate glasses and meltsDoris Ehrt*, Sylvia Flügel

Otto-Schott-Institut, Friedrich-Schiller-Universität Jena, Fraunhoferstr. 6, D-07743 Jena, Germany, e-mail: [email protected]

Silicate glasses with high ZnO content are of interest for various applications, ranging from technical glasses to optical and glass ceramics. From structural effect ZnO is an intermediate oxide and can theoretically act as network modifier and also as network former depending on glass composition, but cannot form a glass per se.

Zinc silicate glasses and melts were investigated beginning with the binary eutectic composition (in mol%) 50 ZnO – 50 SiO2. The effect of alkaline oxides, Li2O 0-10, Na2O 0-20, K2O 0- 20, of alkaline earth oxides SrO 0-2, BaO 0-10, and of higher valence oxides, Al2O3 0-10, B2O3 0-6, La2O3 0-3, ZrO2 0-2, Nb2O5 0-3, Ta2O5 0-3, were studied.

Glasses were prepared in a laboratory scale with high purity raw materials. Different methods were used for investigation of glasses and melts up to high temperature, ~1500 °C.

Large variations of the properties were found, refractive index ne: 1.53–1.66, Abbe-number νe: 44–58, transformation temperature Tg: 465–730 °C; linear thermal expansion coefficient α100-300 °C: 35-140 (×10–7K–

1); density: 2.7–3.60 g/cm3; viscosity temperature (η in d Pas) Tlogη = 4: 775-1115 °C; Tlogη = 2: 1065-1460 °C; electrical conductivity by impedance measurements in the temperature range 200 to 1500 °C (σinΩ–1cm–1) Tlogσ = –8 : 165-500 °C; Tlogσ = –1 : 845-1195 °C.

The crystallisation behaviour was studied and the following crystal phases were detected: as main crystal phase Zn2SiO4 willemite and variations, Li1.14Zn1.43SiO4 (Li3PO4-structure type), BaZn2Si2O7 metastable modifications, Na,Zn-silicates of different types, NaAlSiO4 nepheline, carnegeite, La2Si2O7, NaLa9(SiO4)6O2 (apatite-type), 3D-framework tecto-zinciosilicate structure: K2ZnSi3O8 und Na2ZnSi3O8 which form very stable glasses with extremely low crystallization tendency.

The relations between structure and properties are discussed.

(The work was founded by BMBF, SCHOTT AG and U.L.M. Photonics, contract number 03X4004D.)

Keywords: zinc silicate, glasses melts, viscosity, electrical conductivity, optical properties, crystal phases.



0254 | Optical Properties of nanoporous TiO2 thin films on glass using different pore-forming agents

A. Matthias1*, J. Deubener1, D. Kip2

1Institute of Non-Metallic Materials, Clausthal University of Technology, Germany, e-mail: [email protected]

2Department of Electrical Engineering, Helmut Schmidt University Hamburg, Germany, e-mail: [email protected]

Nanoporous titania thin films on glass are of interest for optical and electronic applications. Pore sizes and their distribution was found to control refractive index and wavelength dispersion. To study the effect of different pore-forming agents synthesis of tetrabutylorthotitanate as Ti precursor, diethanolamine as chelating agent, and ethanol, butanol, terpineol, 1-decanol as solvents were perfomed. Different pore-forming agents were added to the solution, such as poly-ethylenglycol (PEG), cetyltrimethylammonium bromide (CTAB), and pluronic P123. Nanostructure of the porous films using sol-gel dip-coating on glass was studied by microscopy (FESEM, AFM), while optical properties were measured using UV-VIS-NIR spectroscopy and ellipsometry. The porosity of TiO2 film increases with increasing pore-forming agent fraction up to 0.6, which was related to a refractive index change of Dn550nm = 2.15. The results contribute tailoring glass surfaces for fibre based optical gas sensors.

Keywords: nanoporous TiO2 thin films, sol-gel, PEG, CTAB, P123.

Sept. 23 – 8:00-9:45 h – Room B

Glass-Ceramics TC 7 (Chairman: C. Russel)

0079 | Surface or internal nucleation and crystallization of glass-ceramics

W. Höland*, V.R. Rheinberger, C. Ritzberger, E. ApelIvoclar Vivadent AG, Research and Development, Bendererstr. 2,

Li-9494 Schaan, Principality of Liechtenstein

Fluoroapatite (Ca5(PO4)3F) was precipitated in glass-ceramics via internal crystallization of base glasses. The crystals grew in needlelike morphology in the direction of the crystallographic c-axis. HR-TEM, SEM, XRD, and solid state NMR investigations were used to indentify two different reaction mechanisms: precipitation via a disordered primary apatite crystal and a second mechanism in the form of a solid state parallel reaction to rhenanite (NaCa(PO4)3) precipitation. In contrast to the internal nucleation used in the formation of fluoroapatite, surface crystallization was induced to precipitate a phosphate-free oxyapatite of the NaY9(SiO4)6O2-type.

Internal nucleation and crystallization has shown to be a very useful tool for developing high-strength lithium disilicate (Li2Si2O5) glass-ceramics. A very controlled process was conducted to transform the lithium metasilicate glass-ceramic precursor material into the final product of the lithium disilicate glass-ceramic without the major phase of the precursor material. The phase formation processes were studied with XRD (Rietveld method), SEM, HR-SEM and solid state NMR. The combination of all these methods allowed the driving forces of the internal nucleation and crystallization mechanisms to be explained. An amorphous phosphate primary phase was discovered in the process. Nucleation started at the interface between the amorphous phosphate phase and the glass matrix.

Ketwords: analysis, biomaterials, crystallization, glass-ceramics, mechanisms, strength.

0494 | Overview of Glass-Ceramics: Fundamentals and Applications Dr. Ivan A. Cornejo

Corning Research Director, Science and Technology, Corning, NY 14831

The controlled crystallization of glass is utilized to produce glass-ceramics for a wide variety of applications. Some of the advantages of glass-ceramic processing over traditional ceramic processing are: pore free microstructure, better dimensional control, and flexibility in design and geometry patters. In this lecture

INVITeDSPeAKeR



an overview on Glass-Ceramic will be presented, responding to these specific questions: What are glass-ceramics? How to design of glass-ceramics? Product case histories: Corning and non-Corning glass-ceramics. What are the potential new glass-ceramic applications?

Keywords: Corning and non-Corning glass-ceramics, glass-ceramic applications

0392 | Internally nucleated alkali sulfate glass ceramicsLothar Wondraczek

Department of Materials Science, University of Erlangen-Nuremberg, Germany

Knowledge on glass systems in which internal nanocrystallization occurs at high nucleation rates and, hence, leads to high crystal volume fraction and at the same time high crystal number density is still rare. In this talk, a novel such system will be presented. It will be shown that nanocrystalline alkali and alkaline earth sulfates can be precipitated in mixed-network former P2O5-SO3 glasses. Crystallization occurs as a result of bimodal phase separation, and leads to a relict structure of homogeneously distributed crystallites, as will be shown on the basis of analytical high-resolution TEM-EDS, SEAD and EBSD analyses. Crystallization kinetics are assessed by isothermal experiments, and an effort will be made to separate kinetics of phase separation from the kinetics of crystal growth. Two potential applications will be demonstrated:

• thedevelopmentofalkalisulfate–basedglassceramicphosphorswithveryhighemissionintensity;and

• theuseaslow-temperaturesealingmaterialwithstronglyimprovedthermochemicalstability.

Keywords: glass ceramic, nucleation, nanocrystalline.

0252 | Effect of lanthanide ions on the crystallisation of oxyfluoride nano-glassceramics. photonic properties

A. de Pablos-Martín*, F. Muñoz, A. Durán, M.J. PascualInstituto de Cerámica y Vidrio (CSIC), Kelsen 5, 28049 Madrid, Spain, e-mail: [email protected]

The design of oxyfluoride glass-ceramics doped with lanthanide ions is becoming important within materials with photonic applications, like solid state lasers, optical amplifier fibres, etc. Oxyfluoride glass-ceramics combine the transparency and mechanical and chemical resistance of the alumosilicate glasses with the low phonon energy of the fluoride crystals besides having good solubility for lanthanide ions. Recently, the crystallisation of NaYF4 in alumosilicate matrices has been emphasized, triggering the development of glass-ceramics, with double fluorides as crystalline phases.

This work is focussed on the crystallisation of double fluorides in the system SiO2-Al2O3-Na2O-K2O-LaF3. One composition presents mixed alkali effect and after thermal treatments very close to Tg, NaLaF4 crystallises. The second composition possesses K2O as only modifier oxide and shows the crystallisation of α,β- KLaF4. Both compositions develop transparent glass-ceramics due to the nanometric size of the fluoride crystals.

The addition of lanthanide ions, like Tm3+, Yb3+ and Eu3+, modify the glassy structure greatly influencing the crystallisation behaviour. A comparative study of the thermal and structural characteristics between un-doped and doped glasses and glass-ceramics will be shown from dilatometry, viscosimetry, DTA, DSC, TEM, NMR and Neutron Diffraction results.

The optical properties and the possibilities of up-conversion phenomena of these materials will be also discussed. In particular, the distribution of the doping ions between the glassy matrix and nano-crystals through luminescence and emission decay curves has been evaluated. The possible application of the obtained nano glass-ceramics as waveguides has been also investigated.

Keywords: crystallisation, oxyfluoride glass-ceramics, fluoride crystals, lanthanide ions, up-conversion.



0308 | Dissolution of alumina, sintering and crystallization in glass ceramic composites for LTCC applications

Stefan Reinsch1, Robert Meszaros1,3, Maik Rosemann1, Markus Eberstein1,4, Ralf Mueller1*, Joachim Deubener2

1BAM Federal Institute for Materials Research and Testing, Berlin, Germany 2Clausthal University of Technology, Clausthal-Zellerfeld, Germany

3now with Friedrich-Alexander-University Erlangen-Nuernberg, Germany 4now with The Fraunhofer Institute for Ceramic Technologies and Systems

IKTS, Dresden, Germany, e-mail: [email protected]

Sintering and microstructure evolution of calcium-alumo-borosilicate glass/a-Al2O3 com po sites for LTCC applications were studied by heating microscopy, DTA, XRD and SEM. Experiments were focused on constant heating at 5K/min, Fa = 10-25 vol% alumina and mean particle size of » 2 µm for glass and alumina particles as typically used for LTCC. Compo sites ful ly densified at » 810 and 830 °C for Fa = 0.10 and 0.25, respectively, not essentially influ en ced by dissolution of alumina and glass crystallization. Wollastonite crystals were found to grow from the former glass particle surface above 840°C, whereas alumina did not serve as an active nucleation substrate. Above 900°C, however, pronounced growth of anor thite crystals from alumina particles is evident. Diffusion pair experiments on calcium-alumo-borosilicate glasses of different Al2O3 concentration indicate that the Al2O3 concentration of the residual glass canbe substantially increased close to the alumina particles. Rietveld analyses of XRD data for Fa = 0.25 conformingly revealed that anorthite, reaching 60 wt% at 1050 °C, precipitates at the expenses of alumina, which declines from »33wt% to 8wt%, and wollastonite, which fully declines from its maximum of »19 wt%. For Fa = 0.1, the anorthite crystallization and decay of wollastonite is delayed until 1200 °C where anorthite reaches » 40 wt%.

Keywords: LTCC, glass matrix composites, Al2O3-inclusions, glass crystallization, sintering.

0316 | Crystallization kinetics of a 16.9Li2O·5.0ZrO2·65.1SiO2·8.6Al2O3 glass-ceramicOscar R. K. Montedo1*, Robert Meszaros2, Nahum Travitsky2,

Peter Greil2, Dachamir Hotza3, Antonio P. N. de Oliveira3

1*Unidade Acadêmica de Ciências, Engenharias e Tecnologia (UNACET), Universidade do Extremo Sul Catarinense – UNESC – Criciúma-SC, e-mail: [email protected]

2Department of Materials Science, Institute of Glass and Ceramics, University of Erlangen-Nuremberg – Erlangen – Germany

3Departamento de Engenharia Mecânica (EMC), Grupo de Materiais Cerâmicos e Vítreos (CERMAT), Universidade Federal de Santa Catarina – UFSC – Florianópolis-SC

LZSA (Li2O·ZrO2·SiO2·Al2O3) glass-ceramic system has shown high potential to obtain LTCC laminate tapes for several applications, such as screen-printed electronic components, due to its low sintering temperature (below 1000 °C). Because of this and their relatively low temperature of sintering, LZSA glass-ceramics can be considered a potential candidate for obtaining multi-layered structures processed by LOM technology (Laminated Objects Manufacturing) for LTCC. Thus, the crystallization kinetics of a 16.9Li2O·5.0ZrO2·65.1SiO2·8.6Al2O3 glass-ceramic composition was investigated by means of different techniques including differential thermal analysis in non-isothermal conditions. Results showed a crystallization activation energy of about 285 kJ.mol–1 and an Avrami parameter of 1, in good agreement with another techniques.

Keywords: ceramics, glass, glass-ceramic, LZSA, crystallization, kinetics.



Sept. 23 – 10:00-12:15 h – Room B

Glass-Ceramics TC7 (Chairman: J. Deubener)

0141 | Lithium iron phosphate glass-ceramic powder for rechargeable lithium-ion battery

Tomohiro Nagakane1, Akihiko Sakamoto1*, Ken Yuki1, Hideo Yamauchi1, Tsuyoshi Honma2, Takayuki Komatsu2, Meijing Zou3, Tetsuo Sakai3

1*Nippon Electric Glass – Otsu, Shiga, Japan – [email protected] 2Nagaoka University of Technology – Nagaoka, Niigata, Japan

3National Institute of Advanced Industrial Science and Technology – Ikeda, Osaka, Japan

LiFePO4 glass-ceramic powder was developed for the cathode material of the rechargeable lithium-ion battery (LiB). The glass-ceramic was prepared through crystallizing Li2O-Fe2O3-P2O5 glass powder with an average particle size of 2 micrometers under reducing atmosphere. Each glass-ceramic particle consisted of olivine-type LiFePO4 crystallites of which size is in the order of several-hundred nanometers. The crystallinity was more than 90 mass%. It was found that the glass-ceramic particles were covered by an amorphous layer with a thickness of about 20nm. The electrode fabricated with the glass-ceramic powder worked as a cathode of LiB showing discharged voltage of 3.4V. It was also confirmed that the glass-ceramic shows higher water resistance than a conventional cathode material (LiCoO2). After a hot-water immersion test, the decrease of the cathode capacity of the glass-ceramic was less than that of the LiCoO2. This glass-ceramic powder is expected as a novel candidate of the cathode material for LiB.

Keywords: lithium-ion battery, cathode, glass-ceramic, olivine.

0132 | Glass-to-metal seals with titanium and Ti-6Al-4V alloyB. L. Metcalfe*, P. M. Mallinson and J. A. Fernie

Material Science Research Division, AWE Aldermaston, e-mail: [email protected]

A review of the literature on glass-to-metal sealing with titanium and titanium alloys has shown only limited research and widely varying results. Sealing to titanium and titanium alloys is complicated by the high chemical reactivity of titanium which can lead to severe interfacial reactions which degrade the integrity of the interface. Also titanium undergoes an allotropic phase transition at 882.5 °C with a significant volume change. The brittle nature of the oxide layer, formed on titanium above approximately 590 °C in air, can lead to surface cracking. In this investigation a number of different glass compositions, including silicate and boro-aluminate based glasses, which have been proposed for use in glass-to-metal seals are compared to more recent compositions derived for bio-medical use. The high reactivity of the silicate based glasses required very strict control of the reaction conditions to minimise interfacial reactions whereas the less reactive boro-aluminate glasses allowed more flexibility in the sealing conditions and ultimately produced higher quality seals. Investigation of the sealing conditions has allowed the optimisation for sealing to titanium for different glass systems by minimisation of unfavourable interfacial reactions.

Keywords: titanium alloys, silicate, boro-aluminate, glasses, glass-ceramic.

0143 | Oxide glass ceramics for scintillating materialsMathieu Allix1,2*, Francis Millot1,2, Emmanuel Veron1,2,

Sandra Ory1,2, Michael Deschamps, Guy Matzen1,2

1CNRS, UPR3079 CEMHTI, 1D avenue de la Recherche Scientifique, 45071 Orléans cedex 2, France 2Université d’Orléans, Avenue du Parc Floral, BP 6749, 45067,

Orléans cedex 2, France, e-mail: [email protected]

If scintillating materials are today mainly single crystals, they remain costly and are called for being replaced by easy formed and cheaper materials like transparent ceramics or glass ceramics.

We report here the synthesis and the characterization of different transparent/translucent glass ceramic oxide materials, based on Lu silicate or aluminate and related to famous single crystals, such as Lu1.8Y0.2SiO5 (LYSO), Lu2Si2O7, (LPS) and Lu3Al5O12 (LuAG). These designed glass ceramics are obtained from controlled



crystallization of Lu-Si-Al-B-O starting glass compositions. Glass samples containing up to 95%wt of LPS, LYSO or LuAG can be obtained thanks to the use of aerodynamic levitation associated to a laser heating system.

DSC and XRD measurements have first been performed to select valuable starting compositions. The selected glass compositions have then been subjected to specific heat treatments in order to control the crystallization, the ultimate purpose being to obtain a maximum crystallization rate while keeping transparency to ensure scintillation properties. The crystallization processes have been studied in details by in situ high temperature XRD, transmission electron microscopy and NMR and are discussed here since their first steps. Properties, interest and application perspective of such materials are finally discussed.

Keywords: vitrification, crystallization, transparent glass ceramic, scintillating materials.

0285 | HT-XRD study of the Early stage of the crystallization process in lithium alumosilicate glass-ceramicsMartina Dressler1*, Bernd Ruedinger2, Joachim Deubener1

1Institute of Non-Metallic Materials, Clausthal University of Technology, e-mail: [email protected] 2Schott AG, Corporate Research and Technology Development, Mainz

The control of nucleation and crystallization processes is essential for the production of glass-ceramics. High temperature X-ray diffraction (HT-XRD) is a useful tool to analyze in-situ the transformation kinetics of fast crystallizing glasses. In this study the evolution of mean crystal sizes, lattice parameters, and crystalline fractions of model lithium alumosilicate (LAS) glass-ceramics were measured under isothermal conditions and at constant heating rates. With focus on the early stage of crystallization, number densities, steady state nucleation rates, and induction times were calculated. Avrami analyses were performed to reveal partitioning of different growth mechanism of h-quartz-ss crystals for prolonged heating regimes. It was found that the growth of crystals of sizes up to 30 nm (fractions < 80%) is initially controlled by interface processes and later by diffusion. The presented two-step growth mechanism can be used to tailor ceramization programs of glass-ceramics for special applications.

Keywords: HT-XRD, glass-ceramics, crystallization kinetics, LAS-system.

0295 | Crystallization of lithium iron phosphate glasses for lithium ion batteriesK. Nagamine1*, S. Reinsch2, R. Mueller2, T. Honma1, T. Komatsu1

1Nagaoka University of Technology, Department of material science of technology, Japan 2BAM Federal Institute for Materials Research and

Testing, Berlin, Germany, e-mail: [email protected]

Crystallization of lithium iron phosphate glasses was examined in order to improve the performance of LiFePO4 glass-ceramics for practical use in lithium ion secondary batteries. 33Li2O-33Fe2O3-1Nb2O5-33P2O5 glass powders were prepared by conventional melt-quenching, crushing and ball milling. XRD, DTA and microscopy measurements of glass powders for various particle sizes were carried out in air, Ar and a H2

containing atmosphere. In the latter two cases, LiFePO4 and Li3Fe2(PO4)3 were found by XRD for all powders, while only Li3Fe2(PO4)3 were evident for fine powders in air. DTA curves, however, show one sharp peak in any case. It is found that the crystal li zation peak temperatures (Tp) in Ar and in H2 containing atmosphere decrease with decreasing particle size as expected from the surface crystallization observed in bulk samples. In contrast, Tp in air does not sig ni ficantly decreases with decreasing particle size. This finding could hint on a progressive oxi da tion of iron which can increase glass viscosity and Tp. Quite similar DTA curves were observed for Ar and H2 containing atmosphere, indicating that H2 could not affect the overall crystallization ki ne tics at 10K/min by reducing Fe3+ and viscosity.

Keywords: lithium iron phosphate, lithium ion secondary battery, cathode material, glass-ceramics, crystallization.



0403 | SiO2-SnO2 glass-ceramic planar waveguides doped by rare-earth elaborated by the sol-gel process

Christophe Kinowski1*, Odile Cristini1, Bruno Capoen1, Mohamed Bouazaoui1, Pascal Roussel2, Simone Berneschi3, Giancarlo Righini3, Maurizio Ferrari4,

Shivakiran N. B. Bhaktha5, Thanh V. Tran6, Sylvia Turrell6

1PhLAM (CNRS, UMR 8523) and CERLA, Université Lille 1, 59650 Villeneuve d’Ascq, France 2UCCS (CNRS, UMR 8181), Bât. C-7a, ENSCL, 59652 Villeneuve d’Ascq, France

3MDF Lab., IFAC-CNR, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Florence, Italy 4CSMFO Lab., IFN-CNR, Via alla Cascata 56/c, 38050 Trento, Italy

5LPMC, CNRS UMR6622 and Université de Nice-Sophia Antipolis, Parc Valrose, 06108, Nice Cedex 02, France 6LASIR (CNRS, UMR 8516) and CERLA, Université Lille 1, 59650

Villeneuve d’Ascq, France, e-mail: [email protected]

Silica-based nanostructured glass ceramics are of great interest due to their applications towards various photonic devices. The production of active rare earth (RE) nanocrystallites in a glass matrix can give rise to high luminescence efficiency. This class of materials is of great importance in photonics, because they combine the mechanical and optical properties of the glass with a crystal-like environment for the RE ions, where their higher cross-sections can be exploited in order to fabricate more compact devices.

Semiconductor nanoclusters of SnO2 can also be used to transfer energy to RE ions thus compensating efficiently for the small cross section of RE transitions. If RE ions can be doped into semiconductor nanoclusters, then band gap excitation may result in efficient energy transfer thus yielding intense luminescence from the RE ion.

In the present work, we present recent results obtained in developing crack free SiO2 – SnO2 glass-ceramic waveguides with high SnO2 content based on the sol-gel techniques and activated by rare earth ions. The m-line technique is used for the determination of thicknesses and refractive indices. Raman and photoluminescence spectroscopies in the waveguiding configuration are performed to provide information on the structural evolutions of the matrix which result from the formation and the growth of the SnO2 nanocrystals. In situ high-temperature XRD and TEM data have been used to identify the initiation of crystallization.

Keywords: raman spectroscopy, photoluminescence spectroscopy, sol-gel, SnO2 nanocrystals, glass-ceramics, waveguides.

0406 | Preparation and characterization of lead tungsten fluorophosphate glass-ceramics

Roger Gomes Fernandes1, Fábia Castro Cassanjes1, Gaël Yves Poirier1*1Department of Science and Technology – UNIFAL-MG,

Campus de Poços de Caldas, Poços de Caldas-MG, e-mail: [email protected]

Transparent oxyfluoride glass-ceramics containing nanocrystals of heavy metal fluorides were largely investigated due to efficient luminescent properties of rare earthes incorporated inside these nanocrystals. Several oxide glass matrix including silicates, germanates, borates and phosphates can be used as glass formers. The main advantages of phosphate glasses are their small liquidus viscosity and softening temperatures as well as high solubility of heavy metal and rare earth fluorides. However, their applications are limited by their poor chemical and thermal stability.

In this work, transparent glasses were prepared in the ternary system Pb(PO3)2-WO3-PbF2 by the melt-quenching method. Compositions were adjusted to obtain thermally and chemically stable glasses. The dominant crystallization mechanism has been obtained by thermal analyzes of glass samples with different grain sizes. The increase of lead fluoride content results in a progressive internal crystallization mechanism. Further analyzes by DRX and TEM confirmed that PbF2 nanocrystals can be formed by heat treatment on these samples and that transparent glass-ceramics can be prepared in this system.

Keywords: glass-ceramic, phosphate, tungsten, lead fluoride.



0288 | Effect of ceramizing treatment on crystal morphology and properties of spinel (MgAl2O4) nano glass-ceramic composites

Atiar Rahaman Molla*, Sampad BiswasCentral Glass and Ceramic Research Institute, Council of Scientific and Industrial Research (CSIR), India

Transparent glass-ceramics based on crystals of spinel (MgAl2O4) solid solution in a highly siliceous residual glass has been produced from compositions in the SiO2-Al2O3-ZnO-MgO-TiO2-ZrO2 system. The heat-treatment experiment was carried out on the base glass in the temperature range of 950-11000C, at an interval of 500C for 20 hours. Effect of processing parameters on the properties of the material like density, CTE, optical transmissionand refractive index (R.I.) have been reported. High transparency (>80%) has been achieved when the glass was heat-treated at 9500C for 20 h. FT-IR and XRD studies revealed the presence of spinel phase in the heat-treated glass-ceramics. Appearance of cubic crystallites in nano-dimension (20-50 nm) embedded in the glass matrix has been observed from TEM (SAED) and FESEM examination. Hardness values range from 9.63–10.5 GPa while fracture toughness range from 0.85-0.99 Mpam0.5 as determined from micro indentation techniques. Elastic modulus of ranges 66.88-80.26 GPa have been determined from depth sensitive indentation technique. Flexural strength (3 point) of the glass-ceramics heat-treated at 9500C was obtained 212 MPA. Potential products include solar cells, active matrix liquid crystal displays and transparent armors.

Keywords: spinel, electron microscopy, mechanical properties, FT-IR, Optical properties, nano glass-ceramics.

0097 | Determination of the Crystal Nucleation Rates in Glasses from DTA – A Correction

A.A. Cabral1*, E.B. Ferreira2, E.D. Zanotto3

1IFMA, Inst Federal do Maranhão, Departamento de Física, São Luis, MA, Brasil, [email protected] 2Faculdade de Engenharia, UNESP, Univ Estadual Paulista, Departamento de Materiais e Tecnologia, SP, Brasil

3Laboratório de Materiais Vítreos, DEMa, Univ Federal de São Carlos, São Carlos, SP, Brasil, www.lamav.ufscar.br

The determination of key parameters that govern the crystallization kinetics of glasses, the nucleation and growth rates as a function of temperature, I(T) and U(T), respectively, is of great interest in science and technology. An interesting method has been proposed by Ray et al. to determine I(T) in glasses that exhibit internal nucleation using a non-isothermal DTA technique. In this paper, we review the derivation of such method and propose a correction. In order to compare the experimental results with the two different derivations (the original and ours), we determined the number of quenched-in nuclei, Nq, in a Li2Ož2SiO2 (LS2) stoichiometric glass. Bulk glass samples were treated on a DTA furnace according to the following schedule: (1) heated from 24oC up to 620°C at 20°C/min; (2) developed at 620°C for 10 min (crystal-growth treatment); (3) cooled at 20°C/min until 380°C, where they were maintained for 5 min; (4) heated at 15°C/min to 800°C (above the crystallization peak, Tp = 685°C). Then we repeated all the steps above for different samples, changing the time (tG) of the crystal-growth treatment to 15, 20, 30, 35 and 40 min. We found that the values of Nq estimated from our approach are approximately two times larger than the one derived from the original equation of Ray et al. Finally, we propose that the original expressions must be modified to take into account the crystal morphology and crystal impingement.Keywords: crystal nucleation rates, DTA, lithium dissilicate glass.

Sept. 23 – 8:00-9:45 h – Room Tech.

Optical Properties (Chairman: Y. Messaddeq)

0147 | Influence of antimony ion on coloration of optical glassSatoko Konoshita*, Fumio Sato, Satoru Yoshihara, and Akihiko Sakamoto

Nippon Electric Glass Co., Ltd., Otsu, Shiga, 520-8639, Japan, e-mail: [email protected]

We investigated the relation between the antimony content and the coloration in a SiO2-B2O3-Li2O optical glass, and estimated the mechanism of the coloration. Antimony oxide has been used as a refining agent in optical glasses. Nowadays, Sb-free glasses are required because of the environmental issue. However, some optical glasses show yellowish color when antimony oxide is removed. The glass samples were melted in a platinum or an SiO2 crucible. The Sb-free sample melted in the platinum crucible showed an absorption band at 360nm and indicated yellowish color, whereas the sample melted in the SiO2 crucible was colorless



regardless of the antimony content. This means that the coloration in the Sb-free glass occurs under the presence of platinum ion. According to the Ellingham diagram, antimony ions oxidize platinum ions when they coexist. Hence, the mechanism of the coloration is inferred as follows. In Sb-free glasses, platinum ions exist as Pt2+ which has absorption at 360nm, resulting in yellowish color. However, under the presence of antimony ions, platinum ions exist as Pt4+ showing no coloration, because the absorption band lies in the ultraviolet region.

Keywords: optical glass, transmittance, platinum, antimony oxide.

0087 | Structure and properties of strontium niobium phosphate glassesJ.J. Wu1*, H.W. Yung1, Y.S. Haung1, Jian Lin2

1Department of Material Science and Engineering, National united university, Miao-Li 36003, Taiwan 2School of Material Science and Engineering, Tongji University, Shanghai, 200092, China

The structures and optical properties of Nb2O5-SrO-P2O5 glasses have been generally investigated by using Raman spectroscopy, Fourier transform infrared spectroscopy, O1s X-ray photoelectron spectroscopy and 31P solid state NMR. From the results of Fourier transform infrared spectroscopy, adding Nb2O5 to the glasses as the intermediate results in the form of P-O-Nb bonds and Nb-O-Nb bonds. When the content of P2O5 >50 mole%, the Nb2O5 will play the role of glass network modifier. Moreover, the NMR spectra indicated that the glass structures of Q3 and Q2 will be transferred to those of Q2 and Q1, respectively, as the content of Nb2O5 increases. However, the numbers of Nb-O-Nb bonds and [NbO6]3d bonds will be increased when the content of P2O5 <50mole%, due to the [Nb2O5 will play the role of glass network former from the intermediate. When P2O5 decreases to 30 mole%, [NbO6] transferred to [NbO4] and produces new bonds Nb-O-Sr. P2O5/SrO ratio is also utilized to estimate the absorption intensity of the glasses. When the ratio is greater than 1, the addition of Nb2O5 will result in the strong absorption during the wavelength region of 400~850nm. The absorption peak will significantly increases as the content of Nb2O5 increases. On the contrary, the phenomenon of the absorption will not occur and the transmittance of the glass will slightly decrease.

Keywords: refractive index, niobium, visible spectroscopy, raman spectroscopy, X-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy, phosphate glass.

0391 | Optical and spectroscopic properties of soda lime glasses doped with erbium and silver

Zélia Maria Da Costa1, Luiz Carlos Barbosa2, Walter Maigon Pontuschka3, Enver Fernandez Chillcce2, Maria José Valenzuela Bell1, Vírgilio Carvalho dos Anjos1*,

Júlia Maria Giehl3, Alexandre Peixoto do Carmo1, Clayton Antonio Pereira Pires1, Signo Tadeu Reis4, Driely Aparecida Leonídio1

1*Universidade Federal de Juiz de Fora, e-mail: [email protected] 2Instituto de Física Gleb Wataghin, UNICAMP, Campinas – Brazil

3Instituto de Física, USP, São Paulo – Brazil 4Missouri University of Science and Technology

Glasses containing metallic nanoparticles are attracting great interest because they may present enhanced optical properties. In particular, glasses doped with rare earth ions containing metallic nanoparticles have been exploited because the rare earth luminescence may be intensified due to the presence of nanoparticles. The luminescence efficiency may be influenced by energy transfer between the nanoparticles and the rare earth ions.

Soda-lime silicate glasses are attractive materials for the fabrication of low cost integrated optical amplifiers and lasers by using the ion exchange technique due to their good chemical durability and adaptability. One of the main problems associated with this kind of glass is the narrow emission bandwidth at 1.55 micron that reduces their potential application in the wavelength-division-multiplexing (WDM) system if compared with other oxide glasses. Nevertheless, this intrinsic limit may be overcomed by adding another compounds to the glass composition. In order to increase the bandwidth, we have developed a new kind of SLAS glass adding different percentages of Aluminum.

In this work the spectroscopic properties of Soda-lime silicate (SLAS) glasses co-doped with silver and Er3+, namely absorption and emission spectra were measured. Attention is focused in the increase of Er3+ luminescence in the visible and infrared region when silver is added to the glassy host. Additionally, the influence of Al in the bandwidth of the transition at 1.55 mm is analyzed.

Keywords: glasses, erbium, silver, luminescence.



0350 | Plasmon resonance of noble metals nanoparticles In glasses and raman scattering

Eric Nardou1, Dominique Vouagner1, Anne-MarieJurdyc1, Alice Berthelot1, Bernard Champagnon1*1Université de Lyon; Université Lyon 1; UMR5620 CNRS; Laboratoire de Physico-Chimie des Matériaux

Luminescents, Domaine scientifique de la Doua, Bât. Kastler, 10 rue Ampère, Villeurbanne, F-69622, France, e-mail: [email protected]

Plasmon resonance of noble metal (Au, Ag, Cu) nanoparticles in glasses is known from the ancient time as a way to produce coloured glasses. The plasmonic absorption of the nanoparticles can be monitored at different wavelengths by varying their shape or the index of the dielectric matrix surrounding them. It makes it possible to observe Resonant Raman scattering of the nanoparticles and to study the interaction between the nanoparticle and the glassy matrix.

In this presentation we will show the polarized absorption of different glasses containing metallic nanoparticles and discuss the role of the different parameters. Resonant Raman scattering will also be presented and discussed.

Keywords: optical properties, plasmon, raman scattering.

0341 | Silicate glass chemistry behind waveguide amplifiers developmentMartin Mika1*, Frantisek Lahodny1, Linda Salavcova1, Stanislava Stara1, Hana Malichova1,

Jarmila Spirkova1, Blanka Svecova1, Frantisek Ondracek2, Jana Jagerska2, Jiri Ctyroky2, Jiri Oswald3, Giancarlo Righini4, Simone Berneschi4, Gualtiero Nunzi Conti4, Ilaria Cacciari4,

Stefano Pelli4, and Massimo Brenci41Institute of Chemical Technology Prague, Czech Republic, e-mail: [email protected]

2Institute of Photonics and Electronics, AS CR, Prague, Czech Republic, 3Institute of Physical Chemistry, AS CR, Prague, Czech Republic

4IFAC CNR, Optoelectronics Department, Florence, Italy

In the process of developing efficient waveguide amplifiers, the hosting environment for transition and rare earth elements can be properly tuned by tailoring silicate glass composition. In addition, the silicate glass exhibits a good temperature stability, chemical durability, and compatibility with optical fibers. It makes the doped silicate glass a very attractive material for waveguide amplifiers and lasers. In a silicate glass matrix the laser active metals are coordinated by oxygen ligands. The local chemical environment strongly influences active optical properties such as luminescence wavelength, absorption and emission cross-sections, bandwidth, up-conversion probability, and lifetime of excited states. We quantified glass components effects on these properties and interpreted them using the ligand field and optical basicity theories. We utilized these composition-property models in the formulation of optimized glass matrices that are tailored for a particular laser active element. We developed a sodium-zincsilicate glass co-doped with Er and Yb that is suitable for the fabrication of low loss channel amplifiers with the net gain up to 6.7 dB/38 mm long sample. We also report the development of optimal glass matrices suitable for the transition metals Cu and Cr and the rare earth elements Tm, Dy, Nd, Pr, and Ho.

Keywords: silicate glass, transition metals, rare earth metals.

0343 | Experimental survey of the solar transmittance, environmental and mechanical durability of commercial soda-lime-silica glasses for solar energy applications

Joachim Deubener1,2*, Sandra Cramm1, Stefan Dultz3, Harald Behrens3

1Institute of Non-Metallic Materials, Clausthal University of Technology, Germany 2Energie-Forschungszentrum Niedersachsen, Goslar, Germany, e-mail: [email protected]

3Institute of Mineralogy, Leibniz University Hannover, Germany

The use of soda-lime-silica (SLS) glasses as front material for solar applications is driven by cost-benefit calculations. Structure-property relationships of SLS glasses have been reported for individual materials aspects only, e.g. a composition dependent chemical resistance, while a lack of a comprehensive analysis of the optical, chemical, and mechanical performances for solar applications is evident. In this study we surveyed properties of 15 commercial soda-lime-silica glasses of average transmittance from 86 to 91% in the wavelength range from 300 to 2500 nm and weighted by air mass 1.5. An attempt to establish trends between solar transmittance, environmental and mechanical durability with structural parameters, surface



condition, and chemical composition of the glasses will be presented. The results can help to find optimized glass compositions for solar energy applications and to evaluate SLS glasses from different manufacturers and productions lines.

Keywords: soda-lime-silica glass, solar transmittance, environmental durability, chemical durability, solar energy application.

0424 | Synthesis and spectroscopy of the tetraborate glasses, doped with transitional elementsB. Padlyak1,2*, W. Ryba-Romanowski3, R. Lisiecki3, A. Drzewiecki2,

O. Smyrnov2, V. Adamiv1, Ya. Burak1, I. Teslyuk1

1Institute of Physical Optics, 23 Dragomanov Str., 79-005 Lviv, Ukraine, e-mail: [email protected] 2University of Zielona Góra, Institute of Physics, 4a Szafrana Str.,

65-516 Zielona Góra, Poland, e-mail: [email protected] 3Institute of Low Temperatures and Structure Research,

PolishAcademyofSciences,2OkólnaStr.,50-422Wrocław,Poland

The lithium and potassium-lithium tetraborate glasses (Li2B4O7 and KLiB4O7), doped with transitional elements (Cu, Mn and Cr) were obtained from corresponding crystalline compounds by standard glass technology. Tetraborate glasses, doped with Cu, Mn and Cr of high optical quality were synthesised in the air with using corundum crucibles and technological conditions, developed by authors. The Cu, Mn and Cr impurities were added to the basic melt composition in the form of the corresponding oxide compounds (MnO, CuO and Cr2O3) in amounts 0.4 and 1.6 mol. %. The doped tetraborate glasses were obtained by fast cooling of the corresponding melt, heated more than 100 K higher that the melting temperature (Tmelt = 1190 K and 1080 K for Li2B4O7 and KLiB4O7 compositions, respectively) for exceeding of the glass transition point.

On the basis of analysis of electron paramagnetic resonance (EPR) and optical spectra (absorption, luminescence excitation and emission) as well as luminescence kinetics of the Li2B4O7 and KLiB4O7 glasses, doped with Cu, Mn and Cr, it was shown the following:

(i) The Cu impurity is incorporated into the tetraborate glass network as Cu2+ (3d9) paramagnetic and Cu+ (3d10) luminescence centres. The EPR spectra of Cu2+ centres are almost identical in glasses with Li2B4O7:Cu and KLiB4O7:Cu compositions and are characteristic for glassy compounds. Parameters of the Cu2+ EPR spectra (g-values, hyperfine constants and peak-to-peak linewidths) in Li2B4O7:Cu and KLiB4O7:Cu glasses are determined. Characteristic absorption band, peaked near 750 nm is assigned to the 2B1g → 2B2g transition of Cu2+ centres in the tetraborate glass network. An intense UV absorption at λ < 350 nm is related to the Cu2+ → O2– charge-transfer band. Emission bands, peaked near 420 and 470 nm, in the Li2B4O7:Cu and KLiB4O7:Cu glasses belong to Cu+ centres with different local environments in the second coordination shell.

(ii) The Mn impurity is incorporated into the tetraborate glass network as Mn2+ (3d5) and Mn3+ (3d4) centres. Characteristic for glassy compounds EPR spectra of the Mn2+ paramagnetic centres are almost identical in glasses with Li2B4O7:Mn and KLiB4O7:Mn compositions and have been attributed to the isolated Mn2+ ions with broad distribution of crystal field parameters and small clusters of the Mn2+ ions in the trigonally-distorted octahedral sites of the tetraborate glass network. The broad absorption band with maximum around 465 nm is related to the 5Eg → 5T2g spin-allowed transition of the Mn3+ ions and intense absorption at λ < 350 nm is assigned to the Mn3+ → O2– charge-transfer band. Complex emission bands in both Li2B4O7:Mn and KLiB4O7:Mn glasses, peaked around 600 nm belong to the 4T1g → 6A1g transition of the Mn2+ centres.

(iii) The Cr impurity is incorporated into the tetraborate glass network, generally, as Cr3+ (3d3) centres and characterised by typical for glassy compounds EPR and optical spectra. Features of EPR and optical spectra as well as luminescence kinetics of the Cr3+ centres in the Li2B4O7:Cr and KLiB4O7:Cr glasses are considered and discussed.

Keywords: borate glasses, copper, manganese, chromium, EPR, optical absorption, photoluminescence.



Sept. 23 – 10:00-12:15 h – Room Tech.

Bubbles TC14 & 21 (Chairman: D. Koepsel)

0062 | Mathematical model of sulfate fining in a glass tank furnace

Kenji Oda1*, Meguru Kaminoyama2

1*Asahi Glass Co., Ltd. GC-SIBU, Shinyurakucho Bldg. 8F, 1-12-1, Yurakucho, Chiyoda-ku, Tokyo 100-8405, Japan, e-mail: [email protected]

2Department of Chemical System Engineering, Yokohama National University, 79-5, Tokiwadai, Hodogaya-ku, Yokohama-shi, Kanagawa 240-8501, Japan

In this study, we propose a new mathematical model of dissolved SO3 transport in a glass melting furnace, considering secondary decomposition of sulfate. The calculated concentration of SO3 agrees with measured data near the maximum temperature area, hot spot, in an actual glass tank furnace. The effect of onset temperature of secondary decomposition, the maximum solubility of SO3 and concentration of inlet SO3 on sulfate fining is quantified by simulation.

Keywords: glass, furnace, sulfate, fining, decomposition.

0094 | Mathematical models of glass melt refiningKloužek J.*, Nemec L., Jebavá M.

Laboratory of Inorganic Materials, Joint Workplace of the Institute of Chemical Technology in Prague, and the Institute of Inorganic Chemistry of the ASCR, v.v.i., Czech Republic, e-mail: [email protected]

The mathematical modeling of the refining process is important tool for evaluation of the industrial melting efficiency and the glass quality control. The process description is based on the simulation of the kinetics of the single bubble behaviour. Complete mathematical models simulate mass transfer of single gases between bubble and the melt. The application of the model requires precise values of gas properties, namely their diffusion coefficients, solubilities and bulk concentrations. The values are acquired by difficult and time consuming laboratory methods having often limited accuracy. That is why simplified model coming from direct observations of bubble behaviour in melt has been developed. The simplified model of bubble behaviour is based on the assumption of the bubble stationary composition, which is independent from its initial composition and under given temperature and pressure depends only on concentration of gases dissolved in the melt. The application of the simplified model plays important role when formulating the particle distribution models as will be presented in the second part of this work.

The real glass melting tank involves a nonisothermal space with continuous melt flow. Bubbles originated from glass batch or from surface of refractory materials are reacting with the melt and distributed by glass flow and buoyancy force. As a result of this process, the bubble concentration field is formed in the melting space. Two bubble distribution models are presented: 1. The model using particle tracing (the Model of Bubble Representatives) and 2. The model based on flow of polydisperse bubble phase through the melting space (the Convective Model of Bubble Distribution). The verification of bubble distribution models shows that the model of bubble representatives exhibits very good accuracy for calculation of bubble distribution in the real melting space. The accuracy of the convective model of bubble distribution is improving with increasing number of classes of bubble sizes, used for the simulation.

Keywords: Glass Melting, Bubble Removal, Modelling.

0235 | An empirical multi gas change model for bubble in soda lime silicate glassShingo Urata*, Shuji Kabashima

Production Technology Center, Asahi Glass Co., Ltd., 1-1 Suehiro-cho,Tsurumi-ku, Yokohama, Kanagawa, 230-0045, Japan, e-mail: [email protected]

Numerical model of bubble gas change is a key technology to estimate bubble defect source. Because diffusion coefficient, physical solubility and concentration of each gas are essential properties for the modeling, much effort has been continued to measure them accurately. Nonetheless, the accurate properties are not enough to simulate bubble gas change, quantitatively. This may be due to some simplifications in the numerical model. To avoid this difficulty, JEBAVÁ et al. have proposed an empirical procedure to determine

INVITeDSPeAKeR



the properties based on two experiments, high temperature direct observation of bubble diameter change and subsequent gas analysis of the bubble observed. Since this method is effective for practical application, we applied it to construct an empirical multi gas change model for commercial soda lime silicate glass.

The method of subsequent gas analysis by JEBAVÁ et al. requires a certain amount of skill and time. Thus, alternatively, we used conventional method for bubble gas change test by using Pt crucible. In addition, we optimize the properties by iterative calculation using genetic algorithm to reproduce both final bubble diameter and gas composition. The modified empirical method enables us to construct a bubble gas change model with reasonable accuracy.

Keywords: bubble, gas, mathematical model, simulation.

0015 | Mass transfer of a rising bubble in a molten glassFranck Pigeonneau

Surface du Verre et Interfaces, UMR 125 CNRS/Saint-Gobain, France, e-mail: [email protected]

The mass transfer around a rising bubble is studied within the field of glass melting processes where the oxidation-reduction reaction of iron oxides is taken into account. The Sherwood number is determined as a function of the Péclet number based on the terminal rising velocity of the bubble. Two different techniques are used: the first based on the boundary layer theory and the second using a finite element method.

In order to take into account the redox reaction in an unified framework, a modified Péclet number is found as a function of two dimensionless numbers linked to the equilibrium constant of the chemical reaction and the glass oxygen saturation. The Sherwood number, taking into account the chemical reactions, increases with iron content as well as with glass reduction.

The behaviour of an isolated rising bubble in molten glass is examined both experimentally and numerically. The theoretical model to describe bubble shrinkage is based on the preceding results. Bubble size as a function of time is presented where two stages are observed: at short times, the bubble shrinks; at longer times, the bubble size reaches a steady-state value. The comparison between experimental and numerical results is in good agreement when the iron content in glass changes.

Keywords: fining, redox reaction, mass transfer, bubble, numerical simulation, boundary layer theory, Sherwood number.

0095 | Space bubble removal as an industrial processNemec L.*, Jebavá M., Cincibusová P.

Laboratory of Inorganic Materials, Joint Workplace of the Institute of Chemical Technology in Prague, and the Institute of Inorganic Chemistry of the ASCR, v.v.i., Czech Republic, e-mail: [email protected]

The bubble removal from glass melts appears almost exclusively as the separation process. Consequently, the process of separation of small bubbles from usually thick layers of viscous melt is extremely slow and energy consuming. Both energy consumption and performance of the fining process may be quantitatively described by means of process kinetics and utilisation of the fining space.

The descriptions of fining kinetics involve different models of bubble behavior where the bubble growth rate caused by both physical and chemical factors plays a decisive role. Consequently, the experimentally measured bubble growth rates under given conditions give a very useful indication of the glass fining ability. This value gives also preliminary information about processes of bubble nucleation, melt foaming and dissolution enhancement. The glass saturation by gases, the reduced pressure and potentially the application of the additive external force manifest themselves the powerful factors of fining kinetics.

The bubble separation is a macroscopic process dependent from both the space size and bubble movement. Under routine industrial conditions, the forces causing bubble rising and glass flow may be involved in a relative quantity entitled utilisation of the space. The utilisation of the space expresses quantitatively, how the character of glass flow and space size influence the bubble separation process. The application of transversal and longitudinal temperature gradients in a simple model space reveals the beneficial flow structures showing the high utilisation of the space and consequently, the reduced energy consumption, as well as high fining performance of the model space.

Keywords: glass melting, bubble removal, modelling.



0393 | ICG TC21 Modeling of glass melting processes how reliable and validated simulation tools can help to improve glass melting efficiency and productivity

Erik H.P.H. Muijsenberg1

1Glass Service Inc. Rokytnice 60, 75501 Vsetin, Czech Republic, e-mail: [email protected] (Chairman of TC21)

Mathematical modeling of glass furnaces started around 1965. The question is what can these models do and how reliably are the prediction of such models? In 1990 the ICG (International Commission on Glass) started the TC number 21 focusing on “Modeling of Glass Melting Processes”. The aim of TC21 is to share and exchange current practice and to develop the theory and application of mathematical modeling of glass furnaces. The activities of TC21 are carried often our as round robin tests where model results of members are compared to each other and in some case with actual measured data. A step wise validation of different components of the models related to the whole glass furnace is undertaken. The idea is to come up with improvements to improve the mathematical modeling of each member. The paper will show some validation experiments carried out by several authors over the years within, but also without TC21. These validations show a fairly good agreement between measurements and models. Certain errors are more likely to come from unknown glass properties and boundary conditions, than from the mathematical model itself. As example we show the error that can be caused when we do not know the glass properties very well. We also will show how bubbles can be modelled and how we validated results in the past

Keywords: ICG TC21, modeling, validation, furnace optimization, glass quality, bubbles.

0357 | Modeling of the behaviour of a single bubble in a glass meltDetlef Koepsel1*

1*SchottAG, Research and Technology Development, Mainz, Germany, e-mail: [email protected]

The modeling of the fining process can be performed in two different ways:

a) The removal of large bubble ensembles from the glass melt can be modeled using population balance approaches. They usually do not describe the physico-chemical mechanisms of gas transport between a single bubble and the glass melt very precisely but they are especially qualified to predict changes of the total bubble number and the bubble size distribution.

b) Models describing the behaviour of single bubbles provide precise information on the change of bubble size and gas composition in the bubble if the physico-chemical properties of the gases in the glass melt, e.g. redox data, gas solubilities and diffusivities are known.

In the present case a model for a single bubble is explained with special focus on:

• thephysico-chemicaldescriptionofthetransportofthefollowinggasesbetweenabubbleandtheglassmelt: O2, N2, CO2, SO2, H2O, H2S, Sx, NaCl, HCl; problems to model the driving force for the diffusion of O2, SO2 and NaCl/HCl are discussed in detail.

• viscosityandinertialeffects,whichhavetobeconsideredtomodelthe“freezing”ofabubble.

• theinfluenceofsubatmosphericpressure.

• the formation of “reactive condensates” in the bubble in dependence on cooling rate and redoxconditions.

Keywords: bubble behaviour, fining, gas solubility, gas diffusivity, redox conditions.




Sept. 24 – 8:00-9:45 h – Room A

Glass Formation (Chairman: J. Schmelzer)

0363 | Test of stability parameters with Li2O-B2O3 glasses from reluctant to good glass forming compositions

Eduardo B. Ferreira1, Edgar D. Zanotto2*, Steve Feller3

1Faculdade de Engenharia, UNESP – Univ Estadual Paulista, DMT, Guaratinguetá, SP, Brasil *2LaMaV – Laboratório de Materiais Vítreos,UFSCar – Universidade Federal de São Carlos,

DEMa, São Carlos, SP, Brasil, e-mail: [email protected] 3Physics Department, Coe College, Cedar Rapids, IA, USA

The aim of this study was to test the adequacy of 9 glass stability parameters (GS – on heating) to predict glass forming ability (GFA – on cooling). We used several glasses covering a wide range of compositions across the Li2O-B2O3 phase equilibrium diagram – from very reluctant glass forming compositions, with R = Li2O/B2O3 as high as 2.0, to very good glass forming compositions with R = 0.25. Glasses were prepared by the traditional method of melting and by sol-gel. The glass stability parameters were calculated using the characteristic temperature points of DSC thermograms on heating: Tg (glass transition), Tx (onset of the crystallization peak), Tc (maximum of the crystallization peak) and Tm (onset or endpoint of the melting peak). The DSC experiments were carried out at 10 °C/min with powdered samples of 22 to 35 mm. We found that 7 stability parameters give the same trend of GS with composition from R = 0.25 to 0.5. For R > 0.5 the GS is approximately constant within the error limits indicating that composition does not significantly affect the glass forming ability in this compositional range. This general finding qualitatively agrees with our previous successful experience of preparing these glasses continuously with compositions up to and including R = 2.8 (74 mol. % lithia).

Work supported by NSF under grant number DMR 05020518 and DMR 0904615 and by Fapesp #07/08179-9.

Keywords: glass forming ability, glass stability, DSC, Li2O-B2O3, glass, crystallization.

0335 | Study of the crystallization mechanism of silica-titania binary system for high refractive index glass production

Eduardo Ono*, Mirella O. Boery, Tarcio P. Manfrim, Juliana S. dos Santos, and Carlos K. SuzukiUniversidade Estadual de Campinas – Unicamp, Laboratório de Materiais e

Dispositivos Fotônicos, Campinas-SP, e-mail: [email protected]

Silica-titania (SiO2–TiO2) glass is an interesting material for waveguides fabrication due to its high and easy tunability of the refractive index. However, for bulk glasses, crystallization and opacity promoted by a high TiO2 doping (> 12 wt. %) still presents a challenge. In this research, high-purity SiO2–TiO2 glass was synthesized by VAD (vapor-phase axial deposition), a flame aerosol method widely used for optical fiber preform fabrication. SiCl4 and TiCl4 halides were used as precursors for producing SiO2-TiO2 nanoparticles by a flame (oxy-hydrogen) hydrolysis and oxidation reaction. For TiO2 content above 12 wt. %, TEM images of the soot powders showed TiO2 segregation and crystallization in anatase phase, identified by XRD. It was observed that the crystallization level is highly strengthened due to the long resident time of the rotating preform at high flame temperature and intensified in the subsequent consolidation process (1400 ºC for 2 h). By means of this ascertainment, it was possible to decrease the crystallites size and reduce the crystallization level on samples with high TiO2 content (> 20 wt. %) by changing the burner-target distance and flame H2/O2 gas ratio. This result shows the viability of achieving a clear SiO2–TiO2 glass with high refractive index and optical transparency by controlling the crystallization during the deposition process.

Keywords: silica-titania, nanoparticles, crystallization, flame hydrolysis, optical fiber.



0344 | Glass formation and properties of glasses based on the system LA2O3-TiO2 by containerless processing

Hiroyuki Inoue1*, Masashi Kaneko2, Yasuhiro Watanabe1, Atsunobu Masuno1, Jianding Yu3

1Institute of Industrial Science, the University of Tokyo 4-6-1 Komaba Meguro-ku Tokyo, 153-8505 Japan 2Department of Innovative and Engineered Materials, Tokyo Institute of Technology, 4259,

Nagatsuda Midori-Ku Yokohama 226-8502 Japan 3Japan Aerospace Exploration Agency, 3-1-1 Yoshinodai,

Sagamihara, 229-8510 Japan, e-mail:[email protected]

Containerless processing is an appropriate method to search the new glass system or to create glass whose glass-formation ability is low. The containerless processing suppresses the nucleation in molten salt and enables rapid quenching of the melt. In addition, we obtain bulk sample of glasses using the processing, while by using twin-roller quenching small flakes of glasses are only obtained. The vitrification of the binary glass of La2O3-TiO2 has been reported by the twin-roller quenching and the containerless processing already. In this study, we prepared the glasses based on 2La2O3.9TiO2 system added with the third component of Al2O3, Ga2O3, Y2O3, GeO2, ZrO2, HfO2, Nb2O5, Ta2O5 and WO3. The glass transition temperature and the crystallization peak were determined by DTA. We tried to discuss the stabilization of 2La2O3.9TiO2 glass by the addition of the third component except the glass-forming oxide. Moreover, the effect for refractive index and its dispersion were examined.

Keywords: La2O3-TiO2 system, containerless processing, properties.

0421 | The investingation of antemelting on hydrated organic glass forming solutions

Wanderson M. de Abreu1, Antonio V. Cardoso1*, Pia V. Orlien2, Mogens L. Andersen2, Leif H. Skibsted2

1REDEMAT/CETEC – Rede Temática em Engenharia de Materiais – Belo Horizonte – MG, e-mail: [email protected]

2Food Chemistry, Department of Food Science, Faculty of Life Sciences, Copenhagen University- Frederiksberg

The formation of multiple thermal events in hydrated organic glass forming solutions was investigated focusing the occurrence of glass transition and related phenomena. The antemelting, a typical shape on DSC thermograms which precede the ice melting was observed on samples containing more than 40% water content. Thermogram analysis of samples within wide range of water content indicated that antemelting is preceded by the formation of a devitrification peak. When water content is increased this devitrification became too small to be clearly identified. Thermal treatment allowed nucleation and growth of crystals inside these samples, and produced thermograms with more than one glass transitions and lower devitrification peaks. Further thermal treatment produced thermograms displaying thermal event similar to antemelting.

The extensive analysis on three different sugar related glass forming solutions – fructose, honey and caramel colorant hydrated solutions – indicated that antemelting is indeed a complex thermal phenomena which could be related to residual devitrification of low temperature glass associated or not to a remaining higher concentration glasses.

Keywords: antemelting, glass transition, hydrated organic glass formers.

0485 | Alternative route to produce high alkali-phosphate glasses through nitridation

Nerea Mascaraque, Alicia Durán, Francisco Muñoz*Instituto de Cerámica y Vidrio (CSIC), Kelsen 5, 28049, Madrid (Spain), e-mail: [email protected]

Bulk oxynitride phosphate glasses are generally synthesized through the ammonolysis reaction of the melt under an anhydrous ammonia flow below 800ºC, where the nitrogen content depends on glass composition as well as the reaction conditions. Nitrogen substitution for oxygen is known to modify the properties of phosphate glasses. The glass transition temperature, density, elastic modulus, refractive index and electrical conductivity are increased with nitrogen content and, especially, the chemical resistance of the glasses is drastically improved. Another important feature is that nitridation decreases the tendency of the glass to crystallization. However, the use of some elements in the glass composition might reduce the possibilities of nitridation of phosphate glasses by the conventional ammonolysis route due to volatilization, phase separation, reduction reactions or devitrification phenomena. In this work, an alternative way to synthesize oxynitride phosphate glasses is explored using the effect of nitrogen on preventing spontaneous crystallization. In particular, lithium phosphate glasses have been prepared containing nitrogen and elements like fluorine, sulphur or boron, and



their glass forming ability has been studied. The results show that nitrogen allows the formulation of glasses with higher lithium contents respecting to non-nitrided glasses as well as prevents secondary reactions which otherwise reduce glass formability.

Keywords: oxynitride glasses, nitridation, nitrogen, lithium phosphate glasses.

Sept. 24 – 10:00-12:15 h – Room A

New Functional (Chairman: B. Aitken)

0044 | New functionalities in glass via femtosecond laser writing of micro and nano structures

Denise M. KrolDepartment of Applied Science, University of California, Davis, CA, e-mail: [email protected]

Femtosecond laser processing of glass is becoming increasingly important as a method to modify the properties of glass with three-dimensional spatial selectivity. The fs-laser processing technique relies on the fact that focused fs laser pulses can give rise to very high intensities (1014 W/cm2), resulting in permanent modification of the material. By moving the sample relative to the laser focus it is possible to directly “write” micro- and nanostructures inside a glass. These structures can differ from the unmodified material in a wide variety of properties including refractive index, absorption coefficient, crystal structure, morphology etc. and they can be used to create waveguides, photonic crystals and other optical elements. The nature and magnitude of the fs-laser induced changes depend on the interplay between glass composition and laser processing parameters, such as pulse energy, repetition rate, and scan speed.

Our studies, in which the fs laser writing set-up is integrated with confocal fluorescence and Raman microscopy, have shown that confocal spectroscopy is a key tool for understanding the structural changes associated with fs-laser writing in glass. In this talk I will discuss how this technique has been employed to investigate a wide variety of glass systems, including fused silica, phosphate glasses, rare-earth-doped glasses and glasses incorporating semiconductor quantum dots.

Keywords: femtosecond laser processing, nonlinear optics, laser writing, fluorescence spectroscopy, raman spectroscopy, optical materials.

0365 | Femtosecond laser modification dynamics in fused silicaJonathan J. Witcher1*, Luke B. Fletcher1, Neil Troy1, Denise M. Krol1

1University of California, Davis, Department of Applied Science, One Shields Ave. Davis, CA 95616, e-mail: [email protected]

Femtosecond (fs) laser pulses can be used to directly “write” photonic structures, such as waveguides, splitters, and Bragg gratings, inside a glass. This technique has great potential as a fabrication technique for three-dimensional integrated optical components with applications ranging from telecommunications to medical technology.

Despite the advances in device design the mechanism responsible for the femtosecond laser modification of glass is not well understood. While the structural changes that result from modification have been characterized, little is known about the processes occurring between laser absorption and resulting modification. These processes are difficult to study because they occur in very small volumes and on time scales that range from femtoseconds to microseconds.

In this study we have monitored the dynamics of fs-laser modification using a fs pump-probe setup. Fused silica was irradiated using an amplified Ti:sapphire fs-laser system as the pump. The transmission of a broadband probe was measured as a function of pump-probe delay. This transmission data was used to determine the electron density created by the absorption of the fs-laser pump pulse. Peak electron densities and plasma lifetimes were measured for various writing conditions. We will discuss the results in relation to the morphology and structural changes in the glass after fs-laser-induced modification.

Keywords: femtosecond laser modification, optical components, pump-probe, plasma, dynamics, fused silica.

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0255 | Precipitation of Ag Nanoparticles on KPO3-WO3 glass system via thermal treatment

Silvia Santagneli1*, Marcelo Nalin2, Sidney J.L. Ribeiro1, Younes Messaddeq1

1Laboratory Photonic Materials, Chemistry Institute-UNESP, Araraquara-SP, Brazil 2Universidade Federal de São Carlos – UFSCar, São Carlos-SP, Brazil, e-mail: [email protected]

Silver-containing glasses have been prepared by different methodologies including ion-exchange and ion implantation, while the silver nanoparticles embedded in such matrix has been obtained by controlled thermal annealing or laser irradiation. In the present work, the formation of Ag nanoparticles on tungsten based glass system, has been obtained from reduction of ionic Ag+ followed by nucleation and growth using controlled thermal annealing. Vitreous samples were prepared in the KPO3–WO3-AgCl system using conventional melting quenching method. Thermal and structural properties of glasses have been monitored as a function of WO3 content by Differential Scanning Calorimetry (DSC), Raman and solid-state 31P MAS NMR spectroscopy. The formation of Ag-based nanoparticle after annealing has been investigated by UV-Vis spectroscopy and HRTEM. The addition of WO3 to the KPO3 glass leads to a pronounced increase in the glass transition temperature suggesting significant increases in the network connectivity which is in agreement with structural data. Raman data suggests that glasses with low WO3 content present W-O- bonds while glasses containing more than 30% in mol of WO3 present W-O-W bonds. 31P MAS NMR data have shown a downshield around phosphate environment with increase WO3 content. UV-Vis spectroscopy measurement for the samples with different heat treatments shown absorption band centred at 530 nm.

Keywords: nanoparticle, phosphate glasses, NMR, Ag.

0103 | New extrinsic self-healing concept for glassy materialsDaniel Coillot1*, François O. Méar1, Renaud Podor2 and Lionel Montagne1

1*Université Lille Nord de France F-59000 Lille – France ; Unité de Catalyse et de Chimie du Solide, UMR-CNRS 8181, USTL F-59652, e-mail: [email protected]

2Institut de Chimie Séparative de Marcoule, UMR 5257 CEA-CNRS-UM2-ENSCM, Site de Marcoule, BP 17171, F-30207 Bagnols sur Cèze cedex – France

Many efforts in research and development of smart materials are currently driven towards higher performance. These materials have indeed a built-in capability to repair the damages that may occur during use. When damage through thermal, mechanical, chemical or other origin is formed, the material has the ability to heal and restore itself to its original set of properties. Self-healing can be obtained in two ways: extrinsic or intrinsic. Intrinsic self-healing is fully autonomic but requires an external constraint such as temperature increase. On the other hand, extrinsic self-healing involves healing agents encapsulated in the material, and their reactivity is activated by a constraint (mechanical, chemical or thermal).

Our self-healing concept is derived from that developed for polymeric materials. Healing particles are dispersed within the glass or glass-ceramic matrix. The choice of particles will be justified on the basis of their reactivity (monitored by NMR) and thermal characteristics of the matrix (measured with DTA-TG). Self-healing effect is demonstrated by in-situ experiment performed into an Environmental Scanning Electron Microscope (ESEM).

Keywords: glass/glass-ceramic, active particle, self-healing, extrinsic/intrinsic, in-situ experiment, environmental scanning electron microscope (ESEM).

0102 | In situ healing technology for solid oxide fuel cellsDaniel Coillot1, François O. Méar1*, Renaud Podor2, Lionel Montagne1

1*Université Lille Nord de France F-59000 Lille – France; Unité de Catalyse et de Chimie du Solide, UMR-CNRS 8181 ; USTL F-59652, e-mail: [email protected]

2Institut de Chimie Séparative de Marcoule, UMR 5257 CEA-CNRS-UM2-ENSCM, Site de Marcoule, BP 17171, F-30207 Bagnols sur Cèze cedex – France

A key point for the long-term operation of SOFC systems remains the sealing component used for the stack assembly. Over the past decade, different SOFC sealing concepts have been proposed. Among them rigid bonded sealing and compressive sealing have been extensively investigated. Glass and glass-ceramics are currently the developed solutions but they still require significant attention because their brittle nature can lead to fracture and loss of seal integrity and functionality. In this study, we propose a new concept of self-healing for glasses or glass-ceramics, which may increase significantly the life duration of SOFC stacks. The fully autonomic self-healing effect is demonstrated by an in-situ experiment performed into an Environmental Scanning Electron Microscope (ESEM). The crack is simulated by Vickers indentation. SEM clearly shows



that the crack healing occurred within 30 min at 700 °C. Microprobe analysis indicates that the healing is produced by the in-situ formation of a new glassy phase. The performance of these self-healing seals under long-term exposure at high temperature, coupled with thermal cycles is characterized by leak tests. We also characterized the properties of the glass and healing agent composite (e.g. CTE, resistivity, density), to show that the initial properties of the glass are not significantly modified. We thus conclude that the self-healing process can be applied to any glass or glass-ceramic composition.

Keywords: sealing-glass, solid oxide fuel cell (SOFC), self-healing, in-situ experiment, environmental scanning electron microscope (ESEM), leak test.

0085 | Glass-crystal transition in Ge-Sb-Te phase change materials under multiple thermal cycling and annealing

Sergey Kozyukhin1,*, Alexey Sherchenkov2

1Kurnakov Institute of General and Inorganic Chemistry, RAS – Leninsky Pr., 31, Moscow, 119991 – Russia, e-mail: [email protected]

2Moscow Institute of Electronic Technology – Zelenograd, 124498 – Russia

One of the attractive advantages of phase-change memory devices is considered to be increased cycling endurance. Recently we have shown that thermal cycling can lead to the phase separation in Ge2Sb2Te5 material. In this work we compared multiple thermal cycling of Ge2Sb2Te5, GeSb2Te4 and GeSb4Te7, and investigated influence of additional annealing of synthesized materials on thermal stability by the differential scanning calorimetry (DSC).

For all as-deposited amorphous films exo peaks in the temperature ranges 125-190 °C and 200-230 °C were attributed to the transitions from amorphous to fcc structure, and from fcc to the stable hcp phase, respectively. Multiple DSC scanning lead to the appearance of the unknown endo peak in the temperature range 390-415 °C for all compounds. Increase of the number of DSC scanning is accompanied by the increase of the endo peak. XRD measurements revealed existence of at least two phases after multiple cycling.

Additional annealing of synthesized materials was carried out at 775 K in Ar atmosphere. It was found that after the annealing kinetics of the endo peak increase is much slower, which can be attributed to the slowed diffusion processes. So, additional annealing of synthesized powders leads to the sufficient increase of the thermal stability of Ge-Sb-Te materials, which is important for the increased cycling endurance of recording devices.

This work was supported by a grant 08-03-00651 from RFBR.

Keywords: phase-change memory, multiple thermal cycling.

0366 | Magneto-optic effects in germano-silica glass fibers doped with cadmium selenide quantum dots

Pramod R. Watekar1, Seongmin Ju2, Su-Ah Kim2, Seongmook Jeong1, Youngwoong Kim2, Cheol Jin Kim3 and Won –Taek Han1,2*

1Department of Information and Communications 2Graduate Program in Photon Science and Technology, Gwangju

Institute of Science and Technology, Gwangju 500-712, South Korea 3Engineering Research Institute, Gyeongsang National University,

Jinju, Gyungnam 660-701, South Korea, e-mail: [email protected]

We developed germano-silica glass fibers doped with CdSe quantum dots (QDs, size < 5 nm) for magneto-optic applications by using the MCVD process. Presence of quantum dots in glass fiber cores was confirmed by using the visible absorption spectroscopy and the TEM measurement. Effect of concentration of CdSe QDs from 0 to 2 × 1025 dots/m3 in the core of the germano-silica glass fiber on optical absorption and magneto-optic properties was investigated. Glass fibers were single mode in the measurement range of 633 nm.

Magneto-optic sensitivity of CdSe QDs-doped glass fibers was determined at 633 nm by measuring the Faraday rotation angle upon the influence of magnetic field. The mean Faraday rotation angle of the glass fiber with low concentration (2.2 × 1024 dots/m3) of CdSe QDs was measured to be about 27°, while that of the fiber with high concentration 2 × 1025 dots/m3 was about 39° at 0.142 T of magnetic field. On the other hand, the fiber without CdSe QDs showed the Faraday rotation of -15°. Magnetic sensitivity increased from



1.84 to 3.32 and 4.79 rad/T with the increase of the CdSe QDs concentration from 0 to 2.2 × 1024 and 2 × 1025 dots/m3, respectively. This enhanced magnetic sensitivity of CdSe QDs-doped glass fibers was attributed to the high concentration of CdSe QDs.

Keywords: magneto-optic effect,quantum dots, optical fiber: characterization, optical fiber: fabricatio.

Sept. 24 – 14:00-16:15 h – Room A

Crystallization (Chairman: E. D. Zanotto)

0376 | Studies on surface crystallization performed by electron backscatter diffractionWolfgang Wisniewski, Marcus Nagel, Christian Rüssel*

Otto-Schott-Institut, Friedrich-Schiller-Universität Jena, Fraunhoferstr. 6, 07743 Jena. Campus de

In many cases, the surface crystallization of glass results in the formation of oriented structures. The crystallization mechanism which leads to the orientation is often denoted as crystal selection. Here, randomly oriented crystals are formed by surface nucleation. Then they grow and in some distance from the surface, only those crystals will occur which are oriented with their fastest growing axis perpendicular to the surface. All other crystals will hinder each other during crystal growth. In the present study, the systems fresnoite (Ba2TiSi2O8), bariumaluminum borate and cordierite are studied using x-ray diffraction and EBSD. It is shown that in the fresnoite and the bariumaluminum system, the crystals formed immediately at the surface are already oriented, however, the orientation is just another one than in some distance from the surface. We conclude that immediately after the nucleation, i. e. in a distance of some nm from the surface, the thermodynamics of the nucleation process, i. e. the surface energies play a decisive role. Subsequently, the orientation changes and in some distance from the surface only crystals oriented with their fastest growing axis perpendicular to the surface will occur. During this step, the crystallization kinetics is decisive.

Keywords: surface crystallization, oriented crystallization, electron backscatter diffraction.

0375 | The mechanism of nanocrystallization in earth alkaline fluoride systemsChristian Bocker*, Christian Rüssel

Otto-Schott-Instiut, University Jena, Fraunhoferstrasse 6, 07743 Jena, Germany

Thermal annealing of oxyfluoride glasses led to the precipitation of nano crystalline BaF2 or CaF2. A narrow crystallite size distribution and a homogenous dispersion of BaF2 crystallites in the glassy matrix were observed by electron microscopy. The crystallite size distributions were even narrower than predicted by LSW- or B&W growth theory. This led to a good optical transparency of the glass-ceramics. The formation of a highly viscous layer around the crystals which acts as diffusion barrier was proposed and proved by advanced EELS techniques. Diffusion profiles of barium and fluoride at different temperatures were obtained. It turned out that the diffusion of barium controls the crystal growth rate. Using experimental data of viscosity as a function of temperature, the change of the viscosity of the residual glassy phase during crystallization of BaF2 can be described. Structural investigations of glasses and glass-ceramics were performed in cooperation with the CSIC, Madrid, using MAS-NMR. Various samples were analyzed and the role of fluoride during crystallization was clarified. Thermal annealing of some samples led to the crystallization of an orthorhombic modification of BaF2 which is only thermodynamically stable at high pressures. The formation of the orthorhombic phase is due to compressive stresses during crystallization. This is the first experimental evidence of the formation of high pressure during crystallization of glass.

Keywords: oxyfluoride glasses, glass-ceramics, crystal growth, nanocrystallization.



0220 | Peculiar crystal growth and morphology of ferroelastic crystals in rare earth molybdate glasses

Futoshi Suzuki*, Tsuyoshi Honma, Takayuki KomatsuDepartment of Material science and Technology, Nagaoka University of Technology, 1603-1,

Kamitomiokatyo, Nagaoka, 940-2188, Japan, e-mail: [email protected]

Rare-earth (RE) molybdate glasses such as RE2O3-MoO3-B2O3 show the crystallization of ferroelectric-ferroelastic b’-RE2(MoO4)3 in usual heat treatments and laser induced crystallization. Furthermore, crystal lines show self-organized periodic domain structures with periodic refractive index changes. Second Harmonics Generation (SHG) changes periodically depending on self-organized periodic domain structure. To clarify the peculiar crystal growth and morphology of this crystal line, Er3+-doped b’-(Sm,Gd)2(MoO4)3 crystal lines are patterned on the surface of Er2O3-Gd2O3-Sm2O3-MoO3-B2O3 glasses by continuous-wave Yb:YVO4 laser irradiations (wavelength: 1080 nm), and the origin of the periodicity of self-organized domain structures with the refractive index regions in the crystal lines is examined from polarized optical microscope, micro-Raman scattering spectrum. It is found that the periodicity of domain structures changes largely depending on Er2O3 content, i.e., the length of each periodic domain regions increases with increasing Er2O3 content. Considering that the degree of ferroelasticities in b’-(Sm,Gd)2(MoO4)3 crystals decreases due to the incorporation of Er3+ ions, it is concluded that the origin of periodic domain structures in laser-patterned lines is due to spontaneous strains in ferroelastic b’-(Sm,Gd)2(MoO4)3 crystals.

On the other hand, laser induced crystallization method was applied to pattern two-dimensional planar crystals consisting of b’-(Sm,Gd)2(MoO4)3 crystal.

Keywords: rare earth molybdate, laser induced crystallization, ferroelectric-ferroelastic.

0185 | Inelastic light scattering of oxide glasses during heating/crystallization process

Yoshihiro Takahashi1*, Minoru Osada2, Hirokazu Masai1, Takumi Fujiwara1

1Department of Applied Physics, Graduate School of Engineering, Tohoku University, e-mail: [email protected]

2International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS)

The glassy state is a thermodynamically non-equilibrium, and external thermal stimulation will eventually lead to a more stable state, i.e., structural relaxation and crystallization. While these phenomena are recognized to be useful for fabrication of optical device component, the transition state from glass/supercooled liquid (SCL) phase to crystal phase has not been fully understood yet. Inelastic light scattering measurement is one of the powerful techniques to examine chemical bonding and coordination states. We recently verified that in-situ Boson measurement is able to sensitively observe the relaxation and rearrangement of the SCL state. [1-3] In this study, we investigate the nucleation and crystal-growth processes of oxide glasses (mainly silicate) by means of in-situ observation of inelastic light scattering (Boson and Raman region) during heating/crystallization in order to elucidate their crystallization dynamics. Main topics we will deal with are i) structural relaxation below Tg and nanometric heterogeneity, and ii) precursive stage of crystallization.1. Y. Takahashi, M. Osada, H. Masai, T. Fujiwara, Phys. Rev. B 79 (2009) 214204.2. Y. Takahashi, M. Osada, H. Masai, T. Fujiwara, Appl. Phys. Lett. 94 (2009) 211907.3. Y. Takahashi, M. Osada, H. Masai, T. Fujiwara, Appl. Phys. Lett. 94 (2009) 241909.

Keywords: crystallization, nucleation, inelastic light scattering, boson peak, raman spectroscopy, oxide glass.

0323 | Structure and role of titanium as nucleating agent in an aluminosilicate glass

Laurent Cormier1*, Marie Guignard1, Valérie Montouillout2, Nicolas Menguy1, Dominique Massiot2, Alex C. Hannon3, Brigitte Beuneu4

1*IMPMC, CNRS, Université Pierre et Marie Curie, Université Paris Diderot, Paris, France, e-mail: [email protected]

2CEMHTI, CNRS, Université d’Orléans, Orléans, France 3ISIS Facility, CCLRC Rutherford Appleton Laboratory, UK

4Laboratoire Léon Brillouin, C.E.A. Saclay, Gif-sur-Yvette, France

We have investigated the structural rearrangements occurring in the Ti-containing cordierite glass (MgO-2Al2O3-5SiO2) upon nucleation. Neutron diffraction data coupled with Ti isotopic substitution have shown important structural modifications in the Ti environment and difference functions agree with the initial formation of magnesium aluminotitanate (MAT) nuclei, possibly due to preferential linkages between Ti and



[5]Al (Guignard et al., 2009). Simultaneously to the structural changes around Ti, we have also evidenced strong modifications in the remaining glass network, which imply an increasing order in the glass structure early in the nucleation process. This reflects the atomic rearrangements in the glassy part resulting from the diffusion of the chemical species towards the glass/crystal interface. One of these rearrangements is the modification of the Al coordination that varies from tetrahedral to octahedral as the nucleation proceeds (Guignard et al., accepted). The resulting [6]Al can then form new sites favoring the formation or growth of MAT nuclei. Our study emphasizes that the development of structural investigations can give new information at the atomic scale that are essential to improve the picture of nucleation processes in amorphous materials.Guignard et al., J. Phys.: Condens. Matter 21, 375107 (2009).Guignard et al., J. Phys.: Condens. Matter (accepted).

Keywords: glass nucleation, neutron diffraction, NMR.

0310 | Dendritic crystallization in lead oxifluoroborate glasses bellow the glass transition temperature

José E. De Souza1*, Seila R. de Souza1, Jean-Claude M’Peko1, Antonio C Hernandes1

1*Instituto de Física de São Carlos – IFSC/USP, São Carlos-SP, e-mail: [email protected]

Branched fractal crystallization of β-PbF2 was observed after the appliance of a DC field of ~ 3.7V/mm on a B2O3-PbO-PbF2 glass. Although the electrochemical deposition of coatings through liquid electrolytes baths has been discussed elsewhere, the occurrence of this effect in a solid electrolyte is less common. Here, the crystal formation happens well below the glass transition interval, being an electrochemical process in essence. Then, at least in a first approximation, the process can be described in a similar way to that of a liquid system, including an oscillatory character in the nucleation kinetics. The nucleation and growth is clearly biased towards the electric fields and this aspect gives an interesting way of producing glass ceramics, where spatial position and homogeneity of crystals in the surface, as well as the size distribution of them can be controlled. The following parameters were analyzed: the process temperature, the time of DC application and the metal species used as electrode (sputtered gold, painted silver, or a platinum flat plate just with a mechanical contact).

Keywords: lead oxifluoroborate, sub-sub Tg crystallization, dendritic crystallization, electrochemical deposition.

0412 | Phase separation in 0.45SiO2–0.45MgO–0.1(3CaO.P2O5) glass investigated by TEM, sem and afm

Carlos Araújo Queiroz1*1VICARTE – Faculdade de Ciências e Tecnologia – Universidade Nova de Lisboa –

FCT/UNL, P-2829-516 Caparica, Portugal, e-mail: [email protected]

Bulk glass of molar composition 0.45SiO2–0.45MgO–0.1(3CaO.P2O5) presents phase separation comprising aggregated globular structures, patterned at the micrometric scale, shown to correspond to amorphous SiO2 by TEM-EDS. Polished bulk samples examined by SEM after HNO3 etching, which tends to lixiviate preferentially phosphate rich regions, shown that the area surrounding globular aggregates is phosphate-enriched, thus suggesting diffusion governed growth. A concentration profile between nearby globular clusters was obtained by TEM-EDS. The globular aggregates are noticeably harder than the glass matrix, what permitted to reveal their 3-dimensional morphology by AFM examination, being the sample polished so that the harder phase morphology remained fairly preserved, while the glass matrix appears recessed. HF and HNO3 etched samples were also examined by AFM, providing further evidence for the matrix concentration profile, since HF tends to lixiviate preferentially the silicate-enriched regions, while revealing silicate-rich undelimited regions located between nearby clusters. Such regions are seemingly associated with the nucleation of SiO2 amorphous globules, which, hereafter, tend to evolve toward globular clusters. Glass frit grains present heterogeneous poorly defined domains, depicting a fractal kind of morphology, cauliflower-like, mostly patterned at the nanometric scale. The phase separation regimen seemingly evolves from spinodal (frit), towards binodal (bulk glass).

Keywords: TEM, SEM, AFM, phase separation, nanostructures, nucleation, spinodal decomposition.



0324 | Crystallization of GeAsTe bulk glass and thin filmsBruce G. Aitken*, Stephen C Currie and Charlene M. Smith

Corning Incorporated, Corning, NY 14831, USA, e-mail: [email protected]

Certain telluride materials are characterized by unusually high contrast in optical and/or electrical properties between the glassy/amorphous and crystallized state. In particular, compositions on the Sb2Te3-GeTe join, including the so-called “phase change” alloys Ge2Sb2Te5 and GeSb2Te4, have found application in optical and electronic memory. In this study, we report on the physical properties and structure, as studied by calorimetry, reflectance spectroscopy and X-ray diffraction, of analogous materials in which Sb has been replaced by As. Despite the strong tendency to crystallize one of the GexAs2Te

3+x phases, bulk glasses have been made on the As2Te

3-GeTe join with Ge content ranging from 0 to 18%, including glassy GeAs2Te4. Amorphous GeAsTe, GeSbTe and quaternary thin films have been made by pulsed laser deposition. Heat treatment of GeAsTe and quaternary films results in an increase in reflectance from ~40 to ~60% due to crystallization of hexagonal Gex(As,Sb)2Te3+x phases, similar to the behavior of amorphous GeSb2Te4 films. Although the GeAsTe films are characterized by greater reflectance contrast than their GeSbTe analogs, crystallization kinetics are slower, perhaps due to a greater change in short range order between glass and corresponding crystal.

Keywords: nonoxide glass, telluride, thin films.

0009 | Adiabatic nucleation in devitrifying “fragile” oxide glassesErich Meyer1*, Vitorvani Soares1

1Instituto de Física, Universidade Federal do Rio de Janeiro, C.T. – Bloco A, Cidade Universitária, 21945-970 Rio de Janeiro, Brazil, e-mail: [email protected]

A quantitative Adiabatic Nucleation Theory (ANT) is proposed for devitrifying oxide glasses. In contrast to the Classical Nucleation Theory (CNT), the former theory does not consider isothermal heterophase fluctuations which grow, in the supersaturated state, with a certain probability, above a maximum of Gibbs’ potential which is due to the existence of a surface tension. Common fluctuations of the thermodynamic variables (homophase fluctuations) are considered. A few of them go beyond the adiabatic liquid-solid stability limit, become unstable and result adiabatically, if large enough, in a crystalline nucleus of higher entropy. At the first moment, the new nucleus has a different temperature. Additionally, immediately afterwards, in a second step, temperature equalization occurs, followed by a further increase of the total entropy. The present model shows realistic results for “fragile” glasses (following Angel’s classification), T00/Tg > 0.6 where T00 is the Fulcher temperature and Tg is the glass transition temperature, but may fail, when applied to “strong” glasses, T00/Tg < 0.6. This is because the low Fulcher temperature of “strong” glasses invalidates simplifying approximations of the model, as, for example, the extrapolation of the viscosity function (far below Tg) and the approximate validity of the Stokes-Einstein relation.

Keywords: nucleation, glasses, amorphous solids, thermodynamic stability.

Sept. 24 – 8:00-9:45 h – Room B

Bio Glasses TC 4 (Chairman: J. Jones)

0396 | Solid state nmr of bioglasses – new techniques and applications

Mark E. SmithDepartment of Physics, University of Warwick, Coventry, UK CV4 7AL, e-mail: [email protected]

NMR is an increasingly important and informative probe of glasses whose capability still continues to advance very rapidly with increasing multinuclear capability and more sophisticated experiments that enhance the information about intermediate-range order. Some recent technique developments that are especially important for glasses (e.g. two-dimensional correlation techniques), more challenging nuclei (e.g. 17O, 43Ca), as well as some more speculative, but really exciting new techniques in the early stages of development that are just being developed (double angle rotation (DOR), dynamic nuclear polarisation (DNP)) are presented. High field 43Ca magic angle spinning (MAS) NMR applied to apatite has resolved the inequivalent calcium sites, with identification of the sites possible via 1H-43Ca cross-polarisation and 1H-43Ca REDOR (a technique that detects spatial proximity by reintroducing the nuclear dipolar coupling). In

INVITeDSPeAKeR



phosphate glasses new analysis of two-dimensional NMR sequences based on the through bond J-coupling reveals the connectivity of the phosphate chains in glasses. Applications of NMR using a fully multinuclear (1H, 13C, 17O, 23Na, 29Si, 31P and 43Ca) approach is presented of some key bioactive glass systems including calcium silicates, calcium silicate-polymer hybrids and quaternary phosphates with additions of elements such as silver and titanium to modify the dissolution and antibacterial properties.

Acknowledgements: A large range of co-workers and collaborators are thanked, as are EPSRC, the University of Warwick, as well as Birmingham Science City: Advanced Materials Projects 1 and 2, with support from AWM and the ERDF for funding this work.

Keywords: solid state NMR, multinuclear, bioglasses, 43Ca, calcium silicates, phosphates.

0092 | Mechanisms of apatite crystallization in dental glass-ceramicsW. Höland*, V.M. Rheinberger, C. Ritzberger, E. Apel

Ivoclar Vivadent AG, Research and Development, Bendererstr. 2 Li-9494 Schaan, Principality of Liechtenstein

Fluoroapatite (Ca5(PO4)3F) was precipitated in glass-ceramics via internal crystallization of base glasses. The crystals grew in needlelike morphology in the direction of the crystallographic c-axis. HR-TEM, SEM, XRD, and solid state NMR investigations were used to indentify two different reaction mechanisms: precipitation via a disordered primary apatite crystal and a second mechanism in the form of a solid state parallel reaction to rhenanite (NaCa(PO4)3) precipitation. In contrast to the internal nucleation used in the formation of fluoroapatite, surface crystallization was induced to precipitate a phosphate-free oxyapatite of the NaY9(SiO4)6O2-type.

Keywords: biomaterials, dental, fluoroapatite, restoration.

0248 | Surface modification of ferrimagnetic glass-ceramic particles for magnetic drug targeting

Oana Bretcanu*, Sara Ferraris, Marta Miola, Enrica VernèMaterial Science and Chemical Engineering Departement,

Politecnico di Torino, Turin, Italy SP, e-mail: [email protected]

The aim of this work is the surface activation of ferrimagnetic glass-ceramic powders for the treatment of tumours. These powders contain magnetic crystals embedded in a bioactive amorphous phase. Due to their magnetic properties, they can be heated by alternating magnetic fields. Therefore, when implanted into a tumour, these materials can generate the tissue heating under variable magnetic fields. The heating temperature depends on the materials properties, magnetic field parameters (intensity, frequency, position), exposure time and tissue characteristics (cells type, blood flow, tissue density, thermal conductivity, electrical permittivity). The bioactive amorphous phase can be easily functionalised in order to bind specific biomolecules or drugs, joining the heating properties with a more efficient chemotherapy. By suitable functionalisation processes, these materials can have good potentiality for magnetic drug targeting therapy.

The materials microstructure was determined by X-ray diffraction analysis. The morphology of the magnetic crystals was analysed by scanning electron microscopy. The specific power loss was studied by calorimetric measurements, using a magnetic field generator with frequencies up to 200kHz. Surface modification was observed by X-ray photoelectron spectroscopy, infrared spectroscopy, atomic absorption spectroscopy and contact angle measurements. Cytotoxicity studies were performed by using human osteosarcoma cells.

Keywords: functionalisation ferrimagnetic, glass-ceramics, hyperthermia, drug targeting, cancer treatment.

0245 | Surface functionalization of bioactive glasses with alkaline phosphataseEnrica Vernè1*, Sara Ferraris1, Chiara Vitale Brovarone1, Silvia Spriano1, Claudia Letizia Bianchi2,

Alberto Naldoni2, Marco Morra3, Clara Cassinelli3, Elisa Battistella4, Lia Rimondini41Material Science and Chemical Engineering Departement, Politecnico di

Torino C.so Duca degli Abruzzi 24, 10129, Turin, Italy, e-mail: [email protected] 2Dept. Physical Chemistry and Electrochemistry, Milan University, V. Golgi 19, 20133 Milan, Italy

3NobilBio Ricerche, V. Valcastellana26, 14037, Portacomaro (AT), Italy 4Eastern Piedmont University A. Avogadro, V Solaroli 17, 28100 Novara, Italy

Bioactive glasses are able to chemically bond to bone through a hydroxyapatite layer developed on material surface in physiological fluids thanks to the glass composition. This behavior can be described as inorganic bioactivity. Surface functionalization with biologically active molecules is a widely studied research field in scientific literature with the aim to improve implant integration and tissue regeneration (biological bioactivity).



This research work consider the opportunity to conjugate inorganic bioactivity, peculiar of bioactive glasses, and biological bioactivity (of biomolecules) by means of the grafting of an enzyme (alkaline phosphatase – ALP) on bioactive glasses surface.

Glasses with different degree of bioactivity have been considered. Grafting efficacy, bonding stability, enzymatic activity and bioactivity have been evaluated. It has been demonstrated that it is possible to successfully graft ALP to surface of reactive glasses maintaining its activity. A synergistic effect between biological functionalization and apatite forming ability has been observed. Cellular stimulating behavior has been verified in vitro on human osteoblast like cells (MG-63).

The effect of different sterilization techniques on functionalized surfaces has been evaluated. Both sterility and enzymatic activity have been tested before and after sterilization. Finally the effect of packaging and storage conditions has been considered.

Keywords: bioactivity, biological functionalization, tissue-implant interaction, bioactive glasses, sterilization.

0145 | Soluble phosphate glasses for biomedical applications, Dissolution studies and fibres production

Chiara Vitale-Brovarone1*, Daniel Milanese1, Joris Lousteau1, Jonathan C Knowles2, Giorgia Novajra1

1*Materials Science and Chemical Engineering Department, Politecnico di Torino, Corso, Duca degli Abruzzi 24, 10129, Torino, Italy, e-mail: [email protected]

2Division of Biomaterials and Tissue Engineering, Eastman Dental Institute, University, College London, 256 Gray’s Inn Road, London WC1X 8LD, UK

Phosphate glasses (PGs) have a great potential for the fabrication of biomedical temporary devices, due to their solubility in aqueous media with a resorption time that depends on the glass composition. PGs fibres can be an interesting option for the synthesis of tissue engineering constructs, alone or in composite materials with a polymeric matrix.

Three TiO2-containing PGs with different solubility have been developed and completely characterized and then processed in order to obtain fibres. The results showed that, with small variations in the glass composition, it was possible to obtain PGs with a wide range of dissolution rate and that all glasses were biocompatible. The influence of pH, medium and dissolution products on the resorption process have been investigated. Furthermore, several tens of meters of glass fibres with diameters ranging from17 ± 1 µm and 79 ± 2 µm were obtained using a preform drawing approach, demonstrating the control and versatility of the process. The fibers resorption in distilled water was investigated before and after an annealing treatment as well as their mechanical properties. Biological tests on fibers using neural cells are in progress.

Keywords: phosphate glasses, solubility, glass fibres.

0284 | Chemical factors behind bioactivity of glassesLeena Hupa*, Kaj H. Karlsson, Mikko Hupa

Åbo Akademi University, Process Chemistry Centre, FI-20500 Turku, Finland, e-mail: [email protected]

Glasses forming on their surface a dual layer of silica and hydroxyapatite crystals (HAP) in vitro are thought to be bioactive. In vivo the glasses are bonded chemically to bone via the HAP layer. In this presentation we discuss the chemical mechanism of bioactivity of glasses based on recent and previous research work in our research group at Åbo Akademi University. The models for layer formation in vitro as functions of glass composition were used to predict the ability of the glasses to bond to bone. Bone bonding in vivo was interpreted from the layer thicknesses and structures as suggested by the cross-sectional SEM-EDX analyses of the interface between glass and bone. Push-out forces of the implants of different compositions were used to classify the glasses into different reactivities. The comparison of the in vitro and in vivo results indicated that dual layer formation in vitro cannot be used as the only criterion for bioactivity of glasses. In the presentation the role of the detailed site of HAP precipitation will be discussed. It appears as the most bioactive glasses have the tendency to form the HAP precipitate inside the silica layer.

Keywords: bioactive glass, in vitro, in vivo, hydroxyapatite.



Sept. 24 – 10:00-12:15 h – Room B

Bio Glasses TC 4 (Chairman: E. Vernè)

0400 | Bioactive glass and hybrid scaffolds for bone regeneration

Julian R JonesDepartment of Materials, Imperial College London, London, SW7 2AZ

For bone regeneration, a scaffold must stimulate bone growth, dissolving as the bone regenerates. The scaffold must have an interconnected pore network. For new bone to survive, blood vessels must penetrate. Bioactive glasses are ideal candidates but commercially they are only available in a granular form. It is difficult to make porous melt-derived bioactive glasses because they crystallise during sintering. Scaffolds have been developed through the sol-gel glass foaming process. They stimulate new bone growth and fulfil all the criteria for an ideal scaffold except that they are brittle. In vitro tests show the scaffolds can be pre-vascularised prior to implantation by culturing a specific mix of mesenchymal stem cells (MSCs) and human endothelial cells. Sub-micron particles have also been synthesised and MSC response investigated. Particles <250nm diameter are up taken but were not toxic. New compositions of melt-derived glasses have been developed that can be sintered. The gel-cast foaming process has been adapted to produce porous scaffolds. To provide toughness, inorganic/organic hybrid scaffolds, where the inorganic and organic components interact at the nanoscale and are covalently linked, have been developed that can provide control of degradation rates and mechanical properties, e.g. sol-gel silica and enzyme degradable polypeptides. We have developed image analysis techniques for quantifying open pore networks in 3D from X-ray microtomography images.

Keywords: bioative glass, scaffold, porous, sol-gel, hybrid, cell response, nanostrucuture.

0291 | Dissolution kinetics of bioactive glasses by continuos measurementSusanne Fagerlund*, Paul Ek, Leena Hupa, Mikko Hupa

Process Chemistry Centre, Åbo Akademi University, Piispankatu 8, FI-20500 Turku, Finland, e-mail: [email protected]

In this presentation we report ion dissolution from bioactive glasses in aqueous solutions. Understanding the detailed dissolution mechanism is of importance when glasses are developed to different applications. Inductively coupled plasma optical emission spectrometer (ICP-OES) was utilized to continuously measure the concentration profile of the ions dissolved from glass particles in a flow-through reactor. This technique was sensitive enough to continuously monitor the low concentrations of the dissolved ions. Different flow rates (0.08-0.8 ml/min) and temperatures (40-80°C) were used in tests with distilled water. The ion release was studied also in Tris-buffered solution (37°C). In both solutions the ion concentration increased rapidly within the first minutes. At longer flow-through times a more linear dissolution profile was obtained. The results showed a rapid dissolution of alkalis within the first minutes of glass to solution contact. The silica dissolution started to dominate after this stage. The connection of the dissolution behavior with the bioactivity will be discussed.

Keywords: bioactive glass, ion release in vitro, on-line measurement, ICP-OES.

0122 | Processing of bone tissue engineering glass-ceramic scaffolds with adjustable strength and bioactive properties

Chiara Vitale-Brovarone1*, Enrica Verné1, Francesco Baino1

1*Materials Science and Chemical Engineering Department, Politecnico di Torino – Corso Duca degli Abruzzi 24, 10129 Torino, Italy, e-mail: [email protected]

3-D foam-like glass-ceramic scaffolds were fabricated via sponge replication using silicate glass powders of complex composition. By modifying the process parameters for scaffolding (e.g. cycles of sponge impregnation, sintering temperature), it was possible to obtain scaffolds with different structural features and, therefore tuneable mechanical strength. In addition, as the chemical and crystallographic characteristics of the glass-ceramic material influence the scaffold strength and its bioactivity, such properties were also designed by modifying the composition of the starting glass. All the prepared scaffolds exhibited a highly interconnected network of open macropores (100-500 µm) able to effectively mimic the trabecular architecture of natural cancellous bone. The total pores content ranged within 50-70% vol. and the compressive strength varied from 5 to 15 MPa. The in vitro bioactivity was assessed by soaking the samples in SBF for different time frames and

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by evaluating the kinetics of hydroxylapatite formation on the scaffold trabeculae. A high biocompatibility was found in vitro using osteoblast-like cells (MG-63). The prepared scaffolds can be suggested as versatile grafts in bone reconstructive surgery, also for load-bearing applications, thanks to their ease of tailoring, bioactive properties and high mechanical strength.

Keywords: silicate glasses, glass-ceramics, scaffold, sponge replication, scaffold strength, bioactivity, bone grafting.

0414 | The interaction of densification and crystallisation of 45S5 Bioglass® powder for fabrication of tissue scaffolds

Aldo R. Boccaccini1,2 *, Xanthippi Chatzistavrou1 Oana Bretcanu3

1Department of Materials, Imperial College London, London SW7 2BP, UK 2Institute of Biomaterials, Department of Materials Science and Engineering,

University of Erlangen-Nuremberg, Germany, e-mail: [email protected] 3Department of Materials Science and Chemical Engineering, Politecnico di Torino, Italy

There is increasing interest in using partially crystallised Bioglass® scaffolds for bone tissue engineering. These porous structures are fabricated by the foam replica technique from Bioglass® powder. In this study, sintering and crystallisation of 45S5 Bioglass® powder were investigated. Hot stage microscopy and dilatometry showed that the bioactive glass powder sinters in two major steps: a short stage between 500 and 600 °C and a longer stage in the range 850-1100 °C. In relation to the fabrication of porous scaffolds, the optimal sintering conditions were determined to be 1050 °C and 140 minutes for temperature and sintering time, respectively. At these conditions high densification of the foam struts by viscous flow occurs. Differential thermal analysis showed that Bioglass® crystallises at temperatures between 600 and 750 °C, indicating that the material is highly crystallised prior to undergoing significant densification (above 850 °C). The characteristic crystalline phases were identified by Fourier Transformed Infrared Spectroscopy, Transmission Electron Microscopy and X-ray diffraction. The crystallisation kinetics was studied by DTA, using a non-isothermal method. For Bioglass® powder heated at different heating rates (5-30 °C/min) the activation energy was determined. Surface crystallization was identified as the crystallisation mechanism. After sintering at 1050 °C for 140 min, the main crystalline phase detected was Na2Ca2Si3O9. TEM however confirmed the presence of small amount of other silicate phases. The results of this work are useful for the design of the sintering/crystallization heat treatment for fabricating bone tissue scaffolds with varying degree of bioactivity and improved mechanical properties.

Keywords: bioactive glass, sintering, crystallization, porous materials, glass-ceramics, tissue engineering, scaffolds.

0156 | Monolithic glass bone scaffolds with dual nano/macro porosityYuliya Vueva, Alexandra Teixeira, Rui M. Almeida*

Departamento de Engenharia de Materiais, ICEMS, Instituto Superior Técnico, TULisbon, Av. Rovisco Pais, 1049-001 Lisboa, Portugal, e-mail: [email protected]

Sol-gel derived SiO2 – CaO – P2O5 porous glass monoliths with a dual pore structure including nanopores ~ 5–20 nm and macropores ~ 20–200 microns in size have been prepared in the presence of the drying control additive formamide, for possible application as scaffolds in bone tissue regeneration [1-2]. Nanopores are intrinsic to sol-gel processing; the interconnected macropores have been achieved through polymer-induced phase separation together with the sol-gel transition, by adding a water soluble polymer, poly(ethylene oxide), to the precursor sol. The nanopore structure was controlled through the addition of urea. The overall pore size distribution was obtained by mercury intrusion porosimetry. The morphology of the scaffold materials and their pore structure have been studied by scanning electron microscopy. In-vitro tests were used to evaluate bioactivity, confirmed by FTIR and XRD measurements . In-vivo experiments have also been conducted on New Zealand rabbits, showing significant osteoconductivity and bone regeneration.1. Ana C. Marques, Himanshu Jain, Carol Kiely and Rui M. Almeida, J. Sol-Gel Sci. Technol. 51 (2009) 42-47.2. Ana C. Marques, Rui M. Almeida, Amath Thiema, Shaojie Wang, Mathias Falk, Himanshu Jain, J. Mater. Res.

24 (2009) 3495-3502.

Keywords: bioactive glass, monolithic scaffold, sol-gel glass, dual porosity, tissue engineering.



0038 | Strontium substituted bioactive glasses: from concept to in vivo demonstration

MD O’Donnell1*, P Candarlioglu2,3, CA Miller4, E Gentleman2,3, I McCarthy5, F. Allen5, G Blunn5, A Goodship5, MM Stevens2,3

1RepRegen Ltd, London, UK 2Department of Materials, Imperial College London, UK

3Institute of Biomedical Engineering, Imperial College London, UK 4School of Clinical Dentistry, University of Sheffield, UK

5Institute of Orthopaedics & Musculoskeletal Science, UCL, UK

Here we report on the structure, physical properties, in vitro and in vivo performance of a series of bioactive glasses SiO2-Na2O-CaO-SrO-P2O5 where 0-100% of the Ca was substituted with Sr. Characteristic temperatures were obtained using DTA. All temperatures except crystallisation onset (Tx) decreased with Sr addition to a minimum at 50% Sr then increased with higher Sr. Raman spectra showed the glass structure was predominantly composed of linear silicate chains (Q2) and isolated orthophosphate units (Q0). Cell metabolic activity (MTT assay) increased with Sr until cell confluence (14 days). ALP assay showed increased mineralisation with Sr content. LDH assay, LIVE/DEAD and actin-vinculin staining showed all glasses were non-toxic. 10% Sr glass exhibited the highest LDH activity. Sr glasses led to higher cell viability compared to the Sr free glass. 10% Sr glass was implanted in ovine femora. At 90 days defects (1580 N.mm–1) and surrounding bone (1603 N.mm–1) with Sr glass were stiffer compared to the control (942 and 1161 N.mm–1). Defect density was higher with 10% Sr glass (925 mg.cm–3) compared to the control (656 mg.cm–3) and the surrounding bone was similar in density (574 and 554 mg.cm–3). Sr serum levels were close to baseline at all time points. This indicates that implantation of a Sr bioactive glass results in rapid formation of bone with higher material properties in and around the defect in the short-term compared to a conventional bioceramic bone graft.

Keywords: bioactive, bioglass, DTA, raman, structure, in vitro, in vivo.

0292 | 3D fabrication of bioactive glass implantsRobert Meszaros*, Andrea Vander, Lothar Wondraczek

Department of Material Science and Engineering – University of Erlangen-Nuremberg – Germany, e-mail: [email protected]

Bioactive glasses exhibit high surface reactivity as well as resorbtion and osteoconductive properties. They can be used for bone repair, e.g. as bone filler. In some cases, they may also support cell growth. While, in terms of viscosity behavior, a wide working range makes them suitable for sintering by viscous flow, also crystallization may be induced during sintering. In this study we focus on using 3D-printing techniques and subsequent sintering to generate complex, patient-specific inlays and substitutes for unloaded implants. We discuss 3D printing, sintering and subsequent crystallization of 13-93 bioactive glass powder (composition: 53 wt % SiO2, 6 wt % Na2O, 12 wt % K2O; 5 wt % MgO, 20 wt % CaO, and 4 wt % P2O5) depending on powder preparation, sinter additives, green sample preparation, particle size and heating rate. Shrinkage was studied using optical dilatometry, crystallization kinetics by DSC and XRD and the microstructure was analyzed by SEM and micro CT. Feasibility in fabrication of 3D-printed bioactive glass implants is discussed.

Keywords: 3D printing, bioactive glass, glass sintering, shrinkage, bone repair.




Sept. 24 – 14:00-16:15 h – Room B

Miscellaneous Properties (Chairman: M. Baesso)

0221 | Glasses at ultra-low temperatures: interplay of atomic tunneling systems and nuclear magnetic moments

Christian EnssKirchhoff-Institut für Physik, Universität Heidelberg, Im Neuenheimer Feld 227, D-69120 Heidelberg, Germany, e-mail: [email protected]

The low-temperature properties of disordered solids, like glasses or crystals with certain substitutional defects are governed by atomic tunneling systems. Until recently it was believed that the dielectric properties of insulating materials devoid of magnetic impurities should not –or only very weakly– depend on external magnetic fields. New experiments on glasses und crystalline defect systems show in contrast to that a strong magnetic field dependence of the dielectric susceptibility of such materials at ultra-low temperatures. We will discuss polarization echo experiments that show that these effects are caused by tunneling particles with nuclear magnetic moments. Using isotope substitution we demonstrate the role of nuclear quadrupol and nuclear magnetic dipole moments regarding the magnetic field dependence. We also show that tunneling particles with nuclear moments can be used as local probes to investigate the microscopic nature of tunneling systems.

Keywords: insulating glasses, magnetic fields, ultralow temperatures.

0068 | Gas permeation through Al2O3-SiO2 glasses containing metal ionsMasayuki Nogami*, Hiromasa Shiiba, Guihlherme A. Kleine, Tomokatsu Hayakawa

Nagoya Institute of Technology, Showa, Nagoya, 466-8555 Japan, e-mail: [email protected]

Hydrogen gas permeation properties in Al2O3-SiO2 glass doped with Eu3+, Nd3+ and Cu2+ ions were studied by monitoring the gas flowing rate and the hydroxyl formation. The family of Al2O3-SiO2 glasses exhibit the hydrogen gas permeability of 10-13 ~ 10-12 mol/sec/m/Pa at 500 °C, which was higher than 103 times of that in SiO2 glass which is known to have highest permeability in the glasses. This high H2 gas permeability was related with the formation of hydroxyl bonds acting as easy pass way for hydrogen molecules. In the Cu2+-doped Al2O3-SiO2 glass, the Cu2+ ions were reduced into Cu metal particles to diffuse to the surface, followed by vaporization, which enhanced the permeation rate of hydrogen gas. On the other hand, the formation of Eu2+ ions resulted into the decreased permeability.

Keywords: gas, permeation, Al2O3-SiO2 glass, hydroxyl.

0239 | Comparison of residual stress around Vickers indentation in various glass compositions by using birefringence imaging technique

Yoshinari Kato1*,2, Hiroki Yamazaki1, Satoshi Yoshida2, Jun Matsuoka2, Charles R. Kurkjian3

1*Technical Division, Nippon Electric Glass Co.,Ltd., Otsu, Japan, e-mail: [email protected] 2School of Engineering, The University of Shiga Prefecture, Hikone, Japan

3University of Southern Maine, ME, USA

Residual stresses around Vickers indentation in various commercial glass compositions were investigated with a birefringence imaging system, and a relationship between residual stress distribution and crack initiation load is discussed. Crack resistance, which corresponds to crack initiation load in a Vickers indentation test, depends strongly on glass composition. It is known that indentation of glass causes both plastic deformation and irreversible densification, and the former will be the origin of residual stress. In our previous study, glasses showing easier densification by the indentation test result in higher crack resistance. In the present study, birefringence distributions due to the residual stress in various glass compositions were measured, not only in the direction parallel to the load ( "top view"), but also in the direction perpendicular to the load ("side view"). Flat fibers with rectangular cross-section were prepared for the birefringence imaging from the both directions. Circular regions with birefringence were found around the indentation in the top view, and semi-circular ones in the side view image were found. It is clarified that the birefringence distributions, especially in

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the side view image, depend on glass composition. In glasses showing easier densification, a smaller region with birefringence appears. It is expected that the compositional dependence of the birefringence distribution is related to a wide variety of crack resistance with glass.

Keywords: birefringence, crack initiation, residual stress, Vickers indentation.

0261 | Sheet glass strength levels, thermochemically treated with difluorodichloromethane

Vasilii Sharagov1*, Gheorghe Duca2

1*Balti State University “A. Russo” – USB, office 38, Pushkin str., MD 3121, Balti, Republic of Moldova, e-mail: [email protected]

2Academy of Sciences of Moldova – ASM, office 1, Stefan cel Mare bd., Chisinau, MD 2001, Republic of Moldova

The results of determining the mechanical properties of sheet glass, thermochemically treated with difluorodichloromethane are analyzed and summarized. Experiments were held in laboratory and industrial conditions. Regimes of the thermochemical treatment of glass with difluorodichloromethane are the following: temperature – between 300 and 900 °C, duration – between 5 min and 2 h, quantity of gas reagent introduced into the reacting vessel – between 0.1 and 1.0 mol. The mechanical properties of sheet glass were characterized by central symmetrical flexural strength, impact strength and microhardness. The results were subjected to statistical analysis. Differential and integral curves of strength distribution of sheet glass for various regimes of thermochemical treatment were made. A disparity in the strength levels of glass without treatment and of the samples after thermochemical treatment was revealed. The mechanism of strengthening of sheet glass, thermochemically treated with difluorodichloromethane is discussed.

Keywords: sheet glass, thermochemical treatment, difluorodichloromethane, strength levels, statistical analysis, differential and integral curves, mechanism.

0299 | AFM studies of the limit of elasticity in silica glassCiccotti M.1*, Pallares G.1,2, George M.1, Lechenault F.2,1, Rountree C.2, Roux S.3

1Laboratoire des Colloïdes, Verres et Nanomatériaux, Univ. Montpellier 2, CNRS, Montpellier, France 2CEA, IRAMIS, SPCSI, Grp. Complex Systems & Fracture, F-91191 Gif Sur Yvette, Paris, France

3Laboratoire de Mécanique et Technologie, ENS Cachan, Univ. Paris 6/PRES, UniverSud, CNRS, Paris, France, e-mail: matteo.ciccotti@ univ-montp2.fr

Recent atomic force microscopy (AFM) experiments on the fracture of glass in the stress-corrosion regime reported the presence of a nanometric process zone near the crack tip which is still a matter of debate. In this work, we investigate by AFM the limit of elasticity in silica glass in double cleavage drilled compression (DCDC) specimens.

First, a novel Integrated Digital Image Correlation technique is used on consecutive in-situ AFM images of a crack in slow propagation to show that the elastic solution for the surface displacement field is valid down to a distance of 10 nm from the crack tip. The local measurement of the stress intensity factor is also proved on images of 200 nm size.

Secondly, we investigated the roughness properties of fracture surfaces. The height-height correlation functions along 1D sections of the AFM images are known to present two scaling regimes, separated by a cutoff length of the order of few tens of nm. Although this length scale was previously interpreted as a process zone size, we show here that this length could arise from the finite size of the AFM scanning probe.

These results call for prudence regarding previous claims of nanoductile mechanical behaviour of glass.

Keywords: silica glass, elasticity properties, atomic force microscopy, digital image correlation, roughness properties.



0078 | Silica elastic anomaly and high pressure experimentsBernard Champagnon1*, Christine Martinet1,

Thierry Deschamps1, Dominique de Ligny1, Assia Kassir-Bodon1

1Université de Lyon; Université Lyon 1; UMR5620 CNRS; Laboratoire de Physico-Chimie des Matériaux Luminescents, Domaine scientifique de la Doua, Bât. Kastler,

10 rue Ampère, Villeurbanne, F-69622, France, e-mail: [email protected]

Silica anomaly is defined as a minimum of elastic constants when the pressure increases in the elastic domain. High pressure experiments in this domain demonstrate that a correlation can be established between this anomaly and structural observations deduced from Raman scattering experiments1. The low frequency Raman scattering decrease of the intensity, corresponding to the Boson peak, is interpreted as a decrease of the intrinsic inhomogeneity of the glass when a hydrostatic pressure is applied in the elastic domain2. This is correlated with a decrease of the value of the inter-tetraedral angle distribution as deduced from the width of the main Raman band.

Furthermore when the hydrostatic pressure reaches a value higher than 9GPa silica is plastically compressed. In the permanently densified silica elaborated in a such way, the Raman experiments demonstrate that this anomaly does not exist anymore. These results will be compared with Molecular Dynamic Simulations and discussed in the case of the iso-structural GeO2 glass.1. T. Deschamps, C.Martinet, D.de Ligny, B.Champagnon J.Non-Crystalline Solids 355(2009)1095-10982 T. Deschamps, C.Martinet, D.Neuville, D.de Ligny, C.Coussa-Simon, B.Champagnon J.Non-Crystalline Solids

355(2009) 2422-2424

Keywords: silica, high-pressure, raman scattering, elastic/plastic deformation, densified silica, polyamorphism.

0056 | Fabrication of amorphous arsenic-sulphide alloys by on-axis continuous-wave laser depositionJ.M. González-Leal1*, J.A. Angel1, L. Rubio-Peña2, J. Valverde1

1*Department of Condensed Matter Physics, Faculty of Sciences, University of Cadiz, 11510 – Puerto Real (Spain), e-mail: [email protected]

2Department of Systems Engineering and Automatics, Electronic Technology and Electronics, School of Engineering. University of Cadiz, 11002 – Cadiz (Spain)

A number of both physical and chemical methods are known to produce amorphous materials ¾ all of them sharing structural processes occurring at large cooling rates ¾ and evidences of the strong influence of the fabrication technique in the properties of amorphous alloys have been extensively reported in the literature. Recently, after the invention of laser generators, and as the light power was increasing, laser deposition techniques were shown to be suitable for growing a number of amorphous materials, mainly for planar technologies. Thus, pulsed laser deposition of superconductor and semiconductor materials have been largely shown in the past decade, and the interest in the properties of growth materials is motivating intensive research activities to understand the mechanisms underlying this light-assisted deposition technique. It is worth mentioning that the deposition of amorphous alloys by means of continuous-wave laser sources has also been shown, although interestingly their use nowadays seems quite scarce.

We introduce here an original laser-based approach for the deposition of semiconductor materials which, differently to the pulsed-laser deposition uses a continuous-wave laser source, and on-axis geometry with target and substrate facing parallel each other. Its most remarkable characteristic is the concurrent actuation of light during the conformation of the material that is being deposited onto a transparent substrate, as illustrated in Fig. 1. The deposition of amorphous arsenic-sulphide alloys has been successfully shown when using a cw laser source at 532 nm and intensities of the order of 102 Wcm-2, and some properties of the materials deposited lift when compared with the ones observed in the same alloys, but prepared by other fabrication techniques, as melt-quenching, vacuum thermal evaporation and plasma-enhanced-chemical vapour deposition, namely: larger optical bandgaps and also larger refractive-index values have been measured from UV/vis/NIR spectroscopy; a significant reduction of the intensity of the diffraction features, and also changes in the characteristic spacings, have been observed in the X-ray diffraction patterns of the



deposited materials; and a significant increase has been observed in the fusion temperature. Such results will be reported and discussed in the conference, as well as details of the continuous-wave laser deposition method will be supplied.

Figure 1. Sketch of the continuous-wave laser deposition geometry.

Keywords: chalcogenide glasses, laser deposition, X-ray diffraction, optical properties.

0232 | Structural and physical properties of GeXaSYsE1-X-Y glasses with the same mean coordination number

Rong-Ping Wang*, Douglas Bulla, Anita Smith, and Barry Luther-DaviesThe Centre for Ultrahigh Bandwidth Devices for Optical Systems(CUDOS), Laser Physics Centre,

Research School of Physics and Engineering, The Australian National University, Canberra, ACT 0200, Australia, e-mail: e-mail: [email protected]

Five pieces of the bulk glass samples with the same mean coordination number but different chemical compositions (Ge7.5As35Se57.5, Ge10As30Se60, Ge12.5As25Se62.5, Ge15As20Se65, and Ge20As10Se70) were prepared in order to investigate the role of MCN and the chemical composition in determining the physical properties of chalcogenide glasses. We measured the glass transition temperature, density, elastic moduli, Raman and x-ray photoelectron spectra of the glass. The five samples exhibit almost same glass transition temperature, and almost same elastic moduli. The density of the glasses increases, and reaches a maxium value at the glass containing 12.5%Ge, and then decreases with increasing Ge concentration. Raman scattering measurements indicate that, with increasing Ge concentration, the intensity of the corner-sharing vibrational mode of GeSe4/2 tetrahedral at 199cm–1 increases, and that of AsSe3/2 pyramidal unit at 228cm–1 becomes gradually weak. Moreover, some features related to the Se-chains appears in Se-rich sample of Ge20As10Se70. Ge, As and Se 3d x-ray photoelectron spectra show that the evolution of the differrent structural units is in good agreement with the Raman scattering analysis. The present resutls indicate that, the chemical compositions of the glasses with the same MCN have negligible effect on the network connectivity in the five different samples, but indeed change the local chemcial surroundings as evident by Raman and XPS measurements.

Keywords: chalcogenide glasses, GeAsSe, Mean coordination number, Chemical compositions.



Sept. 24 – 8:00-9:45 h – Room Tech.

New Applications of glass (Chairman: J. Martinelli)

0237 | Ultra Thin Glass Sheet: Properties and Potential ApplicationsKatsutoshi Fujiwara1*, Yoshiharu Miwa1, Yasuo Yamazaki1, Tomoki Yanase2, Masahiro Tomamoto1

1LCD Glass Division, Nippon Electric Glass Co.,Ltd., Takatsuki, Japan, *[email protected] 2Technical Division, Nippon Electric Glass Co.,Ltd., Otsu, Japan

An ultra thin glass sheet between 50 with 200 µm in thickness was developed by using the over flow down-draw method. This ultra thin glass sheet has great potential for new applications such as flexible substrates for displays and Li batteries. The ultra thin glass maintains the excellent properties of glass and provides additional functions as a result of its ultra thin nature. The ultra thin glass sheet has a composition of non alkali alumina silicate glass widely used for TFT-LCD glass substrate. Its extremely smooth surface is achieved by overflow forming. Its transmittance is higher than that of ordinary plastic films. And its gas transmission rate is below detection limits, resulting in satisfactory gas barrier property requirements, especially for OLED application. The thinness brings very high flexibility to the glass sheet so that the glass sheet is suitable for roll-to-roll processing. Furthermore the ultra thin glass sheet is environmentally-friendly because of its smaller volume and lighter weight compared with ordinary glass sheet, so it will reduce resource consumption for transportation and waste emission. We believe that the ultra thin glass sheet will contribute to future society.

Keywords: overflow, flexible, gas barrier, ultra thin glass substrate, environmentally-friendly

0093 | Bend insensitive photonic crystal fibersEnver F. Chillcce, R. E. Ramos-Gonzales1, A. C. Bordonalli2,

H. E. Hernández-Figueroa2, Cristiano Cordeiro and Luiz C. Barbosa1*1Universidade estadual de Campinas – UNICAMP, Instituto de Física, Campinas-SP

2Universidade Estadual de Campinas – Faculdade de Engenharia Elétrica – UNICAMP-SP, e-mail: [email protected]

In this work we study the bend loss properties of Photonic Crystal Fibers (PCFs) with several hollow rings (varying from seven to then). PCFs with small (around 4 µm) and large (around 8 µm) core diameters were used for this purpose. The bend loss dependency of the optical fibers was characterized through optical transmittance spectrum using an optical spectrum analyzer (OSA).The transmittance spectra were measured for different bends. The transmittance spectra of PCFs show to be insensitive to bends in comparison to that of conventional optical fibers. These PCFs could be used to Fiber-To-The-Home applications.

Keywords: photonic optical fiber, fiber to the home, optical fiber.

0043 | Glass industry opportunities & challenges in the coming yearsJorma Vitkala

Glass Performance Days – FINLAND, e-mail: [email protected]

The world´s leading glass conference, The Glass Performance Days, has been the hub of the professionals of the industry over a number of years. This presentation summarizes the over 300 specialist addresses delivered at the 11th GPD in June 2009 in Tampere, Finland. Leading trendsetters, designers, industrialists and researchers gathered to chart the course of the future development of the industry faced with a growing need to deliver constantly new and more energy-efficient solutions for architecture and construction.

Designers and producers of insulating glass, intelligent window solutions and façade designs are in a key position in meeting advanced requirements on energy-efficiency. The international glass community is highly interdependent in the promotion of solutions that are technically and economically feasible. Each link in the technology and sourcing chain is dependent upstream on its suppliers and downstream on its customers in



ensuring that solutions match current and future needs and priority issues. Investments need to be targeted effectively and costly mistakes must be avoided. R & D is much helped by open information within the industry in order that all players know in what direction development is headed.

This presentation attaches special weight to the newest glazing and solar technologies, the challenges facing glass industry and the requirements presented by today´s architectural trends. Solar solutions promise rapid and steady growth but place special demands on industrial restructuring, forward-thinking solutions and flexibility on the part of the leading players in the business.

Keywords: GPD, conference.

0382 | High purity TeO2-WO3-(La2O3, Bi2O3) glasses for fiber-opticsV.V. Dorofeev1*, A.N. Moiseev1, M.F. Churbanov1, G.E. Snopatin1, A.V. Chilyasov1,

I.A. Kraev1, V.G. Pimenov1, A.S. Lobanov1, T.V. Kotereva1, L.A. Ketkova1, A.A. Pushkin1, V.V. Gerasimenko1, V.G. Plotnichenko2, A.F. Kosolapov2, E.M. Dianov2

1*Institute of Chemistry of High-Purity Substances of RAS, 49 Tropinin Str, 603950, Nizhny Novgorod, GSP-75, Russia, e-mail: [email protected]

2Fiber Optics Research Center RAS, 38 Vavilov Str, 119991, Moscow, Russia

Reduction in concentration of 3d-transition metals, hydroxyl groups and scattering centers is of great importance to expanding the field of application of TeO2-WO3 glasses to the whole range of their transparency (~0.5-5 µm). TeO2-WO3, TeO2-WO3-La2O3 and TeO2-WO3-La2O3-Bi2O3 glasses of different composition were produced by melting oxide mixtures in platinum or gold crucible at 800 °C inside the sealed quartz device in purified oxygen atmosphere. Ultrahigh-purity initial oxides were used for glasses preparation. The total content of Cu, Mn, Fe, Co and Ni impurities was measured by the atomic-emission spectral analysis with chemical concentration and was not more than 0.5 ppm wt in glasses and below 0.1 ppm wt in the initial oxides.

Crystallisation stability characterized by Tx-Tg =150-190 °C was demonstrated for high purity TeO2-WO3 glasses by DSC measurements. In the La2O3-containing glasses, the thermal effects of crystallization and fusion of the crystallized phases were not observed. The hydroxyl groups absorption coefficients of the tellurite glasses at the maximum of the absorption band (λ ~ 3 µm) lay in the region 0.01-0.001 cm–1. The optical absorption losses, measured by the laser calorimetry method at λ = 1.06, 1.56 and 2 µm, did not exceed 40–120 dB/km. Several optical fibers with optical losses less than 100 dB/km were produced from high-purity TeO2-WO3-(La2O3, Bi2O3) glasses.

Keywords: hydroxyl groups, crystallisation stability, transition metals, TeO2-WO3 glasses, optical losses.

0055 | Glass fiber based catalysts: science and industrial applications Bair S. Bal’zhinimaev

Boreskov Institute of Catalysis of Siberian Branch of Russian Academy of Sciences – BIC – prospekt Akademika Lavrentieva, 5, 630090, Novosibirsk, Russia, e-mail: [email protected]

The novel generation of catalysts based on glass fiber materials of silicate origin was recently discovered for catalysis area. Basing on NMR, IRS, SAXS, XPS, HREM etc the framework structure where Zr(IV) cations serve as a connectors linked with a few SiO4 tetrahedra was proposed. The effective ways of transition ions (Pt, Pd, Ru etc.) incorporation into the bulk of glass and their stabilization in the highly dispersed (<1 nm in size) or in unusual low-valent state, as well as strengthening their acidity and basicity were found. Despite of low content of noble metals (ca. 0.01% wt.) these catalysts showed unique performance in many chemical reactions resulted from the ability of glassmatrix to stabilize the highly dispersed states and to act as a specific membrane permeable for polar or polarizable molecules only.

The specific heat/mass transfer properties, original geometry, high flexibility and high mechnical strength give the way to develop new catalytic technologies and novel reactor design. The set of successful examples of glass fiber catalysts applications in solution of various problems in petrochemistry (selective hydrogenation processes), environmental protection (VOC removal, VOCl’s and dioxins destruction, deNOx, reduction of CO2

emission) are listed.

Keywords: glass fiber materials, catalysts, petrochemistry, environmental protection.



0362 | Electromagnetic wave absorption properties of surface-modified glass fabric reinforcements

Göksu Gürer 1, Özlem Aydın Çivi 2, Arcan F. Dericioğlu1*1*Middle East Technical University, Department of Metallurgical and

Materials Engineering, Inonu Bulv., 06531 Ankara, Turkey, e-mail: [email protected] 2Middle East Technical University, Department of Electrical and Electronics Engineering

In today’s world of intensive wireless communication and data transfer, interaction of electromagnetic waves originating from different sources leading to interference, and hence decrease in the quality and misinterpretation of the transferred data can be avoided by the use of appropriate absorbing and shielding materials. In this study, electromagnetic wave absorption potential of surface-modified glass fiber woven fabrics ordinarily used as reinforcement material in glass fiber-reinforced plastic (GFRP) structural composites has been investigated. Surface conductivities of as-received E-glass woven fabrics were tailored by the application of various metallic coatings. Electromagnetic wave reflection and transmission behavior of single-layered and multilayered, surface-modified glass fabric structures were evaluated at 18 – 27 GHz range (IEEE K Band) using free – space method. Metallic coating thickness, and hence surface conductivity of the glass fabrics was correlated to their electromagnetic wave reflection property. Graded ordering of surface-modified single layers resulted in multilayer reinforcement structures with electromagnetic wave absorption up to 85%. Such multilayered structures are presented as promising reinforcement candidates for electromagnetic wave absorbing polymer matrix structural composites.

Keywords: electromagnetic wave absorption, multilayered composites, glass fiber reinforcement, surface modification, free-space method.

Sept. 24 – 10:00-12:00 h – Room Tech.

Glass Meeting and Forming (Chairman: R. Beerkens)

0495 | Progress and prospect of float process technologyToru Kamihori

Office of President, Asahi Glass Co., Ltd – Shinyurakucho Bldg., 1-12-1 Yurakucho Chiyoda-ku, Tokyo 100-8405 Japan, e-mail: [email protected].

Firstly the progress of a float process technology is overviewed. After referring to the outline of the float process technology and surveying the challenges to overcome, the recent progress is mentioned. We have supplied solutions timely and appropriately to meet increasing needs from markets such as higher quality, wider range of portfolio, more flexible production and lower cost with having been developing the float process technology.

Secondly, the technology platform is introduced, which has supported the progress of the float process and has fertilized itself by being applied to the development as well. And some examples are shown.Finally, the prospect and the outlook of the float process technology for further development are shown. Furthermore, the direction of the evolution and the buildup of the technology platform is pointed out with high expectations.

Keywords: Float process.

0114 | Thermal contact resistance at the glass-mold interface in a container forming process

Raevon M. Pulliam1*, Gerard F. Jones1, Matthew R. Hyre2, Yang Su3, Stephen Austin3

1*Villanova University – VU – Villanova, PA – USA, e-mail: [email protected] 2Virginia Military Institute – VMI – Lexington, VA – USA

3Emhart Glass Research, Inc. – Windsor, CT – USA

The use of computational models to simulate the glass container forming processes is becoming more common. These models are capable of evaluating the effect of IS machine timings, glass conditions, parison design, and mold cooling strategies on final container quality. Accurate simulations must include large surface

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deformations, viscoelastic behavior, conjugate heat transfer, and the contact phenomena at the glass-mold interface. One of the areas of greatest uncertainty in the models is the heat transfer coefficient (htc) between the glass and molds which is critical to determine the spatial and time-varying heat removal. To increase the accuracy of the forming models, a study was initiated to analytically and experimentally quantify htc. A 1D finite-difference model was developed to calculate heat flux from the mold. These measurements were taken in both a controlled experimental setting and on an IS container forming machine at the Emhart Glass Research Center (EGRC). The resultant heat flux was used to determine the glass surface temperature distribution and heat transfer coefficient. A secondary goal of the study was to isolate the effects of operating conditions. The effects of initial mold temperature, initial glass temperature, and pressing pressure on the resulting heat fluxes and htc were determined experimentally. A simplified first order predictive model for heat flux and heat transfer coefficients was developed.

Keywords: blank side, container forming, heat transfer coefficient, glass-mold interface, numerical model, experimental, simulation.

0208 | Lubricants – A simple way for surface improvement of glassHeiko Hessenkemper*, Heide Landfermann-Hessenkemper, Christina Hartwig, Mathias Hötzel

University of Mining and Technology Freiberg- Institute of Ceramic, Glass and Construction Materials

In the past lubricants were only used in the glass industry to control the heat transfer between glass and mould, to optimize the forming process and to reduce the corrosion of the mould material. The project „LubriGlass“ has the goal to develop lubricants for different glass to improve the mechanical and chemical properties of glass. This project is supported by the BMWF.

To improve the glass properties aluminum-enriched lubricants are used. We achieve an increase of the internal pressure in container glass by 30% combined with a decreased standard deviation. This opens up the way for decreasing weight for container glass where. In fact more than 50 percent of all costs by container glass production are influenced by the weight. The use of the lubricants is similar to the normal procedure and therefore it is easy to implement this into the normal production. Another aspect is seen using aluminum-enriched lubricants: The chemical resistant of glass is improved.

The new lubricant can also be used for other glass industries, like table ware or flat glass. The measurement of the hydrolytic stability of lead crystal glass has shown a strong reduction of the lead release well behind the existing limits. For flat glass production an increase of 50% of the hydrolytic resistance is easy to achieve.

Keywords: glass forming, lubricant, hydrolytic resistance, aluminum, strength.

0250 | Origin of in homogeneity in glass meltsMartin Jensen*, Ralf Keding, Yuanzheng Yue

Section of Chemistry, Aalborg University, 9000 Aalborg, Denmark, e-mail: [email protected]

The homogeneity of a glass plays a crucial role in many applications as the inhomogeneities can provide local changes in mechanical properties, optical properties, and thermal expansion coefficient. Homogeneity is not a single property of the glass, instead, it consists of several factors such as bubbles, striae, trace element concentration, undissolved species, and crystallised species. As it is not possible to address all the factors in a single study, this work focuses on one of the major factors: chemical striae. Up to now, the quantification of chemical striae in glasses, particularly, in less transparent glasses, has been a challenge due to the lack of an applicable method. In this study, we have established a simple and accurate method for quantifying the extent of the striae, which is based on the scanning and picture processing through the Fourier transformation. By performing systematic variations of the melting conditions of iron bearing silicate melts, we identify the influence of melting duration, melting temperature, and size of raw materials on the homogeneity. Finally, we attempt to reveal the origin of chemical inhomogeneities of the glass melts in question.

Keywords: homogeneity, striae, melting.



0228 | Peak identification in voltammetry for sulfate doped glass meltsYasushi Kii1*, Masataka Kawaguchi1, Tsutomu Futagami1,

Satoshi Yoshida2, Toru Sugawara2, Jun Matsuoka2 and Yoshinari Miura2

1*Research and Development Division, Nippon Electric Glass Co., Ltd., 7-1, Seiran 2-Chome, Ostu, Shiga 520-8639, Japan, e-mail: [email protected]

2Center for Glass Science and Technology, School of Engineering, The University of Shiga Prefecture, 2500, Hassaka, Hikone, Shiga 522-8533, Japan

Redox behaviors of sulfur species in 14Na2O-10CaO-76SiO2+0.2Na2SO4 (mol%) glass melt were　investigated by differential pulse voltammetry (DPV). The first peak at around –300mV and the second peak at around –500mV were detected in the voltammogram measured at 1300 °C. In our previous works, it was clarified that the second peak was attributed to the sulfate decomposition reaction, “SO42-+2e-　SO2 +2O2-”. In the present work, we attemped to identify the reaction at the first peak. Under varying the experimental parameters such as the pulse width (tp) and the quantity of SO4

2- in the glass melt (CSO42-), it was found that the first peak current was proportional to tp-1, and was almost independent of CSO4

2-. It became also clear that the value of the second peak current was proportional to tp-0.5 and CSO4

2-. It was deduced that the first peak was the pre-peak of the sulfate decomposition reaction, and that it was originated from the adsorption reaction of SO2 on the electrode.

Keywords: sulfate, sulfur dioxide, redox behavior, peak identification, differential pulse voltammetry.

0278 | Experimental set up dedicated to glass formingL. Soudre 1*, Y. Meshaka2 , G. Jeandel3, G. Parent3

1EEIGM, 6 rue Bastien Lepage, 54000 Nancy 2IJL, INPL – EEIGM, 6 rue Bastien Lepage, 54000 Nancy

3LEMTA, UHP, BP 239, 54506 Vandoeuvre-lès-Nancy cedex

Our project aims at simulating and optimizing the handcrafted glass forming process, based on the deformation of glass by increasing temperature within an electric radiant furnace. In this work, two investigation tools were developed in parallel in the frame of a PhD thesis: (1) an original experimental facility and (2) a numerical software both providing data to be compared. Indeed, there is presently a lack of data in the open litterature regarding the two key-parameters of the process: displacements and temperature measured in wide-field during all the operation.

The presentation will focus on the description of the original experimental set up designed around a forming/fusing furnace using only no-contact-devices applied on the upper face of the glass. The displacement measurement is based on two optical technics : image correlation coupled with fringe projection on a 10x14 cm² field. Due to glass transpacy in visible wavelength, the latter methods had to be adapted in order to enable image reflection. Furthermore, an infrared thermometer based on the application of Christiansen’s effect is used to determine the temperature on a 20 × 20 cm² field.

The first results presented here are convincing and will be soon supplemented by further comparisons with our numerical model.

Keywords: glass forming, no- contact measurements, Christiansen effect, image correlation, fringe analysis, pyrometer.



0306 | Electromagnetically enhanced flow in a special melter – physical modeling, numerical simulation and hands-on experienceUwe Krieger1*, Bernd Halbedel1, Vadims Geža2, Andris Jakovičs2, Ronald Iser3

1*University of Technology Ilmenau, Institute of Materials Engineering, Department of Inorganic-Nonmetallic Materials, – Ilmenau (Germany), e-mail: [email protected]

2University of Latvia, Faculty of Physics and Mathematics, VTPMML – Riga (Latvia) 3JSJ Jodeit GmbH – Jena-Maua (Germany)

The optimization of glass melting is concentrated on energy reduction of the production process. Nevertheless the homogenization of the glass melt has to be obtained with an advanced level even with higher pull or reduced energy consumption. To achieve this additional or improved techniques are required.

The scope of our work is the investigation and practical application of electromagnetic flow control which can be used for the acceleration of flows or modification of flow pattern and gives prospect to expand into an innovative technology for the homogenization in glass melts.

The glass melt flow is electromagnetically enhanced by the Lorentz force, i.e. by the interaction of an electric current density and a magnetic flux density. The setup consists of two cylinders in a collinear arrangement which act as a feeder. The main component of the magnetic field is oriented in axial direction and results in an additional, azimuthal flow due to the radial electric current density.

Physical modeling is used for the verification of numerical models which provides the analysis of essential relations and optimization of the equipment.

An individual designed magnet system is adapted on a special melter (JSJ Jodeit GmbH) for the production of high-tech glasses e.g. applied for dental technology. Nevertheless in first experiments soda-lime glass is used which allows the collection of critical points. Details of the startup and practical experience can be addressed.

Keywords: electromagnetic flow control, Lorentz force, homogenization, special melter.

0420 | Micro through hole fablication process for glass substrateJunji Kurachi1*, Hirotaka Koyo1, Masanori Shojiya2, Koichi Sakaguchi3, Keiji Tsunetomo4

1*Technical Research Lab., Nippon Sheet Glass Co.,Ltd., 2-12-13 Konoike, Itami, Hyogo 664-8520 Japan, e-mail: E-mail:[email protected]

2Building Products R&D (Japan), Nippon Sheet Glass Co.,Ltd., 2-12-13 Konoike, Itami, Hyogo 664-8520 Japan 3R&D Department, Nippon Sheet Glass Co., Ltd. , 3-5-27 Mita, Minato-ku, Tokyo 108-6321 Japan

4Research & Development Department, Specialty Glass Business Line, Nippon Sheet Glass Co, Ltd., 2, Chitose-cho, Yokkaichi-City, Mie 510-0051 Japan

Borosilicate glass substrate containing TiO2 was irradiated with 355nm second harmonic YVO4 laser under specified focus condition. With a galvano mirror, an individual laser pulse was shone at a different position. After irradiation, modified area of lower refractive index was formed at each irradiated position. The modified areas penetrated from irradiated surface to the other surface. The substrate was etched with etchant containing hydrofluoric acid. Because the modified areas were chemically weaker than mother glass, they were removed selectively by hydrofluoric acid and through-holes were formed. Maximum aspect ratio (thickness of substrate/diameter of holes) was about 15. The diameters of through-holes could be under 100 micrometers and could be adjusted arbitrary with selecting appropriate etching time. Because this process is free from mechanical or thermal stress, through holes can be arranged close to each other. So, these holes can be utilized as through substrate electrode.

Keywords: laser, etching, through-hole.



Sept. 24 – 14:00-16:15 h – Room Tech.

Environment and Sustainability (Chairman: F. Nicoletti)

0041 | Investigations on Na2O-H2O-SO2-CO2-containing flue gases from glass meltersA. Neumann1*, W. Wilsmann1, R. Conradt1

1RWTH Aachen University-RWTH-Institute of Mineral Engineering-Aachen, Germany, e-mail: [email protected]

The removal of noxious and air pollutant substances from exhaust gases makes an important contribution to environmental protection and has become a routine procedure in the glass industry. Nevertheless process control is still based on empirical data and on the experience of the plant operators. In the past, the occasional and unexpected occurrence of aggressive fluxes in the e-filters has bothered several operators. This is unsatisfactory since the occurrence could not be attributed in a clear way to any unfavourable boundary conditions. Thus, during the past years until today many researches have been investigated the Na2O-H2O-SO2-CO2-system. However, neither the overall interrelationship nor the specific correlation for the flue gas cleaning was clarified. Investigations are presented on the thermodynamic and kinetic conditions in Na2O-H2O-SO2-CO2-containing flue gases. The thermodynamic conditions are investigated by thermal analyses coupled mass spectroscopy and the kinetic behavior was studied by observation in a self constructed condensations tube. Investigations are particularly focused on the formation of liquid and solid sodium pyrosulphates and sodium bisulphates, as well as on their occurrence inside the flue gas filters.

Keywords: flue gases, environment, e-filters, NaHSO4/Na2S2O7, condensation, thermodynamic, kinetic.

0177 | Variety of programs underway through glass manufacturing industry council to reduce energy and emissions in the production of major glass types

Michael GreenmanGlass Manufacturing Industry Council, Westerville, Ohio, e-mail: [email protected]

The GMIC is managing a series of programs that will significantly reduce energy required for melting glass and reduce emissions from glass production. Some directly, others indirectly. Programs include increasing usable strength of glass, increasing availability of recycled glass to melters, development of effective waste heat recovery technologies, and introduction of new, higher efficiency melting technologies. Each program will be described and their progress levels identified with expected times to completion.

Keywords: lightweight, efficiency, waste heat, recycling, strength, submerged combustion, microwave.

0398 | Characterization of ashes from incineration of chromium-tanned leather shavings and their application as colorant in soda-lime container glass

Diego Mendes1, Marcio M. Guimarães2, Marcos H. Gibim2, Samuel M. Toffoli3*1Saint-Gobain Vidros, Fábrica Água Branca – Embalagens – São Paulo, Brazil

2Saint-Gobain Vidros, Centro Técnico de Elaboração do Vidro (CETEV) – São Paulo, Brazil 3Polytechnic School – University of São Paulo – São Paulo, Brazil, e-mail: [email protected]

In the leather industry, there are many problems concerning waste disposal, since they can be toxic or carcinogenic. Nowadays, leather shavings are incinerated, and the remaining ashes are disposed in class 1 landfills. The ash is composed, in average, by 70 wt.% of chromium oxide. The glass industry uses chromite, a mineral composed by a solid solution of iron and chromium oxides, to obtain the green color in soda-lime glasses. The ashes could be a cheaper alternative to chromite as glass colorant, reducing the mineral extraction, and giving a proper destination to the chromium-tanned leather waste. In this paper, the ashes were characterized in terms of their mineralogical composition (X-ray diffraction), chemical composition (X-ray fluorescence), granulometric distribution (sieving), and were observed in a scanning electron microscope. Preliminary melting experiments, in laboratory scale, were carried out using a typical soda-lime glass composition, so that the final glass contained 2 wt.% of Cr2O3 from either chromite or ash. The glass samples were compared in terms of their chemical composition, bubble distribution, homogeneity and color (L*a*b* system and transmittance curve). The analysis of the results indicated that both sources of chromium showed similar performances. Upscale tests are now required, but it is expected that chromite can be replaced by the ashes, in industrial scale, thus resulting in savings for the glass industry and many environmental benefits.

Keywords: ash, chromium, leather, chromite, colorant, soda-lime glass.



0074 | Applications of hybrid air-fuel/oxy-fuel glass melting technologyEdson E. Basilio1, Michael E. Habel2, Kevin A. Lievre2, Matthew J. Watson2*

1Air Products Brasil Ltda, São Paulo-SP 2Air Products and Chemicals, Inc. Allentown, PA, USA, e-mail: [email protected]

The Cleanfire® HGM™ (Hybrid Glass Melter) furnace combines oxy-fuel combustion over the unmelted batch and air-fuel combustion over the refining zone of a glass melting furnace. This offers a number of advantages over both air-fuel and oxy-fuel furnaces. Compared to an air-fuel furnace, the HGM furnace provides increased production, improved glass quality, fuel savings, better furnace temperature control, and a more stable batch pattern. Compared to 100% oxy-fuel, the HGM furnace delivers similar production levels, reduced levels of foam on the glass surface, lesser quantities of liquid oxygen stored at site for back-up, and lower overall oxygen costs.

Two on-the-fly field implementations of HGM furnaces are presented. In the first, the regenerators for ports #1 and #2 had failed, and the desire was to maintain production while the regenerators were repaired. Several oxy-fuel applications were used during the repair, enabling the evaluation of different types of retrofit options available for HGM furnaces. In the second example, a furnace was scheduled for rebuild; however the desire was to maximize production until the end of the furnace campaign. Initially oxy-fuel boost burners coupled with lancing and general oxygen enrichment were used to maintain production levels. As the regenerators continued to deteriorate, the lances were moved down-tank and replaced by water-cooled Cleanfire® ThruPort™ oxy-fuel burners. Field observations and a summary of the benefits are presented.

Keywords: Hybrid Glass Melter, furnace, oxy-fuel, regenerator repair, oxygen, lancing, boost, ThruPort, HGM.

0115 | New solutions for the valorisation of glassy residues produced by municipal waste incinerators

Hreglich S.1, Falcone R.1, Tucci A.1*, Favaro N.1 , Bertuzzi P.2, Ercole P.2 *, Ramon L.2 ,1Stazione Sperimentale del Vetro – SSV, Venezia-IT

2SASIL S.p.A. – Brusnengo (BI)-IT, e-mail: [email protected]

In EU about 60 millions ton/year of glassy residues are produced by municipal waste incinerators (MWI). 50% of the production is recycled by the construction industry as filling material. The remaining is disposed in landfills at high costs. From 2010 the research project VALIRE co-financed by the EU LIFE+ program proposes advanced technological solutions for the reuse of slags and flying ashes produced by MWI as secondary raw materials (SRM). The partners involved are SASIL, an Italian company specialized in the treatment of recycled raw materials, SSV (Italian Glass Research Centre) and the Department of Materials Engineering of Padua University (Italy), experts on the vitrification of industrial wastes. The slags produced by MWI are quite inhomogeneous but, due to the lower hardness of the non-glassy components, two fractions could be separated by grinding process: a finer fraction rich in Ca and Mg silicates and a coarser one more homogeneous than the starting slag. The improved glassy fraction can be used combined to other SRM (including flying ashes from MWI) in batches for the production of: glass foams, stone and slag wools and glass ceramic products for external paving. Industrial solutions and economic benefits foreseen are: the volume reduction of waste disposal in landfill; saving of natural raw materials; reduction of energy consumption in the production process; new “ecologic” products with added value.

Keywords: vitrification, slag, fly ashes, glassy building materials, energy saving, waste incinerators.



0211 | Energy efficiency simulations using fully coupled and controlled regenerative furnace model

Miroslav Trochta1*1Glass Service, Inc., Vsetin, Czech Republic, e-mail: [email protected]

Full 3D CFD modeling of glass furnaces is increasingly becoming a standard tool for predictions of energy balance and glass quality. State of the art 3D furnace models usually include energy transfer inside the furnace and between furnace and the surroundings.

Real regenerative furnaces are complex systems with complex interactions among regenerators, combustion chamber(s), glass melt and control systems. To achieve good accuracy and realistic response of numerical models of glass furnaces, especially in optimization studies aimed at energy savings, the models should include all these interactions.

GS Glass Furnace Model has been enhanced to have the 3D regenerator model integrated with the furnace model. Thus, changes inside the furnace influence behavior of regenerators and vice versa. Behavior of the control system is mimicked too – gas and air flow rates and other inputs are automatically adjusted to maintain specified temperatures at controlled thermocouple locations.

An example case study, focused on energy savings, on an industrial size cross-fired regenerative float furnace, is presented. The study demonstrates how the model reacts on changes in furnace design and operating parameters. The cases are compared and differences in energy balance and glass quality are interpreted.

Keywords: CFD, Numerical Model, Furnace Simulation, Regenerator, Energy Balance, Furnace Control, Heat Transfer.

0457 | Down converting coating based on ZnS:Mn nanoparticles embedded in sol-gel or polymer matrixMarta Dai Prè1, Alessandro Martucci1*, Joao Antonio Bomfim 2

1Università di Padova, Dipartimento di Ingegneria Meccanica Settore Materiali, Italy 2Centro Ricerche Plast-optica, Amaro (UD), Italy

Thermalization is one of the main mechanisms leading to losses in solar cells: when an electron–hole pair with energy greater than the band gap is created, the excess energy is lost as heat because electron and hole relax, respectively, to the conduction and valence band edges. Thermalization losses can be reduced via down-conversion where, for example, a photon with twice the energy of the band gap is converted into two photons with exactly the energy of the band gap. Among the different investigated down-converting materials, ZnS doped with transition metal ions appear the more interesting.

A stable and narrowly distributed dispersion of Mn-doped ZnS (sphalerite) nanoparticles (NPs) with an average diameter of 1-2 nm, has been synthesized via chemical precipitation without using any surfactant. The surface of the NPs has been functionalized with acrylic acid for compatibilization with SiO2-ZrO2 sol-gel hybrid organic-inroganic matrix and polymethylmetacrylate (PMMA) matrix. A thorough morphological and optical characterization of the NPs is proposed. A high nonlinearity in the response of the material is evidenced, with the maximum of luminescence obtained with 5% mol Mn doping. The structure and the optical properties of the nanocomposites have been also characterized.

Keywords: sol-gel, ZnS:Mn, down conversion, nanocomposite, photoluminescence, nanoparticles.

Round TableUsable Glass Strength Coalition

M. Greenman (chairman)



Sept. 25 – 8:00-9:45 h – Room A

Glass Surfaces (Chairman: C. Pantano)

0492 | Adsorption reactions and polymer interfaces with multicomponent glass surfaces

Carlo G. PantanoDepartment of Materials Science and Engineering, Materials

Research Institute, The Pennsylvania State University, Pennsylvania, USA

There is much known about small-molecule adsorption and polymer bonding on high-surface-area amorphous silica and silica films on silicon, but much less so in the case of multi-component silicate glasses and glass fibers. Of particular significance for organic coatings and polymer adhesives is the atomic-scale chemical heterogeneity of multi-component glass surfaces with respect to adsorption and interfacial bonding, and in the case of aqueous systems, the simultaneous leaching and hydration of the glass surface. We have used a variety of experimental techniques to probe glass surfaces and surface adsorption directly, and computer simulations to guide and help interpret the experimental work (NMR, FTIR, XPS, NEXAFS, IGC, and TPD). The specific effects of boron, sodium and water interacting with alcohol and carboxylic-acid functionalities at the surface of multicomponent silicate glasses will be emphasized.

Keywords: glass surfaces, multicomponent silicate glasses, polymer interfaces.

0051 | Precise XPS depth profile of soda-lime-silica glassusing C60 ion beamYuichi Yamamoto*, Kiyoshi Yamamoto

Asahi glass Co., Ltd.,1150 Hazawa-cho Kanagawa-ku Yokohama Japan, e-mail: [email protected]

Ar ion sputtering is one of the most accepted techniques for depth profiling in practical X-ray photoelectron spectroscopy (XPS) analysis, while this technique is known to be inadequate for quantitative analysis of glass including mobile ions such as soda-lime-silica glass. Buckminsterfullerene (C60) ion sputtering has been recently recognized to suppress the degradation of organic materials1,2, while the application has not been reported for inorganic materials yet. Here, for the precise depth profiling on glass surface, C60 ion sputtering was applied to suppress the migration of mobile ions in glass. In our best knowledge, it is the first time to succeed the precise XPS depth analysis of soda-lime-silica glass (70.4SiO2, 0.9Al2O3, 7.3MgO, 7.8CaO, 13.6Na2O in mol%) without compositional change by using C60 ion sputtering3. The precise analysis revealed that the ion implantation during Ar ion sputtering principally resulted in the compositional change due to the migration of mobile ions.1. Y. Yamamoto, N. Shirota and K. Yamamoto, J. Surf. Sci. Soc. Jpn. 28 (2007) 348.2. Y. Yamamoto, S. Higashi and K. Yamamoto, Surf. Interf. Anal. 40, 1631 (2008).3. Y. Yamamoto and K. Yamamoto, J. Non-Cryst. Solids 356, 14 (2010).

Keywords: C60 ion sputtering, XPS, depth profile, soda-lime-silica glass, Ar ion sputtering.

0234 | Lead crystal glass corrosion in ethanol and acidsHelena Hradecka, Veronika Hornychova, Stepan Pech, Ales Helebrant*

Faculty of Chemical Technology ICT Prague – Department of Glass and Ceramics – Prague, Czech Republic, e-mail: [email protected]

The lead crystal glass samples (24 wt% PbO) prepared by blowing or pressing were corroded in 4% acetic acid, in 50% ethanol, in distilled water and in dilute HCl (pH 3, 4 or 5). The corrosion can be described by selective leaching of potassium and lead as result of interdiffusion in glass surface. The glass network dissolution can be neglected in this case. The most rapid leaching was found in acetic acid which seems to be an appropriate testing solution. The lowest leached amounts were observed in ethanol. Increasing pH in HCl solution leads to decreasing of leaching rate both for K and Pb. However, neither after long-term leaching (158 days) in acetic acid the Pb concentration in leachate did not exceed the maximal limits permitted by ISO 7086 standard for 24 hours. The forming process and following treatment of glass can influence the chemical durability considerably. Both K and Pb are leached faster from cullet samples prepared from pressed glass compared to the blowed one. Decreased Pb concentration was found in near surface of both chemically and flame polished glass, compared to unpolished samples. This fact resulted in slower leaching of Pb from

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polished samples into acetic acid. XPS measurements also documented the difference in potassium and lead concentration profiles in different places of glass product which can influence the results obtained by different type of leaching tests.

Keywords: lead crystal glass, glass corrosion.

0497 | Structure and reactivity of glass surfaces from atomistic computer simulationsAlastair Cormack1*, Antonio Tilocca2 and Jincheng Du1

1Kazuo Inamori School of Engineering, New York State College of Ceramics at Alfred University 2Department of Chemistry, University College London, e-mail: [email protected]

Many properties of glasses, ranging from chemical durability or bioactivity, to crack propagation are governed ultimately by the atomic scale structure of the surface of the glass. This is because it is at this level that the chemical processes which control these properties operate. In this presentation, we will discuss the application of atomistic computer simulation techniques to the development of a picture of the surface structure of silicate glasses and the nature of the reactive sites which exist on these surfaces. Both classical and quantum mechanical approaches are used because they each have their own advantages. We will describe the structure of the reactive sites in terms of defect structures, that is, structural features which do not exist in the corresponding bulk glasses. We will also show how water molecules, both isolated, in the gas phase (typical of environmental species), and in liquid water, interact with the glass surface. Both physisorption and chemisorption are observed.

Keywords: glass surfaces, glass structure, atomistic simulations, molecular dynamics, first principles calculations.

0183 | Optical properties of pittsburgh glass subjected to mechanical and chemical treating

Janusz Jaglarz

Instytute of Physics, Cracow University of Technology Fizyki, Ul. Podchorążych 1, 30-084 Kraków, E-mail: [email protected]

The growth of plants vegetation produced in solar houses depend of total energy passing to the inside. The energy transfer is mainly depend on total light reflectance. The lower reflection coefficient, the more energy coming in. According to reliable sources reducing 1% of total reflection coefficient cause 3% increase of plant biological mass. Decrease of reflectance one may be to achieve by deposition of thin films with strict thickness fulfilled negative interference conditions. There is expensive and complicated technology. Alternatively the lowering of reflectance may be obtain by mechanical or chemical roughening of one side of glass slab. Particularly susceptible for surface modifications is glass obtained in Pittsburgh technology. In this work the optical properties of glasses studied by the means classical and non-standard measurement method have been presented namely TIS (total integrated scatter) BSDF (bidirectional scatter distributution function), speckle methods and optical profilometry. For micro and nanoscale characterization of glass surface the complementary AFM measurements were performed. The studies show significantly decrease lowering promising resulting the chemical glass surface processing.

Keywords: optical reflectance, surface chemical, mechanical treating.



Sept. 25 – 8:00-9:45 h – Room B

Electrical Conductors (Chairman: J.L. Souquet)

0238 | Mechanochemical synthesis of lithium ion conducting oxide glasses with high Li2O Content

Akitoshi Hayashi, Daisuke Furusawa, Keiichi Minami and Masahiro Tatsumisago*Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University,

1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan, e-mail: [email protected]

All-solid-state lithium rechargeable batteries with inorganic solid electrolytes have attracted much attention as a power source with high energy density and high safety. A lot of studies about lithium ion conduting oxide glass electrolytes have been reported. The increase of lithium ion concentration in glass electrolytes is an effective technique to prepare highly conducting glasses1. Although most oxide glasses were prepared by the melt quenching method, glasses with high alkali content have been prepared by the mechanochemical method using a planetary ball mill apparatus2. In the present study, oxide glass electrolytes in the systems Li2O-MxOy (M=B, P, Si, Ge and Al) were prepared via mechanochemical route.

FT-IR and Raman spectra suggested that local structure of the mechanochemical glasses was similar to that of the melt-quenched glasses. The glasses with high Li2O content exhibited relatively high conductivity as lithium ion conducting oxides; the conductivity of the pelletized glass at the orthoborate composition 75Li2O • 25B2O3 (mol%) was 3.4 × 10-7 S cm-1 at room temperature. Mechanochemical synthesis is a useful route for developing oxide glass electrolytes with high lithium ion concentration.1. M. Tatsumisago et al., J. Non-Cryst. Solids, 95-96 (1987) 857-864.2. A. Hayashi et al., J. Am. Ceram. Soc., 84 (2001) 477-479.

Keywords: lithium ion conductor, solid electrolyte, oxide glass, lithium battery, mechanochemical synthesis.

0086 | Ionic glasses like ionic crystals or electrolytic solutions?Jean Louis Souquet

Laboratoire d’Electrochimie et de Physicochimie des Matériaux et des Interfaces, Grenoble-INP, BP 75, 38402 Saint Martin D’Hères Cedex, F

Since ionic glasses are ionic solids and supercooled liquids, their ionic transport properties can be approached by two different ways.

The first one consists to extend to them the usual punctual defect theory currently developed for transport in ionic crystals. Diffusion studies suggest that, for alkali or silver conductive oxide glasses, defects would be interstitial cationic pairs, for instance two alkali cations sharing a same non-bridging oxygen. These positively charged defects, migrating from one non-bridging oxygen to another one are the effective charge carriers. Following an alternative description, these interstitial pairs can be considered as resulting from a partial self-ionisation as observed in weak electrolyte solutions.

The discontinuity in the ionic migration mechanism below and above the glass transition temperature provide an original way to calculate the concentration and mobility of interstitial pairs in the supercooled and glassy states whose numerical values are coherent with data obtained by other different techniques on ionic crystals or electrolytic solutions.

The usual concepts developed for the thermodynamic of solutions allow a quantitative interpretation of the high sensibility of ionic conductivity to glass composition.

Finally, ionic glasses being an intermediate state between solid and liquid electrolytes, allow the reunification of two apparently different approaches.

Keywords: ionic conductivity defects, mobility, charge carrier, thermodynamics.



0258 | Improvement of electrochemical performance of all-solid-state lithium secondary batTeries by using Li2S-P2S5 solid electrolyte thin films

Atsushi Sakuda1*, Akitoshi Hayashi1, Takamasa Ohtomo2, Shigenori Hama2, Masahiro Tatsumisago1

1Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan

2Battery Research Div., Toyota Motor Corporation, Higashifuji Technical Center, 1200 Mishuku, Susono, Shizuoka 410-1193, Japan

Glass and glass-ceramic solid electrolytes in the system Li2S-P2S5 have high lithium-ion conductivity of 10-4-10-3 S cm-1 at room temperature1. The glass electrolytes have been prepared by melt quenching and mechanical milling techniques. In this study, amorphous Li2S-P2S5 thin films were prepared by pulsed laser deposition, and the electrolyte thin films were applied for bulk-type all-solid-state lithium secondary batteries. The chemical composition and local structure of the 80Li2S·20P2S5 (mol%) thin films were in good agreement with those of the 80Li2S·20P2S5 glass powder prepared by mechanical milling. The lithium-ion conductivity of the 80Li2S·20P2S2 thin films was about 10-4 S cm-1 at 25 oC. The electrolyte/electrode composite materials were prepared by coating the 80Li2S·20P2S5 electrolyte film onto the LiCoO2 electrode particles. The all-solid-state lithium secondary batteries using the 80Li2S·20P2S5-coated LiCoO2 were charged and discharged, and exhibited excellent cyclability. The battery performance of the cell using 80Li2S·20P2S5-coated LiCoO2 was highly improved in comparison with that of the cell using non-coated LiCoO2. An effective lithium-ion conducting path to the LiCoO2 electrode was formed by the electrolyte coatings on the LiCoO2 particles. The electrolyte-coating technique allows us to fabricate all-solid-state lithium batteries with large energy density.1. A. Hayashi, K. Minami, and M. Tatsumisago, J. Non-cryst. Solid. 355 (2009) 1919-1923.

Keywords: solid electrolyte, glass electrolyte, lithium battery, all-solid-state battery, thin film, pulsed laser deposition.

0244 | Mixed conduction in tungsten phosphate glass systemIsaias Oliva1*, Atsunobu Masuno1 and Hiroyuki Inoue1

1Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro, Tokyo 153-8505 Japan, e-mail: [email protected]

It has been found that tungsten phosphate glasses presented mixed conduction behavior after the absorption of hydrogen. The glass system 45xMO1/2- 45(1-x)WO3- 25NbO5/2- 30PO5/2 (M = alkali ion and x = 0.5,...,1.0) were prepared and heat-treated under hydrogen atmosphere. The electrical conductivity analysis using impedance measurement was applied changing the alkali or the content of the alkali in the composition. In both cases, the hydrogen was absorbed into the glasses and the conductivity increased with the amount of the absorption. It was found that in the high alkali region the alkali ion was responsible for the conduction mechanism. On the other hand, the electronic conduction became predominant and the increase of the conductivity was remarkable in the high WO3 region. In the middle x region, the conductivity reached a minimum, indicating of the mixed conduction. The minimum conductivity was, however, relatively high compared with other mixed conductor glasses.

Keywords: phosphates glasses, transition metal ion, mixed conduction, electronic-ionic conduction, heat treatment.



0293 | Characterization and optimization of TMO containing glassesCristina Siligardi1, Consuelo Mugoni1,*, Guido Ori1, Monia Montorsi1

1*Dipartimento di Ingegneria dei Materiali e dell’Ambiente, Facoltà di Ingegneria, Università di Modena e Reggio Emilia, Via Vignolese 905, Modena, Italy, e-mail: [email protected]

Glasses containing transition metal ions (TMI) are known to show different kind of functional properties, such as semi-conduction and peculiar optical and magnetic properties. Electronic conduction in these glasses is determined by the presence of the TM ions in different valence states and the conductivity can be described in terms of small polaron hopping between the low and the high valence states of TMI1,2.

Many studies are reported on the conductive properties of vanadium and copper based glasses, in which a great importance is related to the different V and Cu oxidation and coordination states they present in relation of the structural and functional properties that can be obtained, as the case of electron conductivity properties.

The addition of a modifier cation strongly affect the conduction mechanism makes them mixed electronic-ionic conductors3,4, which are of potential interest in solid-state devices.

For these reasons, different Vanadium-based and Copper-based glass systems (Silicon and Phosphorous as Network former) has been chosen as starting compositions, to quantify the effect of the Vanadium and Copper content on the physical properties of the glass material. X-ray Diffraction (XRD), Raman spectroscopy, Differential thermal analysis, heating microscope, Scanning Electron Microscopy (SEM) and X-ray absorption spectroscopy (XPS) have been used to characterize the glasses. The behavior of the conductivity has been studied as a function of TMO/Network former ratio.1. MURAWSY L., CHUNG C.H., MACKENZIE J.D., J. Non-cryst. Solids, 32 (1979), 91.2. SAYER M., MANSINGH A., Non-crystalline semiconductors, Vol. III, M.Pollak (Ed.), CRC Press, Boca Raton,

FL,USA, 1987.3. J. BARCZYNSKI, L.MURAWSKI J.Non-Cryst.Solids, 307-310(2002), 1055.4. J. BARCZYNSKI, L.MURAWSKI, SAMATOWICZ D.,Solid State Ionics, 157 (2003), 157.

Keywords: conductivity, transition metal ions, glasses.

0113 | Study of physical and structural properties of 50B2O3-15PbO-(35-x)Li2O-xNa2O and 50B2O3-15PbO-(35-x)LiF-xNaF glasses

Fábio A. S. Ferreira1*, Antonio C. Hernandes1

1Grupo de Pesquisa Crescimento de Cristais e Materiais Cerâmicos(CCMC), Instituto de Física de São Carlos, Universidade de São Paulo- USP. CEP 13560-970 São Carlos, SP, Brasil,

e-mails: www.ccmc.ifsc.usp.br, [email protected]

A phenomenon known as mixed alkali effect (MAE) is observed when two types of alkali ions are introduced into a glassy network. It represents the non-linear variations exhibiting a minima or maxima in many physical properties associated with the alkali ion movement and structural properties, when one type of alkali ion is gradually replaced by another, keeping the total alkali content constant [1]. We have modified some borate glassy systems to study optical and structural properties in the last 10 years. In this work the goal was to verify if there is (or not) the non-linear behavior in 50B2O3-15PbO-(35-x) Li2O-xNa2O and 50B2O3-15PbO-(35-x) LiF-xNaF glasses. The effect of F into glassy network will be discussed. Glass transition temperature, density and ionic conductivity measurements have showed the occurrence of MAE. Infrared and Raman studies showed changes from 3 to 4 in the coordination number of boron.1. N. Srinivasa Rao et al, Physica B 404 (2009) 1785-1789.

Keywords: MAE, borate glasses, ionic conductivity.



0429 | Microstructural and electrical characterization of phase separated glasses: use of near field microscopy

A. A. Piarristeguy1, M. Ramonda2, M. Ribes1, A. Pradel1*1Institut Charles Gerhardt Montpellier, Équipe Physicochimie des Matériaux Désordonnés et Poreux,

CC1503, Université Montpellier 2, Pl. E. Bataillon, F-34095 Montpellier Cedex 5, France 2Laboratoire de Microscopie en Champ Proche (LMCP), Université de

Montpellier II, F-34095 Montpellier Cedex 5, France

Ge-Se(S) glasses have been widely studied due to their extended vitreous domain involving the study of a great variety of properties and their correlation with structure and composition. In particular the electrical properties are strongly affected by the addition of metals (Li+, Na+, Ag+).

The combined investigation of electrical conductivity by complex impedance spectroscopy (CIS) and microstructure by Electric Field Microscopy (EFM) helped us to characterise the electrical heterogeneousness existing in several Ag-based chalcogenide glasses. While the (Ag2S)x(GeS)60(GeS2)40-x glasses were shown to be homogeneous, sulphide (Ag2S)x(GeS2)100-x and (Ag2S)x(As2S3)100-x and selenide Agx(Ge0.25Se0.75)100-x glasses show heterogeneousness. Such heterogeneousness is the electrical signature of a phase separation existing in the glasses. The obtained data helped us in identifying the phase separation and the subsequent percolation threshold as being responsible for the large jump occurring in the conductivity curve of these materials.

An electrical characterization of the micro(nano)phases present in the Agx(Ge0.25Se0.75)100-x glasses was carried out using two complentary techniques of near field microscopy, i.e. the Electric force microscopy (EFM) and the conducting atomic force microscopy (C-AFM)). Changes in the relative permittivity were found for both phases when the silver content is changed. Furthermore, the sensitivity of the C-AFM technique revealed current variations of a few pico-amperes in the Ag-rich phase for the different glass compositions. This result confirmed that the increase in conductivity of the Ag-Ge-Se samples in the region of high ionic conduction (x > 8-10% at.) arose from an increase in conductivity of the Ag-rich phase and not from an increase in amount of Ag-rich phase with a fixed composition and conductivity.

Keywords: Ag chalcogenide glasses, phase separation, near field microscopy, conductivity.

Sept. 25 – 8:00-9:45 h – Room Tech.

New Glasses/Blisters TC14&11 (Chairman: S. Toffoli)

0377 | Low poisson ratio perfect glasses formed by amorphising zeolites

G.N. Greaves1*, F. Kargl21Centre for Advanced Functional Materials and Devicesm – Institute of Mathematics and Physics,

Aberystwyth University, Aberystwyth SY23 3BZ, UK, e-mail: [email protected] 2Institute of Materials Physics in Space, German Aerospace Center,

Helmholtz Association, Linder, Höhe, 51147 Köln, Germany, e-mail: [email protected]

By using in situ X-ray diffraction, inelastic X-ray scattering and magic angle spinning NMR we have identified glasses with very low Poisson Ratios formed during the collapse of zeolite crystals. The glasses also have very low entropy and are “ideal” or “perfect”. By approaching the glass transition from below rather than from above, the crystallisation problems that face melt-quenching procedures in the search for these unusual and rare amorphous materials can be minimised. The amorphisation process separates into a displacive crystalline-amorphous transition resulting in the low entropy phase followed by a disordering amorphous-amorphous transition leading to a higher entropy phase equivalent to glass made by the conventional melt-quenching route. From the relaxation time which governs microporous collapse the kinetic fragility of the low entropy glassy phase is found to be much lower than for a conventional melt and the glass transition temperature higher. Moreover the degrees of non-ergodicity, mechanical non-deformability and chemical order obtained spectroscopically for these low entropy glass are significantly greater than for melt-quenched glasses. In particular Poisson’s ratio for these “perfect glasses” is close to zero whilst the melt fragility during amorphisation is virtually twice the strength of liquid SiO2, the model strong liquid.

Keywords: glass transition, low entropy glasses, microporous materials, zero poisson’s ratio, super strong.

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0361 | Strontium chloro-antimonite glassesMarcel Poulain1*, Mostepha Iezid2, Fayçal Goumeidane2, Messaoud Legouera2, Ronan Lebullenger1

1Sciences Chimiques, Université de Rennes 1, Campus Beaulieu, F-35042 Rennes 2Laboratoire de Génie Mécanique, Université Mohamed Khider, Biskra, Algéria

Among Heavy Metal Oxide Glasses, antimonite glasses attract an increasing interest because they easily form glasses in a large number of chemical systems. Since the pioneering work of Dubois and Portier1, numerous oxyhalide systems based on Sb2O3 have been investigated. This work reports glass formation in multicomponent systems based on the Sb2O3- SrCl2 association. The observed limits of the vitreous areas are given in the Sb2O3-SrCl2-CdCl2 ternary system and in selected areas of quaternary systems: Sb2O3-(0.5RCln+0.5SrCl2)-CdCl2; Sb2O3-CdCl2-(0.7SrCl2+0.3BaCl2); Sb2O3-SrCl2-(0.5ZnCl2 0.5CdCl2) with R= (Li, Na, Ca). In most cases Sb2O3 concentration must be kept between 50 and 90 mol %.

Glass transition temperature Tg is close to 300 °C. The thermal stability range Tx-Tg is larger than 100 °C for most glasses. Surprisingly enough, Tg value increases when chloride content increases. This evolution is discussed by reference to structural hypothesis. Refractive index is close to 2. Both refractive index and Vickers microhardness decrease with Sb2O3 content. The evolution of the elastic moduli is reported in the (90-x) Sb2O3 xCdCl2 20SrCl2 series of glasses.1. B. Dubois, H. Aomi, J.J. Videau, J. Portier, P. Hagenmuller, Mater. Res. Bull. 19 (1984) 1317.

Keywords: heavy metal oxide glasses, physical properties.

0045 | Formation and properties of nitrogen rich glassSharafat Ali*, Bo Jonson

School of Engineering, Department of Chemistry –Glass Group Linnæus University SE-351 95 Växjö, Sweden. corresponding Author: Sharafat Ali, e-mail: [email protected]

Oxynitride glasses are a branch of high performance glasses, obtained by incorporation of nitrogen atoms into oxide glass network. It has been widely established that the incorporation of a relatively small amount of nitrogen leads to a significant change of the glass network, and therefore to a strong change of the properties. Oxynitride glasses have traditionally been synthesized by melting mixtures of glass modifier metal oxides, SiO2 and Si3N4, yielding glasses with nitrogen content up to typically ca. 30 e/o. However, a novel synthesis method (developed by our group), in which the modifier is introduced as a pure metal or metal hydride has enabled the preparation of oxynitride glasses with significantly higher concentrations of nitrogen up to 60 e/o as well as modifier additives up to 45 e/o. The obtained glasses are found to be homogenous, translucent gray to opaque black. Compare with their oxide glass counterparts, oxynitride glasses show high values of glass transition temperature (1050oC), microhardness (10.50 GPa), Young’s modulus (151 GPa) and refractive index (1.93).

Keywords: oxynitride glass, glass forming region, high nitrogen content, glass transition temperature, hardness, refractive index.

0410 | Overview about sources of blisters from refractories – issue of blister tests – necessary improvements

Dr. Michael DunklDr. M. Dunkl Consulting, Meerbusch, Germany

Beside of knots, cords and stones, blisters in glass are the most important and refused glass defects. The source of a large amount of the blisters is their generation due to their contact with the glass melts. The most important possible sources of the blister formation on the boundary- or reaction layer refractory material / glass melt will be discussed.

For the determination of the blistering rate many different measurement methods are used. Their results are usually not really comparable. The issue of different blistering tests will be presented. Therefore it is necessary to develop a standard test procedure which is affordable and reliable. A joint group of TC11 / TC14 is working to develop a standard test procedure which is affordable and reliable.

Under consideration of all known advantages and disadvantages of the various blistering tests and the important influences to their issues, the necessary improvements will be discussed.

Keywords: refractory materials, bonded and fused-cast, AZS, alumina, zirconia, testing, blistering, glass melting furnaces.



0358 | Mechanisms of blister formation at refractoriesDetlef Koepsel1*

1*SchottAG, Research and Technology Development, Mainz, Germany, e-mail: [email protected]

Refractories represent an important source of blisters in glass melts causing an undesired “background” blister level. In order to decrease the number of refractory blisters the mechanisms of blister formation have to be understood first of all.

There are different sources and mechanisms of blister formation:• bubbles forming if closedpores in the refractorymaterial areopenedduring the refractory corrosion

process;• bubblesformingduetosurfaceimpurities,whichareespeciallyobservedinthebeginningofaglasstank

journey;• bubblesformingduetobulkimpuritiesintherefractorymaterials,suchascarbon,nitrogenandpolyvalent

elements;• bubblesformingduetosupersaturationofgasesinthecorrosionboundarylayer.

These different mechanisms cause different initial gas compositions of the bubbles, which have to be known in order to assign bubbles found the product to the right source, i.e. the refractory material or to any other source in the glass melting tank.

In the lab scale the best method to analyse “fresh” refractory bubbles is the Raman spectroscopy. This method can provide information on the gas composition of bubbles adherent to the refracrory interface. With other methods such as mass spectrometry only bubbles detached from the refractory interface can be analysed. In this case the bubble had some time to change the gas composition. This in turn impedes the understanding of the bubble formation mechanism.

Keywords: refractory blister formation, electrochemistry, supersaturation, refractory corrosion.

0394 | Studying bubble glass defects caused by refractory materialsErik H.P.H. Muijsenberg1*, Jiri ullrich1

1Glass Service Inc. Rokytnice 60, 75501 Vsetin, Czech Republic, e-mail: [email protected]

Glass is mostly transparent material not only at low temperatures but also in the melting temperature region. This property makes possible to continually observe, record and evaluate some phenomena or processes taking part in a glass melt. The high temperature observation (HTO) procedures being useful in the chemical engineering research can be thus introduced into the examination of the refractory blistering.

The selected refractory sample is inserted into the glass melt at given high temperature; the bubble release from the surface is recorded. Visual inspection of the video files from the tests as well as the evaluation of the bubble quantities above the sample surface in dependence on time provide the comparison of the tested samples. The duration of the test is 2-5 days; generally it depends on the testing temperature and composition of the used glass. The limitation of the test is usually silica crucible corrosion and glass leak.

Resulting from many bubble gas analyses provided within the past years, most of origins of the bubble defects are refractory related. The bubble evolution by different mechanisms on the phase boundary refractory-glass melt deteriorates considerably the quality of glass and sometimes even accelerates the local refractory corrosion as well. The detailed knowledge of the bubble releasing process provides also valuable information for furnace engineers in case that they are seeking for reduction of defect bubbles in produced glass.

Bubbles in glass melts mostly undergo a complicated history, characterized by their interaction with glass, which affects bubble fundamental properties: their size and composition in particular. The history of different types of defect bubbles is thoroughly examined by laboratory tests which reveal bubble arising mechanism from refractories, describe bubble sizes and analyze their composition under conditions of industrial glass melting. The knowledge base of bubble properties may be obtained, usable for comparison between laboratory modeled and industrially produced bubble defects and thus for identification of the industrial defect bubble source

Keywords: ICG TC11, refractory defects, glass quality, bubbles.

14:00-18:00 h General CTC Meeting

16:30-19:00 h Poster Presentations, Tuesday, Sept. 21 Posters #0016-0200

17:30-19:30 h Varshneya´s Glass Course


0016 | Polyphosphate coacervate glasses as a host for vitamin C

encapsulationMaurício A. P. Silva*,

Douglas F. Franco, Luiz F. C. de OliveiraUniversidade Federal de Juiz de Fora – UFJF, Juiz de

Fora-MG, e-mail: [email protected]

Calcium polyphosphate glasses containing L-ascor-bic acid (vitamin C) where prepared by the coacer-vation route, at room temperature. The resultant biocompatible glasses containing different vitamin C concentrations were analyzed via thermal analysis, Raman and Infrared spectroscopy. The spectro-scopic techniques indicate that the vitamin C was successfully incorporated in the glassy structure. The kinetics of the vitamin C liberation in aqueous medium reveals that this new material can be used as a time-controlled source of the vitamin C. Due to the biocompatibility property of the material used in the glass composition, the use of polyphosphate coacervate glass can be envisaged as a new host for different cosmetic and medical products. The simple synthesis method and the use of room temperature for the glass preparation raise the financial interest for commercial purposes.

Keywords: polyphosphate coacervate, room temperature glass, vitamin, biocompatible glass.

0032 | Theory of pore formation in a “stretched” dioside glass:

generalized gibbs approach Jürn W. P. Schmelzer1*, Alexander S. Abyzov2,

Attila R. Imre3, Vladimir M. Fokin4,5

1*Institute of Physics, University of Rostock, 18051 Rostock, Germany,

e-mail: juern-w.schmelzer@uni-rostock,de 2 National Science Center, Kharkov Institute of Physics and Technology,

Academician Street 1, 61108 Kharkov, Ukraine 3 KFKI Atomic Energy Research Institute,

1525 Budapest, POB 49, Hungary 4 Vavilov State Optical Institute, ul. Babushkina 36-1,

193 171 St. Petersburg, Russia 5 Department of Materials Engineering,

Universidade Federal de São Carlos – UFSCar, CEP 13565-905, São Carlos-SP, Brazil

In accompanying contributions, abundant evi-dence of formation of pores in crystallization process-es of small samples of under-cooled diopside glass-forming melts is given, when the samples crystallize from the outer boundaries. The basic mechanism is supposed to be the following: Due to the density misfit of the crystal and liquid phases, the growth of the crystalline layer leads to an uniform stretching of the encapsulated liquid and, similarly to cavita-

tion in simple liquids, to nucleation of a single pore. Pore formation is followed by its fast growth, which eliminates elastic stresses and, therefore, the condi-tion for nucleation of further pores. A first theoretical analysis of pore nucleation of such samples is per-formed in mentioned contributions in terms of the classical Gibbs approach. As shown there, the clas-sical theory overestimates the work of critical bubble formation by a factor of the order two. In the present contribution, it is demonstrated that the generalized Gibbs approach provides a more adequate descrip-tion of the process of pore nucleation as compared with the classical nucleation theory and allows also in a quantitatively correct way to interpret pore forma-tion in the considered elastically stretched liquids as cavitation-like processes caused by elastic stresses.

Keywords: crystallization, pore formation, nucleation theory.

0039 | Evaluation of novel strontium bioactive glass coatings

M. D. O’Donnell1, S. Newman2, P. Candarlioglu3,4, E. Gentleman3,4, N. Lotfibakhshaiesh3,4,

A. Amis2,5, J. Cobb2, M. M. Stevens3

1RepRegen Ltd, London UK 2Department of Surgery and Cancer,

Imperial College London, UK 3Department of Materials, Imperial College London, UK

4Institute of Biomedical Engineering, Imperial College London, UK

5Department of Mechanical Engineering, Imperial College London, UK

Here we report on the structure, physical proper-ties, in vitro and in vivo performance of a series of ten bioactive glasses (SiO2-Na2O-K2O-CaO-SrO-MgO-ZnO-P2O5) where 0, 10 and 50% of the Ca was sub-stituted with Sr. Glasses showed apatite formation comparable to Bioglass (45S5) as determined using spectroscopy and diffraction techniques. Thermal analysis showed high stability (Tx-Tg) and crystallisa-tion was suppressed compared to 45S5. Human osteosarcoma cells were cultured in glass dissolu-tion products. Metabolic activity (MTT) increased with time and was similar for all glasses and control (45S5). Bone nodule formation (ALP) was signifi-cantly higher than the control and increased with in-creasing Sr content up to confluency (14 days). Min-eralisation was also confirmed with alizarin red S and tetracycline staining. Actin-vinculin staining showed normal cell morphology, attachment and spread-ing for cells on all glasses. Osteocalcin-collagen1α staining showed normal mineralisation at early times. Ti6Al4V cylinders were plasma sprayed with the 50% Sr glass and implanted into rabbit tibia with hydroxy-apatite (HA) used as a control. At 6 weeks maximum pushout shear strength was: 3.24 + 0.90 (glass) and 3.52 + 0.78 (HA) MPa. At 12 weeks: 4.28 +

Poster PresentationsTuesday, Sept. 21

Poster Presentations, Tuesday, Sept. 21


1.26 (glass) and 3.43 + 0.66 (HA) MPa. These re-sults suggest Sr bioactive glass coatings may have the potential to offer improvements in performance in vivo compared to conventional ceramics such as HA and Bioglass for hard tissue regeneration.

Keywords: bioactive, DSC, raman, SEM, coating, in vitro, in vivo.

0040 | Oxy-float high performance, low emission and reduced capital

investment furnace designAbílio Tasca1, William Kobayashi2, James Yuan3,

Wang Zong Wei4, Zuo Ze Fang4

1White Martins Gases Industriais Ltda., Diadema, SP, Brazil

2Praxair, Inc., Tonawanda, NY, USA, [email protected]

3Praxair China Investment Co. Ltd., Shanghai, People Republic of China

4China Triumph International Engineering Co., Shang-hai, People Republic of China

Successful implementation and proven results of oxy-fuel combustion system in several types of glass melting furnaces since late 1980s encour-age designing high performance oxy-float furnaces. The expectation for future oxy-float furnaces is high regarding low energy consumption, lower capital in-vestment, low pollutant emission and long furnace campaign. CTIEC with large experience in float glass line design (designed over 100 float lines in Asia) and Praxair with large experience in oxy-fuel combustion and glass furnace conversion to oxy-fuel conducted an extensive work to design a high performance oxy-float furnace. The results show that specific energy consumption as low as 1425 kWh/t or 1130 kWh/t with preheated batch and cullet can be achieved with Praxair’s proprietary technologies DOC low momen-tum oxy-fuel burners and Tall Crown Furnace concept without any negative impact on the glass quality. DOC oxy-fuel burner promotes adjustable flame coverage in wide span furnaces like float glassmelter, ultra low NOx and excellent heat transfer characteristics. Tall Crown Furnace concept has been proved to extend the furnace campaign in container glass furnaces due to the minimization of alkali species volatilization with low specific energy consumption. The combina-tion of Tall Crown Furnace and DOC burners allows oxy-float furnaces to be built with commercial silica refractory crown which significantly reduce the capital investment with long furnace campaign.

Keywords: oxygen, combustion, float, oxy-fuel, heat, recovery, modeling.

0046 | Stress induced pore formation and phase selection in a

crystallizing streched glass Vladimir M. Fokin1*, Alexander S. Abyzov2, Jürn W. P. Schmelzer3, Edgar D. Zanotto4

1*Vavilov State Optical Institute-ul. Babushkina 36-1, 193 171 St. Petersburg, Russia,

e-mal: [email protected] 2National Science Center, Kharkov Institute of Physics and Technology-Academician Street 1,

61108 Kharkov, Ukraine 3Institut für Physik, Universität

Rostock -18051 Rostock, Germany 4Vitreous Materials Laboratory,

Department of Materials Engineering, Federal University of São Carlos – UFSCar,

CEP 13565-905, São Carlos-SP, Brazil

In this work we experimentally investigate and theoretically describe the nucleation of a pore in small samples of under-cooled diopside liquid when it is enclosed by a hard crystalline surface layer. The formation of the surface crystalline layers begins with nucleation and growth of single diopside crystals. At the moment of impingement of these crystals on the sample surface, the crystallization pathway switches to a wollastonite-like (WL) phase. The WL crystal phase produces less elastic stress energy than diop-side crystals due to its lower density, which is closer to the liquid density. The relative content of the two crystalline phases can be changed by a variation of sample size. Due to the density misfit, the growth of the wollastonite-like crystalline layer leads to uni-form stretching of the encapsulated liquid and finally to nucleation of a pore, which is followed by fast growth up to a size that eliminates elastic stresses and, therefore, the condition for nucleation. Pore nucleation occurs in a very narrow range of nega-tive pressure indicating that the process proceeds via homogeneous nucleation. This result is corroborated by theoretical calculations of elastic stress fields and their effect on nucleation. Good qualitative agree-ment between experiment and theory is found.

Keywords: crystallization, elastic stresses, pore, nucleation.



0047 | Elastic stresses in crystallization processes in finite domains

Alexander S. Abyzov1, Jürn W. P. Schmelzer2, Vladimir M. Fokin3*

1National Science Center- Kharkov Institute of Physics and Technology- Academician Street 1,

61108 Kharkov, Ukraine 2Institut für Physik, Universität Rostock-18051

Rostock, Germany 3*Vavilov State Optical Institute- ul. Babushkina 36-1,

193 171 St. Petersburg, Russia, e-mail: [email protected]

The effect of elastic stresses on crystallization processes in finite domains is analyzed. Two cases are considered: (i.) crystallization of the internal part of a finite domain and (ii.) crystallization from the boundaries. First, the computations are performed for the case that both the ambient and newly formed phases can be considered as Hookean elastic solids. Finally, the effect of viscous relaxation of the matrix on the magnitude of stresses is estimated for the different situations analyzed.

Keywords: crystallization, elastic stresses.

0052 | MoZrO2 increased corrosion resistance –

higher strength for glass melting Elísio Ferreira Neto

PLANSEE South America LTDA., Rua Álvaro Anes, 46, cjto. 23 – São Paulo-SP, e-mail: [email protected]

Electrical heating by means of Molybdenum glass melting electrodes (GME) is state of the art technol-ogy in today’s glass production. Nevertheless, cor-rosion of the GME’s causes material costs as well as production losses during electrode pushing. In particular in Sb2O3- and SO4

2-- refined glasses as well as in brown and green glasses the corrosion of Molybdenum is considerable. In order to reduce such corrosion effects, a doped Molybdenum grade, MoZ-rO2, was developed which offers a corrosion rate 25 to 50% lower than for pure Molybdenum. In addition this material offers improved mechanical high tem-perature properties and increased creep strength.

The presentation will show test results from small scale investigation as well as practical experiences with MoZrO2 GME’s in industrial glass tanks.

Keywords: zirconium, electrode, GME, resistance, corrosion.

0053 | Molybdenum glass tank reinforcements –

experiences and insights lisio Ferreira Neto

PLANSEE South America LTDA., Rua Álvaro Anes, 46, cjto. 23 – São Paulo-SP, e-mail: [email protected]

The low corrosion rate in glass melt and the extra ordinary strength of Molybdenum is well known to the glass producers due to widely used products such as glass melting electrodes, stirrers and nozzles. 10 years ago a new beneficial product made from molyb-denum has been introduced in glass melting tanks: Glass Tank Reinforcements (GTR). Since then more than 70 GTR projects have been realized to protect the throat, bubbler and wall areas. Less corrosion of the bricks leads to a significantly better glass qual-ity due to stable melting conditions. In opposite to Chromium bricks the use of Molybdenum avoids any glass discoloration. Based on the wide experience in the past, recently a new design principle for GTR’s in highly corrosive glass qualities such as borosilicate and opal glass was developed.

The presentation will cover project studies and the new GTR design approach in detail.

Keywords: glass tank, reinforcements, borosilicate, corrosion, molybdenum.

0054 | Effect of 2SiO2/RE2O3 substitution on the Structure, ionic

conductivity and water solubility of a sodium borosilicate glass

O. Majérus1*, D. Caurant1, N. Li1, P. Barboux1,

T. Charpentier2, Anne Soleilhavoup2, D. de Ligny3, F. Devreux4

1 Laboratoire de Chimie de la Matière Condensée de Paris (UMR-CNRS 7574) – ENSCP

(Chimie-ParisTech) – 75231 Paris, France, e-mail: [email protected]

2 CEA, IRAMIS, Service Interdisciplinaire sur les Sys-tèmes Moléculaires et Matériaux –

CEA Saclay – 91191 Gif-sur-Yvette, France 3 Laboratoire de Physico-Chimie des Matériaux

Luminescents, UMR-CNRS 5620 / Université Claude Bernard Lyon 1 – Domaine Scientifique de la Doua –

69622 Villeurbanne cedex, France 4 Laboratoire de Physique de la Matière Condensée,

Ecole Polytechnique-CNRS, 91128 Palaiseau, France

Rare Earths (RE) bearing glasses are of interest for their optical properties. Beside, a significant amount of RE (about 10 wt% RE2O3) will occur in future French nuclear waste glasses with higher waste load. In view of this and in the general context of glass structure- glass properties relationships studies, we focussed on the effect of RE oxide addition on the structure, ionic conductivity and water solubility of a sodium borosilicate glass, when RE2O3 is substituted for 2SiO2 (RE = Y, La or La + Eu). 11B, 29Si and 23Na MAS NMR, Raman and Eu3 + optical spectroscopies



were the structural tools, providing evidence for the depolymerizing effect of the RE2O3 addition and the competition with B2O3 for Na + charge compensation. The activation energy for ionic diffusion (measured by impedance spectroscopy at high T) slightly increases while the prefactor decreases with the substitution, suggesting that the Na + ions are slightly less mobile in the RE-rich glasses. The glass solubility in water was estimated in static and pH-controlled conditions (S/V = 2 cm-1, T = 80°C and pH = 8,5) and the alteration layer was characterized by IR-ATR and 1H-29Si CP MAS NMR. This layer is less polymerized with increasing RE2O3 content which may explain the higher leached fractions observed.

Keywords: glass structure, borosilicate, rare-earths, MAS NMR, ionic conductivity, water solubility.

0064 | Fuel combustion with supplementary oxygen.

Implications on polluting components of the combustion gases

Andreea David1*, Dorel Radu1

1Politehnica University of Bucharest, Bucharest, Romania, e-mail: [email protected]

Fuels burning with supplemental oxygen or with pure oxygen is a relatively simple method of in-tensifying combustion. The consequence of using supplemental or pure oxygen for combustion is the capacity increase of any thermal assembly where a combustion process takes place, including glass melting furnaces.

In this paper it is given a mathematical model of the burning process of methane gas when using for combustion a mixture of air and oxygen. The math-ematical model consists of a set of equations for the mass balance referring directly to the reactants and combustion products, and also taking into consider-ation the gas dissociation reactions.

The results of the mathematical model are: the nature and partial pressure of the hot gases’ compo-nents, their volume, dissociation heat and theoretical temperature of the flame. A special attention is given to the gases which may have a pollutant effect when released into the atmosphere (CO2, CO, NOx).

In the same time, radiative power of the hot gases is calculated with respect to %O2 used for the com-bustion, and also with respect to the coefficient of air in excess.

Keywords: glass melting furnace, supplementary oxygen, combustion, dissociation.

0066 | Defects induced by γ– and laser beam irradiation and thermal behavior of silver nanoparticles in

tellurite glasses Júlia M. Giehl1, Walter Maigon Pontuschka1,

Luiz Carlos Barbosa2, Enver Fernández Chillcce2, Sarah I. P. M. N. Alves1,3,

Zélia M. Da Costa Ludwig4

1Instituto de Física da Universidade de São Paulo, 187 Rua do Matão – Travessa R, CEP 05508-090, São Paulo – SP, Brazil, e-mail: [email protected]

2Laboratório de Materiais Vítreos, UNICAMP, Box 6165, CEP 13083-970, Campinas – SP, Brazil

3Departamento de Ciências Exatas e da Terra, UNIFESP – Campus Diadema, Rua Prof. Artur Riedel, 275 – Jd. Eldorado, 09972-270 – Diadema – SP, Brazil

4Departamento de Física ICE, Universidade Federal de Juiz de Fora, CEP36036-330, Juiz de Fora – MG, Brazil

Precipitation of silver metal and/or oxide of nano-clusters embeddead in thermally treated Ag-Na ion-exchanged in tellurite glasses was investigated by OA. The Lorentzian-adjusted OA curves of silver nanoparticles plasma resonance were analyzed. Pre-viously γ-irradieted and laser beam samples exhibited TL peaks and the EPR spectra identified a TeOHC, NBOHC and TeEC centers, but no Ag0 response was detected. The silver nanoparticles are known to intro-duce desired third-order optical nonlinearities in the composites, at wavelengths close to the characteris-tic surface-plasmon resonance of the metal clusters.

Acknowledgments – FAPESP and CNPq (Instituto do Milenio de Fluidos Complexos), for the financial support.

Keywords: tellurite glasses, silver nanoparticles.

0069 | Chemical state of silanol group in silica particles studied by diffuse

reflecttance infrared fourier transform Toshio Suzuki*, Noriaki Shimodaira,

Kiyoshi Yamamoto Research Center ASAHI Glass Co., LTD. 1150

Hazawa-cho, Kanagawa-ku, Yokohama-shi Kanagawa 221-8755, Japan, e-mal: [email protected]

The chemical state of silanol groups in ground silica glass is investigated by means of diffuse re-flectance infrared fourier transform (DRIFT) spec-troscopy. IR method is especially useful to analyze the silanol groups because of much information, high sensitivity and easy preparation. DRIFT is easier than transmission method to analyze the ground silica glass. We have investigated the assignment and the behavior change of surface and interior si-lanol groups by measuring the ground silica glass in various humidity and heat-treated silica particles. It is succeeded that the surface silanol band is clearly distinguished interior one by analyzing the silica par-ticles which include the low silanol concentration. From the investigation to silica particles with the low



silanol concentration, the behavior change has been understood for surface and interior silanol groups as follows. Silanol concentrations on the silica surface are varied by grinding the silica glass in various hu-midity. By heat-treatment of the ground silica glass to 600 °C, the hydrogen bonded pair and geminal silanol groups are eliminated. Further heat-treatment of the ground silica glass up to 1100 °C leads to the dehydration of interior silanol group. However, the isolated silanol group on the silica surface is never dehydrated even at 1100 °C.

Keywords: silanol group, silica glass, silica particles, diffuse reflectance infrared fourier transfor, DRIFT.

0070 | Chemical state analysis of sulfur in glass by means of

conventional x-ray fluorescene Yuichi Suzuki*, Tatsuya Miyajima,

Masaya Matsunaga, Tomoyuki Tsujimura, Atsuyoshi Takenaka, Kiyoshi Yamamoto

Research Center ASAHI Glass Co., LTD. 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi Kanagawa 221-8755, Japan, e-mail: [email protected]

It is important to understand chemical state of various polyvalent ions in glass because a reduction-oxidation reaction of the polyvalent ion affects to glass quality such as bubble generation, coloration. In this study, the chemical state of sulfur has been investigated in soda-lime silicate glass by means of X-ray absorption fine structure (XAFS), X-ray fluores-cence (XRF).

From the XAFS investigation, sulfur exists only as sulfate ion or sulfide ion in the glass. In the XRF investigation, standard materials with various oxidation numbers indicate the chemical shift in a XRF spectrum (S-Kα), and the oxidation number shows a linear correlation with S-Kα peak energy value. That means measurement of average oxidation number in glass is possible using conventional XRF. Furthermore, Sulfur Redox (sulfide ion/Total sulfur) can be calculated by taking XAFS results in account.

Keywords: Soda-lime silicate glass, chemical state.

0072 | Green and red emissions in tellurite glasses doped with Er3 +/yb3 + and the influence of

metallic nanoparticicles Carlos T. Amâncio1, Davinson M. da Silva1,

Luciana R. P. Kassab2, Jonas J. Neto3, Niklaus U. Wetter 3, Cid B. de Araújo4

1Escola Politécnica da Universidade de São Paulo – EPUSP, São Paulo – SP

2Faculdade de Tecnologia de São Paulo – FATEC-SP – São Paulo – SP

3Instituto de Pesquisas Energéticas Nucleares – IPEN-SP – São Paulo – SP

4Departamento de Física – UFPE – Recife – PE, e-mail: [email protected]

Metal-dielectric nanocomposites like glasses con-taining silver and gold nanoparticles have been at-tracting large attention in the last years. In particular these materials doped with rare-earth ions are prom-ising materials since rare earth ions luminescence may be intensified in the presence of the nanopar-ticles. Both energy transfer between the nanopar-ticles and rare-earth ion and/or enhancement of local field which interacts with rare-earth ion located in the proximity of the nanoparticles may contribute for quenching, or enhancement of the luminescence. In this work we investigate for the first time the be-havior of infrared-to-visible upconversion (UPC) lu-minescence from Er3 + -Yb3 + doped TeO2-PbO-GeO2 glasses containing metallic nanoparticles (NPs). The enhancement of Yb3 + concentration normally causes the increase of the green and red emissions. The purpose of this work is to study the interference of the metallic nanoparticles in Yb3 + → Er3 + energy transfer mechanism The samples were prepared by the traditional method of melting/casting process. Optical excitation was achieved with a laser operating at 980 nm in resonance with the Yb3 + transition (4F5/2 → 4 F7/2 ). Transmission electron microscopy using a 200 kV equipment was performed to investigate the nucleation and growth of the nanoparticles.

Keywords: tellurite glass, upconversion luminescence, rare earth, metallic nanoparticles.



0075 | Er and Nd-doped yttrium aluminosilicates and yttrium

aluminozirconates Anna Prnová1, Radovan Karell1,

Alena Domanická1, Anna Piatriková1, Branislav Hruška1, Róbert Klement1,

Dušan Galusek1, Peter Šimurka2

1Vitrum Laugaricio, Joint Glass Centre of the IIC SAS, TnU AD, FChPT STU and RONA, a.s., Trenčín, Slovak

Republic, e-mail: [email protected]

2Institute of Inorganic Chemistry, Slovak Academy of Sciences, Bratislava, Slovakia

Er and Nd-doped yttrium aluminosilicates and aluminozirconates with SiO2 and ZrO2 content rang-ing from 5 to 20 mol. % have been prepared by flame synthesis from powder precursors in the form of glassy or partially crystalline microbeads with di-ameters up to 40 μm. The prepared glasses were characterized from the point of view of their basic properties (morphology, density, possible presence of crystalline phases, glass transition temperature, UV-VIS and photoluminescence characteristics), and the relations between the composition and the properties are discussed and evaluated. The microbeads are in-tended as precursors for preparation of bulk glasses by their sintering by viscous flow under pressure.

Keywords: yttrium aluminosilicate, yttrium aluminozirconate, Er and Nd doping, flame synthesis, microbeads, optical properties.

0076 | Thermodynamic instability near the glass transformation temperature

Valery B. Kokshenev Departamento de Física, Universidade

Federal de Minas Gerais – UFMG, Belo Horizonte, MG, e-mail: [email protected]

The structural transformation, happening under cooling rates preventing formation of the long-rage crystalline order, is essentially a crossover from the high-temperature thermally equilibrated ergodic state to low-temperature non-ergodic glassy states characteristic of amorphous solids. Similarly to Kauzmann’s thermodynamic instability indicating non-Arrhenius relaxation-temperature behavior, re-searchers have long searched for any signature of the underlying “true” ergodic-non-ergodic transition emerging at a certain ergodic-instability temperature Te. In this study, the relaxation timescale is analyzed within a self-consistent thermodynamic cluster description combined with the cluster percolation concept. The violation of the ergodic hypothesis is found through the crossover from the Gaussian to Poisson cluster-volume fluctuations, indicating at Te instability of the compact-structure “ergodic” clusters transforming into hole-like glassy structure. An equa-tion for the temperature Te is proposed in the mate-rial-independent form provided the ergodic instability boundary in different glass forming materials. This

boundary is tested by the experimental data avail-able for organic and inorganic supercooled liquids, glass-forming polymers and metal alloys. In all cases the temperature of ergodic instability is located below and close to the glass transformation temperature Tg, detected by differential scanning calorimetry. The financial support by CNPq is acknowledged.

Keywords: kauzmann catastrophe, ergodic theorem, time relaxation scale, glass models, cluster-volume fluctuations, amorphous solids, supercooled liquids.

0077 | Effects of glass forming histories on the crystallization

kinetic of the 20Li2O-80TeO2 glass Eudes B. Araújo, Elio Idalgo

Faculdade de Engenharia de Ilha Solteira, UNESP – Univ Estadual Paulista, Departamento de

Física e Química, CEP 15385-000, Ilha Solteira – SP, Brazil, e-mail: [email protected]

Physical properties of glasses depend strongly on the glass-forming histories. Residual stresses and the number of nuclei formed during glass prepara-tion present an intrinsic dependence with the ther-mal history of a glass. The adequate knowledge of the correlation between physical properties and the glass-forming history is indispensable for a correct interpretation of several processes in glasses, in particular the crystallization kinetic. In the present work, tellurite 20Li2O-80TeO2 glasses were prepared with identical nominal composition but with different glass-forming histories. Differential Scanning Calo-rimetry (DSC) and X-Ray Diffraction (XRD) techniques were used to study the effects of the glass-forming histories on the thermal and structural properties of these glasses. The γ-TeO2 (metastable), α-TeO2 and α-Li2Te2O5 phases were identified during the controlled devitrification in this glass. From DSC measurements, considering the deconvolution of the crystallization peak, the activation energies as-sociated to γ-TeO2 and α-TeO2 phases presented es-sentially the same value at around 296±3 kJ.mol-1, while the activation energy associated to α-Li2Te2O5 phase was 327±1 kJ.mol-1. DSC results suggested that heat annealing immediately after quenching at temperatures around Tg and longer times are favor-able to produce local ordered regions in the glass without necessarily increasing the nuclei number.

Keywords: crystallization, nucleation, tellurite.



0081 | Bi-incorporation effects in glassy arsenic selenides studied

with high-resolution XPS Sergey Kozyukhin1*, Roman Golovchak2,3,

Oleh I. Shpotyuk2, Bill Heffner3, Himanshu Jain3

1Institute of General and Inorganic Chemistry of RAS, Leninsky Pr. 31, Moscow 119991-

Russia, e-mail: [email protected] 2Lviv Scientific Research Institute of Materials of SRC “Carat”, 202, Stryjska str., Lviv, UA-79031 – Ukraine 3Department of Materials Science and Engineering,

Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015-3195 – USA

Enhancement of electrical conductivity with addi-tion of copper, indium, silver, calcium and some other chemical elements is generally observed in chalco-genide glasses (ChG), but none of them changes their p-type of conduction. In recent studies it has been reported that the Bi doping of some germanium chalcogenides can result in the sign reversal of the thermopower from p- to n-type. However, the struc-tural changes introduced by Bi in the vitreous matrix of Se-based ChG are not well understood up to now.

In this work, we have exploited high-resolution X-ray photoelectron spectroscopy (XPS) to estab-lish the role of Bi in the structure of typical Se-rich glasses, such as As-Se. Specifically, we have investi-gated changes introduced by a small addition (up to 4 at.%) of Bi in the electronic subsystem of As10Se90, As20Se80 , As30Se70 and As40Se60 ChG.

It is shown, that small addition of Bi (approximate-ly up to 1 at.%) into eutectic composition As20Se80 (i.e. As19Se80Bi1 glass) results in the formation of coordination defect pairs Bi4

+ – Se1- and As4

+ – Se1-.

Increase in Bi concentration (up to 4 at.%) leads to the formation of mixed As2Se3-Bi2Se3 nanocrystallites in all of the investigated glasses including the eutec-tic composition.

Keywords: chalcogenide glass, X-ray photoelectron spectroscopy, defects.

0083 | A link between structural glasses and supercooled liquids: first observation of the two-level tunneling

states via configurational entropy Valery B. Kokshenev

Departamento de Física, Universidade Federal de Minas Gerais – UFMG, Belo Horizonte,

MG, e-mail: [email protected]

Aiming to describe a universal behavior in amor-phous solids, independent from their chemical composition, Anderson with co-workers and Phillips independently proposed in 1972 a seminal tunneling two-level-system (TLS) concept. Remarkably that in 1965 the TLS hypothesis was anticipated by Adam and Gibbs who suggested the two-state minimal-size clusters in supercooled liquids (cooperatively rearranging regions) characterized by the minimal

configurational entropy (the excess liquid-over-solid entropy observable through the heat capacity in both supercooled liquids and crystals) Smin = kB lnP, with P = 2. However, in spite of much efforts made to verify the TLS hypothesis via thermodynamic measurements in glass forming polymers (P = 3 was reported), organic liquids (P>>2), and plastic crystals (e.g. P = 6, for cyanoadamantane) no TLS-similarity unifying all glasses was established. In this study we show that the researches did not take into consideration renormalization conditions imposed on the occupation numbers of relaxing units. New re-lationships between the observable thermodynamic and dynamic characteristics are therefore analyzed in light of the TLS concept in molecular liquids, some polymers and networks, available from the literature. As demonstrated, the glassy embryonic clusters are universal in all glass formers. The financial support by CNPq is acknowledged.

Keywords: configurational entropy, dynamic and thermodynamic glass models, amorphous solids, supercooled liquids.

0089 | Simulation of ultrashort heat pulses on vitreous thin plates – application to the determination of

dynamic constants André Monteil1*, Stéphane Chaussedent1

1 Université d’Angers, Laboratoire de Photonique d’Angers, 2, bd Lavoisier, 49045 Angers, Cedex 01 –

France, e-mail: [email protected]

When a thin plate is submitted to a mechanical perturbation it vibrates at proper frequencies with a damping depending on the microscopic properties of the materials. To provoke oscillations a heat im-pulsion acts like a mechanic one. Using Molecular Dynamics techniques we performed numerical simu-lations of silica thin plates (figure 1) submitted to thermal impulsions. We found that the damped oscil-lations (see figure 2) can be used to obtain both the sound velocity and other mechanical properties of the studied material together with their dependence in temperature. Submitting the sample to several successive thermal quenches, a quench echo was also observed as G.S. Grest et al. have proposed thirty years ago for a simple glass model [1]. The



physical properties that were drawn from these nu-merical experiments are strongly dependant on the atomic potential used in the simulation procedure.

Figure 1. partial view of the surface of the SiO2 plate. Silicon atoms are in yellow and oxygen atoms in red.

Figure 2. Pressure oscillation following a thermal quench from 1000 to 300K for a 14.3 nm thin plate of vitreous silica.

1. G.S. Grest, S.R. Nagel and A. Rahman, Solid State Commun. 36, 875 (1980)

Keywords: molecular dynamics, glass simulation, dynamic and thermal properties.

0091 | Supercontinuum generation using small core photonic crystal fibers

Enver Fernandez Chillcce1, Italo O. Mazali2, Aldario Boldonalli3, Cristiano Cordeiro1, Hugo Figueroa3, Luiz Carlos Barbosa1*

1Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin, Departamento de Eletrônica Quântica,

CEP 13083-900, Campinas – SP, Brazil 2Universidade Estadual de Campinas, Instituto de

Quimica, Cidade Universitaria Zeferino Vaz, CEP 13083-970, Campinas – SP, Brazil

3Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e Computação,

CEP 13083-970, Cidade Universitaria Zeferino Vaz, CEP13083-970, Campinas – SP,

Brazil, e-mail: [email protected]

In this work we study the supercontinuum gen-eraton using small core silica photonic crystal fibers (PCFs). The core of the PCFs varying from 1.0 to 2.0 μm was possible changing the external fiber diam-

eter. The PCFs have structures which consist of small hollows. The supercontinum light, that extends from blue to near infra-red region, was obtained using a femtosecond 785 nm Ti:Saphire laser with 450mW pump power. The blue light generated is very intense, which could be used to fluorescence applications as biological.

Keywords: photonic crystal optical fiber, nonlinear optical fiber, supercontinuum generation.

0096 | Structure and properties of strontium niobium phosphate glasses *J.J. Wu1, S.W. Yung1, Y.S. Haung1, Jian Lin2

1Department of Material Science and Engineering, National united university, Miao-Li 36003, Taiwan

2School of Material Science and Engineering , Tongji University , Shanghai 200092, China

The structures and optical properties of Nb2O5-SrO-P2O5 glasses have been generally investigated by using Raman spectroscopy, Fourier transform infrared spectroscopy, O1s X-ray photoelectron spectroscopy and 31P solid state NMR. From the results of Fourier transform infrared spectroscopy, adding Nb2O5 to the glasses as the intermediate results in the form of P-O-Nb bonds and Nb-O-Nb bonds. When the con-tent of P2O5 >50 mole%, the Nb2O5 plays the role of glass network modifier. Moreover, the NMR spectra indicated that the glass structures of Q3 and Q2 are transferred to those of Q2 and Q1, respectively, as the content of Nb2O5 increases. However, the numbers of Nb-O-Nb bonds and [NbO6]3d bonds are increased when the content of P2O5 <50mole%, due to Nb2O5

plays the role of glass network former from the inter-mediate. When P2O5 decreases to 30 mole%, [NbO6] transferred to [NbO4] and produces new bonds Nb-O-Sr. P2O5/SrO ratio is also utilized to estimate the absorption intensity of the glasses. When the ratio is greater than 1, the addition of Nb2O5 results in the strong absorption during the wavelength region of 400~850nm. The absorption peak significantly increases as the content of Nb2O5 increases. On the contrary, the phenomenon of the absorption is not occur and the transmittance of the glass slightly decreases.

Keywords: refractive index, niobium, visible spectroscopy, raman spectroscopy , X-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy, phosphate glass.



0098 | Composition and temperature dependences of elastic properties on

lithium germanate glasses Kazuhiro Kaneda, Seiichi Mamiya*,

Yu Matsuda, Seiji Kojima Graduate School of pure and Applied Sciences,

University of Tsukuba, Tsukuba, Ibaraki 305-8573, Japan, e-mail: [email protected]

Elastic properties of glassy materials are the cur-rent topics in material sciences. The microscopic structure of alkali germanate glasses, which are utilized as the optical fiber and infrared transmitting glass, changes dramatically with the composition. Physical properties also show the marked tempera-ture dependence above a glass transition tempera-ture (Tg). Therefore, it is important to measure the elastic properties such as sound velocity and elastic moduli over the wide temperature range from 25 oC to 1100 oC.

It is difficult by the conventional ultrasonic pulse-echo method to measure the elastic properties of the thin and fragile glasses and at high temperatures. Only Brillouin spectroscopy enables us to investigate the elastic properties of such samples at high tem-peratures by using a finely focused laser beam with no contact and no destruction of a sample.

In this study, the composition dependences of lithium germanate glasses (LGG) are investigated at room temperature, and temperature dependences of the selected compositional glasses are investigated up to 1100 oC using a compact infrared image fur-nace, by a Sandercock-type Fabry-Perot interferom-eter.

Keywords: elastic property, glass transition, sound velocity, high temperature, Brillouin spectroscopy, lithium gernmanate glass (LGG).

0099 | Influence of doping upon the structure and optical characteristics

of amorphous Ge2Sb2Te5

Sergey Kozyukhin1,*, Vera Kudoyarova2, Huy Phuc Nguyen1, Alexey Smirnov2, Viktor Lebedev3

1Kurnakov Institute of General and Inorganic Chemistry, RAS – Leninsky Pr., 31 – Moscow, 11999 –

Russia, e-mail: [email protected] 2Ioffe Physico-Technical Institute, RAS –

Politekhnicheskaya, 26 – St-Petersburg, 194021 – Russia 3Konstantinov Institute of Nuclear Physics, RAS – Orlova Roshcha, Gatchina, Leningrad region, 188300 – Russia

Ge2Sb2Te5 (GST) is one of the materials that are commonly used as a data storage media for phase change random access memory (PCRAM). In this study, the influence of doping with Bi, Sn or In upon the structure and the optical characteristics of GST has been determined using a variety of techniques including Raman micro-probe spectrometry, X-ray diffraction (XRD), Rutherford backscattering (RBS)

(backscattering of deuterons with energy Ed = 1 MeV) and a variable incident angle spectroscopic ellipsometer.

The films were thermally evaporated in the vacuum chamber onto unheated substrates using previously synthesized compositions. The RBS data have shown that distributions of all dopants on a thickness of the films are uniform. Doping maintains the NaCl-type crystalline structure of GST but expands the lattice due to the larger atomic radii of dopants. The Raman spectra of all amorphous films performed two broad peaks B = 130 cm–1 and C = 150 cm–1 which could be interpreted as different vibration modes of het-eropolar bonds in GeTe4-nGen tetrahedron. The doping causes the changing of Raman shift and it testifies to the changing of chemical bond lengths and bond-ing angles. The optical properties of the films were determined under two incident angles of 600 and 700 by a spectroscopic ellipsometer operating from 0.12 to 3.27 eV. It was shown that the optical contrast in the doped samples increases steadily with increas-ing wavelength and shows a high optical contrast of more than 20% in the wavelength range of 400 to 1000 nm.

Keywords: chalcogenide films, Raman spectroscopy, phase change memory.

0100 | Surface shape reconstruction from reflection image of color

striped pattern Yoshiyuki Sonda*

Asahi Glass Co., Ltd. Production Technology Center, Yokohama-shi, Kanagawa, 230-0045,

Japan, e-mail: [email protected]

We present a new method to measure surface shape of automotive glass. The method is based on reflection image analysis and enables non-contact measuring. Therefore, it can be applied to online inspection and quick feedback to forming process. The distinction between the method and others is that color imaging system is introduced for accurate reconstruction. Our measurement system consists of multiple color cameras, a reference pattern and PCs. The reference pattern printed with 8 colors has both vertical and horizontal striped patterns. PCs calculate normal vector distribution of target glass from reflec-tion images. Color information helps for specifying position of reference points and accurate calculation of normal vector. PCs finally output surface shape by numerical integration. We compare the proposed method with contact measurement method. Experi-mental results on actual automotive glass show ef-fectiveness of our method.

Keywords: surface shape reconstruction, 3D-measurement, reflection image, online-inspection, automotive glass.



0105 | Structural features in multicomponent aluminosilicate glass-ceramics revealed by solid-state NMR

A. Ananthanarayanan 1,2, G.P. Kothiyal 2, L. Montagne 1* and B. Revel1

1*Université Lille Nord de France F-59000 Lille – France, Unité de Catalyse et de Chimie du Solide, UMR-CNRS 8181, USTL F-59652,

e-mail: [email protected] 2Technical Physics and Prototype Engineering Division, Bhabha Atomic Research Centre,

Mumbai 400085, India

Glass-ceramics are polycrystalline materials formed by controlled crystallization of glasses, which exhibit outstanding thermo-physical, mechanical and chemical properties. As a result, glass-ceramics find application in hermetic sealing for various applica-tions, for instance in Solid Oxide Fuel Cells (SOFC). The properties of glass-ceramics can be optimized by controlling the type and morphology of crystalline phases, which are generally characterized with XRD.

We present here a set of results from multinuclear NMR that brought new information complementary to XRD, but also provided specific insights into the structure of glass-ceramic materials. Phase separa-tion could indeed be detected before crystallization occurred, and an unexpected boron-containing crys-talline phase has been observed on NMR spectra. NMR also enabled us to conclude that P2O5 does not act as a nucleating agent for alumino-silicate and zinc silicate glasses. In addition, using NMR we could also study the evolution of the residual glass during the nucleation and growth processes, and relate it to the nature of the crystalline phases that are formed.

We shall also illustrate the application of multi-nuclear NMR on alkali/alkaline earth based glasses used for sealing applications. Despite the multi component compositions, we were able to extract valuable structural insights that are complementary to XRD.

Keywords: glass-ceramics, MAS-NMR, crystallization.

0110 | Phosphorous oxynitride glasses: properties, structure and their potential

application as solid electrolytes Nerea Mascaraque,

Francisco Muñoz*, Alicia Durán Instituto de Cerámica y Vidrio (CSIC), Kelsen 5, 28049,

Madrid (Spain), e-mail: [email protected]

Solid state electrolytes for rechargeable batter-ies have attracted much attention in the last years because of the numerous advantages they provide respecting to the use of liquid ones. Within this field, glassy electrolytes, such as lithium sulphides or phosphates, are playing a major role. This con-tribution presents a review of the state of the art of oxynitride lithium phosphate glasses for lithium bat-

tery applications. First, the properties of LiPON bulk oxynitride glasses are described. From the structure of oxynitride glasses belonging to the binary sys-tem Li2O-P2O5, as determined by Nuclear Magnetic Resonance, a model for the increase in the electrical conductivity as a function of the nitrogen content has been proposed. Secondly, the mixed former effect in phosphate glass compositions is studied as well as the suitability of their nitridation. The results on glasses with composition Li2O-M2O3-P2O5 (M=B,Al) and their oxynitride counterparts are presented. The addition of either former or intermediate second ox-ides in the glass composition, as well as the nitrogen/oxygen substitution through ammonolysis, produces notable increments in the ionic conductivity of the parent phosphate glasses. Fluorine containing lithium phosphate glasses are also being synthesized and their nitridation explored, which have demonstrated to be compatible.

Keywords: oxynitride glasses, solid-state electrolytes, lithium batteries, electrical conductivity, glass structure

0111 | Influence of dopants on the processes of local inelasticity in selenium

Alexander Gorshkov1, Anastasia Kabanskaya1, Sergey Kozyukhin2*, Viktor Lomovskoy1

1A.N.Frumkin Institute of Physical Chemistry and Electrochemistry, RAS – Leninsky Pr., 29 –

Moscow – Russia 2Kurnakov Institute of General and Inorganic

Chemistry, RAS – Leninsky Pr., 31 – Moscow – Russia, e-mail: [email protected]

The study of the glassy and crystal selenium was carried out by the method of an internal friction. It was shown that three relaxation processes were observed in the glassy selenium on the temperature dependence curve of dissipative losses at constant frequency of external deforming influence. These pro-cesses were observed at different temperatures. The basic kinetic unit of these processes is a structural -Se-Se- unit and these units induce the phenom-ena of local inelasticity (occurrence of the module defect). The studied inelasticity processes were ob-served at the temperatures much below than that for thermal decay of covalent bonds in selenium. The mechanism of occurrence of the observed relaxation processes is caused by the mobility or ability of the internal rotation of the structural – Se – Se – unit. The observed internal rotation is realized at microscale and segmental structural levels.

The studying of influence of the amorphous and crystal selenium phase mix on relaxation phenomena is carried out in the present work. The crystal phases of selenium represent itself a hexagonal crystal structure (γ – selenium) and a monoclinic crystal one (α – selenium). The role of dopant atoms (sulphur and tellurium) is revealed in relaxation dissipative



processes, and the changes of physic-mechanical (elasticity modulus) and thermodynamic (free activa-tion energy) characteristics are calculated.

This study was supported by RFBR (projects 10-01-00534 and 09-03-90456).

Keywords: selenium, internal friction, relaxation processes.

0112 | Spectroscopy of CR3 +, Nd3 +

co-doped borosilicate glass: Towards a solar-energy-pumped laser gain medium

M. Hughes1*, S. Mizuno2, H. Ito2, K. Hasegawa2, T. Suzuki1 and Y. Ohishi1

1Research Center for Advanced Photon Technology, Toyota Technological Institute, 2-12-1 Hisakata,

Tempaku, Nagoya 468-8511, Japan 2Frontier Research Center, Toyota Central R&D Labs., Inc, Nagakute, Aichi 480-1192, Japan,

e-mail: [email protected]

We present the spectroscopy of a novel Cr, Nd co-doped borosilicate glass which may have applications as a solar energy pumped laser gain medium. Cr-doped borosilicate glass displays three broad absorp-tion bands centered at 359, 444 and 642 nm. These are attributed to transitions to the 4T1(

4P), 4T1(4F) and

4T2(4F) states of Cr3 + in octahedral coordination, re-

spectively. Emission, when excited at both 455 and 655 nm, peaks at 855 nm with a width of 250 nm. The quantum efficiency (QE) of this emission was 0.6%. We calculated the crystal field strength (Dq/B) on the Cr ion to be 2.15 and the C/B ratio was 4.32. In the of Nd-doped borosilicate glass, the QE and lifetime decreased as the Nd content was increased from 0.1 to 1 mol.%. In the co-doped glass, Cr is used as a sensitizer to increase the absorption efficiency of broadband excitation. We measured the efficiency of the transfer process from Cr to Nd by measuring the QE of a pair of samples; one was co-doped, the other was doped with Nd only. The transfer QE had a maximum of 20% at Nd and Cr concentrations of 0.5 and 0.1 mol.%, respectively.

Keywords: solar laser, borosilicate, glass.

0118 | Effect of nucleating agent on crystallization process

of kinescope glass cullet Manuela Reben1*, Jan Wasylak1, Magda Kosmal2

1AGH-University of Science and Tachnology in Cracow, Faculty of Materials Science and

Ceramics, al. Mickiewicza 30, 30-059 Cracow, e-mail: [email protected]

2Institute of Ceramics and Building Materials Division of Glass and Building Materials,

Lipowa 3, 30-702 Cracow

The aim of the paper was to investigate the crys-tallization process of kinescope glass cullet nucleated by TiO2. The glass cullet was taken from the front part

of CRT based on barium-strontium glass, free of lead. With the aim of valorising these waste glasses, in this paper preliminary results reached on the possibility of transforming glass cullet into glass ceramic used as was presented. The barium silicate glass-ceramics were developed in the SiO2-Al2O3-BaO-SrO-Na2O-TiO2 system. The hetereogeneous nucleation agent TiO2 was added to the base glass. The effect of crystalliza-tion produced by addition of TiO2, to glass-ceramic was studied using structural and thermal techniques. The nucleation and crystallization experiments were carried out on the basis of differential thermal analy-sis (DTA/DSC), X-ray diffraction (XRD), scanning elec-tron microscopy (SEM).)

Keywords: glass ceramic, nucleating agents, silicates, glass cullet.

0119 | The weight decrease of glass packaging using various methods BB,

PB, NNPB and hot end coating Krzysztof Czarnacki1, Piotr Nieprzecki2,

Jan Wasylak3*

1Pol-Am-Pack S.A. Odział Huta Szkła “ORZESZE” w Orzeszu

2Pol-Am-Pack S.A.., ul. Jasnogórska 1, 31-358 Cracow, Poland

3*AGH – University of Science and Technology in Cracow, Faculty of Materials Science and Ceramics,

al. Mickiewicza 30, 30-059 – Cracow, e-mail: [email protected]

The aim of the thesis is to show research results of the mechanical resistance of glass containers us-ing a new method of hot-end coating by nanopar-ticles of aluminum compounds. The research results of internal pressure, vertical load resistance and im-pact resistance of glass packaging was shown. One of the most common methods of forming small glass containers alongside the Blow & Blow method is the Narrow Neck Press & Blow method. The use of this method gave the possibility of much better control of glass distribution in glass packaging which brought about the possibility of decreasing more than 20% of the weight of glass containers without influencing the mechanical resistance. The Narrow Neck Press and Blow process gave the possibility to decrease the wall thickness of glass containers in comparison to the Blow & Blow and Press & Blow methods; a possibility which is to be explained in the following thesis.

Keywords: BB, PB, NNPB methods, aluminum compound, hot end coating.



0120 | InvestiGation of nickel sulphide inclusions in soda lime flat glass

Manuela Reben1*, Jan Wasylak1, Sebastian Bielecki2

1AGH-University of Science and Tachnology in Cracow, Faculty of Materials Science and Ceramics, al.

Mickiewicza 30, 30-059 Cracow, e-mail: [email protected]

2Glassworks “EWA”, ul. Stalowa 27, 33-103 Tarnów, Poland

A problem of the spontaneous tempered glass breakage caused by nickel sulphide inclusion is dis-cussed. The studies proved that formation of nickel sulphide in the glass melt during manufacturing process is very difficult, moreover in some cases not possible. The various sizes of NiS inclusions were introduced to flat glass panels during a high temperature process. The panels were annealed and next tempered. The tempered glass panels, which included the NiS stones, were investigated by mi-croscopic (SEM) method and characterized by EDAX analysis. The sizes of all nickel sulphide inclusions were defined. The samples were analysed by elas-tooptic studies. The heat soak test was carried out on the glass panels. The obtained results will help to solve the problem of forming nickel sulphide inclu-sions.

Keywords: soda lime flat glass, nickel sulphide inclusion, spontaneous glass breakage.

0121 | Deposition of inorganic-organic, color coating on glass; physic-chemical

and technological aspects Maria Łączka1*, Marek Nocun1,

Agnieszka Terczyńska1, Sławomir Kwaśny1, Edward Szneler2, Katarzyna Cholewa-Kowalska1

1AGH University of Science and Technology, Faculty of Materials Science and Ceramics,

Departament of Glass Technology and Amorphous Coatings, Krakow, Poland, e-mail: [email protected]

2Jagiellonian University, Faculty of Chemistry, Krakow, Poland

Properties modification of glass products by thin coatings deposition of various functionality is popular method in the glass processing. One of the solutions, in this case, is deposition of coloured sol-gel coating ORMOCER characterized by various, intensive colour and good mechanical and chemical properties. In our research coloured organic-inorganic coatings TGTi and TGZr on glass plates and bottles were ob-tained by two methods: dip-coating and spraying. The hybrid host TGTi matrix were prepared of TEOS (tetraethyloorthosilicate), GPTMS (3-glycidoxypropyl-trimethoxysilane) and TEOT (tetraethyloorthotitanate) while TGZr host matrix has been prepared of TEOS, GPTMS and TPOZ (zirconium tetrapropoxide). Organic dyes of ORASOL type were used in order to obtain the colour. The 29Si MAS NMR study and viscosity measurements were conducted for sols after various

periods of their ageing. It has been found that kind of used inorganic modifiers (Ti- and Zr-compounds) do not influence on kinetic of hydrolysis and poly-condensation reactions in examined sols. However, the changes of TGTi sol viscosity with a time were faster than that of TGZr sol. It indicates that faster formation of TGTi gels is first of all caused by physi-cal agglomeration of sol particles. From our research it follows that viscosity of sol influences on quality, thickness and colour intensity of hybrid coatings. On this base the most favourable viscosity values of sol has been established for both deposition process: dip-coating and spraying.

Keywords: sol-gel process, hybrid materials, NMR spectroscopy, dip-coating method, sol viscosity.

0123 | Sol-gel bioglass as component of biocomposites

J. Kokoszka1*, K. Cholewa-Kwalska1, M. Laczka1

1AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Deptartament of Glass Technology and Amorphous Coatings, Krakow,

Poland, e-mail: [email protected]

Ceramic materials called bioglasses are char-acterized by the ability to create permanent and stable bond with bone tissue, and can stimulate the bone tissue to faster regeneration. Bioglasses can be obtained by melting method or sol-gel process. Gel-derived bioglasses show higher bioactivity than melted ones due to high surface area and lower temperature processing resulting in presence SiOH groups on the surface.

Incorporation of gel-derived bioactive glass into a metal, polymer or hydroxyapatite matrix offers signifi-cant biological advantages like promotion of bioac-tive properties of material and its better integrity with the host tissue. In this study we manufactured three kinds of composites based on: Titanium or PGLA or HA with gel-derived bioglass as a component.

The composites were fabricated in form of foils (PGLA/Bioglass) and pellets (Ti/Bioglass and HA/Bio-glass). Obtained materials were characterized under phase composition (X-ray diffraction) and mechanical properties. Incorporation of bioglass into PGLA and HA matrix resulted in improvement of mechanical properties in comparison with based materials. The objective of this study was to investigate behaviour of these materials after exposure in a simulated body fluid (SBF). We expected that the bioglass additions can promote apatite formation on the materials sur-face during contact with SBF which indicates bioac-tive properties of materials. Surface characterization was carried out by scanning electron microscopy with EDAX analysis before and after immersion in SBF.

The Ti/Bioglass composites showed initial stage of crystallization of apatite forms after 14 days in SBF, PGLA/bioglass and HA/bioglass composites de-



veloped a uniformly apatite layer after contact with simulated body fluid for 10 or 14 days which indi-cates high bioactive properties of these materials.

Keywords: bioglass composites, hydroxyapatite, titanium, PGLA, bioactivity, simulated body fluid.

0124 | Residue flat glass: recycling in the form of filler in asphalt mixturesVilany S. Pereira*, Crislene R. da S. Morais,

Edna L. da Silva, Albaniza A. TavaresUniversidade Federal de Campina Grande – UFCG,

Campus de Campina Grande, Campina Grande – PB, e-mail: [email protected]

The environmental impacts caused by the action of man over nature, has grown dramatically in recent years due to technological development. As a result, there is an increase in the consumption of raw ma-terials and production of solid waste. The recycling of solid waste generated by industries for use as alternative raw materials has been carried out suc-cessfully in many countries, aimed at concerns about the environment, improving health and safety of the population, etc. One of the aspects of this practice is the paving. This study aims to evaluate the use of waste flat glass as a filler in asphalt mixtures. To this end, promoted characterization tests of glassy residue, such as infrared spectroscopy, chemical analysis, diffraction of X-ray, among others, in order to obtain their chemical. It was realized, mechani-cal tests on asphalt mixture as a whole in order to evaluate the physical and mechanical stability. It can be concluded that the effect of, waste glass on the asphalt mixture does not differ from those made with conventional materials and may be, so, used effec-tively in asphalt paving.

Keywords: recycling, characterization, paving.

0125 | Coordination and valence state of transition metal

ions in alkali borate glasses Agnieszka Terczynska-Madej1*, Katarzyna

Cholewa-Kowalska1, Maria Laczka1

1 AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Department of Glass and Amorphous Coatings Technology, Ave. Mickiewicza 30, Cracow, Poland, e-mail: [email protected]

Borate glasses of the type 20R2O·80B2O3, where R = Li, Na and K, were coloured by doping with transition metal ions (Co, Ni, Cr and Mn). The glasses were obtained by melting at the temperature 1150 oC. For these glasses were recorded optical ab-sorption in UV-NIR range. Analysis of the spectra al-lows to determine coordination and oxidation states

of the doping transition metal ions. Changes of their coordination or oxidation are presented as a function of the optical basicity Λ after Duffy.

Cobalt and nickel occur in examined borate glass-es as divalent ions (Co2 + , Ni2 + ) mainly in octahedral coordination, but tetrahedral coordination state of cobalt is also possible. Chromium and manganese occur in borate glasses in various oxidation state, though Cr3 + and Mn3 + ions in octahedral coordina-tion are dominant. A decrease of the electronega-tivity of the modifiers (Li→Na→K) and increase of the glass matrix basicity cause a shift of oxidation/reduction equilibrium towards higher valence of the transition metals (Cr6 +, Mn3 +).

Keywords: transition metal ions, coordination environment, oxidation state, UV-NIR spectroscopy, optical basicity.

0129 | Evoluation of screw-caps closure for pharmaceutical glass container

Sandra Balan M. Jaime1*,, Rosa M. V. Alves1, Paula Fernanda Janetti1, Danielle Ito1

1* Centro de Tecnologia de Embalagem – CETEA do Instituto de Tecnologia de Alimentos – ITAL,

Campinas – SP, e-mail: [email protected]

The purpose of this study was to evaluate the influence of the torque of plastic screw-caps ap-plied to glass containers for pharmaceutical products relative to tightness and moisture barrier properties. It was evaluated 5 types of glass containers with nominal capacity ranging from 30 to 200 mL and finish diameters of 18, 24 and 28 mm. The screw-caps were applied on the glass containers with two torque intensities, as suggested at the United States Pharmacopoeia. The storage test was conducted during a period of 90 days under conditions of con-trolled temperature (40 ± 2) °C and relative humidity (75 ± 5)%RH to determine the water vapor trans-mission rate (WVTR) of the glass packaging system. Glass has a high moisture barrier property due it is free of porosity which was confirmed in the WVTR re-sults, especially when tightness and effective closure system. A small decrease in the WVTR results was observed for the glass packaging with largest finish diameter, regardless of the nominal capacity of the glass container. The intensity of application torque did not show a significant influence in the WVTR pa-rameter.

Keywords: pharmaceutical glass container, torque, wvtr – water vapor transmission rate.



0133 | Physical properties and structure of alkali borovanadate glasses

Joseph North*1, Jason Maldonis1, Alexander Ramm1, Steve Feller1, Heidi Feller2,

Ashlea Betzen1, Mario Affatigato1, Scott Kroeker3, and Vladimir Michaelis3

1Coe College, Cedar Rapids, Iowa, USA, e-mail: [email protected]

2Simpson College, Indianola, IA, USA 3University of Manitoba, Winnipeg, Manitoba, CA

We have studied the physical properties of alkali borovanadate glasses of the form RM2O.B2O3.KV2O5. Our specific goal was to obtain measurements of the glass forming limits, the glass transition tempera-tures (Tg), and densities and relate them to models for the atomic arrangements. The glass families stud-ied include lithium and cesium borovanadates across a wide range of alkali-to-boron ratios (R), for several fixed borovanadate ratios (K). 11B and 51V NMR data were measured and used in this study.

Work supported by NSF under grant number DMR 05020518 and DMR 0904615.

Keywords: NMR, structure, borovanadates, Tg, density.

0134 | Effect of refractive index profile on bending induced optical

loss of bend-insensitive optical fiber Seongmin Ju1, Pramod R. Watekar2,

Seongmook Jeong1, Youngwoong Kim1, Young Sik Yoon3, Yeong Seop Lee3, Jinhan Kim3, and Won-Taek Han1,2*

1*Graduate Program of Photon Science and Technology 2Graduate School of Information and Mechatronics, Gwangju Institute of Science and Technology – 261 Cheomdan-gwagiro, Buk-gu, Gwangju, South Korea

3Samsung Electronics Hainan Fiberoptics-Korea Co. Ltd. – 94-1, Imsoo-Dong, Gumi, Gyeong-Buk, South

Korea, e-mail: [email protected]

With the advent of fiber-to-the-home (FTTH) ap-plications in the optical fiber communication, much attention has been paid by various research groups to manufacture bend-insensitive optical fibers with innovative designs satisfying the requirements of the FTTH standard [1,2]. Several methods have been proposed to get better bend-insensitivity with single-mode condition, which are the typical examples of the so-called bend-insensitive optical fibers (BIFs), such as modification of mode-field diameter, incor-poration of nano-hole cladding layers, and depres-sion of cladding index. However, these methods are complex, expensive and have limited bend insensitiv-ity of 1~0.03 dB/loop at 10 mm of bending diameter and also have a difficulty in splicing with the com-mercial single-mode optical glass fiber.

In this paper, we report the fabrication of the BIFs with low-index trench by the modified chemi-cal vapor deposition and fiber drawing process. The

BIFs showed the tremendously low bending loss of 0.005 dB/loop at 1550 nm for the bending diameter of 10 mm. We have also investigated regarding the effect of trench structures on bending insensitivity. As the width of low-index trench of the fiber increased, the bending loss was found to decrease. It was also found that the addition of depressed cladding lay-ers and low-index trench next to core of the fiber is attractive because of no change in core diameter, so that no difficulty regarding the splicing with com-mercial single mode fiber arises.1. Draka (2009), BendBrightXS at http://www.

drakafibre.com.2. P. R. Watekar, S. Ju and W. –T. Han, “Single-

mode optical fiber design with wide-band ultra low bending-loss for FTTH application,” Optics Express, 16, 1180-1185 (2008).

Keywords: fiber-to-the-home, optical fiber, bend-insensitive optical fiber, low-index trench cladding layer, bending loss, modified chemical vapor deposition, draw tower.

0137 | A method to measure the surface viscosity of nano-scale

particles by using the cylinder model based on the viscous sintering

Long Shao*, Tadayuki Inaba, Akio Koike, Yasuji Fukasawa

Research Center, Asahi Glass Co., Ltd., 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa, 221-8755, Japan, e-mail: [email protected]

Cylinder model, which is proposed by Scherer, is widely used to predict the viscous sintering rate of nano-scale particles. However, our experimental results showed that sintering rate predicted by us-ing bulk viscosity in the cylinder model tended to be different from the actual sintering rate. It appeared that the surface viscosity, which is necessary in the model, was different from the bulk viscosity. In this study, the surface viscosity of nano-scale silica par-ticles was obtained by fitting the viscous sintering rate of the sintering experiments. As a result, the surface viscosity obtained from sintering rate was lower than the bulk viscosity under the same tem-perature. Furthermore, the surface viscosity wildly varies depending on the water vapor concentrations in the atmosphere. From these results, the changes of the activation energy of the surface viscosity with the water vapor concentrations were estimated. Fi-nally, our prediction method of the viscous sintering rate of nano-scale particles as well as the surface viscosity of the particles was confirmed by comparing the simulation results of the sintering rate under a different temperature with experimental results.

Keywords: nano-scale particles, surface viscosity, bulk viscosity, sintering rate, activation energy, viscosity sintering, cylinder model



0138 | Design of nonlinear optical KNbO3 based crystallized

glasses and crystal line patterningKeitaro Kioka, Tsuyoshi Honma,

Takayuki Komatsu Department of Materials Science and Technology,

Nagaoka University of Technology, 1603-1 Kamitomioka-cho, Nagaoka 940-2188, Japan,


Nonlinear optical KNbO3 based crystals were synthesized from 40K2O-25Nb2O5-35B2O3 (KNB), 40K2O-25Nb2O5-25B2O3-10Al2O3 (KNBA) or 20K2O-10Na2O-25Nb2O5-45SiO2 (KNNS) glasses by using a conventional glass-ceramics method. The KNB glass without Al2O3 precipitates KNbO3 phase together with an impurity phase, but the KNBA glass with Al2O3 pre-cipitates only KNbO3 phase. It was also found from X-ray diffraction analysis that KNNS glass precipitates only (K,Na)NbO3. Crystallized samples showed clear second harmonic generations. For laser patterning of KNbO3 and (K,Na)NbO3, CuO-doped (2 mol%) KNB, KNBA, and KNNS glasses were prepared, and Yb:YVO4 fiber laser (wavelength: λ=1080 nm) was irradiated onto their glass surfaces. In laser irradiations (power: P = 0.9 W, scanning speed: S = 8 mm/s) to CuO-doped KNB glass with an optical absorption coefficient of α = 4.5 cm-1 at λ = 1080 nm, only a metastable phase was crystallized, but in laser irradiations to CuO-doped KNBA glass with α = 4.2 cm-1 the formation of KNbO3 crystals was confirmed from micro-Raman scattering spectrum measurements. (K,Na)NbO3 crystals were patterned on the surface of CuO-doped KNNS glass with α = 5.0 cm-1 by laser irradiations (P = 1.2 W, S = 7 mm/s). The effect of Al2O3 and Na2O additions on the formation and morphology of KNbO3 based crystals was discussed.

Keywords: glass, KNbO3, laser-induced crystallization.

0139 | Crystallization and spectral analysis of Sm3 + doped

CaO-Al2O3-SiO2 glass ceramics Peijing Tian*, Jinshu Cheng,

Ye Liu, Weihong Zheng Key Laboratory for Silicate Materials Science and

Engineering of Ministry of Education, Wuhan University of Technology-Wuhan 430070-China,


Sm3 + doped CaO-Al2O3-SiO2 glass ceramics have been prepared via sintering. The crystallization and optical properties of the glass ceramics were studied by X-ray diffraction, scanning electron microscope, and fluorescence spectra. The results showed that the main crystal phase in the glass ceramics was wollastonite (CaSiO3), as well as little anorthite (Ca(Al2Si2O8)), and the glass ceramics can emit red light under the excitation of long UV and blue lights.

With the content of Sm3 + gradually increasing, the luminescent intensity of the glass-ceramics also in-creased. The luminescent intensity of glass-ceramics is much larger than the corresponding glass, and the heat treatment time has little effect to the glass-ce-ramic microstructure, morphology and luminescence properties.

Keywords: luminescence, crystallization, CaO-Al2O3-SiO2, glass-ceramics, Sm3 +, wollastonite, anorthite.

0146 | Effect of ZrO2 on the chemical durability of bismuth-based glass

Catia Fredericci1*, Henry Felelgara2

1Instituto de Pesquisas Tecnológicas do Estado de São Paulo – IPT- São Paulo – SP

2 Ticon Tintas Condutivas Ltda – Diadema – SP, e-mail: [email protected]

Glasses that fuse at low temperature and pres-ent low toxicity, containing Bi2O3, SiO2, and B2O3 have been developed as lead-free glasses for glass enam-els for automotive application in black bands and defrosting systems. Nowadays, there is a tendency to increase the severity of corrosion test for these enamels. More rigorous chemical durability tests of them have been developed, specially using hot acidic medium due to the aggressive environmental conditions that this material are submitted, such as acid rain. In this work it was studied the chemical durability of Bi2O3-SiO2-ZnO-TiO2-ZrO2-B2O3 glass thick films, heat treated previously at 700oC/5min, in acidic medium (0,1 N H2SO4, 80oC). Surfaces of the attacked samples were analyzed by scanning electron microscopy, energy dispersive spectroscopy, micro-Raman spectroscopy, infrared spectroscopy and X-ray diffraction. The heated thick film presented Bi4Ti3O12 besides Bi4(SiO4)3 and Zn2SiO4 as crystalline phases dispersed in the glass matrix. The results indi-cated that ZnSiO4 and the glass matrix were severely attacked by the acidic solution. Bismuth titanate and bismuth silicate did not show any marked attack.

Keywords: chemical durability, bismuth, automotive, crystallization.

0148 | Internal residual stresses in sintered and commercial low expansion

Li2O-Al2O3-SiO2 (LAS) glass-ceramics Francisco C. Serbena1*, Viviane Oliveira Soares2,

Oscar Peitl2, Edgar D. Zanotto2

1*Department of Physics, State University of Ponta Grossa, PR, Brazil, e-mail: [email protected]

2LaMaV – Vitreous Materials Laboratory, Department of Materials Engineering,

Federal University of São Carlos, SP, Brazil

XRD measurements of thermal residual stresses using Synchrotron radiation in monolithic samples of a newly developed LAS glass-ceramic produced by sintering and in a commercial LAS glass-ceramic,



CERAN® (produced by the traditional nucleation and growth treatments), revealed that the residual stress level is negligible. This result contradicts predictions of theoretical modeling. Grain-boundary microcrack-ing due to the thermal expansion anisotropy of vir-gilite is an unlikely mechanism. The elimination of stress was attributed to microcracking of the residual glass phase in the microstructure.

Keywords: residual stress, glass-ceramic, Li2O-Al2O3-SiO2, Virgilite, X-ray diffraction, microcracking.

0152 | Sintered low expansion Li2O-Al2O3-SiO2 (LAS) glass-ceramic

Viviane O. Soares1, Oscar Peitl2, Edgar D. Zanotto2

1Programa de Pós-graduação em Ciência e Engenharia de materiais – UFSCar, São Carlos-SP

2Vitreous Materials Lab-DEMa, Universidade Federal de São Carlos – UFSCar,

São Carlos – SP, e-mail: [email protected]

A new low expansion LAS glass-ceramic was pro-duced by sintering with concurrent crystallization. Its microstructure, thermal expansion coefficient, and some mechanical properties are compared to those of commercial glass-ceramic CERAN, which is pro-duced by the traditional nucleation and growth heat treatments of a monolith. In both cases the crystal-line phase is a high-quartz solid solution with negative volume expansion. The sintered glass-ceramic show only 1.4% residual porosity and similar dimensional stability than CERAN, from room temperature to 500 °C. However, its hardness and elastic modulus are slightly inferior.

Keywords: glass-ceramic, sintering, crystallization, thermal expansion.

0155 | Structure and properties of coloured hybrid materials

Katarzyna Cholewa-Kowalska1*, Maria Łączka1, Agnieszka Terczyńska-Madej1

1AGH University of Science and Technology, Faculty of Materials Science and Ceramics,

Departament of Glass Technology and Amorphous Coatings, Krakow, Poland, e-mail: [email protected]

Hybrid materials with inorganic and organic struc-tural units can be used to generate functionalized coatings on a variety of substrates (eg. ceramics, glass). By processing at temperatures below 150 °C, the formation of inorganic-organic network structures using the sol-gel approach is possible. Recognising the structure of these materials is very important for the controlling of their production process as well as of their properties.

The goal of this paper was obtaining inorganic-organic gels and characterization of their structure by means of spectroscopic methods. These materi-als have been produced from tetraethoxyorthosi-

lanene (TEOS) and/or phenyltriethoxysilane (PhTES), 3-glycidoksypropyltrimethoxysilane (GPTMS) and zirconium isopropoxide or tetraethylorthotitanae. The gels were subjected to thermal treatment at the tem-perature range of 40-400 oC. Then, infrared spectra (FTIR) of obtained gels were measured as well as 29Si MASNMR examination were conducted.

From our results it follows that all hybrid materi-als heating up to 200 oC have a network structure with a siloxane backbone and are mainly cross-linked by T2and T3 species (materials without TEOS) with a presence of Q units (hybrid based on TEOS). After thermal treatment at 300 oC, in the case of materials without TEOS, there occurr changes consisting in the decay of peaks deriving from the T2and T3 species which means the decay of hybrid structures at this temperature. At this temperature the hybrid structure is retained only in the case of gels with addition of titanium.

Materials with TEOS show increase intensity of peaks connecting with Q units, which means that the hybrid structures are partly decomposed.

Keywords: sol-gel process, organic- inorganic materials, NMR spectroscopy, FTIR spectroscopy, hybrid structure.

0157 | On the formation of a secondary crystalline phase in biosilicate®

Bruno P. Rodrigues1*, Murilo C. Crovace1, Oscar Peitl Filho1, Edgar D. Zanotto1

1 Laboratório de Materiais Vítreos – Departamento de Engenharia de Materiais – Universidade Federal de São Carlos, LaMaV/DEMa/UFSCar – São Carlos, SP,


The Na2O-CaO-SiO2-P2O5 bio glass-ceramic Bio-silicate®, developed and patented by our group, may exhibit a minor, secondary, crystalline phase for cer-tain heat treatments. The relevant fact is that phase enhances the in vitro bioactivity in SBF of fully crystal-lized samples, reducing the onset time of hidroxycar-bonateapatite (HCA) formation from 10 hours (single phase samples) to 4h, which is even shorter than the onset time for the golden standard Bioglass® 45S5, 6 hours. This secondary phase is a yet unknown phosphate with a volume fraction < 0,02. In order to increase the crystallized fraction of this secondary phase, samples with two and three times the original concentration of P2O5 were prepared and the amount of secondary phase was quantified along with the ef-fect of the added P2O5 on the crystal nucleation and growth curves of the primary phase.

Keywords: bio glass-ceramics, crystallization, Biosilicate®.



0159 | Effect of bioactive glass micro and nanoparticles on the behavior of cemetoblasts cells

Sandhra M. Carvalho1, Agda A. R. Oliveira1, Maria F. Leite2, Marivalda M. Pereira1*

1*Departments of Metallurgical and Materials Engineering – Federal University of Minas Gerais,

Brazil, e-mail: [email protected] 2Departments of Physiology and Biophysics –

Federal University of Minas Gerais, Brazil

Cementum is essential for regeneration of peri-odontal tissue. However details on the proliferation and differentiation of the cells present in this tissue, cemontoblasts, are still unclear. Bioactive glass is a bone repairing material with high bioactivity and biocompatibility. Many studies have shown increased proliferation and collagen production by osteoblast cells in the presence of bioactive glasses. Cemento-blasts may have a similar response to bioactive glasses. To evaluate this hypothesis, in this study cementoblasts from teeth of rats were isolated and their response to bioactive glass particles were stud-ied. Bioactive glass micro and nanoparticles were synthesized using two different sol-gel routes. To ob-tain nanoparticles high energy ultrasound was used during sol-gel synthesis. We assessed the effects of the ionic product of dissolution of bioactive glass mi-cro and nanoparticles on the cells. The results show an increased cell viability by Trypan blue and MTT as-say for cementoblast cell populations in contact with ionic products of bioactive glass particles. It was also observed that the increase in cell viability was larger for nanoparticles compared to microparticles. These results were confirmed by BrdU assay. These obser-vations suggest that bioactive glass is an interesting material to be used for cement regeneration through tissue engineering.

Keywords: cementoblasts, bioactive glass and nanoparticles.

0160 | In vitro bioactivity of chitosan-polyvinyl alcohol-bioactive

glass composite membranes Luisa L. S. Dias1, Geovanni S. Diniz1,

Roberto Moreira2, Marivalda M. Pereira1*

1*Departments of Metallurgical and Materials Engineering – Federal University of Minas Gerais,

Brazil, e-mail: [email protected] 2Departments of Physics –

Federal University Of Minas Gerais, Brazil

Tissue Engineering strategy for the regeneration of cementum, essential for the periodontal tissue, will involve the culture of cells present in this tissue, cemontoblasts, on an appropriate substrate. It was shown that the viability of cementoblasts is increased in the presence of the ionic product of dissolution of bioactive glass particles. Therefore, one approach to obtain adequate substrates for cementoblast cul-ture is the development of composite membranes

containing bioactive glass. In this study composite films of chitosan- polyvinyl alcohol-bioactive glass containing different glass contents were developed. The glass phase was introduced in the material by a sol-gel route, leading to an organic-inorganic hybrid. The films were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) with Electron Dispersive Spec-troscopy (EDS) and X-Ray Diffraction (XRD) analysis. Bioactivity tests were conducted by immersion of the films in SBF (Simulated Body Fluid). Films contain-ing up to 30% glass phase could be obtained. The formation of calcium phosphate was observed after immersion of the films. A calcium phosphate layer formed faster in materials containing higher bioac-tive glass contents. In the hybrid containing 30% bioactive glass, a complete layer was formed after 24 hours immersion, showing the high bioactivity of this material.

Keywords: bioactive glass, chitosan, PVA, membranes, sol-gel.

0161 | Effect of high pressure in the Li2O × 2SiO2 mechanical properties

Silvio Buchner1*, Carlos M. Lepienski 2, Paulo Soares 3, Naira M. Balzaretti1

1*LAPMA, Laboratório de Altas Pressões e Materiais Avançados, Physics Institute, UFRGS, Porto Alegre-RS,

e-mail: [email protected] 2LabNano, Laboratory of Nanomechanical

Properties, Physics Department, UFPR, Curitiba – PR

3Department of Mechanical Engineering, PUCPR, Curitiba – PR

The aim of this work was to investigate the ef-fect of high pressure treatment on the mechanical properties of monolithic samples of a Li2O × 2SiO2 (LS2) glass. The hardness and elastic modulus were evaluated by instrumented indentation using a Berkovich tip. The fracture patterns and cracks after indentation at low loads with cube corner indenter were investigated.

The hardness and elastic modulus of the samples submitted to high pressure (2.5 GPa, 4GPa and 7.7 GPa) at room temperature decreased with increasing pressure compared to the pristine sample. The hard-ness and elastic modulus of the samples submitted simultaneously to high pressure (2.5 GPa, 4GPa and 7.7 GPa) and high temperature increased noticeably. The high temperature range was 455 °C during 2 h for nucleation followed by 610 °C during 0.5 h for crystal growth. These results indicate that the high pressure treatment under high temperature improved the mechanical properties of LS2.

Keywords: high-pressure, mechanical properties, lithium disilicate, glass ceramic.



0162 | Evaluation of Iron-phosphate glasses for sealing applications

Signo T. Reis1, Jose R. Martinelli2*, Newton K.T. Horimouti 2

1Materials Research Center, Missouri University of Science and Technology, Rolla, MO 65409, USA

2Nuclear and Energy Research Institute, Sao Paulo – SP, Brazil, e-mail: [email protected]

Solid oxide fuel cells (SOFC) consist of different materials functioning as anode, cathode, and elec-trolyte. Since reducing and oxidizing atmospheres are required to make the cell operational, sealing of these components is indispensable. However, to stack pla-nar cells, and consequently, to raise the generated voltage of these devices, metallic interconnectors are also required. The present work evaluates novel Iron-phosphate glasses as sealant of ceramic to metallic parts usually used as SOFC components, being an al-ternative to current alkaline earth silicate glasses de-signed for that purpose. The need for this alternative material stems from the high melting temperature e processing conditions adopted by the current sealant technologies, and, the deleterious crystalline phases usually formed in the metal-sealant interface. The glasses developed in the present work are processed to form dense glass-ceramics which provide the req-uisite of high mechanical and chemical stability in reducing and oxidizing environments in temperatures between 650 and 800 oC over 500 hrs. The crystal-lization was investigated by using differential thermal analysis, hot-stage microscopy, and scanning elec-tron microscopy. The evaluated glass compositions contain 60 mole% of P2O5 or less, and hence they fall outside the compositional range proposed for other iron phosphate glasses used for radioactive waste encapsulation.

Keywords:

0163 | Synthesis and characterization of glass and glass-ceramics

produced from “red mud” Heveline Vieira1*, Frank F. Sene1,

José R. Martinelli1, Ulisses S. Prado1

1*Instituto de Pesquisas Energéticas e Nucleares – IPEN, Centro de Ciência e Tecnologia de

Materiais, Cidade Universitária, São Paulo – SP, e-mail: [email protected]

The aluminum production process causes an en-vironmental degradation because relatively high en-ergy consumption is required, there is gas discharge, and solid and liquid waste disposal. “Red mud” is a byproduct from that process. For each kilogram of produced aluminum, 1.8 Kg of “red mud” is disposed in large pounds for decantation, and finally ground leveled. The “red mud” composition comprises com-pounds which could potentially be used raw materials to produce ceramic and glasses; hence a reduction of the environment degradation can be achieved. In the present work, the use of “red mud” as a raw ma-

terial to produce glass and glass-ceramics is investi-gated. The original composition is modified by adding conventional glass formers and modifiers. Glasses were produced by melting different mixtures of red mud and glass formers and modifiers in a electric furnace, annealed to reduce thermal stresses, and heated treated to cause a controlled crystallization. The material was analyzed by Differential thermal analyses, X-rays diffraction, and X-rays Fluorescence Energy Dispersive Spectrometry. The chemical cor-rosion in water was also evaluated and compared to regular glasses.

Keywords: red mud, glass, glass-ceramics.

0165 | Optical and thermochromic properties of bismuth based oxide

glasses containing silver Rauber D. Pereira, Marcelo Nalin*1

1Departamento de Química – Universidade Federal de São Carlos – UFSCar, São Carlos – SP – Brazil

New compositions of glasses in the system Bi2O3-GeO2-Ga2O3-BaO-AgCl have been systematically studied as a function of the AgCl content. Thermal and structural properties of glasses have been in-vestigated by DSC and Raman spectroscopy while optical properties have been studied by M-Lines and UV-Vis spectroscopies. Results had shown that the color of the glasses is strongly dependent of the cast-ing temperature even for composition free of silver. Samples with different percentages of AgCl have been submitted to thermal annealing during differ-ent times and the optical properties of such glasses have been studied by UV-Vis spectroscopy. Anneal-ing process, performed below Tg does not influence the optical properties of the glasses. On the other hand, preliminary results have shown that for thermal treatments above Tg, an absorption band arises in the visible range (~500 nm). That absorption has been attributed to the presence of surface plasmon resonance suggesting the formation of Ag-based nanoparticles. Complementary measurements, such as, transmission electron microscopy and chemical analysis have being processed in order to confirm such assumption.

Keywords: glasses, bismuth, silver, thermochromic, optical properties.



0167 | Structural study of mixed alkali borate glasses containing lead oxide

Juliana M. P. de Almeida1, Antonio C. Hernandes2

1,2Grupo de Pesquisa Crescimento de Cristais e Materiais Cerâmicos, Instituto de Física de

São Carlos (IFSC), Universidade de São Paulo – USP. CEP 13560-970 São Carlos – SP, Brazil,

e-mails: www.ccmc.ifsc.usp.br;

[email protected]; [email protected]

The influence of Li2O substitution by Cs2O in the short-range order structure of mixed alkali borate glass containing lead oxide has been studied by vi-brational spectroscopy. Several compositions in the 50B2O3 – 15PbO – (35-x)Li2O – (x)Cs2O (0 ≤ x ≤ 35) mol% vitreous system were prepared by the melt quenching technique and characterized by X-ray dif-fraction (XRD), infrared absorption and micro-Raman spectroscopy. XRD results indicated that glasses with x ≤ 20 mol% are completely amorphous. The samples with high Cs2O content presented the CsB(OH)4.2H2O and Cs2B4O7.5H2O crystalline phases due to absorption of water from atmosphere. Differ-ences in the FT-IR spectra were observed mainly in the ~1169 – 1550 cm-1 region, which correspond to B-O stretching vibrations of trigonal BO3 units. The Raman spectra of the glasses with low Cs2O con-tent (x ≤ 15 mol%) indicated the presence of metaborate chains and rings, BO3 units and six-membered ring arrangements containing one or two BØ

‑4 tetrahedra (Ø, bridging oxygen). For

the samples with x ≥ 20 mol% the six-membered ring arrangements becomes dominant. The addition of Cs2O also favored the increase of the peak at ~149 cm-1, which have been assigned to the symmetric Pb-O stretch in the PbO4 pyramidal configuration.

Keywords: alkali borate glass, raman, infrared, mixed alkali effect.

0168 | Analytical solution for mode-mismatched thermal

lens spectroscopy with glass-air heat coupling

Luis C. Malacarne1, Nelson G. C. Astrath1, Mauro L. Baesso1, Stephen E. Bialkowski2

1Departamento de Física, Universidade Estadual de Maringá, Maringá-PR, Brasil

2Department of Chemistry and Biochemistry, Utah State University, Logan, Utah, USA, e-mail: [email protected]

In this work we present an improved theoretical description of the mode-mismatched thermal lens effect on glasses using models that account for heat transport both within the glass samples and out to the surrounding coupling air medium. Analytical and numerical Finite Element Analysis (FEA) solutions are compared and subsequently used to model the

thermal lens effect that would be observed using continuous laser excitation. FEA model results were found to be in excellent agreement with the ana-lytical solutions for some glasses used as matrix for solid state lasers. The model results show that heat transfer to the air coupling medium introduces only a minor effect when compared to the solution obtained without considering axial air-sample heat flux for practical examples. On the other hand, the thermal lens created in the air coupling fluid has a relatively more significant effect on the time-dependent photo-thermal lens signals.

Keywords: thermal lens, sample-fluid heat coupling, photothermal techniques.

0170 | Thermal lens and interferometric method for glass transition and thermo physical properties measurements in

Nd2O3 doped borate glasses Nelson G. C. Astrath1, Francine B. G. Astrath1,

Alysson Steimacher1, Antonio N. Medina1, Antonio C. Bento1, Mauro L. Baesso1,

Carlos Jacinto2, B. Karthikeyan3

1Departamento de Física, Universidade Estadual de Maringá, Maringá-PR, Brasil

2Instituto de Física, Universidade Federal de Alagoas, Maceió-AL, Brasil

3Department of Physics, National Institute of Technology, Tiruchirappalli, India, e-mail: [email protected]

In this work the time resolved thermal lens meth-od is combined with interferometric technique, the thermal relaxation calorimetry, photoluminescence and lifetime measurements to determine the thermo physical properties of Nd2O3 doped borate glasses as a function of temperature up to the glass tran-sition region. Thermal diffusivity, thermal conductiv-ity, fluorescence quantum efficiency, linear thermal expansion coefficient and thermal coefficient of electronic polarizability were determined. The results showed the ability of the thermal lens technique and the interferometric method as remote techniques to perform the measurements very close to the phase transition region which unlike conventional calori-metric methods these techniques provide absolute values for the measured physical quantities and is advantageous when low temperature scanning rate is required.

Keywords: thermal lens, optical interferometry, thermal relaxation calorimetry, borate glass.



0171 | Material characterization with top-hat cw laser induced thermal lens

and thermal mirror techniques Francine B. G. Astrath1, Nelson G. C. Astrath1,

Luis C. Malacarne1, Paulo R. B. Pedreira1, Antonio C. Bento1, Mauro L. Baesso1, Jun Shen2

1Departamento de Física, Universidade Estadual de Maringá, Maringá – PR, Brasil

2National Research Council of Canada, Institute for Fuel Cell Innovation, Vancouver – BC,

Canada, e-mail: [email protected]

In this work, theoretical models for top-hat cw laser induced spectroscopies of thermal lens and thermal mirror are derived. With the same probe and top-hat excitation lasers, an apparatus is set up to concurrently measure both thermal lens and thermal mirror effects of transparent samples. With the theo-retical models and the experimental apparatus, not only optical and thermal properties are measured, but also the fluorescence quantum coefficient and the temperature coefficient of the optical path length of a fluorescent sample are simultaneously determined with no need of any reference sample. Mechanical properties also could be measured. Opaque samples are also studied using top-hat cw laser thermal mirror to determine thermal. This work shows that the com-bined top-hat cw laser photothermal techniques are useful for non-destructive evaluation of both trans-parent and opaque samples with a less expensive non-TEM00 Gaussian laser.

Keywords: thermal lens, thermal mirror, top-hat excitation, photothermal techniques.

0172 | Hidroxy Carbonate Apatite (HCA) formation on Biosilicate®

Murilo C. Crovace1*, Bruno P. Rodrigues2, Ana Candida M. Rodrigues2,

Oscar Peitl Filho2, Edgar D. Zanotto2

1*Programa de Pós-Graduação em Ciência e Engenharia de Materiais – UFSCar,

Campus de São Carlos, São Carlos – SP, e-mail: [email protected]

2Laboratório de Materiais Vítreos (LaMaV) – UFSCar – São Carlos – SP

The formation of Hydroxycarbonateapatite (HCA) on Biosilicate® submitted to two different heat-treat-ments was investigated using “in vitro” bioactivity tests. Biosilicate® is a crystalline P2O5-Na2O-CaO-SiO2 glass-ceramic. When the material is submitted to a modified heat-treatment, the formation of a sec-ondary phase takes place. Optical microscopy and SEM indicated that this secondary phase grows with dendritic morphology at the grain boundaries of the main phase. Biosilicate® and the two-phase material were exposed to an acellular SBF solution, during periods of time varying from 1 to 48h. The evolu-tion of the surface changes was followed by FTIR and the kinetic of Hydroxycarbonateapatite (HCA) forma-tion was compared with that of the golden standard

45S5 Bioglass®. For Bioglass® the formation of HCA occurred within 6h exposure to SBF. Despite its low amount, the presence of this secondary phase on Biosilicate® decreased the time-lag for the beginning of the development of HCA from 10h to 4h. Thus, the rate of HCA formation in the investigated samples is comparable to Bioglass® and faster than in commer-cial bioactive materials, such as apatite ceramics.

Keywords: bioglass, crystallization, bioactivity.

0173 | Induced crystallization of eulytite phase (Bi4Ge3O12) below glass transition interval of bimuth germanate glasses

Seila R. de Souza1*, José E. de Souza1, Antonio C. Hernandes1

1 Grupo Crescimento de Cristais e Materiais Cerâmicos – CCMC, Instituto de Física de

São Carlos – IFSC, Universidade de São Paulo – USP, São Carlos – SP, Brazil, e-mails: [email protected]; [email protected]

Bismuth germanate glasses are interesting mate-rials due to their physical properties and their unique structural characteristics caused by the coordination changes of bismuth and germanium atoms. Vitreous materials of the system (100-x)GeO2-xBi2O3 having similar properties of the eulytite crystal (Bi4Ge3O12) are of great interest for their potential applications as scintillator detectors. Moreover, glasses having ade-quate scintillator properties consists an advanced for the development of scintillator detectors due to their sizes, mechanical strengths, easy preparation, and lower manufacturing costs, when compared to single crystals or polycrystalline ceramics. Glasses in the composition of 80GeO2-20Bi2O3 in mol% and doped with 0.2 mol% of CeO2 were prepared by the melt-ing/quenching technique at 1100°C, in Pt crucibles. We have been reporting the role of silver in a novel process to obtain translucent crystallized glasses by inducing the formation of the Bi4Ge3O12 scintillator phase on the surface of the samples at temperatures 30°C below their glass transition (Tg ~ 480 °C).

Keywords: bismuth germanate glasses, crystallization, glass transition.

0174 | The local structure and the influence of ceria addition on properties

of bimuth germanate glasses Seila R. de Souza1*, José E. de Souza1,

Antonio C. Hernandes1

1 Grupo Crescimento de Cristais e Materiais Cerâmicos – CCMC, Instituto de Física de São Carlos – IFSC, Universidade de São Paulo – USP, São Carlos –

SP, Brazil, e-mails: [email protected]; [email protected]

Glasses containing bismuth are interesting materials due to their physical properties. Bi2O3 in combination with GeO2 can form glasses that



have been studied to their potential use in optical devices and for their unique structural characteris-tics. Therefore, in order to extent the applicability of these glasses, their doping with different cations and structural characterization represents a hot research topic. Glasses of bismuth germanate system were investigated concerning their thermal and structural properties. It was observed that the glass structure is formed basically by GeO4 tetrahedral units and they also have the formation of the GeO6 octahedral. BiO2 was considered a network former by observing the presence of octahedral BiO6 and pyramidal BiO3 groups in the local structure of the samples. A band observed at 1103 cm-1 in the IR spectrum of the undoped glass was attributed to the Bi-O-Ge and/or Bi-O-Bi linkage vibration and it has shifted to lower wavenumbers after the CeO2 addition, which reflects changes in the glass network. Cerium oxide was an efficient oxidant agent to prevent the darkening of the glasses, probably associated to the reduction of Bi ions. However, CeO2 was incorporated as a local network modifier in the glass structure even at con-centrations of 0.2 mol%.

Keywords: bismuth germanate glasses, local structure, FT-IR, micro-raman.

0178 | Crystallization kinetics and electrical conductivity of 1Na2O·2CaO·3SiO2 glasses with small Li2O additions

Tiago De Marchi Mosca*1, Leonardo Sant’Ana Gallo1, Bruno Henrique Teider1,

Ana Cândida Martins Rodrigues1, Edgar Dutra Zanotto1, Vladimir Mihailovich Fokin2

1*Vítreous Materials Laboratory, LaMaV, Materials Engi-neering Departament, Federal University of São Carlos,

C.P. 676 – CEP 13565-905 São Carlos – SP, Brazil, e-mail: [email protected]

2 S. I. Vavilov State Optical Institue, Babushkina 361, St. Petersburg, 193171, Russia

Only a few systematic studies about crystal-lization kinetics versus glass composition are avail-able in the literature. In this work, steady-state nucleation rates and crystal growth rates of a solid solution phase of 1Na2O·2CaO·3SiO2 crystal were estimated for a 1Na2O·2CaO·3SiO2 glass with up to 7.5-mol % Li2O. The maximum nucleation rate, Imax º I(T=Tmax), increases with increas-ing Li2O up to 4.3 % and then drops. This behavior correlates with evolution of reduced glass transition temperature Tgr = Tg/Tm confirming a tendency ob-served for other silicate glasses- the lower is Tgr the higher is Imax. Moreover, measurements of electrical conductivity as a function of the lithium oxide con-centration show the existence of a minimum near the composition of 4.3% Li2O. This minimum may be associated with the mixed alkali effect and confirms an anomalous behavior in the diffusivity mechanisms occurring in this composition. With exception of the

stoichiometric 1Na2O·2CaO·3SiO2 composition, the DSC crystallization peaks of the Li containing glasses are non-symmetrical. For compositions with the highest Li2O content, two DSC crystallization peaks overlap, which indicates the presence of a second crystalline phase. This fact is corroborated by optical microscopy analysis, which allows a clear distinction between these phases.

Keywords: crystallization kinetics, nucleation and crystal growth rates, electrical conductivity, stoichiometric 1Na2O·2CaO·3SiO2 glasses, glass composition, classical nucleation theory.

0179 | Neodymium doped silicaluminates thin glasses

prepared by the sol-gel route for use in laser dentistry

Fátima R. A. Fonseca1*, Crislene R. da S. Morais1, Norma M. S. de Oliveira 1,

Crisneide R. da S.Coqueiro1, Sebastião A. dos S. Dantas2

1Departamento de engenharia de materiais, PPGCEMat,Universidade Federal de Campina Grande – UFCG, Rua Aprígio Veloso, 882 CEP-58.109-970

Campina Grande-PB, Paraíba-Brasil 2Unidade Acadêmica de Engenharia Elétrica,

CEEI, Universidade Federal de Campina Grande-UFCG, Rua Aprígio Veloso, 882, CEP 58109-970

Campina Grande –PB, Brasil, e-mail: fá[email protected]

The synthesis of silicoaluminates glasses doped with rare earth (RE) and Nd3 + is currently a major challenge for developing integrated optical devices such as lasers, optical amplifiers and devices for dental lasers. In this study monoliths Al2O3-SiO2 glass doped with Nd3 + were prepared by sol-gel route. Were used as precursors for oxide glass, aluminum acetate and tetraehoxisilane, Si (OC2H5)4 (TEOS), while the Nd2O3 neodymium oxide was introduced as a dopant. The molar ratio of silica / alumina / neodymium was 2 / 0.5 / 0, 01, respectively. The preparation of the gel from solution and subsequent drying and aging, occurred at room temperature in airtight containers. The glass obtained was then heat treated at 200 °C. After treatment at 200 °C, monoliths were obtained. The composition, microstructure and surface mor-phology of glasses were investigated by X-ray diffrac-tion (XRD), scanning electron microscopy (SEM) and vibrational spectroscopy in the infrared (IR). Analysis of incidence of X-ray diffraction (XRD) and scanning electron microscopy (SEM), the monoliths of high purity were obtained, characterized by homogeneity of composition and microstructure.

Keywords: glasses, sol-gel route, rare earths, laser dentistry.



0180 | Fentosecond laser modification of BAO-B2O3-SIO2 based glass

V. R. Mastelaro*, P. Brajato, W. Avansi Jr, A. J. G. Otuka, G. F. B. Almeida,

F.E.G. Guimaraes, C. R. Mendonca Instituto de Física de São Carlos, Universidade de

São Paulo, Av Trabalhador São Carlense 400, São Carlos – SP, Brasil, e-mail: [email protected]

Femtosecond laser micromachining has received considerable attention because of its ability to struc-ture materials in three-dimensions. When femtosec-ond laser pulses are focused in the material, the light intensity at the focal volume is enough to induce multi-photon absorption, leading to changes in the material. In this work, we investigate femtosecond laser micromachining in a 15SiO2 – 42.5BaO – 42.5B2O3 glasses undoped and doped with CeO2 and Ag2O glass using 150 fs , 775 nm from a Ti:sapphire laser system at a 1 KHz repetition rate. The pulses were focused with an f = 15 cm lens (beam diameter of 25 mm) onto the sample, which was translated at constant speed. Structural modification on the glass were observed through UV-Vis absorption and fluorescence microscopy when the samples were ir-radiated with pulse energies ranging from 8 mJ up to about 30 mJ. We also observed that the laser induced modification could be erased by heating treatment at 400o C during 40 minutes.

Keywords: fentosecond laser, glasses, structural modification, optical properties.

0181 | Recycling of waste vitreous of the type in soda-lime in

manufacturing parts decorative crafts Norma Maria Silva de Oliveira1, Fátima Roneiva Alves Fonseca1,

Crislene Rodrigues da Silva Morais1

1Departamento de Ciências e engenharia de materiais-PPGCMat-UFCG, Rua Aprígio Veloso, 882

Campina Grande – PB, CEP 58109-970

This paper presents a comparative study on the use of glassy residue on clothing for decorative craft pieces using the technique fusing, these residues represent a huge loss to the environment, since glass is not biodegradable, thus requiring a proposal for a technological reuse of this material is discarded at the landfill in the city of Campina Grande – PB. Against the requirement not to add other substances with waste vitreous using simple technologies and low-cost, aiming at saving energy and raw materials for the production of these pieces. The glassy residue used for this manufacture will be called a common glass or soda-lime glass.

Keywords: fusing, residues of glass, recycling

0189 | Hafnium environment in LaBS and ABs glasses for plutonium immobilization

Sergey. V. Stefanovsky1*, Andrey A. Shiryaev2, Ian. V. Zubavichus3, James C. Marra4

1 State Unitary Enterprise of the City of Moscow – United Ecology, Technology and Research

Center for RAW Management and Environmental Remediation (SIA Radon) – Moscow – Russia, e-mail: [email protected]

2Institute of Crystallography RAS – Moscow – Russia 3RRC “Kurchatov Institute” – Moscow – Russia

4Savannah River National Laboratory – Aiken – USA

Six borosilicate glasses with lanthanide boro-silicate (LaBS) and alkali borosilicate (ABS) composi-tions containing HfO2 (as a PuO2 surrogate) and two glasses containing both HfO2 and PuO2 were pre-pared by melting in Pt crucibles at 1500 °C. All the glasses either were fully homogenous or contained minor Hf free phases. X-ray absorption spectroscopy data showed Hf in all the glasses was present in a tetravalent state. Hf4 + ions were normally more ho-mogeneously distributed in the LaBS glasses than Pu ions since the second co-ordination shell was not clearly appeared. The first co-ordination shell was split into two to three components. The major com-ponent corresponded to a Hf ‑‑O interatomic distance of 2.06 ± 0.02 with a population of 4.5 ± 0.5 Å that was close to Pu‑‑O distance in the first shell in the structure of the Pu-bearing glass. There was also a shorter distance (1.65±0.05 Å with a population of ~1.3-1.6) similar to that observed for Pu, which was influenced by crystal chemistry factors. As followed from Fourier Transforms, the majority of the Hf had a coordination number (CN) ≈ 6 and an environment in the form of axially squeezed octahedron. Wavelet analysis showed that the nearest environment of the Hf ions was filled with light elements (O, Al, B, Si). The nearest heavy atom (probably Gd) was positioned at a distance of 2.7±0.1 Å.

Keywords: borosilicate glass, hafnium, plutonium, Wavelet analysis, X-ray absorption spectroscopy.

0190 | Measurement of leach rates of radionuclides from vitreous waste

forms in a soxhlet apparatus Alexander V. Ochkin1*, Alexei O. Merkushkin1,

El’dar P. Magometbekov1, Sergey V. Stefanovsky2

1*D. Mendeleev University of Chemical Technology, Institute of Modern Energy Materials and

Nanotechnology – Moscow – Russia, e-mail: [email protected]

2State Unitary Enterprise of the City of Moscow – United Ecology, Technology and Research

Center for RAW Management and Environmental Remediation (SIA Radon) – Moscow –



Russia, e-mail: [email protected]

Vitreous and ceramic materials are perspec-tive as high and intermediate level waste forms. Various long-term procedures are normally applied to measuring leach rates of waste elements including radionuclides. Some accelerated leach procedures, in that number using a Soxhlet apparatus were pro-posed. While the specimen for long-term tests is made as a thin plate or disc, accelerated tests are performed with powdered samples. Surface area is either calculated in suggestion that the particles have certain geometry and size or measured using a BET method (low temperature argon sorption). Leach rate remains constant (and equal to that from monolithic specimen) only at some relatively small mass of the sample. Increase of mass of the sample over certain value resulted in reduction of leach rate. Moreover, reduction of leach rate was observed at decreasing of leachate flow rate through the powdered sample. The most probable reason is the saturation effect. Therefore, mass of the powdered sample must be limited depending on the nature of the waste form. Accelerated Soxhlet procedure is preferable for glass-crystalline waste forms when crushing of the material leads to formation of both predominantly amorphous and predominantly crystalline particles differently partitioning of waste elements.

Keywords: BET method, leach rate, saturation, Soxhlet apparatus, vitreous waste form.

0192 | Percolative inward diffusion in iron-bearing diopside glass-ceramics

Morten M. Smedskjaer*, Yuanzheng Yue Section of Chemistry, Aalborg University,

Sohngaardsholmsvej 57, DK-9000 Aalborg, Denmark, e-mail: [email protected]

The so-called inward cationic diffusion is a diffu-sion process of network-modifying cations from the surface towards the interior of a glass. The diffusion occurs due to the reduction of polyvalent ions. In this work, we have shown that the inward diffusion degree of divalent cations decreases with increasing degree of crystallization in iron-containing diopside glass-ceramics, especially when the degree of crys-tallization is above 80 vol%. Below this critical degree of crystallization, the diffusion extent decreases only slightly with the degree of crystallization. No cationic diffusion is observed in the fully crystalline materials. The critical value might be attributed to a percolation transition from an interconnected to a disconnected glass phase. In earlier studies, we have shown that the inward diffusion approach can be used to create hard and durable surfaces on silicates glasses due to the formation of a SiO2-rich surface layer. Therefore, the findings in this work might be used to design glass-ceramics with improved surface properties,

i.e., by first making the glass crystallize to a degree below the critical value, and then making the inward diffusion occur via reduction of polyvalent ions.

Keywords: glass-ceramic, diffusion, diopside, percolation, surface modification, reduction.

0195 | Preparation of novel transparent glass-ceramics containing fluoride crystals

Takenobu Suzuki*, Shin-ichiro Masaki, Kento Mizuno, Yasutake Ohishi

Research Center for Advanced Photon Technology, Toyota Technological Institute, 2-12-1, Hisakata,

Tempaku-ku, Nagoya 468-8511, Japan, e-mail: [email protected]

Novel transparent glass-ceramics were prepared by controlled heat-treatment of NaF-YF3-Al2O3-SiO2 oxyfluoride (NYASOF) and LiF-YF3-Al2O3-SiO2 oxy-fluoride (LYASOF) glasses. The precipitated crystalline phases confirmed by the powder X-ray diffraction patterns of them were NaYF4 and LiYF4. The activa-tion energy of crystallization evaluated by differential scanning calorimetry curves was about 437 and 155 kJ/mol for NaYF4 and LiYF4 crystallization, respective-ly. The activation energy for NaYF4 is comparable of single bond energy of Si-O, indicating crystallization accompanying reconfiguration of the glass network. On the other hand, crystallization of LiYF4 could oc-cur without reconfiguration of the glass network. The average size of the crystallites was estimated as less than 10 nm from the width of the diffraction peaks. The transparency of the glass-ceramics was kept. Furthermore, the ultra-violet absorption edged of NASOF glass was shifted to shorter wavelength by crystallization. These crystalline phases could be doped with trivalent rare-earth ions by the substi-tution of trivalent yttrium sites. These novel glass-ceramics would be promising candidate materials for efficient optical fiber amplifiers and fiber lasers.

Keywords: transparent glass-ceramics, NaYF4, LiYF4, crystallization mechanism.

0196 | Quantum efficiency of ND3+-doped glasses

under sunlight excitation Takenobu Suzuki1*, Hiroyuki Kawai1, Hiroyuki Nasu1, Mark A. Hughes1,

Shintaro Mizuno2, Hiroshi Ito2, Kazuo Hasegawa2 and Yasutake Ohishi1

1Research Center for Advanced Photon Technology, Toyota Technological Institute, 2-12-1, Hisakata,

e-mail: [email protected] 2Frontier Research Center, Toyota Central

Research and Development Labs. Inc., 41-1, Yokomichi, Nagakute-cho, Aichi 480-1192 Japan

Quantum efficiency of 1.06 μm emission from Nd-doped borosilicate, tellurite and fluoride glasses under natural sunlight excitation was investigated. A



quantum efficiency measurement system for natural sunlight was constructed. Reliable and reproducible data could be obtained by using the system. The quantum efficiency under natural sunlight excita-tion showed a maximum Nd3 + concentration for all glasses, though the quantum efficiency under laser excitation at about 800 nm, which matches an ab-sorption peak wavelength of Nd3 + , decreased mono-tonically with Nd3 + concentration as expected from concentration quenching. It was revealed that glass hosts that have the low effective phonon energy and the low absorption by host glass are preferable for natural sunlight excitation. Among three glass sys-tems examined in this paper, fluoride glass matches such conditions (phonon energy ≈ 500 cm-1, UV-ab-sorption edge ≈ 300 nm). The quantum efficiency of Nd-doped fluoride glass was as high as 70 % under sunlight excitation. Fluoride glass would be a promis-ing candidate glass for laser media in efficient solar pumped fiber lasers.

Keywords: qunatum efficiency, sunlight, Nd-doped glasses.

0197 | Glass-ceramics from industrial wastes from egypt

Luisa Barbieri1, Mohamed M. Farag2, Esmat M. A. Hamzawy2, Isabella Lancellotti1,

Cristina Leonelli1*

1*Departament of Materials & Environmental Engineering , Univinersity of Modena &

Reggio Emilia, 41125 Modena, Italy, e-mail: [email protected]

2Glass Reserch Dep, National Rsearch Centre, Dokki P.C 12622 Cairo Egypt

Waste remediation and inertization by vitrifica-tion techniques are exploited mainly when major chemical and chemical waste constituents are silicates or aluminosilicates. In this work the use of local weathered basalt and an industrial hazardous waste, heavy metals in a calcium sulphate matrix, as starting materials for glass-ceramics production is reported. The crystalline phases in altered basalts are anorthite, olivine and hematite while in the industrial waste is calcium sulphate and its hydrated phase in citrogypsum. To ameliorate the volume crystallization TiO2 and CaF2 were added to the batches as nucleat-ing agents. The parent glasses, brown and amber in colour as a consequence of iron content of the basalt have been fully crystallized in 2 hrs the temperature range of 800-1100 °C. Crystallization of the prepared glasses was studied by x-ray diffraction and energy dispersive scanning electron microscopy. Bulk crys-talline microstructures with crystals size ranging from

0.25 to 5 microns were identified as aluminium diop-side, anorthite, hematite and pseudobrookite. How-ever, in low citrogypsum containing glass-ceramic microstructure presents fine to ultrafine grains while in high citrogypsum-containing samples, more pro-nounced crystals are obtained. Vickers’ microhard-ness of glass-ceramic materials ranged from 660 to 740 HVN.

Keywords: waste, weathered basalt, calcium sulphate, citrogypsum, glass-ceramics, anorthite, nucleating agents.

0200 | Flame aerosol nanostructured titanium dioxide for coating:

a control of crystallite size and fase by oxy-hydrogen flame

Mirella N. de O. Boery1, Eduardo Ono1, Tárcio P. Manfrim1, Juliana S. Santos1,

Carlos K. Suzuki1 1 Universidade Estadual de Campinas – UNICAMP,

Campus de Campinas, Campinas-SP, e-mail: [email protected]

TiO2 (titanium dioxide) powders and nanoparticles have been largely used in toners and cosmetics. Nowadays, they are mainly focused in photocataly-sis, antibacterial coatings, dye-sensitized solar cells, etc. Within the field of photocatalysis, the photo-catalytic activity of TiO2 coatings depends on TiO2 nanoparticles properties such as crystallite size and fase (anatase/rutile). In this research, flame aerosol method was used to synthesize TiO2 nanoparticles by hydrolysis and oxidation of TiCl4 (titanium tetra-chloride) for glass coating. The oxy-hydrogen flame was provided by a five concentric nozzle silica burner, in which gases configuration were TiCl4 (O2 as car-rier gas)/N2/H2/N2/O2 from central to the outer tube. Titania nanoparticles were deposited in a vitreous silica target and collected with no calcinations for characterization. X-ray diffraction was used to iden-tify each TiO2 nanoparticles phase and scanning electron microscopy was used to observe the size and morphology of nanoparticles. Pure anatase was obtained with H2/O2 ratio ≤ 1.0, and up to 52 wt% of rutile was obtained with H2/O2 ratio > 2.0. Anatase crystal grain size varied from 25 to 38 nm, estimated by Scherrer formula. The amount of TiCl4 was also a significant experimental variable for controlling the phase composition and crystal grain size.

Keywords: titanium dioxide, nanoparticles, anatase, rutile, x-ray diffraction, scanning electron microscopy.

8:00-18:00 h ICG CTC, SteCo and Council Meetings

16:30-19:00 h Poster Presentations, Wednesday, Sept. 22 Posters #0201-0359

17:30-19:30 h Varshneya´s Glass Course


Poster PresentationsWednesday, Sept. 22

0201 | The nucleation of silver nanoparticles In Tm3 + doped

germanate glasses Thiago A. A. Assumpção1*, Davinson M. da Silva1, Luciana R. P. Kassab2, Anderson S. L. Gomes3,

Cid B. de Araújo3, Nikluas U. Wetter4

1Escola Politécnica da Universidade de São Paulo – EPUSP, São Paulo-SP

2Faculdade de Tecnologia de São Paulo – FATEC-SP, São Paulo-SP

3Departamento de Física – UFPE, Recife-PE 4Centro de Lasers e Aplicações – IPEN, São Paulo –

SP, e-mail: *[email protected]

Due to the possibility of modifying the optical properties of glasses, heavy-metal oxide glasses containing metallic nanoparticles (NPs) have been largely investigated in the last years. In this work, we present the influence of silver NPs nucleation in PbO-GeO2 glasses. These glasses have already proved to be adequate host for the NPs nucleation [1-4]. The influence of the heat-treatment time on the nucle-ation of silver NPs in Tm3 + doped PbO-GeO2 glasses was investigated. The melting-quenching technique was used and two different ways for the heat-treating were adopted for the reduction of Ag + and nucleation of silver NPs; the differences on the nucleation were observed using the transmission electron microscopy (TEM) images. We also report the influence of the NPs in the infrared-to-visible frequency upconver-sion (UPC) luminescence of Tm3 + ions. The emission spectra were performed by exciting the samples with a cw 1050 nm ytterbium laser and observing the UPC in the blue-red region. The enhanced UPC emission is attributed to the local field effect in the proximity of NPs.1. Gómez et al., Appl. Phys. Lett. 92, 141916 (2008).2. da Silva et al., Appl. Phys. Lett. 90, 081913

(2007).3. Jiménez et al., J. Appl. Phys. 104, 054313 (2008).4. Kassab et al., Appl Phys. Lett. 94, 101912 (2009).

Keywords: heavy metal oxide glasses, silver nanoparticles, upconversion of Tm3+.

0203 | Microscopic relationship among properties of potassium

germanate glasses Seiichi Mamiya*, Kazuhiro Kaneda, Yu Matsuda,

Masao Kodama, Seiji Kojima Graduate School of Pure and Applied

Sciences, University of Tsukuba, e-mail: [email protected]

Germanate glasses are applied to glass fibers or optronics. However, they have not been studied intensively so far. Therefore we investigated potas-sium germanate glasses. We prepared potassium

germanate glasses xK2O·(100-x)GeO2 (x indicates K2O mol%) in the composition range of 0 ≤ x ≤ 52 by the solution method.

Potassium germanate glasses show “germanate anomaly” i.e. adding potassium oxide to germania glass, the physical property of potassium germanate glasses shows a maximum or minimum in their composition dependences. We have studied potassium germanate glasses by Raman scattering, Brillouin scattering and differential scanning calorimetry (DSC). Raman spectra, sound velocity and glass transition temperature are investigated by Raman scattering, Brillouin scattering and DSC respectively.

First, we have studied the K2O composition dependence of Raman spectra, we find that K2O composition of the density maximum is approximately 10 mol% using the curve fitting method. Second, sound velocity and elastic moduli are investigated by Brillouin scattering measurement. The K2O composition that their maximum occurs is approximately 15 mol%. Third, the K2O composition dependence of glass transition temperatures is measured by DSC. The K2O composition of the maximum of glass transition temperatures is approximately 19 mol%.

In the presentation, we will discuss the origins of these anomalies on the basis of the glass structures.

Keywords: germanate anomaly, potassium germanate glasses, solution method, glass transition temperature, curve fitting method.

0205 | Fabrication of LiMnxFe1-xPO4 crystals via the glass–ceramic route and

their lithium ion battery performance Tsuyoshi Honma1, Takayuki Komatsu1

1Department of Materials Science and Technology – Nagaoka University of Technology, Japan,


The olivine-type LiMnxFe1-xPO4 crystals are fab-ricated through the crystallization of Li2O–MnO2–Fe2O3–P2O5 glasses, and the lithium ion battery performance (electrochemical charge/discharge patterns) for the glass–ceramics with LiMnxFe1-xPO4 crystals is examined. It is found that homogeneous glasses are obtained for the stoichiometric composi-tions corresponding to LiMnxFe1-xPO4 with 0 < x < 0.8 in a conventional melt-quenching method in air. The heat treatment of the mixtures of glass powders and glucose (5 wt%) at crystallization temperatures in a reducing atmosphere of 7%H2–93%Ar gives the for-

Poster Presentations, Wednesday, Sept. 22


mation of the olivine-type LiMnxFe1-xPO4 crystals. The charge/discharge curves exhibit the plateaus at the voltage of ~3.4 and 4.1 V.

Keywords: lithium ion batteries, cathode material, lithium iron phosphate, LiFePO4.

0209 | Structural relaxation and electrical conductivity in a window glass

Mariana Moura Machado1, Oscar Peitl1, Ana Candida Martins Rodrigues*1

1Universidade Federal de São Carlos – UFSCar, São Carlos – SP, Brazil, e-mail: [email protected]

We present experimental data on the evolution with time of the electrical conductivity of a window glass. Samples were heat treated at different tem-peratures above and below the glass transition, thus leading to different fictive temperatures. The changes in electrical conductivity with time were then mea-sured, by impedance spectroscopy, at a constant temperature near the glass transition, Tg. At this temperature, electrical conductivity decreases with time for a sample previously heat treated at a higher temperature, while an increase with time is observed for a sample previously heat treated at a lower tem-perature. Changes in electrical conductivity are main-ly due to structural relaxation. Structural relaxation time was thus calculated by fitting the experimental data using a modified Maxwell expression.

Keywords: structural relaxation, relaxation time, electrical conductivity, Impedance spectroscopy.

0212 | Nanoindentation behaviors of SiO2–CaO–Na2O glasses with TiO2, ZrO2

and HfO2 under low temperature Mirabbos Hojamberdiev*, Harrie J. Stevens

New York State College of Ceramics, Alfred University, Alfred, NY 14802, United Status,


The annealing treatment is of primary interest to estimate the ratio of densification to a total indenta-tion volume of soda lime silicate glasses with TiO2, ZrO2 and HfO2. The elastic properties and microhard-ness increased with increasing the amounts of addi-tives (0, 1, 2, 4 and 8 mol.%) in the following order: reference glass < Glass + TiO2 < Glass + ZrO2 < Glass + HfO2. This trend is directly related to the packing ions present in the glass structure and the strength of the individual bonds. Nanoindentation experiments were performed using a universal hy-draulic testing machine fitted with a 1 mm diameter spherical tungsten carbide ball-mounted indenter. The effects of 25°C and 100°C on the nanoindena-tions made in those glasses were studied as function of time up to 48 h. On the basis of the depth change of the ponds at low temperature, nanoindentation behavior of each glass sample was evaluated. The experimental results showed that the rate of elastic

response of the nanoindentations resulted from the gradual expansion of the structure in the direction of the applied tension took place in the following ac-celeration sequence: reference sample < Glass + TiO2 < Glass + ZrO2 < Glass + HfO2. Since annealing temperatures were low, the internal pressure raised by disentangling of structural elements might play an important role in elastic recovery of the nanoindenta-tions at low temperature. All the indented samples exhibited three main behaviors: elasticity, viscoelas-ticity, and permanent viscous flow.

Keywords: nanoindentation, silicate glass, elastic response, thermal treatment.

0214 | Characterization of Ce3 + doped CAS glass for visible optical application Franciana Pedrochi1,2,3*, Alysson Steimacher1,2,3,

Marcio J. Barboza1, Luis H.C. Andrade4, Sandro M. Lima4, Antonio N. Medina1,

Mauro Luciano Baesso1, Yannick Guyot2, Georges Boulon2

1Universidade Estadual de Maringá – UEM, Maringá – PR

2Laboratoire de Physico-Chimie des Mate´riaux Lumi-nescent – Universite´ Claude Bernard Lyon 1,

Villeurbanne – France 3*Universidade Federal do Maranhão – UFMA, Campus de II, Imperatriz – MA, e-mail: [email protected]

4Universidade Estadual de Mato Grosso do Sul – UEMS, Dourados – MS

Rare earth ion-doped materials have been suc-cessful applied for photonic sources. Trivalent rare earth ion Ce3 + in glasses presents large absorption in the UV region and shorter luminescence lifetime. Those properties are desired for applications in imag-ing, lithography, optical data recording, solid state lasers, scintillators and displays. Emission spectrum of Ce3 +-doped calcium aluminosilicate glasses (CAS) has been reported in this work. The interest in the CAS glass is because they present a good combi-nation of optical, thermo-optical and mechanical properties, which include transparency in the IR up to ~5mm, when prepared under vacuum conditions (OH-free). In this work three samples of CAS glass were prepared, with 0.25, 0.5 and 1 wt% of CeO2. The absorption spectra for CAS glasses showed an intense peak centered at 340 nm, which increases with the concentration of CeO2. A broad and strongly intense blue emission centered at ~480 nm has been recorded with excitation wavelength at 410 nm. The results of emission lifetime did not present significant differences with the doping concentration, with values around 50 ns. The emission spectra as a function of temperature were performed from room temperature up to 400 ºC and the quantum effi-ciency was determined using the Arhenius equation.

Keywords: visible luminscence, optical properties, aluminosilicate, cerium, rare-earth.



0215 | Ti3 + doped calcium aluminosilicate glasses for visible optical aplications

Franciana Pedrochi1,2,3*, Alysson Steimacher1,2,3, Marcio J. Barboza1, Luis H.C. Andrade4, Sandro M. Lima4, Antonio N. Medina1,

Mauro Luciano Baesso1, Yannick Guyot2, Georges Boulon2

1 Universidade Estadual de Maringá – UEM, Maringá – PR

2Laboratoire de Physico-Chimie des Mate´riaux Luminescent – Universite´ Claude Bernard

Lyon 1, Villeurbanne – France 3*Universidade Federal do Maranhão – UFMA, Campus de II – Imperatriz – MA, e-mail: [email protected]

4Universidade Estadual de Mato Grosso do Sul – UEMS, Dourados – MS

Recent works have shown a broad emission band in the visible region (~450-800 nm) and long life time (~170 ms at room temperature) for low-silica calcium aluminosilicate glass LSCAS:Ti doped samples, with luminescence properties that raise possibilities of using this system for the development of lasers in the class of that with Ti3:Al2O3 crystals. In order to improve the thermal optical properties and verify the SiO2 content influences over the calcium aluminosilicate glasses (CAS), samples were pre-pared with different concentrations of SiO2 (30-34 wt %) and 2 wt % of TiO2. The glasses were prepared under vacuum atmosphere and the obtained doped samples presented a browned color. The measure-ments of absorption coefficient showed a large op-tical absorption band (centered in ~500 nm) that indicates the presence of Ti3 + , which was confirmed by EPR measurements. The EPR results showed that the ration Ti3 + /Ti4 + is higher in CAS samples that of LSCAS. The luminescence spectra presented a broad emission band from ~450 nm to 750 nm and life time around 150 ms. The intensity of luminescence emission was lower to CAS than LSCAS due the higher reabsorption effect for those samples, what was dependent on the doping concentration.

Keywords: Visible luminscence, optical properties, aluminosilicate.

0216 | Nd3 + doped cas glasses: thermo-optical and luminescence

spectroscopy investigation A. Steimacher*1,2, M. J. Barboza1

, A. M. Farias1, F. Pedrochi2, N.G.C. Astrath1, J. H. Rolling1, A. C,

Bento1, M. L. Baesso1, A. N. Medina1

1Departamento de Física, Universidade Estadual de Maringá – Maringá, PR, Brasil

2Universidade Federal do Maranhão – Campus Imperatriz – Imperatriz, MA, Brasil,


Previous works have been shown that Calcium Aluminosilicate glass(CAS), when prepared under vacuum atmosphere, are good candidate for solid

state laser media hosts and optical devices due to their thermal, optical and mechanical properties. These observations led us to investigate the thermo-optical properties and emission spectra as a function of temperature of the Nd3 + doped CAS glasses. This is because many optical systems are submitted to temperature changes that can cause damage to the host and other dislike effects, such as quenching of the emission or self-focusing. In this work, two series of CAS glasses doped up to 5 wt% of Nd2O3 were prepared and characterized. Were performed measurements of thermal coefficient of optical path length (dS/dT), thermal lens spectroscopy (TLS) and emission spectra of the glasses. Measurements of specific heat (cp), thermal diffusivity (D), optical ab-sorption and emission lifetime were also carried out. The results are discussed in terms of Nd2O3 content and for different matrix composition. Comparison with other glasses, like LSCAS (Low-silica calcium aluminosilicato) is also presented.

Keywords: Nd3+ glasses, Calcium Aluminosilicate, luminescence, emission quenching, thermo-optical properties.

0217 | Spectroscopic investigation of Yb3 + -doped oh- free calcium

aluminosilicate glasses A. Steimacher1,3,4*, F. Pedrochi1, M. J. Barboza1,

A. N. Medina1, A. C. Bento1, M. L. Baesso1,

L. H. C. Andrade2, S. M, Lima2, Y. Guyot3, G. Boulon3

1Universidade Estadual de Maringá, Maringá, PR, Brasil 2Universidade Estadual de Mato Grosso do Sul,

Dourados, MS, Brasil 3Université Claude Bernard, Lyon. Lyon, France

4Universidade Federal do Maranhão, Campus Imperatriz, Imperatriz – MA, Brasil,


Rare earth (RE) doped glasses are an important class of material due to the many optical applications envisaged, including active media for glass lasers. In this work, two series of calcium aluminosilicate glasses, doped up to 11 wt% Yb2O3 were prepared. The first one was prepared with silica content of 7 wt% (LSCAS) and the second one with silica content ~30 wt% (CAS). These glasses were produced under vacuum conditions and are transparent in the infra-red spectral range up to 5 mm. The Yb3 + was chosen as doping due to improvements of high performance GaAs and InGaAs laser diodes with wavelengths between 900 and 1100 nm. This has renewed the interest in ytterbium doped materials for applications in high efficiency (>50%) and high-power (>50 W/cm) diode-pumping laser systems. The absorption and fluorescence spectrum, the lifetime and the up-conversion emission of Yb doped glasses have been measured at room temperature and the results are



discussed as a function of Yb2O3 concentration. The results reinforce this material as a candidate for laser application.

Keywords: Yb3+ , OH-free glasses, luminescence spectrum, upconversion, emission lifetime.

0223 | Manufacture of oxide glasses using laser heating of levitating pellets

Prabesh Dulal1, Matt Burch1, Rick Weber2, Steve Feller1, Mario Affatigato1

1Physics Department, Coe College, Cedar Rapids, Iowa 52402, United States

2Materials Development Inc., Arlington Heights, IL 60004, United States

We report on glass formation of aluminates, alkali and alkaline earth-borates, and other glass systems manufactured using a laser aero-levitation system. By using high temperatures (>2700 °C) and containerless processing we have been able to synthesize glasses that would have been impossible to make through traditional furnace techniques, and carried out property and structure characterization. We have looked at the glass formation of the group II metal (Mg, Ca, Sr, Ba) oxide binaries in the alu-minate system, with an emphasis on the effect of the ionic field strength. Our report will also cover the possibility of polyamorphism in the alkali and alkaline earth borates, studied as a function of the process-ing temperature. Finally, our work will include attempt at glass formation for exotic systems like pure oxide glassformers like pure TeO2 and Sb2O3, and binaries like Na2O-Bi2O3.

Work supported by the United States National Science Foundation under grant numbers DMR-0904615 and MRI-0922924.

Keywords: aluminates, glassmaking, laser processing, borates, containerless processing.

0224 | Redox behaviors of antimony or arsenic ions in silicate melts by

differential pulse voltammetry Satoshi Yoshida1*, Takahiko Sudo2,

Yuki Nishikawa2, Mitsuo Kato1, Toru Sugawara1, Jun Matsuoka1, Yoshinari Miura1, Yasushi Kii3

1*Center for Glass Science and Technology, The University of Shiga Prefecture, Hikone,

Shiga, Japan, e-mail: [email protected] 2Department of Materials Science, The

University of Shiga Prefecture, Hikone, Shiga, Japan 3Research and Development Division, Nippon Electric Glass Co., Ltd., Ostu, Shiga, Japan

It has been well known that the redox behaviors of multivalent ions in glass melt influence various kinds of properties, such as chemical refining. In this study, redox behaviors of antimony or arsenic ions in 16Na2O-10RO-74SiO2 (mol%, R = Mg, Ca, Sr, Ba) glass melts were investigated by differential

pulse voltammetry. The redox ratios of each ion in every glass composition at a given temperature were estimated from the peak potentials in each voltam-mogram. It is found that the redox equilibria shift to reduced states with increasing temperature. The [Sb3 +]/[Sb5 +] and [Sb0]/[Sb3 +] ratios for Ba contain-ing glass is larger than those for Ca or Sr containing glasses. In other words, the redox ratio of antimony ion in the glass melt cannot be explained based on the basicity concept of the melt. It is not the case for arsenic ions in these glasses. The [As3 + ]/[As5 +

] and [As0]/[As3 +] ratios decrease from Mg glass to Ba glass at any temperature. It is suggested that the redox states of multivalent ions in alkali silicate melts are affected not only by the basicity of melt but also by the stability of complex ion in the melt.

Keywords: differential pulse voltammetry, glass melt, refining, redox equilibrium.

0225 | Indentation- and fracture-induced structural

change of sodium borosilicate glasses Yoshinori Nishikubo1, Satoshi Yoshida1*,

Toru Sugawara1, Jun Matsuoka1

1*Department of Materials Science, The University of Shiga Prefecture, Hikone,

Shiga, Japan, e-mail: [email protected]

It is known that glass is densified under a high compressive stress. Densification changes the net-work structure of glass into the one in more dense state. Densification of glass also occurs during an indentation test. In this study, indentation-induced densification of glass with the composition 20Na2O-40 × B2O3-(80-40 x)SiO2 (mol%, x = 0, 0.5, 1, 1.5) is investigated by using a Vickers indenter. The structural change under the indentation is evaluated by Raman spectroscopy. The structure of indented glass is compared with that of unstressed glass. In addition, the structure of fractured surface of the glass fiber, which failed at several GPa under a two-point bending test, is also measured, and compared with the structure of pristine fiber. It is found that the peak assigned with the Si-O-Si bending vibration shifts to higher wavenumbers as the indentation load increases. It is also suggested that a high tensile stress causes a distinct structural change of sodium borosilicate glass fiber.

Keywords: structural change, indentation, fracture, two-point bending, raman spectroscopy, sodium borosilicate glass.



0226 | Effects of low power laser irradiation on lead and

barium vanadate glasses Jason Hah, Landon Tweeton, Ruhil Dongol,

Cory Faris, Prabesh Dulal, Steve Feller, Mario Affatigato

Physics Department, Coe College, Cedar Rapids, Iowa 52402, United States

As part of a continuing study on the effect of laser irradiation on vanadate glasses, we report on a final investigation on structural changes induced by low power 785 nm irradiation. At these power levels, the structure appears to slowly reorganize towards more crystalline arrangements, and the effect is cumula-tive. Thus, prior irradiation biases the glass towards more rapid crystallization upon further exposure to the laser light. Raman characterization of lead meta-vanadate glasses points to growth in the band at 860 cm-1, typically assigned to V-O-V ‘bridge’ vibra-tions, accompanied by a decrease in the 950 cm-1 band, usually associated with V-O stretching modes. It is thus likely that the glass begins to rearrange into longer chains, leading to the increase in V-O-V bridges, enhancing its similarity to the orthorhombic BaV phase. Other low power measurements with EDX (not reported) indicate that there are no chemical composition changes in the irradiated areas.

Work supported by the United States National Science Foundation under grant numbers DMR-0904615, DMR 0502051, DMR-MRI-0722682, and DMR-MRI- 0320861.

Keywords: lead vanadate, barium vanadate, laser irradiation, structure, raman, EDX.

0229 | Glass-ceramics containing nano-crystallites of oxide semiconductor

Hirokazu Masai1, Yoshihiro Takahashi1, Takumi Fujiwara1, Toshinobu Yoko2

1 Department of Applied Physics, Tohoku University, Japan

2 Institute for Chemical Research, Kyoto University, Japan,

e-mail: [email protected] glass-ceramics containing nano-

crystallites of TiO2 or ZnO have been fabricated. It is notable that these crystallites, especially TiO2, were precipitated as a single phase from glass matrix. Al-though oxide-semiconductors possess high refractive index, the obtained glass-ceramics containing these nano-crystallites showed transparency by control of the chemical composition and the heat-treatment process. We have demonstrated that addition of Al2O3 plays important rule for crystallization behavior of oxide semiconductors as well as preparation of ho-mogeneous glass matrix. It has also found that metal oxide that can belong to both intermediate group and network modifier group is the key for the transparent glass-ceramics containing oxide semiconductor. The

obtained TiO2 glass-ceramics show photocatalytic properties whereas ZnO glass-ceramics show exci-tonic photoluminescence. Together with examination of glass composition, several approaches for func-tionalization at the surface of glass-ceramics will be reported on the day. Since these oxide semiconduc-tors have been widely used in industrial, the obtained glass-ceramics are expected to be novel functional glass-based devices using their unique and func-tional property.

Keywords: glass-ceramics, oxide semiconductor, nano-crystallites, TiO2, ZnO.

0233 | Vitreous materials based on SIO2 for photonic applications

Horatiu Niciu1*, Dorel Radu2, Cristina Vasiliu3, Adrian Manea4, Cristiana Grigorescu3,

Daniela Niciu1, Anghel Ioncea5, Hermine Stroescu6

1National Glass Institute, Theodor Pallady Blv., No.47, Sector 3, 032266, Bucharest, Romania,

e-mail: [email protected] 2University “Politehnica” of Bucharest, Faculty of

Applied Chemistry and Materials Science, 1 Polizu Str., Sect.1, Bucharest, Romania

3National Institute of Research and Development for Optoelectronics INOE 2000, 1 Atomistilor Str., P.O. Box MG-5, Magurele, Jud. Ilfov, Romania

4National Institute for Materials Physics, 105 bis Atom-istilor Street, Bucharest-Magurele,

P.O. Box MG-7, Code 077125, Romania 5METAV CD, No 31 C.A. Rosetti Str.,

Sect. 2, Bucharest, Romania 6Institute of Physical Chemistry, Spl. Independentei

202, Bucharest 77208, Romania

The essential difficulties in producing SiO2 based vitreous materials with photonic applications are the homogeneity of lanthanide ion in the host lattice, the content of hydroxyl ions and a high degree of transparency. The purpose of the experiments re-garding the SiO2 based vitreous materials synthesis was to choose the method to insert Nd2O3 in the



oxide system. The sol-gel method was used in order to obtain multi-component powders from pseudo-homogenous sols.

The vitreous product was obtained through ther-mal treatments in controlled atmosphere.

In the samples obtained from the experiments the Nd3 + characteristic absorbtion domains were ob-served through UV-VIS spectrophotometry analysis. UV-VIS fluorescence was evaluated by excitation at 220 and 300 nm.

The Raman investigations highlighted the charac-teristic vibration spectra for SiO2 glass and the char-acteristic vibrations for O-H, Si-Cl, Al-H bonds. The photoluminiscent bands correspond to the radiative transition 4F3/2 to 4I9/2 of Nd3 + .

The results of quantitative elemental microanaly-sis through energy dispersive analysis of X-rays re-vealed the uniformity of dopant concentration in the vitreous matrix.

The advantages of using the SiO2 doped pow-der for vitrification are the simplified synthesis, the process can be monitored more efficiently and the material defects can be eliminated in the synthesis phase.

Keywords: sol-gel preparation, Nd-doped silica glass, fluorescent radiation.

0240 | Hole trap centers induced by X-ray irradiation on Yb doped silica glasses

Edson H. Sekiya, Masaru Amano, Kazuya Saito Toyota Technological Institute, Research

Center for Advanced Photon Technology, Japan, e-mail: [email protected]

Yb doped silica glass has been used to produce high power fiber laser. Generally, co-dopants such as Al and/or P have been used to suppress Yb cluster-ing, and consequently enhance the lasing efficiency. Moreover, the addition of dopants in silica glass favors the formation of photo-induced defects that can decrease the laser performance. Normally these defects appear as a pair of electron/hole trap center and present absorption in the UV-Vis-nearIR region.

In this work, Yb doped silica glasses co-doped with Al and/or P were prepared by MCVD method with a special system that supplies all compounds in vapor-phase/gasses. X-ray irradiation (Mo, λ = 0.71Å) was used to induce defects formation. UV-Vis-IR and ESR (electron spin resonance) spectroscopy were used to analyze defects. Using ESR measurements, defects such as Al-OHC, P-OHC, Si E’ center, P2 and Yb3 +

signal were observed. The increase of Al concentra-tion increases the Al-OHC population on Yb:Al doped silica samples. The Yb doping decreases the Si E’ center and P2 populations, respectively on Yb:Al and Yb:P doped silica samples. Furthermore, the Yb3 +

signal decreases with the irradiation time, indicating that an electron trap center is formed by the change

of Yb3 + to Yb2 + . More details of the influence of dopants concentration in defects formations and its relationship with absorption measurements will be presented.

Keywords: fiber laser, silica glass, Yb:Al:P doping, ESR, hole and electron trap centers.

0241 | Molecular dynamics simulation of collision-induced devitrification André Monteil1*, Stéphane Chaussedent1,

Nossair Ziani2, Marcos A. Couto dos Santos3

1Université d’Angers, Laboratoire de Photonique d’Angers, 2, bd Lavoisier, 49045 Angers, Cedex 01 –

France, e-mail: [email protected] 2Département de physique – Faculté des

sciences – Université des sciences et technologie d’Oran, BP 1505 El M’naouar Oran – Algeria

3Department of Physics – Federal University of Sergipe, Brazil

Molecular Dynamics (MD) simulations have been extensively used for the modeling of disordered glass structures and their physical properties. Particularly we have shown recently the possibility to study a glass devitrification [1,2]. In this work we performed MD numerical simulations of ionic implantation on the surface of a silica thin plate that mimic ion beam deposition. As a consequence of the ion bombing and depending on the beam energy and on the tar-get size several physical phenomena were studied: penetration depth and impact damage, sputtering, clustering of deposited ions, damped oscillations of the plate in relation to energy dissipation, local melt-ing and induced crystallization (Figure 1).

1. M. A. P. Silva, J. P. Rino, A. Monteil, S. J. L. Ribeiro and Y. Messaddeq, J. Chem. Phys., 121 (2004) 7413-7420

2. G. Dantelle, M. Mortier, A. Monteil, S. Chaussedent and M. A. P. Silva, J. Chem. Phys., 127 (2007) 094509

Keywords: molecular dynamics, glass simulation, collisions, devitrification, dynamic and thermal properties.



0246 | Energy transfer in ND, ER codoped fluoride glasses

Shintaro Mizuno1*, Hiroshi Ito1, Kazuo Hasegawa1, Hiroyuki Kawai2, Hiroyuki Nasu2, Mark A. Hughes2,

Takenobu Suzuki2 and Yasutake Ohishi2 1Frontier Research Center, TOYOTA Central R&D Labs. Inc., 41-1, Yokomichi, Nagakute-cho, Aichi 480-1192

Japan, e-mail: [email protected] 2Research Center for Advanced Photon Technology, Toyota Technological Institute, 2-12-1, Hisakata,

Tempaku-ku, Nagoya 468-8511, Japan

The fluorescence characteristics of Nd, Er codoped fluoride glasses were investigated. Er was codoped as a sensitizer of solar pumped fiber laser (SPFL). Er singly doped fluoride glass absorbed a part of the ultraviolet and visible light which could not be ab-sorbed by Nd. Under simulated sunlight illumination, Er singly doped fluoride glass displayed four emission bands with peaks at 550, 848, 977, and 1533 nm. These were attributed to the 4S3/2-

4I15/2, 4S3/2-

4I13/2, 4I11/2-

4I15/2 and 4I13/2-4I15/2 electronic transitions of

Er, respectively. Quantum efficiency measurement was carried out using an integrating sphere and an simulated sunlight. The quantum efficiency under the simulated sunlight excitation showed a maximum of 70 % at 0.5 mol.% ErF3. The 1.05 mm emission of Nd was observed from Nd, Er codoped glasses excited at 380 nm, this excitation wavelength is only absorbed by Er. Thus, energy transfer from Er to Nd occurred in Nd, Er codoped fluoride glass. It follows from this that Nd, Er codoped fluoride glass could be used as a sensitized laser medium under sunlight pumping.

Keywords: energy transfer, Nd,Er codoping, sunlight.

0247 | Synthesis and characterization of silicon oxycarbide nanotubes derived from template-guided organosilicates

Sabrina G. Faria1, Ana L. E. Godoy2, Marco A. Schiavon1*

1 DCNAT – Departamento de Ciências Naturais, Univer-sidade Federal de São João Del Rei – UFSJ, Campus

Dom Bosco, CEP 36301-160 São João Del Rei – MG, Brasil, e-mail: [email protected]

2CTM – Centro de Ciência e Tecnologia de Materiais, Instituto de Pesquisas Energéticas e Nucleares –

IPEN, CEP 05508-000 São Paulo – SP, Brasil

Organossilicate nanotubes derived from methyl-trietoxysilane (MTES) and vinyltrietoxysilane (VTES) were synthesized using ammonium tartarate as template, by the sol-gel process. From the pyrolysis of these materials at temperatures of 1000, 1200 and 1500 oC, were obtained nanotubes of silicon oxycarbide (SiOC) glasses. The precursors and the fi-nal products were characterized by TG-DTA, FTIR and XRD, and the morphology of the materials was ex-amined by optical and scanning electron microscopy

(SEM). It was confirmed the preservation of tubular morphology of the glassy material derived from hybrid organic-inorganic.

Keywords: nanotubes, silicon oxycarbide, template, sol-gel process.

0249 | Effect of crystallisation degree on hardness of glass-ceramics

Martin Jensen*, Morten M. Smedskjaer, Yuanzheng Yue

Aalborg University, Section of Chemistry, Aalborg, Denmark, e-mail: [email protected]

The dependence of hardness of basaltic glass-ceramics on their crystallisation degree has been explored by means of differential scanning calorim-etry, optical microscopy, X-ray diffraction, and Vickers indentation. Different degrees of crystallisation in the basaltic glasses have been obtained by varying the temperature of heat treatment. The change of the relative degree of crystallisation with the heat treat-ment temperature can be described by an empirical model established in this work. It is found that the hardness of the glass phase decreases slightly with an increase in the degree of crystallisation, while that of the crystalline phase drastically decreases. The predominant crystalline phase in the glass has been identified as the pyroxene augite. The hardness of the augite crystals is in the range of the hardness of a similar pyroxene, i.e., a pure diopside crystal. The hardness of the pure diopside crystal has been both measured and calculated using first principles. The calculated values agree with the measured ones.

Keywords: Hardness, glass-ceramic, crystallisation, heat treatment, basalt

0251 | XAFS study on local structures of iron and titanium

ions in borosilicate glass Shinsaku Nishida1*, Shingo Nakane1, Hiroki Yamazaki1, Shigeru Yamamoto1,

Hironori Ofuchi2, Akihiko Kajinami3, Toshihiro Okajima4, Norimasa Umesaki2

1Nippon Electric Glass Co., Ltd., 7-1, Seiran 2-Chome, Otsu, Shiga 520-8639, Japan

2Japan Synchrotron Radiation Research Institute, SPring-8 1-1-1 Kouto, Sayo, Hyogo 679-5198, Japan

3Center for Environmental Management of Kobe University, Rokkodai, Nada, Kobe, Hyogo 657-8501, Japan

4Kyushu Synchrotron Light Research Center, 8-7 Yayoigaoka, Tosu, Saga 841-0005, Japan

The local structures of iron (Fe) and titanium (Ti) ions in borosilicate glass were investigated by X-ray absorp-tion fine structure (XAFS) analysis for understanding of the light transmittance change by the sample prepara-tion conditions. The spectra of Fe K-edge and Ti K-edge regions were measured using synchrotron radiation



at beamline BL14B2 of SPring-8 in Japan. Oxidation states were discussed with X-ray absorption near edge structure (XANES) spectra, and the coordination num-ber of oxygen and the ionic distance to oxygen ions around Fe or Ti ions were evaluated from the analysis of extended X-ray absorption fine structure (EXAFS) spectra. The local structures of Ti ion didn’t show the change by the sample preparation conditions. On the other hand, the local structures of Fe ion showed the change by the sample preparation conditions. These results suggest that the change of oxidation state and/or inter ionic distance between Fe and oxygen ions lead visible light absorption of the borosilicate glass. Their relations are also discussed using the results of first-principles calculations.

Keywords: XAFS, light transmittance, iron, titanium, oxidation state, coordination number, inter ionic distance.

0253 | The structure of glasses based on molybdenum and potassium phosphate: a combinade nmr, Raman

spectroscopy and x-ray diffraction study Silvia H. Santagneli, Sidney J.L. Ribeiro, Younes Messaddeq, Matthias T. Rinke2, Rashmi Deshpande2, Hellmut Eckert2

1Laboratory Photonic Materials, Chemistry Institute-UNESP, Araraquara-SP, Brazil,

e-mal: [email protected] 2Institut für Physikalische Chemie, Westfälische

Wilhelms-Universität Münster, Germany

MoO3 containing glasses are for great interest be-cause of the specific thermal, mechanical and opti-cal properties. The extent and ability of incorporating MoO3 in glasses strongly depends on the glass former. The present work deals with the investigation of the binary glass system (1-x))KPO3 – xMoO3, with x varying from 0 to 0.7. Vitreous samples shown a good opti-cal quality up to 50% MoO3. The structural evolution of the vitreous network was monitored as a function of composition by Differential Scanning Calorimetry (DSC). The results indicate that addition of MoO3 to the KPO3 glass melt leads to a pronounced increase in the glass transition, suggesting a significant in-crease in network connectivity due to the formation of P-O-Mo connectivities. A detailed structural model was developed by the combination of Raman scatter-ing and variety of complementary solid-state NMR for 31P and 95Mo nuclei. The Raman spectra suggest that the Mo6 + ions are only bonded to some non-bridging oxygen atoms (Mo-O- or Mo=O bonded species). 31P magic angle spinning (MAS)-NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages, respectively. These sites are denoted as Q(2)

0Mo, Q(2)1Mo and Q(2)

2Mo, respectively. These results are supported by 95Mo NMR Quad-

rupolar Carr-Purcell-Meiboom-Gill (Q-CPMG) pulse sequence. The results indicate that the formation of Q(2)

2Mo linkages is favored over mixed Q(2)1Mo.

Keywords: phosphate glass; 31P-NMR; 95Mo-QCPM-NMR.

0257 | Structural and porosity studies of a compacted glass

Reshma R. Desai1*, J. A. Erwin Desa1, D. Sen2

1*Department of Physics, Goa University, Taleigao Plateau, Goa 403206,

India, e-mal: [email protected] 2Solid State Physics Division, Bhabha Atomic

Research Centre, Trombay, Mumbai 400085, India

Silica microspheres with an average diameter between 90 to 109 μm were compacted under a pressure of 2T and sintered at 640 0C to yield rigid pellets1. The porosities of these compacts continu-ously decreases from 57% free volume (from bulk densities) with sintering time. These changes are reflected in breaking stress values as a function of applied strain. The latter is a saw-tooth function that owes its shape to the fact that the number of nearest neighbors attached to a given microsphere increases with sintering time. The examination of pores within a compact by Small Angle Neutron Scattering showed that pore separations less than 400 Å are not ob-served. These measurements were repeated at lower momentum transfer values and evidence has been found for the growth of larger pores and their separa-tions as a function of sintering time. These findings are of relevance in separation and filtration applica-tions. For pellets kept at 840 0C, the individual mi-crospheres begin to coalesce and form a continuous mass of glassy material for which the porosity is seen to be substantially decreased. Diffraction studies of the latter confirm their silicate structures.

Keywords: Microspheres, porosity, small angle neutron scattering.

0259 | Salt waste encapsulation in mechanical activated glass

Malgorzata Ciecinska1*, Pawel Stoch1

1AGH – University of Science and Technology, Faculty of Material Science and Ceramics, al. Mickiewicza 30,

30-059 Krakow, Poland, e-mail: [email protected]

Vitrification is the most effective method of the hazardous waste immobilization. Toxic elements are incorporated into glass structure. Encapsulation of waste in glassy matrix by sintering waste with grinded glass mixture is one of the effective method of salt waste immobilization. Mechanical treatment of pre-cursor glass increase its reactivity and makes easer toxic elements immobilization. This process increase surface energy and at the same time increase of its crystals nucleation activity. Encapsulation of chloride salt waste in mechanically activated phosphorous glasses (above 50 mas. % P2O5) from the P2O5–



Al2O3–R2O and P2O5–Fe2O3–R2O system were inves-tigated. CaCl2 as a model salt waste was used, mix-tures CaCl2 and activated glass powder were sintered and properties of sinters were studied. XRD, DSC, SEM-EDS, ICP methods were used in the investiga-tion. Chemical components exchange and NaCl and Ca phosphate in phosphate glass matrix formation in sinters were observed. Mechanical treatment of all tested glasses increase its tendencies for crystalliza-tion. Measurement of leachability confirmed increase of the chemical durability of sinters. The obtained results showed that mechanically activation of glass increases waste loading capacity and effectiveness of salt waste encapsulation as method of its immo-bilization.

The work was supported by Project NN507458037 of the Ministry of Science and Higher Education of Poland.

Keywords: glass, glass – ceramics, mechanical activation, waste immobilization.

0260 | Mechanical activation of phosphate waste glasses

Pawel Stoch1*, Malgorzata Ciecinska1

1 AGH – University of Science and Technology, Faculty of Material Science and Ceramics, al. Mickiewicza 30, 30-059 Krakow, Poland, e-mail: [email protected]

Influence of the long time chemical activation of glass powders by mechanical grinding, on the struc-ture and properties of phosphate glass was studied. Glasses from the P2O5 – Al2O3 – R2O and P2O5 – Fe2O3 – R2O systems for waste immobilization were investigated. The influence of the mechanical activa-tion of batch on melting and components volatility and the change of structure, crystallization ability and physical and chemical properties of glass grains were studied. XRD, FTIR, DSC, SEM-EDS methods were used in the investigations. The long time mechanical treatment accelerates the glass batch melting and improves glass structure homogeneity, reducing the temperature and increases crystallization ability of the obtained glass grains. This is the result of the sur-face energy increase and at the same time increases of its crystal nucleation activity. However too long mechanical treatment diminishes the crystallization ability as a consequence of glass internal structure distortion. However some wastes are stronger bond-ed in crystals than in amorphous structure. Modifying activation procedure properly to glass composition and waste specify one may increase the effective-ness of waste in glass encapsulation method.

The work was supported by Project N N507 458037 of the Ministry of Science and Higher Edu-cation of Poland.

Keywords: glass, glass – ceramics, mechanical activation, waste immobilization.

0264 | Structural studies of coated and compacted glass microspheres

Wilson Vaz1 , J. A. Erwin Desa1*, P. S. R. Krishna2, A. B. Shinde2

1*Department of Physics, Goa University, Taleigao Plateau, Goa 403 206, India,

email: [email protected] 2Solid State Physics Division, B.A.R.C.,

Trombay, Mumbai 400 085, India

The coating and compacting of glass microspheres of average diameter 100 μm to form rigid yet porous pellets may yield enhanced properties of the coating compound. If a catalyst is the coating, the increased surface-area-to-volume ratio leads to better efficien-cy of the catalyst. In this work, compounds such as nickel, silver, lanthanum cobaltate and a luminescent glass have been coated onto these microspheres.

Neutron scattering data with the High Q dif-fractometer at Dhruva reactor upto a Qmax of 15 Å-1 have been collected. The structure of the uncoated compact was seen to be similar to a silica glass in its short-range structure but more compacted in its intermediate order. The nickel-coated compact showed reflections with lower d-spacings indicating the nickel compound to be no longer the pure metal. Borate glasses containing oxides of Pr and Nd in five different relative concentrations in the glass1 were also coated onto the microspheres. Neutron diffrac-tion data of these showed the diffracted intensity of the coating as being appreciably different from the original borate glass. Similarly, lanthanum cobaltate has been coated and its structural changes are dis-cussed. Thus, the coating’s structure needs to be characterized before its usage.1. J. A. Erwin Desa, Wilson A. Vaz, Brenda L. De

Souza and Manju Singh, Glass Technology – Eur. J. Glass Sci. and Tech. Part A, 50(4), 230-232(2009).

Keywords: glass microspheres, catalyst, luminescent glass, neutron diffraction.

0265 | Degradation of the czech art nouveau glass mosaic

Dana Rohanova1*, Tomas K. Hajek1, Silvie Svarcova2, Martin Mika1, Ales Helebrant1

1*Faculty of Chemical Technology ICT Prague – Department of Glass and Ceramics, Prague, Czech

Republic, email: [email protected]

2Institute of Inorganic Chemistry – Czech Academy of Sciences – Rez, Czech Republic

During Art Nouveau period number of remark-able glass mosaics was created. The research of two examples is submitted in this presentation. The first group of materials (glass tesserae and mortar) comes from St. Simon and Juda church (external wall) nearby town Slany and the second one from the castle Holovousy chapel. Both were originated at the beginning of the 20th century. Researched through the methods as optical microscopy, SEM/EDS, XRD



as well as XRD-F the consequences of chemical glass composition and its morphology including mortar’s influence on mosaic glass corrosion were studied. These glass mosaics are at least one hundred years fully exposed to environment. The glass mosaics mostly belong to the system SiO2 – PbO – Na2O. Glass is extremely heterogeneous and opacified with both SnO2 and Sb2O3. The deterioration of glasses mosaics surprisingly is not too high, prevailing num-ber of glasses are in good condition. The chemical bond between the glass and the mortar was found out, there is Na+ – Ca2+ ion exchange between upper layer of mortar and glass. In respect to our observa-tion the deterioration of the glass mosaic is caused mostly by decay of mortar than glass corrosion.

Keywords: Art Nouveau, glass mosaic, degradation.

0266 | Calculation of physical properties in alkali borosilicate

glasses based on the structural unitsHiroyuki Inoue1, Atsunobu Masuno1,

Yasuhiro Watanabe1, Keiichiro Suzuki2, Toru Iseda2

1Institute of Industrial Science, the University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan

2New Glass Forum, 3-21-16 Hyakuninn-cyou, Shinjyuku-ku, Tokyo 169-0073, Japan,

email: [email protected]

In alkali borosilicate glasses the coordination number of oxygen around a boron atom and the number of bridging oxygen in SiO4 tetrahedra change with the molar ratios of alkali oxide to boron oxide and silica to boron oxide. Moreover, there are BO3 triangles with 3, 2 and 1 bridging oxygen atoms, BO4 tetrahedra and SiO4 tetrahedra with 4, 3, 2, and 1 bridging oxygen atoms and the proportions of these structural units have been examined already. In this study, the proportions of boron-oxygen polyhedra were referred to the model formulated by Budh-wani et al. and the proportions of the bridging oxygen atoms of SiO4 tetrahedra were referred to the NMR analysis by Maekawa et al. We can obtain the addi-tive factor of the effect of each structural unit on the physical properties of the glasses, such as molar vol-ume, refractive index, mean dispersion, glass transi-tion temperature, Young’s modulus. We obtain the root mean square deviations of the calculated values from the experimental data presented in INTERGLAD. The results of the comparison show that the struc-tural analysis and the formulation of the structural units are useful to predict the physical properties of the glasses.

Keywords: borosilicate glass, calculation of properties, structural unit, Interglad.

0270 | Characteristics of the surface layers of industrial

glasses, thermochemically dealkalized with acid gases

Gheorghe Duca1, Vasilii Sharagov2*1Academy of Sciences of Moldova – ASM, office 1, Stefan cel Mare bd., Chisinau,

MD 2001, Republic of Moldova 2*Balti State University “A. Russo” – USB, office 38, Pushkin str., MD 3121, Balti,

Republic of Moldova, email: [email protected]

The paper investigates the composition and the structure of the surface layers of the indus-trial glasses for different purposes, thermochemically dealkalized with acid gases. Experiments were held in laboratory and industrial conditions. The subjects of investigation were sheet glass samples, bottles and jars of colorless glass, bottles of green glass, ampoules made from medical glass, illuminating glassware made from transparent colorless and milk glasses. HCl, HF, CF2Cl2, CHF2Cl, SO2, NO2, CO2 and mixtures of these gases were used as gas re-agents. Regimes of the thermochemical treatment of glass with gases are the following: temperature – between 300 and 900 0C, duration – between 1s and 2 h, quantity of gas reagent introduced into the reacting vessel – between 0.01 and 1.00 mol. The effect of regimes of thermochemical treatment with gases on the thickness and the degree of dealkaliza-tion of the surface layers of industrial glasses was defined. The dependence of the physical and chemi-cal properties of glassware on the composition and structure of its surface layers, dealkalized with differ-ent gases reagents was revealed for the first time.

Keywords: industrial glasses, thermochemical treatment, acid gases, regimes, dealkalization, surface layers, physical and chemical properties.

0271 | Study of optical and opto electronic constants of

potassium halide single crystalA. K. Verma1, C. B. Ojha2*, A. K. Shrivastava3

1Govt. Post Graduate College Dholpur, Rajasthan (India) 328001

2, 3School of Studies in Physics, Jiwaji University Gwalior (474011), M.P. (India),

emails: [email protected], [email protected]

KCl, KBr, and KCl-Br (equimolar composition) with well known NaCl structure [space group Fm3m and point group m3m (Oh)] were grown by Czochralski technique with different dopents. The grown Crystals were subjected to XRD for phase identification and lattice parameter determination. Optical absorption spectra were recorded in the wave length range from 200 to 900 nm. The results indicate that these alkali halides are transparent in visible region of spectrum. On irradiation with X-ray, they show absorption band in the visible region of spectrum. Valance electron, plasma energy, enthalpy formation of a Schottky



pair, density of ‘F’ center, formation and dissociation energy of ‘F’ center, activation energy, energy sepa-ration between outer valance band, the difference in the optical electro negativity values of the cation and anion, direct band gap, refractive index, molar refractivity, ‘F’ center absorption frequency, density of Schottky defect and electronic polarizability before and after irradiation were calculated. Presence of defect alters the atomic / ionic distribution and is ex-pected to change in the electronic level in the vicinity of the defect via forbidden gap. Present paper reports the affect of doping on these parameters. The results can be explained on the basis of elastic interaction in between the anion of different ionic radii due to size misfit in solid solution.

Keywords: potassium halide, valance election, plasma energy, activation energy and enthalpy of formation for a schoottky pair, electronegativity polarizability and refractive index molar refractivity.

0272 | Structures of samarium and dysprosium borate glasses

Mathias B. Lawrence 1*, J. A. Erwin Desa1, Reega P. K1, Snehal P. Joshi1, V. K. Aswal2

1*Department of Physics, Goa University, Taleigao Plateau, Goa 403206, India,

email: [email protected] 2Solid State Physics Division, Bhabha Atomic

Research Centre, Trombay, Mumbai 400085, India

A set of borate glasses containing oxides of Sm and Dy in five different relative concentrations have been prepared. The rare earth contents varied from 11 mole % Sm2O3 but no Dy to 5.36 mole % Dy2O3 but no Sm and 3 glasses containing both rare earths. The FTIR spectra have confirmed the borate host structures from the presence of BO4, BO3 and B-O stretch bands. The X-ray diffraction data are also those of borate structures. UV-Visible data show absorption peaks due to 4f electronic states of Sm and Dy. The successful linear combinations of these spectra in the same relative ratios as the Sm and Dy compounds occur in the glasses and indicate1 that the 4f states of the rare earth ions in the glasses do not interact. These data are compared to similar glasses containing Nd and Pr and are found to be in agreement with them. 1. J. A. Erwin Desa, Wilson A. Vaz, Brenda L. De Souza

and Manju Singh, Glass Technology – Eur. J. Glass Sci. and Tech. Part A, 50(4), 230-232(2009).

Keywords: borate glasses, rare earth oxides, UV visible, FTIR, X-ray diffraction.

0273 | Asbestos vitrification and Valorization: glass-ceramics for thermal storage of solar energy

Julien Lambert1,2, Guy Matzen1,2, Valérie Montouillout1,2, Sandra Ory1,2,

Emmanuel Véron1,2, Catherine Bessada1,2, Patrick Echegut1,2, Ulysse Michon3,

Amélie Hacala3, Xavier Py4

1CNRS, UPR3079 CEMHTI, 1D avenue de la Recherche Scientifique,

45071 Orléans cedex 2, France 2 University of Orléans, Avenue du Parc Floral,

BP 6749, 45067 Orléans cedex 2, France 3 INERTAM, 471 route de Cantegrit,

BP 23, 40110 Morcenx, France 4 CNRS, UPR8521 PROMES, University of Perpignan

Via Domitia, Rambla de la Thermodynamique, Tecnosud, 66100 Perpignan, France

Electric energy produced by thermal solar power plant is highly dependent on sunshine conditions. In order to manage fluctuations and tune up the electric production with customers demand, it is necessary to convert and to store this solar energy into thermal energy. A possible material for thermal storage is a calcium aluminosilicate based glass, called Cofalit, resulting from asbestos wastes vitrification (French ANR project SESCO: Solar Energy Storage on Cofalit).

The purpose of this work is to characterize the structural properties of this asbestos glass. However, due to the observed variations of composition of the glass, we propose the description of a representative glass model (SiO2-Al2O3-CaO-MgO-Fe2O3). Thermal analysis between ambient temperature and 1200°C indicate that once the glass is crystallized, the ob-tained ceramic is thermally stable. The cooling rate responsible for the existence domains of ceramic and glass is determined from a high temperature XRD study. Crystallization monitoring of the glass-ceramic is achieved using XRD and DSC. The obtained crys-talline phases are completely characterized by SEM and 29Si and 27Al MAS NMR.

Keywords: glass-ceramic, crystallization, vitrification, asbestos wastes, solar energy.



0274 | Temperature dependence of the absorption spectra of Nd3+-containing

silicate and borate glass meltsGoro Aso1,3, Satoshi Yoshida1,2,

Toru Sugawara2,1, Jun Matsuoka1* 1*Department of Materials Science, School of

Engineering, The University of Shiga Prefecture, Hikone, Japan, e-mail: [email protected]

2Center for Glass Science and Technology, School of Engineering, The University of

Shiga Prefecture, Hikone, Japan 3Present address: Graduate School of Human and Environmental Studies,

Kyoto University, Sakyo, Kyoto, Japan

Understanding high temperature properties of glass melts is important to improve glass manu-facturing process. Among the properties, basicity of glass melts is related to the redox equilibrium of transition metals and refining agents. Estimation of basicity will also give us many information about the reactivity of glass melts with refractories and noble metals. In the previous studies, basicity is estimated through the measurement of refractive index or the activity of oxide anion. In this study, we used Nd3+ as a probe of basicity and measured the absorption spectra of Nd3+-containing sodium silicate and bo-rate glass melts from room temperature to 1200K by using a high temperature spectrometer. 4S3/2 and 4F5/2 peak intensities of f-f transition tend to decrease by increasing the temperature for both glasses. On the other hand, intensity of hypersensitive transition 4G5/2 didn’t show temperature dependence, and the intensity of 2H11/2 transition shows a complicated temperature dependence. From these results, Judd-Ofelt parameters were calculated and served for the basisity estimation.

Keywords: basicity, optical absorption spectra, melt, rare-earth, neodymium, silicate, borate.

0276 | Organic–inorganic hybrid materials doped

with rare earth metals ions Elzbieta Zelazowska1*, Ewa Rysiakiewicz-Pasek2,

Maria Borczuch-Laczka3

1*Institute of Ceramics and Building Materials – Ddivision of Glass and Building Materials

in Cracow, 30-702 Krakow, ul. Lipowa 3, Poland, e-mail: [email protected]

2Institute of Physics, Wroclaw University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland

3Faculty of Materials Science and Ceramics, AGH University of Science and Technology,

Al. Mickiewicza 30, 30-059 Krakow, Poland

Sol-gel derived materials doped with rare earth metal ions (III) (Cerium, Terbium and Dysprosium) and small amounts of lithium ions have been pro-duced by sol-gel method. Tetraethyl orthosilicate (TEOS), poly(methyl methacrylate) (PMMA, M.W. 12 000), ethyl methacrylate ethylene glycol dimethacry-

late and some other organic additions and solvents were used as precursors of the hybrid organic-inor-ganic hosts (ca 20-40% of organic parts). The gel materials obtained were aged at room temperature for at least three weeks and dried in an electric drier at temperatures of 80 °C. The materials obtained were investigated for morphology, composition and structural properties by scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDX, X-ray diffraction (XRD), X-ray photoelec-tron spectroscopy (XPS) and Fourier transform infra-red spectroscopy (FTIR, KBr technique). The UV-VIS spectroscopic characteristics and luminescence spectroscopy results were obtained for hybrids coat-ed into thin layers on glass. optical The excitation and emission luminescence spectra have been reg-istered and an influence of the host microstructure and organics content of the materials obtained was analyzed.

Keywords: sol-gel, hybrid materials, luminescence, rare earth.

0277 | Diffusion time and non-radiative relaxation time in lscas doped with

binary oxide mixtures Eu and VNilson E. Souza Filho1, Ana C. Nogueira1, Antônio N. Medina1, Mauro L. Baesso1,

Antônio C. Bento1*, Helion Vargas2, E. C. Silva2

1Universidade Estadual de Maringá – UEM, Maringá – PR

2 Universidade Estadual do Norte Fluminense Darcy Ribeiro – Campos dos Goytacazes – RJ

The phase resolved photoacoustic (PRPA) tech-nique is a powerful tool for studies of the signal of dif-ferent constituents of composite sample for resolving their individual spectra at fixed modulation frequency. If two bands centered at the wavelengths λA and λB in the PA spectra are identified, we can measuring nonradiative relaxation time τr in a solid, this time represents the mean value of times of each center takes to generate the heat in sample. The finite times that the heat generated at these absorption centers takes to diffuse to the sample surface (sample-air interface) and generate the acoustic signal is called characteristic diffusion time τβ within optical absorp-tion length lβ. Since that whether known the pre-dominant thermal mechanism that generate photo-acoustic signal, a phase-shift expression can be used for determinate τβ. The mathematic expression of phase-shift for thermal expansion (SPA ∝ w -1) and for thermal diffusion (SPA ∝ w -3/2) is well known and was elaborate another phase-shift expression that is like a combination of thermal expansion with thermal diffusion (SPA ∝ w -1 ≤ ν ≤ -3/2), for a



thermally thick optically transparent sample. The pro-posed model is experimentally tested using low silica aluminosilicate glass doped with Eu and Vn.

Keywords: RG theory, thermal expansion, thermal diffusion, phase resolved photoacoustic, nonradiative relaxation time, characteristic diffusion time, silica aluminosilicate glass (LSCAS).

0279 | Sol-gel derived hybrid materials doped with Eu3+ and Sm3+ ions

Elzbieta Zelazowska 1,*, Ewa Rysiakiewicz-Pasek2, Maria Borczuch-Laczka3

1Institute of Ceramics and Building Materials, Division of Glass and Building Materials in Cracow, 30-702

Krakow, ul. Lipowa 3, Poland, e-mail: [email protected]

2Institute of Physics, Wroclaw University of Technology, Wybrzeze Wyspianskiego 27,

50-370 Wroclaw, Poland 3Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow, Poland

The sol–gel procedure has been used for prepara-tion of the hybrid organic-inorganic materials doped with rare-earth (Eu3+ and Sm3+) and lithium ions. Tetraethoxysilane (TEOS), AlCl3⋅ 6 H2O and ethyl methacrylate, butyl methacrylate, ethyl acetoacetate and some other organic compounds were used as the inorganic and organic precursors, respectively. The resultant materials were aged for three weeks at ambient temperature and dried for 3 hours at 80 °C –125 °C. Scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDX), Fourier-Transform Infrared Spectroscopy (FTIR, KBr technique), Nuclear Magnetic Resonance 29Si MAS NMR and X-ray diffraction (XRD) were used to char-acterize the morphology and structure of the hybrids obtained. The excitation and emission spectra were recorded at room temperature using fluorescence spectrometer equipped with a pulsed xenon lamp as the excitation source. UV-visible absorption spectra were measured with spectrophotometer. Structural properties of the hybrid materials have proved to be strongly dependent on organic additives. Photolumi-nescence (PL) intensities increasing with the organic part and lithium ions content (20-40%, 0.1-0.2%, respectively) and decreasing with water content were observed. The dominant emission peak at about 616 nm in the PL spectra corresponds to 5D0 → 7F2 transi-tion of Eu3+.

Keywords: sol-gel, hybrid materials, luminescence, rare earth.

0280 | Electrical and structural characterization of Li1+xAlxTi2-x(PO4)3

glass-ceramicsAna Candida Martins Rodrigues1, José Luis Narváez Semanate*2

1Universidade Federal de São Carlos – UFSCar, São Carlos – SP

2*Programa de Pós-graduação em Ciência e Engenharia de Materiais – LaMaV – UFSCar,

São Carlos – SP, e-mail: [email protected]

Li1+xAlxTi2-x(PO4)3-LATP glass-ceramics were ob-tained by single (SHT) and double (DHT) stage heat treatments. For SHT samples, Scanning Electron Microscopy (SEM) revealed a microstructure with a bimodal grain size distribution with small grains local-ized around larger grains. Backscattered electrons images, energy dispersive spectroscopy analysis and X-ray diffraction showed that, small grains are a sec-ond solid solution of the same structure and with a composition close to that of the LATP main phase. It is shown that, in the case of a SHT, the ionic con-ductivity increases when the temperature treatment increases. For samples obtained by DHT, i.e., a heat treatment to induce nucleation followed by a second one for crystal growth, the ionic conductivity tends to increase when the duration of the nucleation treat-ment is reduced. It was also shown that samples obtained by DHT with a final treatment at 900 °C presented higher electrical conductivity than samples obtained by SHT at the same temperature. Thus, in the case of SHT, the crystallinity of the samples is the main parameter governing the electrical conductiv-ity. For a same crystallinity, as it is the case of DHT samples, the electrical conductivity tends to increase with the average grain size.

Keywords: glass-ceramics, crystallization, impedance spectroscopy, grain size, crystallinity.

0281 | Rethinking of Glass transition temperature data

V. S. Minaev1,2,*, S. P. Timoshenkov2, V. V. Kalugin2

1State Unitary Enterprise “Scientific-production center “Spurt “, Russia

2Moscow Institute of Electronics Engineering (Technical University), Russia, e-mail: e-mail: [email protected]

The concept of polymer-polymorphoid structure of glass and glassforming liquid (CPPSGGL) [1,2] pro-poses a new view at the temperature and process of glass transition.

Tamman in 1933 proposed the symbol Tg and the term “glass transition temperature” for the tem-perature at which the viscous-flow liquid turns into a brittle solid. Highly viscous flow of liquid – “region of transformation”, “glass transition” – is characterized by almost straight line of viscosity sharp rise (fall) in the range of ~108...~1015 Pa∙c. In the 1014-1016 Pa∙s curve “viscosity-temperature” undergos sharp bend, corresponding to transition into the brittle



state (Winter-Klein, Nemilov), characterized by Tg, proposed by Tamman. The free energy of activation of viscous flow E*η at viscosity 1015 Pa∙s in a simple substances is near to the dissociation energy of chemical bonds (Nemilov), that associates with the transformation of “viscous-flow ↔ a brittle state.”

In [1,2] is shown that the generally accepted glass transition temperature Tg at the viscosity of 1012,3 Pa∙s is a reverse temperature Trev of structure frag-ments (polymorphoids) interconversion of different polymorph modifications (PMs) without translational symmetry (long-range order), but with near- and intermediate-range orders, wich is an analogous of the interconversion temperature of crystalline PMs. Ignorance of this fact led to an erroneous attribu-tion of symbol Tg to temperature and meaning “glass transition temperature”.

Summarizing the data of Tammann, Winter-Klein, Nemilov and [1,2], we can say that the viscosity of the glassforming substance ~ 108 Pa∙s character-izes by the beginning of the transformation process “supercooled liquid – solid glass”, the viscosity of ~ 1012,3 – characterizes the temperature of the reverse of polymorphoids of high- and low-temperature PMs in viscous-flow liquid, the viscosity of 1015 Pa∙s char-acterizes Tamman’s temperature of the glass transi-tion (Tg).1. V.S. Minaev, In: Semiconducting Chalcogenide

Glass I. Glass Formation Structure and Stimulated Transformation in Chalcogenide Glasses. Eds. R. Fairman and B. Ushkov. V.78 of Semiconductors and Semimetals. Elsevier Academic Press. Amsterdam, New York. 2004. Chap.4. Pp.139-179.

2. V.S. Minaev, J. Optoelectron. Adv. Mater. 2009. V.11. N12. P.1946-1949

Keywords: glass transition temperature, polymorphoid, viscosity.

0282 | Glass sintering: modeling and experimental test of particle shapeAnne J. Barbosa1*, Raphael M. C. V. Reis1, Eduardo B. Ferreira2, Miguel O. Prado3,

Edgar D. Zanotto1

1*LaMaV – Laboratório de Materiais Vítreos, Departamento de Engenharia de Materiais,

Universidade Federal de São Carlos, SP, Brasil, e-mail: [email protected]

2 Faculdade de Engenharia, UNESP – Universidade Estadual Paulista, DMT, Guaratinguetá – SP, Brasil

3Comisión Nacional de Energía Atómica, Centro Atómico Bariloche, Materiales

Nucleares, Bariloche, Argentina

The classical model of Frenkel (F) allows one to predict the density of compacts of monodispersed spherical glass particles in the initial stage of sinter-ing, whereas the Clusters model extends the use of the F model to a size distribution. However, a de-viation from F is found when the particles are not spherical. To account for the effect of particle shape on the sintering kinetics, an empirical constant ks,

denominated shape factor, is used to fit the mea-surements of shrinkage or densification of a compact as a function of time or temperature. The fitted ks values reported in the literature vary from 1.8 to 3.0. Nevertheless, when one uses the Clusters model to compare the sintering kinetics of spherical particles with that of irregular (crushed) particles having the same (original) size distribution, one is comparing not only shapes, but also different packings. Thus, the effect of particle shape on the sintering kinetics deserves further attention. In this paper we propose and demonstrate a way to describe irregular particle shapes and their effect in the kinetics of viscous flow sintering. Finally we make a first attempt to incorpo-rate the influence of different morphological param-eters related to irregular particles into the Clusters model.

Keywords: clusters model, shape factor, sintering, glass ceramics, irregular particles.

0290 | A study of bulk and films of TeO2-ZnO glasses

R. Raj Kumar1, A. K. Bhatnagar1,2

1School of Engineering Sciences & Technology 2School of Physics, University of Hyderabad,

Hyderabad 500046, India, e-mail: [email protected]

Tellurite glasses are being extensively investigated because of their excellent optical and other applica-tion oriented properties. Here, we present results on (100-x).TeO2-x.ZnO, where x = 30, 35 and 40, and 70.TeO2-(30-x).ZnO-x.PbO where x=10, 15, 20, bulk glasses and a comparative study of bulk and films of 70.TeO2-30.ZnO. Bulk glasses were prepared using conventional quenching and films were prepared by RF sputtering. X-ray diffraction confirmed glassy na-ture of both. The energy gap (Eg) values for (100-x).TeO2-x.ZnO glasses decreased with x by about 5% as x changed from 30 to 40 (Eg = 3.39 eV for x = 30). The addition of PbO resulted in decrease of Eg by approximately 20% but it did not change much with increase in PbO content. Films of 70.TeO2-30.ZnO were deposited on glass and fused quartz substrates under different Oxygen partial pressures and had thickness of ~100nm. Surprising Eg value of films on glass substrates turned out to be about 15% higher which further slightly increased with oxygen pressure. Films on quartz substrates showed higher energy gap values (Eg ≅ 4.45 eV) with the same Oxygen partial pressure. These results along with other measure-ments like AFM and Raman studies on these glasses as well as with Er2O3 doping will be presented and discussed.

Keywords: optical properties, oxygen partial pressure, quartz and glass substrates, afm and raman studies.



0296 | Nonlocal effects on the low-temperature behavior of

non-crystalline solidsNelson G. C. Astrath, Ervin K. Lenzi,

Luiz R. EvangelistaDepartamento de Física, Universidade Estadual de

Maringá, Avenida Colombo, Maringá, Paraná, Brasil, e-mail: [email protected]

Since the pioneer work of Zeller and Pohl, it is well known that the thermal properties of non-crystalline solid are very different from the crystalline ones [1]. Despite a series of important contributions, a complete explanation starting from the elementary excitations for the specific heat data in the low tem-perature region is still lacking. In this work, we in-vestigate the role of nonlocal effects represented by fractional terms in the kinetic energy on the descrip-tion of the thermal behavior of the specific heat of non-crystalline solids at very low temperature [2]. We discuss the possible role of a simple model formed by the direct sum of two Hamiltonians, one of which is obtained by incorporating fractional derivatives in the kinetic energy of a conventional Hamiltonian, and another one accounting for the presence of phonons in the system [3]. Some experimental data are used to support the proposed description.1. R. C. Zeller and R. O. Pohl, Phys. Rev. B4, 2029

(1971).2. E. K. Lenzi et al. Eur. Phys. J B62, 1484 (2008)3. E. K. Lenzi, N. G. C. Astrath, R. Rossato, and L. R.

Evangelista, Braz. J. Phys., 39, 2A, 507 (2009).

Keywords: specific heat, glassy systems, fractional calculus.

0297 | Gold nanoparticles-based glass filters: immobilization of gold

nanorods on a glass surfaceDenis Gentili1, Mauro Comes-Franchini1, Cristina Siligardi2, Consuelo Mugoni2,*,

Guido Ori2, Monia Montorsi21Dipartimento di Chimica Organica “A. Mangini”,

Facoltà di Chimica Industriale, Università di Bologna, Viale Risorgimento 4, 40136, Italy

2,Dipartimento di Ingegneria dei Materiali e dell’Ambiente, Facoltà di Ingegneria,

Università di Modena e Reggio Emilia, Via Vignolese 905, Modena, Italy,


Glasses with optical functionalities are important also for a number of specific technological applica-tions, such as decorative coatings, catalysis, optical filters, non-linear optical materials, etc..[1] Different methods exist in order to provide glasses with very special optical behavior, and metal nanoparticles rep-resent a widely used solution for this purpose. Noble metal nanostructures have attracted much interest because of their unique properties, including large optical field enhancements resulting in the strong scattering and absorption of light.[1] Gold nanorods

(GNRs) are promising nanostructures because of their unique and fascinating anisotropic optical and physical properties.[1] Longitudinal plasmon reso-nance (LPR) band of GNRs can be tuned from the visible to near infrared (NIR) wavelength range by changing their aspect ratio (length-to-width ratio).[1] The unique optical properties of gold nanorods suggest that they may have potential applications in coatings for optical control (filter with gold), as solar radiation control on windows.[2]

This work demonstrate the feasibility to immobi-lize GNRs on a solid-support as a glass slide. Fur-thermore, the importance of changing the surface chemistry of GNRs[3] has been demonstrated in view to transfer the peculiar optical properties of GNRs on a solid-state support as a glass surface in view of optical device-field application prospects.1. P. K. Jain, X. Huang, I. H. El-Sayed and M. A. El-

Sayed, Acc. Chem. Res. 2008, 41, 1578.2. X Xu, TH Gibbons, MB Cortie, Gold Bulletin, 2006,

39, 4, 156.3. D. Gentili, G. Ori and M. Comes Franchini, Chem.

Commun., 2009, 5874.

Keywords: gold nanorods, surface functionalization.

0300 | In vitro behaviour of hybrid zirconia/ polycaprolactone composites

Michelina Catauro1*, Flavia Bollino1, Duilio Verardi1, Cristina Leonelli2

1*Department of Mechanical and Aerospace Engineering – Second University of Naples –

Via Roma 21, 81031 Aversa – Italy, e-mail: [email protected]

2Department of Materials and Environmental Engineering, University of Modena and Reggio Emilia,

Via Vignolese 905, I-41100 Modena, Italy

The aim of this research was to sintesyze, by using the sol-gel technique, new hybrid organic-inorganic materials for bone tissue engineering with a biode-gradable polyester, the poly-ε-caprolactone (PCL) and zirconia as inorganic matrix. The sol–gel technique is based on the hydrolysis and polycondensation of metal alkoxides. Hybrid inorganic/organic ZrO2-5wt% Y2O3/PCL composites, containing 0, 6, 12, 24, 50 wt% of the organic component, were synthesized by using zirconium propoxide Zr(OC3H7)4 and yttrium chloride YCl3 as inorganic precursor and polycapro-lactone (PCL) as organic precursor.

A FITR analysis was used to study chemical inte-raction between the components. The structure of interpenetrating network was realized by hydrogen bonds between Zr-OH group in the sol-gel interme-diate species and carboxylic group in the repeating units of the polymer proved by the presence on FTIR spectra of 3200 cm-1 and 1650 cm-1 bands.

Biocompatibility of tested materials was investiga-ted in vitro on Balb/c 3T3 mouse fibroblasts by MTT assay. Annexin V-FITC and propidium iodide co-stai-ning was performed and analyzed by flow cytometry. Human mesenchymal stem cell (hMSC) were seeded



on specimens and cell proliferation was evaluated by Alamr Blue Assay. Furthermore cell differentiation was investigated by measuring alkaline phosphatase activity. These hybrid composites were biocompatible

Keywords: sol-gel, organic/inorganic hybrid, biocompatibility.

0301 | Preparation and characterization of geopolymers as hard tissue

prostheses materialsMichelina Catauro1*, Flavia Bollino1, Duilio Verardi1, Isabella Lancellotti2,

Luisa Barbieri2, Cristina Leonelli21*Department of Mechanical and Aerospace Engineering – Second University of Naples –

Via Roma 21, 81031 Aversa – Italy, e-mail: [email protected]

2Department of Materials and Environmental Engineering, University of Modena and Reggio Emilia,

Via Vignolese 905, I-41100 Modena, Italy

Geopolymers are inorganic polymerirs emerging in many fields as innovative materials. This paper focuses on their potentional application as hard tis-sue prostheses. Geopolymers, in fact, because of their nextwork structure, possess the ability to link to bone matrix. The work presents complete FT-IR, SEM/EDS and XRay studies of several geopolymer formulations obtained changing water content, water to solid content and curing conditions, maintaining constant the ratios among Na-Al-Si. The presence of zeolitic phases has been observed by XRD at the sur-face of the material. The amorphous matrix is typical of sodium aluminosilicates with stretching bands at 950-1250 cm-1 and at 420-500 cm-1. In order to study their bioactivity, samples of the different mate-rials were soaked in a simulated body fluid (SBF), the bioactivity of the synthesized geopolymers has been showed by the formation of a layer of hydroxyapatite on the surface of the materials.

Keywords: Geopolymers; spectroscopy; biomaterials

0302 | Structural investigations and crystallization tendency of soda-lime borosilicate glasses

containing lanthanides: effect of Al2O3 addition

Daniel Caurant1, Isabelle Bardez1,2, Odile Majérus1*, Pascal Loiseau1,

Nolwenn Chouard1,2,Thibault Charpentier3, Philippe Vermaut4, Jean-Luc Dussossoy2

1Laboratoire de Chimie de la Matière Condensée de Paris (UMR-CNRS 7574) – ENSCP

(Chimie-ParisTech) – 75231 Paris, France, e-mail: [email protected]

2Laboratoire d’Etudes et Développement de Matrices de Conditionnement – DEN/DTCD/SCDV, CEA Marcoule – Bagnols-sur-Cèze, 30207, France

3CEA, IRAMIS, Service Interdisciplinaire sur les Systèmes Moléculaires et Matériaux – CEA Saclay – 91191 Gif-sur-Yvette, France

4Laboratoire de Métallurgie Structurale (UMR-CNRS 7045) – ENSCP (Chimie-ParisTech) –

75231 Paris, France

For more than thirty years, borosilicate glasses represent the main kind of matrix used industrially to immobilize highly radioactive nuclear wastes. As lanthanides represent one of the most abundant families of fission products in these wastes, it is important to study how lanthanide cations are incor-porated in the glassy network and how their solubil-ity may be affected by composition changes. In this paper, we studied the impact of Al2O3 addition on properties, crystallization tendency and structure of a glass belonging to the system SiO2-B2O3-Al2O3-ZrO2-Na2O-CaO-Ln2O3 (Ln = La,Nd) by varying the ratio R = ([Na2O]+[CaO])/([Na2O]+[CaO]+[Al2O3]) from 0.35 to 1. Our interest was mainly focused on the environment of Ln3+ cations, on the glassy network structure and on Na+ cations distribution by using a multispectroscopic approach: Nd optical absorption and EXAFS, Zr EXAFS, (29Si,27Al,11B,23Na) MAS NMR and Raman. Simple silicate, borate and alumino-silicate glasses containing lanthanides were used as structural references. It appears that the structural role of lanthanide cations changes from a modifier role for peralkaline composition (R > 0.5) to a charge compensator role of (AlO4)

- units for peraluminous compositions (R < 0.5). A strong decrease of glass crystallization tendency (apatite Ca2Ln8(SiO4)6O2) is observed for peraluminous compositions.

Keywords: lanthanides, neodymium, glass structure, EXAFS, optical absorption, crystallization, apatite.



0303 | Production of photonic crystal fiber based on heavy oxide glasses for non linear applications

Danilo Manzani1*, Igor Skripachev1, Younés Messaddeq1, Sidney J. L. Ribeiro1

1Universidade Estadual Paulista – UNESP, Instituto de Química, Araraquara – SP,

Brazil, e-mail: [email protected]

Photonic crystal fiber (PCF) or microstructured fibers, has been studied widely, either to obtain a high nonlinearity, due the enhancement of optical nonlinearity in PCF achieved by high confinement of light. High nonlinearity fibers achieved by the syner-gism between the fiber microstructuration and glass composition. In this work, vitreous preforms have been prepared and characterized in the systems based on tellurite, phosphate and lead phosphate glasses, containing high concentration of heavy oxide atoms, such bismuth, lead and tungsten. For the design of performs, an alternative process to the stack and draw is proposed in order to avoid the ex-cess of losses due to this technique. Microstructured performs have been developed by drilling technique, with two different clad microstructuration (hexagonal and triangular shapes), both with a solid core. We will describe elaboration and optical characterizations of oxide glasses photonic crystal fibers, and then dis-cuss about the conditions to be considered to reach low loss highly non-linear oxide glasses fibers, es-pecially concerning the elaboration of performs and the control of the dispersion. The attenuation was obtained and will be presented with a discrete mea-surement at 1.06 and 1.55 μm as well as a spectral attenuation curve in the near infrared.

Keywords: feavy oxide glasses,non linearity, photonic crystal fibers, near infrared.

0304 | Structural investigation of lead phosphate glasses by

NMR and raman spectroscopyDanilo Manzani1*, Karina Rancan1,

José F. Schneider2, Silvia H. Santagneli1, Younes Messaddeq1, Sidney J. L. Ribeiro1

1*Universidade Estadual Paulista – UNESP, Instituto de Química, Araraquara – SP, Brazil,

e-mail: [email protected] 2Universidade de São Paulo – USP, Instituto de Física de São Carlos, São Carlos – SP, Brazil

Glasses with high lead concentration have some interesting features such as low melting tempera-tures, large wide glass formation region, high re-sistance against devitrification and good radiation shielding for γ-rays. In this work, glasses were syn-thesized according to the composition rule PbHPO4 –WO3 (10% ≤ WO3 ≤ 70%) by the melting-quenching method. A structural investigation was carried out as a function of tungsten concentration using 207Pb and 31P NMR, EXAFS on Pb LIII edge, DSC and Raman

scattering. The local environments around Pb were analyzed by 207Pb-NMR using the QCPMG spin-echo technique. In the compositions without tungsten, Pb was found in sites with an average coordination number (CN) estimated between 8 and 9. As WO3 is introduced in the glass, the electronic density around 207Pb is strongly perturbed with respect to the highly symmetric state in the W-free glass, revealing the appearance of Pb-O-W bonds, confirmed by Raman scattering. The average CN for Pb decrease as a func-tion of the concentration of WO3, attaining a plateau for glasses with 40%WO3≤70%, corresponding to a variation of CN of -1 with respect to the W-free glass. The state of the phosphate network was probed with 31P high-resolution NMR, showing the appearance of phosphate units establishing P-O-W bonds.

Keywords: lead phosphate glasses, coordination number, nuclear magnetic resonance, EXAFS.

0305 | White light generation in rare earth doped germanium bismuth

tellurite glasses and optical fibersYannick Ledemi1*, Danilo Manzani1,

Sidney J.L. Ribeiro1, Younés Messaddeq1

1Universidade Estadual Paulista – UNESP, Instituto de Química, Araraquara – SP, Brazil,


Recently, upconversion multicolor (red, green and blue) and white fluorescences have been exten-sively investigated in glasses by doping with different combinations of rare earth ions. In this work, we report the infrared to visible upconversion of Tm3+/Yb3+/ Ho3+ triply doped germanium bismuth tellurite glasses by exciting with a laser diode at 980 nm. The composition of the host matrix chosen for this study is 65TeO2-15GeO2-10Bi2O3-5K2O-5Li2O. The glass samples were investigated by DSC, Raman scat-tering, FT-IR and m-line technique to measure the refractive index The glass samples obtained showed high thermal stability against crystallization and good optical properties. Finally, step index optical fibers with triply doped core have been successfully obtained from this system using“sucking method”. Attenuation and fluorescence spectra for optical fiber were obtained.. The dependence of the Tm3+, Ho3+, Yb3+ concentrations and ratios on their visible and infrared emissions upon excitation at 980 nm has been studied. Colour tunability as a function of pump power is also reported.

Keywords: Tm3+/Ho3+/Yb3+ ions doping, tellurite glass, optical fiber, upconversion fluorescence..



0307 | On the diffusion coefficient for crystal growth and

viscous flow in diopside glassDaniel R. Cassar¹*, Marcio L. F. Nascimento¹,

Edgar D. Zanotto¹, Vladimir M. Fokin², V. P. Klyev²

*1PPG-CEM,Vitreous Materials Lab, LaMaV, Universidade Federal de São Carlos – UFSCar,

São Carlos-SP, Brazil, e-mail: [email protected]

2S.I. Vavilov’s State Optical Institute – St. Petersburg, Russia

Diopside (CaO.MgO.2SiO2) glass reveals predomi-nant surface (heterogeneous) crystallization when sufficiently heated. We measured crystal growth rate data, U(T), and analyzed them together with viscosity data for glass samples of the same batch in the range 740–954 °C (Tg = 723 °C). Two different crystal morphologies were detected by optical and electron microscopes. Growth of crystals nucleated on the sample surface stopped by the formation of crystals of the second morphology. X-ray diffraction revealed that the external layer and the inner layer are composed by different phases, i.e.: diopside and a wollastonite solid solution, respectively. But both phases have similar chemical composition. The two crystal types exhibited similar growth rates. Most intriguing, we observed that the growth rates of diop-side at sufficiently low temperatures (below 1.08Tg, viscosity = 100 MPa.s) are systematically higher than those predicted by the screw dislocation model when the diffusivity is calculated by the Stokes-Einstein/Eyring equation using viscosity. A change of growth mechanism at this temperature cannot yet be completely ruled out, but this discrepancy strongly suggests a possible breakdown of SE/E equations at such high viscosity level.

Keywords: crystal growth, diopside, glass, crystallization, diffusion, viscosity.

0309 | Characterization of whitlockite in 3Cao.P2O5-SIO2-MGO bioactive

glass-ceramic systemJuliana K. M. F. Daguano1*,

Claudinei dos Santos1,2, Paulo A. Suzuki11*Departamento de Engenharia de Materiais/ Escola de Engenharia de Lorena – EEL/USP –

Lorena – SP, e-mail: [email protected] 2Centro Universitário de Volta Redonda, Campus

Três Poços, UNIFOA – Volta Redonda – RJ

Bioglasses obtained by 3CaO.P2O5-SiO2-MgO system, present high amount of Whitlockite-phase, after crystallization process. This crystalline phase is a phosphate based on calcium-magnesium solid-so-lution, with Ca2,589 Mg0,411(PO4)2 composition, being also known as β-Tricalcium phosphate. The TCP has a low dissolution rate, as well as interesting features of chemical stability and mechanical strength, which meets the requirements to be a resorbable material

for bone restoration. Therefore, it is interesting to characterize the phase structure of Whitlockite. The glasses of composition 52.75% CaO.P2O5- 30% SiO2 – 17.25%MgO (%wt.) were heat-treated at tempera-tures ranging from 775°C to 1100°C, for 4h and 8h. The samples were analyzed by High Resolution X-Ray Diffraction (HRXRD). The crystal structure of Whit-lockite was refined by Rietveld method, showing the effect of time and temperature of heat treatment in lattice parameters and the unit cell volume of phase. Also through the Rietveld method was possible to quantify the Whitlockite percentage in different glass-ceramics. The coefficient of thermal expansion was also determined by measurement of lattice param-eters at high temperature and subsequent Rietveld refinement. The results obtained are compared with literature data.

Keywords: bioglass, crystallization, whitlockite, 3CaO.P2O5-SiO2-MgO-system, high resolution x-ray diffraction, rietveld analysis, coefficient of thermal expansion.

0314 | Hydrogen storage in glass capillaries – h-diffusion and

mechanical strength Peter Ried, Martin Gaber,

Martin Beckmann-Kluge, Michal Gula, Miriam Grueneberg,

Kai Holtappels, Ralf Mueller BAM Federal Institute for Materials Research and

Testing, Berlin, Germany , e-mail: [email protected]

The energy density of today’s hydrogen storage systems in combination with fuel cells bridges the gap between batteries and liquid hydrocarbons. The efficient conversion of chemical energy into electri-cal energy is a major advantage to existing systems supplying electrical energy for a large number of stationary and mobile applications on demand. Hol-low glass spheres and glass capillaries are research targets for safe and economic storage of hydrogen under high pressures in addition to state of the art high-pressure-cylinders. Hydrogen permeability and mechanical strength are key requirements for the aimed applications as light energy storage systems. Especially glass capillaries are dedicated for fast stor-ing and discharging of hydrogen. Therefore, concepts for the determination of the hydrogen permeability through capillaries of different glass compositions under high pressure gradients are presented. The method requires special handling regarding high filling pressures up to 700 bar. Burst pressure tests were applied to evaluate the mechanical strength of capillaries.

Keywords: hydrogen storage, glass capillaries.



0317 | Evaluation of the masking effect of opaque fedspatic

ceramics for metal ceramic restorationsWashington Steagall Junior1*,

José Roberto Martinelli2, Glauco Fioranelli Vieira3

1*Universidade de São Paulo Faculdade de Odontologia – FOUSP, Campus de São Paulo,

São Paulo – SP, e-mail: [email protected] 2Instituto de Pesquisas Energéticas e

Nucleares CCTM, IPEN, São Paulo – SP 3Universidade de São Paulo Faculdade de Odontologia

– FOUSP, Campus de São Paulo, São Paulo – SP

The objective of this study was to evaluate the masking effect of two brands of opaque ceramics (Vintage Halo-VH and Noritake–NO), on shades A1, A35, and B3, through the infinite optical thickness equation (IOT), from the Kubelka Munk (KM) algo-rithm, when a translucent material becomes effec-tively opaque. For each brand and shade, a total of six specimens 12 mm in diameter (three with 2mm and three with 0.64mm thick), were prepared. All specimens were submitted to a polishing procedure, followed by a reflectance analysis in a spectropho-tometer with an integration sphere (optical range 400-700 nm).The reflectance spectra were analyzed by the KM algorithm, and the IOT was determined in millimeters. The data were treated with ANOVA and Tukey tests. The value of 0.3mm of opaque was chosen as a qualitative (clinical) limit for a metal ceramic restoration. The results were shade dependent. Samples were named according to the type of ceramic and shade. The infinite thickness was VHA35 (1.07 ± 0.16a); NOA35 (1.15 ± 0.14a); NOA1 (1.36 ± 0.23ab); NOB3 (1.40 ± 0.15ab); VHA1 (1.50 ± 0.14ab); VHB3 (1.79 ± 0.09b). The VHA35 ceramic showed the greatest masking effect, and the lowest IOT. The VHB3 had the lowest mask-ing, and the greatest IOT. The mean values of IOT for all ceramics were three to five times greater than 0.3 mm (p < 0.05).

Keywords: fedspatic dental porcelains; kubelka munk theory, infinite optical thickness, spectrophotometry, masking effect, restorative dentistry.

0318 | Elastic moduli of Bioglass and bioactive glass-ceramic of the

3CaO.P2O5-SIO2-MGO systemJuliana K. M. F. Daguano1*,

Claudinei dos Santos1,2, Ervino C. Ziemath3

1*Departamento de Engenharia de Materiais – EEL/USP, Lorena – SP, e-mail: [email protected]

2Centro Universitário de Volta Redonda – UNIFOA, Campus Três Poços, Volta Redonda – RJ

3Departamento de Física – IGCE/UNESP – Rio Claro – SP

Glasses based on the 3CaO.P2O5-SiO2-MgO sys-tem present high bioactivity aiming the use as bone restorations. The crystallization process improves the mechanical properties of the material, extending the

possibilities of their use. However, materials used in implants need of low elastic modulus, close to the bone, avoiding the problem known as “stress shield-ing”. In this work, glasses of composition 52.75% CaO.P2O5- 30% SiO2 – 17.25% MgO (%wt.) were heat treated at 700 °C, 725 °C, 775 °C, 975 °C and 1100 °C, for 4h. The samples were analyzed by XRD and the amount of residual amorphous phase was determined. Density measurements were carried out using the He-gas pycnometer method, and porosity was evaluated by the geometric method and the Ar-chimedes method. The elastic moduli were found by the pulse-echo method. Samples V700, V725 and V775 presented Young’s moduli near 90GPa, while the samples V975 and V1100 presented values close to 130GPa. Although the results of Young’s modulus is lower for glass, for the selection of a bulk biomaterial it is necessary to take into account other factors such as mechanical strength and bioactivity.

Keywords: bioglass, crystallization, 3CaO.P2O5-SiO2-MgO-system, elastic moduli, pulse-echo method.

0319 | Luminescence at 1550 nm in Yb3+-Er3+ co-doped calcium aluminosilicate glassesMarcio J. Barboza1, Aline M. Farias1,

Jurandir H. Rohling1, Antonio N. Medina1, Idelma A. A. Terra2 and Luiz A. O. Nunes2

1Universidade Estadual de Maringá – UEM – Maringá – PR, e-mail: [email protected]

2Instituto de Física de São Carlos – USP, São Carlos – SP

In this work two series of Yb3+-Er3+ co-doped calcium aluminosilicate glasses were prepared under vacuum atmosphere. The first one [34 – (2 + x)/3]CaO + [27,9 – (2 + x)/3] Al2O3 + [34 – (2 + x)/3]SiO2 + 4,1MgO + 2Yb2O3 + xEr2O3 (CAS) and the second [47,4 – (2 + x)/3]CaO + [39,5 – (2 + x)/3] Al2O3 + 7SiO2 + 4,1MgO + 2Yb2O3 + xEr2O3 (LSCAS) were melted having x = 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 wt%. The thermo-optical and thermal properties were determined using photothermal techniques, op-tical interferometry and the thermal relaxation calo-rimetry. These properties were almost constant as a function of the erbium content. The energy transfer processes between Yb3+-Er3+ ions were also investi-gated through luminescence measurements. The lu-minescence lifetimes values, at 1535 nm, increased as a function erbium concentration due to interac-tions between Er3+ ions. In addition, a decrease of the Yb3+ (at 980nm) luminescence was observed, followed by an increase of that of Er3+, at 1550 nm, what was attributed to the energy transfer processes between Yb-Er when pumped at both 915 and 975 nm, respectively.

Keywords: glass, aluminosilicate, luminescence, lifetime, erbium, ytterbium.



0320 | Mechanisms of optical bleaching of silver containing particles

in photo-thermo-refractive glassJulien Lumeau, Leonid B. Glebov

CREOL, The College of Optics and Photonics, University of Central Florida, 4000 Central Florida Blvd,

ORLANDO, FL 32816-2700, e-mail: [email protected]

Photo-thermo-refractive (PTR) glass is a photo-sensitive multi-component glass which is commer-cially used for the recording of volume holographic elements and finds many applications in advanced laser systems. Refractive index decrement in this glass is observed after UV exposure followed by thermal development. This procedure also causes the appearance of Ag containing particles that can be then optically bleached by using the second har-monic of a Nd:YAG laser. Despite the broad usage of this method, its mechanisms are still unclear. In this paper, we present a systematic study of the bleaching kinetics versus incident energy per pulse and bleaching dosage. No beaching of Ag containing particles occurs for energy density in laser pulses be-low 0.1 J/cm2 while above 1 J/cm2, the efficiency of bleaching saturates. Efficiency of bleaching depends on the type of particles to be bleached (Ag, AgBr…). Using a simple model of short pulse laser interac-tion with nano-particles embedded in glass, we show that the temperature of the Ag containing particles reached during the laser interaction is large enough to produce complete dissipation of these particles which is expected to be the main mechanisms of optical bleaching.

Keywords: photosensitivity, optical glasses, non-linear laser interaction, nanoparticles.

0322 | Luminensce and thermo-optical properties of calcium aluminosilicate

glasses doped with Er2O3

Aline M. Farias1*, Marcio J. Barboza1, Jurandir H. Rohling1, Antonio N. Medina1, Idelma A. A. Terra2 and Luiz A.O. Nunes2

1*Universidade Estadual de Maringá – UEM, Maringá – PR, e-mail: [email protected]

2Instituto de Física de São Carlos – USP, São Carlos – SP

In this work a set of calcium aluminosilicate glasses doped with different concentrations of er-bium was prepared. The composition was (34-x/3)CaO + (27,9-x/3)Al2O3+(34-x/3)SiO2 + 4,1MgO + xEr2O3, having x = 0,5; 1; 2; 4; 6; 8. The samples were melted in vacuum atmosphere, to eliminate the presence of OH- radicals, and were studied through the measurements of optical, thermal, thermo-optical and spectroscopic properties. Mass density and refractive index presented increased behavior as a function of doping concentration. The values of specific heat, thermal diffusivity and temperature

coefficient of the optical path length (dS/dT) were almost constant for all samples. On the contrary, significant changes in the luminescence lifetime at 1550 nm were observed, varing from 8 to 12.6 ms, what was associated with interactions between Er3+ ions. These results showed that as low is the Er2O3 concentration lower will be the emission intensity at 1550 nm, important information in terms of possible use of this glass for the development of lasers at 1550 nm.

Keywords: glass, erbium, calcium aluminosilicate, luminescence, lifetime.

0327 | Structural changes between glass and melt: the window glass

Laurent Cormier1*, Georges Calas1, Brigitte Beuneu2

1*IMPMC, CNRS, Université Pierre et Marie Curie, Université Paris Diderot, Paris, France,

e-mail: [email protected] 2Laboratoire Léon Brillouin, C.E.A.

Saclay, Gif-sur-Yvette, France

Understanding the structural modification be-tween glasses and liquids for silicates is an important issue from a fundamental, geological or technologi-cal point of view. The optimal compositions of many commercial glasses (such as window glass) are close to the ternary 75SiO2-15Na2O-10CaO. Despite its importance for our daily life, the window glass struc-ture is still poorly understood and almost nothing is known on its melt structure though it can be a major constraint to understand heating processes in furnaces.

In this study we have investigated the structural evolution between glass and melt using neutron dif-fraction from room temperature up to the liquid state (7C2 diffractometer, LLB, France). The experimental data have been coupled with numerical simulations (Molecular Dynamics + Reverse Monte Carlo). As well known for silicates, the basic structural units SiO4 does not change with temperature. However, the neutron diffraction data show changes in both the structure factors and correlation functions. These modifications affect mainly the medium range order-ing. The modeling of the structure allows a better un-derstanding of these modifications and a description of the cation (Na, Ca) environments and distributions within the silicate network.

Keywords: glass, melt, structure, neutron diffraction.



0328 | Photonic crystal fibers for generation of non-linear optical

effects in the infraredM. El-Amraoui1, J.Fatome1, , F. Smektala1,

J.C. Jules1, G. Gadret1, S. Salaun1, G. Renversez4, I. Skripachev2, F.C. Polachini2,

Y. Messaddeq2, J.Troles3, L. Brillant4

1 Institut Carnot de Bourgogne, UMR 5209 CNRS-Université de Bourgogne, Av. A. Savary,

21078 Dijon, France 2Institute of Chemistry − UNESP, P.O. Box 355,

Araraquara, SP, CEP 14801-970, Brazil 3Laboratoire Verres et Ceramiques, UMR,

CNRS 6512, Universite Rennes I, Rennes, France 4Institut Fresnel, UMR 6133 CNRS- Université Paul

Cézanne Aix-Marseille 3, Avenue Escadrille Normandie Niemen, 13397 Marseille, France

Possibility to generate efficient non linear effects above 2 μm is of great interest nowadays. High intrin-sic transparency of chalcogenide glasses allows to reach this spectral region and their high non linearity can be increased by the design of photonic crystal fiber geometry. In this work, we present some results of fabrication and optical characterizations of As2S3 microstructured optical fibers. Two types of fibers, both with a solid core, have been developed. The first one presents three and four rings of holes in a hexagonal arrangement. The second one is made of a small hanged core linked to the fiber clad region by three supporting struts. The background level of losses is from 0.34 to 0.7 dB/m at 1.55μm for fiber with three rings of holes.

Dispersion characteristics of PCF have been mea-sured. The value of zero material dispersion for PCF based on As-S glass was shifted for approximately 3 mm. The results show the possibilities of material dispersion correction with the use of PCF based on chalcogenide glass.

Super-continuum (giant spectral broadening of the light pulse) was obtained in the infrared range of spectrum. Bandwidth of super-continuum exceeds 30 times in comparison to excitation source param-eters in the near IR region.

Keywords: . photonic crystal fiber (PCF), PCF for infrared, arsenic sulfide glass.

0332 | Control of ultraviolet transparency of silica glass

synthesized by vapor-phase methodJuliana S. dos Santos*, Eduardo Ono,

Tarcio P. Manfrim, Mirella O. Boery, Carlos K. Suzuki

State University of Campinas – UNICAMP, Faculty of Mechanical Engineering, Department of

Materials Engineering, Campinas – SP, e-mail: [email protected]

Silica glass synthesized by vapor-phase method has been considered the best material among commercial optical glasses currently available for employing as optical element in litho tools. Knowing that high transparency in UV region is an essential requirement for such purpose, this work describes the effect of consolidation atmosphere (He flux) and temperature on UV transparency of silica boules synthesized by VAD (vapor-phase axial deposition) method. After the deposition stage, boules were con-solidated in an electric furnace for 2 hours by varying the He flux in the interval 750–1750 sccm and the temperature from 1380 to 1500 °C. Consolidated samples of 5 mm thickness were characterized by optical absorption spectrophotometry to measure the optical transmittance in the 300 nm wavelength. Silica boules with the highest transmittance of 91 % were obtained by adjusting the He flux at 1250 sccm. This He content was enough for a complete pores collapsing into the material. Above this flux, the consolidation furnace temperature decreased, and consequently, boules with high degree of po-rosity was obtained. Also, 1470 °C was the best temperature found to consolidate the nanoparticles. Above this limit, at 1500 °C, it was noticed a start of material crystallization.

Keywords: silica glass, vapor deposition method, optical transparency.

0333 | PhotoluminescenCe emission in undoped lead oxifluoroborate glasses

José E. De Souza1*, Seila R. de Souza1, Luis Borrero1, Francisco E. G. Guimarães1,

Jean-Claude M’Peko1, Antonio C. Hernandes1

1*Instituto de Física de São Carlos – IFSC/USP, São Carlos – SP, e-mail: [email protected]

Oxifluoroborate systems have been widely studied due to its large window transmission, high refrac-tive index, good stability and a large glass forming region. However, to the best of our knowledge, any photoluminescence emission (PL) in undoped glasses of these systems has been reported. Here, the compositions 50BO1.5-(50-x)PbO-xPbF2, with x = 0, 5, 10, 15 and 20 cationic percentages were studied in terms of its optical properties. The excitation spectra were recorded between 280 nm up to 500 nm, with the detection kept in 590 nm, and the maximum intensity varies from 330 nm for



composition with x = 20 until 370 nm for the one where x = 5. The emission spectra (200-1100nm) show a broad PL band centered on 600 nm when the glasses are excited with UV light (300-400 nm) and the intensity also depends on the composition, increasing with the addition of PbF2. The PL emission becomes larger and larger when falling the tempera-ture to cryogenic levels and where the losses through non-radioactive process are minimized. The actual agent involved in PL of undoped lead oxifluoroborate glasses remains unclear, although Pb2+ ions can be quoted as the main responsible for emitting.

Keywords: undoped lead oxifluoroborate glasses, photoluminescence emission, Pb2+ ions.

0334 | Waveguides amplifiers of erbium doped GeO2-PbO-Ga2O3 glasses

written with femtosecond laser Davinson M. da Silva1, Luciana R. P. Kassab2,

Anderson S. L. Gomes3, Thiago Lemos3

1Escola Politécnica da Universidade de São Paulo – EPUSP, São Paulo – SP

2Faculdade de Tecnologia de São Paulo – FATEC-SP, São Paulo – SP

3Departamento de Física – UFPE – Recife, PE, e-mail: [email protected]

Active waveguides have been produced for the first time in an erbium-doped GeO2-PbO-Ga2O3 glass. The glass was produced by the melt-quenching technique and channel waveguides were written in the glass using a 100fs Ti:Sapphire laser system delivering 800nm pulses at 1kHz repetition rate. The channels were written with different laser pulse ener-gies and scan speeds. The passive and active opti-cal properties of the waveguides are reported. The minimum value of total loss is 8.4 dB and the best condition for the optical amplification at 1550nm under 980 nm excitation is obtained for 5mW laser power using 0.05 mm/s for the scan velocity. In this case the maximal internal gain obtained is 3dB which is similar to the gains reported in the literature for sili-cate and phosphate glasses codoped with Yb3+ and Er3+. The results obtained in the present work are promising for the fabrication of Er-doped integrated amplifiers lasers based in GeO2-PbO-Ga2O3 glasses.

Keywords: active waveguides, laser writing, germanate glasses, femtosecond laser processing of materials, ultrafast laser.

0336 | Windshield armor with complex geometry

Diniz Pereira Gonçalves1, Wagner Farias da Rocha2, Tetunori Kajita3,

Francisco Cristóvão Lourenço de Melo4

1Comando Geral da Tecnologia Aeroespacial – São José dos Campos – SP, e-mail: [email protected]

2Comando Geral da Tecnologia Aeroespacial – São José dos Campos – SP, e-mail: [email protected]

3*Divisão de Materiais/Instituto de Aeronáutica e Espaço, AMR/IAE/CTA – Comando-Geral de

Tecnologia Aeroespacial – São José dos Campos – SP, e-mail: [email protected]

4Divisão de Materiais/Instituto de Aeronáutica e Espaço, AMR/IAE/CTA – Comando-Geral de Tecnologia

Aeroespacial – São José dos Campos – SP, e-mail: [email protected]

The development of windshield armor with com-plex geometry for a Brazilian EMB314 Super Tucano aircraft is presented in this work. The windshield is composed of layers of soda-lime glass, polycarbon-ate and polyurethane. Tests were performed at Brazil-ian Air Force Research Laboratory (CTA) to evaluate the armored windshield properties such as ballistic and bird impact resistance, environmental conditions and optical requirements.

Keywords: armor, windshield, bird impact, armored glass.

0339 | Influence of alkaline earth on the structure of aluminate glassesMarina Licheron1,2*, Valérie Montouillout1,2,

Sandra Ory1,2, Francis Millot1,2, Daniel R. Neuville3

1CEMHTI- CNRS, 1D Avenue de la Recherche Scientifique, 45071 Orléans Cedex- France 2Université d’Orléans, Faculté des Sciences,

45067 Orléans cedex 2, France 3CNRS-IPGP, 4 Place Jussieu, 75005 Paris, France

On the contrary to the calcium aluminate glasses, few works on aluminate glasses containing strontium and barium are reported. Recently, we have elabo-rated new MO- Al2O3 glasses with different amounts for MO between 32 and 75 % (M = Ba or Sr). Glassy samples are obtained from the contactless free cool-ing of liquid drops using an aerodynamic levitation furnace.

In this work, the effects of alkaline earth on the density and Tg were discussed and the structure of glasses was analysed by Raman and 27Al NMR spec-troscopies. Unpolarized Raman spectra were mea-sured at room temperature on a T64000 Jobin-Yvon confocal micro-Raman spectrometer equipped with a CCD detector. The 514.532 nm line of a coherent 70 Ar+ laser was used as the exciting source. The evo-lutions of intensity and frequency of Raman bands were discussed in terms of nature and size of the modifier cation. 27Al MAS and MQ-MAS NMR experi-ments were used to characterize the local environ-



ment of aluminium in the network. Even if aluminium is mainly tetracoordinated to oxygen, and the number of bridging oxygen vary between 2 and 4 around Al. An accurate estimation of the population of differ-ent aluminium sites was obtained by the simulation of both MQ-MAS and quantitative MAS spectra. The role of the alkaline earth cation on the depolymerisa-tion of the aluminate network is discussed.

Keywords: glasses, aluminates, alkaline earth, raman, NMR.

0340 | Synthesis and structure of new SrO-Y2O3-Al2O3 glasses

Marina Licheron1,2*, Dominique de Ligny3, Didier Zanghi1,2, Valérie Montouillout1,2, Sandra Ory1,2,

Francis Millot1,2 and Daniel R. Neuville4

1CEMHTI- CNRS, 1D Avenue de la Recherche Scientifique, 45071 Orléans Cedex- France 2Université d’Orléans, Faculté des Sciences,

45067 Orléans cedex 2, France 3Université de Lyon, Université Lyon 1, LPCML

UMR 5620, 69622 Villeurbanne, France 4CNRS-IPGP, 4 Place Jussieu, 75005 Paris, France

Y2O3-Al2O3 compounds doped with rare earth elements are used in pumped lasers[1] or scintilla-tors [2]. However, their aptitude to vitrify is quite low compared to other aluminate glasses. They can not be elaborated using the classical melting-quenching process, in a standard furnace. We used an aerody-namic levitation furnace where the heating is per-formed using two CO2 lasers. The association of high temperature melting (around 2000 °C) and very fast quench (300 K/s) insures the formation of strontium yttrium aluminates glasses.

The influence of strontium content on density and Tg is discussed and the structure of obtained glasses is systematically investigated by 27Al MAS and MQ-MAS NMR and EXAFS/XANES at the Sr and Y K-edges at high temperature. Al speciation varies as a function of chemical composition and Sr/Y ratio and temperature. These results are compared with our recent Raman and NMR structural investigations in alkaline earth aluminate binary systems [3]. 1. D.L. Yu and D.Y. Tang, “Experimental study of a

high-power cw side-pumped Nd:YAG laser,” Opt. Laser Technol. 35, 37-42 (2003).

2. S. Belogurov et al, “Characterization of Yb:YAG and Yb:YAP scintillators by means of LAAPD at temperature around 100 K*1”, Nucl. Instrum. Methods Phys. Res. A 461, 361 (2001)

3. M. Licheron, V. Montouillout, F. Millot and D.R. Neuville, “Raman and 27Al NMR structure investigations of aluminate glasses : (1-x)Al2O3 – x MO, with M=Ca, Sr, Ba and 0.5<x<0.75)”, J. non Crystal. Solid (submitted).

Keywords : glasses, aluminates, rare earth, XANES, EXAFS, NMR.

0347 | Temperature dependency of the simultaneous removal behavior of SOx,

HCl and B2O3 by Ca(OH)2 in the exhaust gas from the furnaceRyota A.1, Takashi. M1, Yasuo. H1

1AGC Reserch Center – JPN, e-mail: [email protected]

Some acid gases, SOx, HCl and B2O3 etc, are emitted from the furnace when borosilicate glasses are melted. For the removal of these gases, dry gas cleaning system with Ca(OH)2 is usually used around 450K, because above 450K SOx and HCl do not still condensate, and below 450K SOx and HCl was known to be effectively removed. But around 450K B2O3 is not removed sufficiently from our experi-ments.

To study the removal behavior of B2O3 coexisting with SOx and HCl by Ca(OH)2, a pilot plant experi-ments were carried out in the temperature range of 400-600 K using “bag filter” which was one of the most popular dry cleaning systems. The sorption capacity of Ca(OH)2 for SOx, HCl and B2O3 were evaluated by the wet analysis measurement of the gas concentration before and after the bag filter.

According to our results, the removal behavior of SOx, HCl and B2O3 by Ca(OH)2 changed with temperature dynamically and complicatedly. The temperature dependence for HCl and SOx was same tendency, but that for B2O3 was completely op-posite. It seemed that the sorption of HCl and SOx interrupt that of B2O3.

Keywords: boron, Sox, HCl, Ca(OH)2, bag filter, exhaust gas.

0351 | Recycling of the waste glass to the art

Sureyya Oskay Istanbul Universitys – Vocational School of Technical

Sciences – Avcilar Campus,Istanbul, TURKEY, e-mail: [email protected]

Glass, West Asia, starting from Iraq, Egypt, Mesopotamia, Syria, the Mediterranean and Europe, extending to the sand has emerged as one of the adventure. Advice from the raw materials are the core of Nature, is formed after melting can be mixed in certain proportions. Again and again to enter into production, is a material that can be converted back forever. With the development of glass industry in our country every year for recycling the thousands of tons of broken glass industry was established many. Waste, the polluter is important is to reach the recycling sector. Window to window glass that is cut incorrectly companies bring to our school and thus solving the waste problem as well as training to support very large. Waste glass is colorful and shape as a result of research we do on the form and color richness artistic studies were obtained. Fusion technique, known in our country in recent years and



become quite common is a glass processing tech-niques. A fusion glass, compared with normal glass price is quite expensive. Glass painting and tradi-tional painting techniques perform operations with lower costs to make the original work is possible. Has inspired artists from colorful tulips. Glass directed to research the idea has to do. Models created in the process of preparation of tulips, templates are pre-pared glass is cut; colored by the fusion technique has been shaped.

Keywords: glass, fusion, recycling.

0353 | Catalytic properties of titanium and titanium-silicon oxide layers

prepared by sol-gel methodMarek Nocun* Slawomir Kwasny

AGH – University of Science and Technology, Department of Material Science and Ceramic, 30-059 Kraków, Al. Mickiewicza 30 Poland,


Glasses with catalytic effect are of much interest recently as catalytic layer is very effective in reduc-ing of pollutants witch leads to reduction in cleaning costs. There are several methods of TiO2 preparation with good catalytic properties, but sol-get technique offers opportunity to enhance catalytic effect by pre-cise optimization of the composition and microstruc-ture of the layer. The study concerns optimization of the composition and preparation technology of catalytic layers based on SiO2-TiO2 system. Catalytic effect was studied using rhodamine B as a sensor. UV-VIS and photoelectron spectroscopy ware the main research tools used in this study.

Keywords: catalytic effect, titanium layer, sol-gel, rhodamine B.

0355 | Determination of mobility and charge carriers concentration from ionic conductivity data in silver iodide/silver phosphate glasses above and below

glass transition temperatureMarcio Luis Ferreira Nascimento 1,2*,

Ana Candida Martins Rodrigues3

1*Vitreous Materials Lab, Institute of Humanities, Arts & Sciences, Federal University of Bahia, Rua Barão de Jeremoabo s/n, PAF 3, Ondina University Campus, CEP 40170-115 Salvador – BA, Brazil,

e-mail: [email protected] 2PROTEC, PEI — Postgraduate Program in Industrial

Engineering, Polytechnic School, Federal University of Bahia, Rua Aristides Novis 2, Federação, CEP 40210-630 Salvador – BA, Brazil

3Laboratório de Materiais Vítreos, Departamento de Engenharia de Materiais, Universidade Federal de São

Carlos, CEP 13565-905 São Carlos – SP, Brazil

Conductivity data in the xAgI⋅(1‑x) AgPO3, glassy system (0 < x < 0.5) have been collected below and above their glass transition temperatures (Tg). A microscopic model assumes that the ionic displace-ment results from the migration of interstitial posi-tively charged cationic pairs whose concentration is an activated function of temperature. Below Tg, their migration is also an activated mechanism but a “free volume” mechanism prevails above this temperature.

The fit of conductivity data to this model in the whole temperature range, allows the determina-tion of charge carriers formation and migration en-thalpies. For the six investigated compositions, the charge carrier’s formation enthalpy decrease with x (0.86 to 0.25 eV), while migration enthalpy remains constant, close to 0.13 eV.

Using these values, mobility and charge carriers concentration to ionic conductivity in the glassy state may be then separately calculated.

Mobility values at room temperature are identical to those previously measured by Hall effect tech-nique (6 ± 2) × 10−4 cm2/V⋅s and independent of AgI content. The ratio of the number n+ of charge carriers with the total number n of silver cation, n+/n, is estimated between 6 × 10−8 and 6 × 10−3 at this temperature. These values are in accordance with the defect theory and the weak electrolyte theory extended to ionic conductive glasses.

Keywords: silver ionic conductivity, mobility, hall effect, defect theory, weak electrolyte theory, ravaine-souquet model.



0359 | Structure of silico-phosphate glasses studied

by mas nmr and ftir methodsMaciej Sitarz 1*, Bulat Katarzyna1,

Zbigniew Fojud 2, Zbigniew Olejniczak 3

1Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Cracow, Poland

2 Institute of Physics, Adam Mickiewicz University, Poznań, Poland

3Institute of Nuclear Physics PAN, Cracow, Poland Faculty of Materials Science and Ceramics,


Silico-phosphate glasses of NaCaPO4-SiO2, NaCaPO4-AlPO4-SiO2 and NaCaPO4-BPO4-SiO2 sys-tems have been the subject of the presented investi-gations. Silico-phosphate glasses are well known bio-materials as well as precursors for glassy-crystalline materials obtained by controlled crystallization of glass. The interest in glassy-crystalline materials is due to their specific properties which combine prop-erties of glasses with those of crystalline materials. Design of new glassy-crystalline materials requires the detailed knowledge of the precursor glass struc-ture. The analysis of the amorphous materials struc-ture due to the lack of long-distance order, is rather studied by NMR, FTIR and Raman spectroscopy, which are sensitive for short-distance order, than by x-ray methods.

The main goal of the present work is detailed structure analysis of the silico-phosphate materials studied by NMR, FTIR and Raman methods. Spec-troscopic studies in the far infrared (FIR) range have made it possible to establish that all the investigated samples have been amorphous giving no distinct bands in FIR Middle infrared (MIR) and Raman in-vestigations together with mathematical spectra decomposition into component bands have shown that the glasses from NaCaPO4-SiO2, NaCaPO4-AlPO4-SiO2 and NaCaPO4-BPO4-SiO2 system exhibit domain structure. It was confirmed by 23Na 31P, 27Al and 11B NMR studies. 27Al NMR investigations have shown that all aluminium is in tetrahedral coordina-tion (network forming cation). 11B NMR investigations have shown that boron is in tetrahedral and triangle coordination.

Investigations of silico-phosphate materials from NaCaPO4-SiO2, NaCaPO4-AlPO4-SiO2 and NaCaPO4-BPO4-SiO2 system have made it possible to deter-mine the influence of aluminium and boron on the silico-phosphate glasses structure.

This work was supported by Polish Ministry of Science and Higher Education under Grant No. N N507393135.

Keywords: biomaterials, bioglass, glass structure, glass-ceramic.

16:30-18:30 h Poster Presentations, Friday, Sept. 24 Posters #0368-0487

19:30 h Conference Bouquet Churrascaria Fogo de Chão


0368 | Eu3+ doped phosphotungstate and phosphate/Carboxy-methyl-cellulose

low temperature glassesAnne J. Barbosa1*, Felipe C. C. Reis2,

Lauro J. Q. Maia3, Luis D. Carlos4, Rute A. S. Ferreira4, Younès Messaddeq2,

Sidney J. L. Ribeiro2

1*LaMaV – Laboratório de Materiais Vítreos, Departamento de Engenharia de Materiais,

Universidade Federal de São Carlos, Sáo Carlos – SP, Brasil, e-mail: [email protected] /

2LaMF – Laboratório de Materiais Fotônicos, Departamento de Química Geral e Inorgânica,

Universidade Estadual Paulista, Araraquara – SP, Brasil 3Instituto de Física, Universidade Federal de Goiás, Goiânia, Brasil

4Departamento de Física, Universidade de Aveiro, Aveiro, Portugal

Sodium polyphosphate is a water soluble inorgan-ic polymer displaying interesting coordinating proper-ties towards metal ions that have led to several tech-nological applications ranging from water softening to colloidal stabilization. In water, the interaction of polyphosphate chains with electrolytes such as Ca2+ or Mg2+ salts leads to the separation of two phases, one highly viscous, rich in colloidal particles, the “co-acervate”, and other very poor in colloidal particles, “the equilibrium liquid”. One of the interesting points related to polyphosphate coacervates is that low temperature processing can lead to low temperature phosphate glasses that can find several new applica-tions in materials science. In this work phosphotung-state and phosphate/carboxy-methyl-cellulose(CMC) low temperature glasses were prepared containing Eu3+. Characterization techniques included MEV, FTIR and RAMAN spectroscopy, X-Ray and luminescence measurements. Relatively strong Eu3+ red emission was observed and studied as a function of composi-tion. Emission quantum efficiency was also evaluated and it was found to increase with the increase in the tungstate content. Potential applications for these news low temperature glasses optics are shown.

Keywords: coacervate, Eu3+, glasses, polyphosphate, tungstate, carboxy-methyl-cellulose.

0370 | Using ZnO and Er2O3 as decolorants in the manufacture

of tablewareNoel Nóbrega Pinto1, Oscar Peitl2, Ana Candida Martins Rodrigues2*

1Nadir Figueiredo Industria e Comercio Av. Morvan Dias Figueiredo, 3535, Vila Maria, São Paulo –SP, Brazil

2Universidade Federal de São Carlos – Departamento de Engenharia de Materiais- Laboratório de Materiais

Vítreos, São Carlos – SP, Brazil

Residual color from iron ions in raw materials is a decisive factor in the quality of soda lime products manufactured for domestic use. This impurity has a negative effect on the visual aspect of housewares, causing glass manufacturers to focus continuous efforts on controlling it. Because the industry uses natural raw materials, the iron content is variable, making it difficult to maintain the same redox condi-tions in the furnace. In commercial flint glasses, the Fe2+/ Fe3+ ratio is responsible for the final color of the product, which may display a greenish shade. In order to align the color to market demands, the glass industry must minimize the effect of the presence of iron oxide by adding decoloring agents to the glass batch.

In this work, ZnO and Er2O3 were added as decolo-rants to standard formulations (maximum 200 ppm Fe2O3) for the production of commercial tableware. Batches of 100g of raw material mixtures were melt-ed in ZAS crucibles in an electric furnace. The trans-mittance in the wavelength of visible light was then measured in the resulting glass. Satisfactory results were achieved when calcium oxide was replaced par-tially by 3.5 wt% of zinc oxide. However, the addition of small amounts of ZnO raises costs considerably. On the another hand, the use of 0.071 % of Er2O3 proved more feasible, since the results indicate it is possible to reduce the quantities of other decolorants such as selenium and cobalt while keeping the glass transmittance up to at least 92%.

Keywords: decolorant, flint glass, iron oxide, residual color, tableware.

Poster PresentationsFriday, Sept. 24

Poster Presentations, Friday, Sept. 24


0372 | On fragile, moderate, strong and ‘superstrong’ silica glass types

Marcio Luis Ferreira Nascimento1,2*1*Vitreous Materials Lab, Institute of Humanities,

Arts & Sciences, Federal University of Bahia, Rua Barão de Jeremoabo s/n, PAF 3,

Ondina University Campus, CEP 40170-115 Salvador – BA, Brazil, e-mail: [email protected]

2 PROTEC, PEI, Postgraduate Program in Industrial Engineering, Polytechnic School, Federal University of

Bahia, Rua Aristides Novis 2, Federação, CEP 40210-630, Salvador – BA, Brazil

We analyzed extensive literature data on silica viscosity, η, between the glass transition, Tg, and the melting point, Tm, for four of five types of commer-cial silica glasses. η is extremely dependent on the impurity level (i.e., including OH‑, alkali metals or chlorine), much more than in multi-component, de-polymerized, silicate glasses. The breakdown of silica glass structure due to impurities promotes more ‘fragile’ systems. Theoretically, “superstrong” silica

glass should have a fragility value ( )( )

10log/

gg T T

dm

d T Tη

=

=

near 17 considering the Vogel-Fulcher-Tammann-Hesse (VFTH) empirical law ( )10 0log /A B T Tη = + ‑ (η in Pa⋅s) – where A, B and T0 are constants. It is clear that calculated m values depend on how to proceed using such constants as free. To reduce the number of adjustable parameters, it was considered the following possibilities: i) A =‑5 fixed and varied B and T0; ii) A and B free and T0 restricted; iii) all three parameters free. Considering the reduced chi-square (χ2), values show that: i) in wide temperature range Arrhenius behavior 10log ' '/A B Tη = + is not appli-cable, just VFTH; ii) T0 is lower than Tg, as expected, taking into account all possibilities; iii) Considering hypothesis where A = ‑5 is fixed, strong (m = 17.7) up to moderate (m = 39.3) silica glasses were ob-tained. iv) Some SiO2 types presented near the same fragility values. v) Fragility concept can be useful to classify different types of silica glasses. vi) It is thus possible to preview new and even fragile silica struc-tures.

Keywords: silica, fragility, viscosity, viscous flow, vogel-fulcher-tammann-hesse equation.

0379 | Glass formation and structure of Li2B4O7-NaF system

L.A. Gasparyan, K.B. KnyazyanInstitute of General and Inorganic Chemistry,

10 Argutyan 2 distruct, Yerevan 375051, Armenia

It is known that introduction of fluorine in oxide glass formation systems favours glass formation broadening and obtaining glass with original charac-teristics.

The glass is synthesized in platinum crucible, in an electric furnace at 900-1100 0C temperature environment for 60 minutes. The study of Li2B4O7-NaF system showed, that in case of average speed of fusion cooling (102 Kmin-1) a huge area of glass formation is arisen. Transparent and flakiless glasses are formed in case of NaF till 65 mol%, meanwhile in case of 65-80 mol% cooling fusion opalescent glass is extracted. In case of a large amount of fluoride the fusion is crystallized. As a result of research, it is discovered that there exist two areas of glass formation in the mentioned pseudo-binary system and in 15-25 mol% area of NaF interruption of glass formation is connected with the formation of fluorine containing congruent fusing Li8B16O28

,NaF combina-tion. It is expressed with maximum temperature on the melting diagram. It was shown, that 30-50 mol% fluoride containing glass is inclined to crystallization.

According to the results of x-ray analuses it turned out that in case of 20-40mol% fluoride con-tent, especially crystallized phases are considered to be low temperature Li4B10O17, Li2B8O13 borons, where main forming groups are BO3, BO4, LiO4 and LiO6 in case of more amount of fluoride (> 40mol%) in the result of glass crystallization, except the main borons, LiBOF4 and NaBOF4 oxy-fluorides are extracted.

Keywords: opalescent glass, pseudo-binary system, crystallization, glass formation, crucible.

0380 | Effect of fluoride on the physico-chemical properties, crystallization processes and

glassformation of the BaO–B2O3–2AlF3∙3LaF3 system

Karen A. Nalbandyan1*, Nikolay B. Knyazyan2, Nora M. Harutyunyan3

Institute of General and Inorganic Chemistry of NAS RA, Argutyan str.10, District 2,

0051, Yerevan, Armenia, e-mails: [email protected],

[email protected]

Glasses of the fluorine containing borate system, in contrast to glasses of the oxide-borate system, have great value and are obviously important for



researchers, because they are studied to a less ex-tent and new quality glasses with extreme properties could be obtained on their basis.

Specific effect of fluorine ion on the phenom-ena of glass formation and crystallization, glasses’ structure and properties in the borate glass-forming system has been identified.

Glass-forming region of the BaO–B2O3–2AlF3⋅3LaF3 system has been researched. It has been found out that in the BaO–B2O3–AlF3/LaF3 system glass-forming region is in the following intervals: feeding up to 45 mol% of BaO in the section of BaO–B2O3 and up to 25 mol% of 2AlF3⋅3LaF3 in the section of B2O3–AlF3/LaF3, homogenous transparent glasses are obtained. Introducing more fluorine causes crystallization of glass-forming melt and sharp rise of the liquidus temperature.

By means of DTA data of glasses of the BaO–B2O3–2AlF3⋅3LaF3 and B2O3–2AlF3⋅3LaF3 systems de-pendences of the liquidus temperature and tempera-ture interval of crystallization on the fluoride content have been designed.

As a result of X-ray phase analyses of crystal-lized samples of the BaO–B2O3–2AlF3⋅3LaF3 system glasses it has been found out that glasses crystal-lization causes mainly separation of BaO∙Al2O3⋅B2O3, 2Al2O3⋅B2O3 and La(BO2)3 compounds and partially 9Al2O3⋅2B2O3, Al3BO6, LaBO3, La3BO6 ones. Together with fluoride increase, intensities corresponding to AlF3 and LaF3 compounds are more pronounced on the diffractograms.

Physico-chemical properties of glasses of the BaO–B2O3–2AlF3⋅3LaF3 system have been studied; it has been identified that the glasses are fusible, have high values of refractive index (1.574÷1.712), wide regions of variation of density 2.5÷4.15 g/cm3), thermal coefficient of linear expansion (TCLE) (67÷81⋅10-7 0C) and vitrification temperature.

As a result of IR-spectroscopic analyses it has been determined that in parallel with fluorides intro-duction, coordination transformations of BO3↔BO4 and AlO4↔AlO6 run in the whole concentration region. Within the region of glass formation, com-pounds are separated, in the structure of which boron and aluminum appear mainly by three and six coordination numbers. Fluoride introduced promotes reduction of constraint degree of the glass structural network, generation of shorter borate and fluorine-borate anion groups.

Keywords: borate glass-forming system, glass-forming region, liquidus temperature, physico-chemical properties, DTA, X-ray phase analyses, IR-spectroscopic analyses.

0383 | Production and properties of high-purity TeO2-ZnO-Na2O-Bi2O3 and

TeO2-WO3-La2O3-MoO3 glassesA.N. Moiseev1, , V.V. Dorofeev1*, A.V. Chilyasov1, I.A. Kraev1, M.F. Churbanov1, G.E. Snopatin1,

A.A. Pushkin1, V.V. Gerasimenko1, T.V. Kotereva1, V.G. Pimenov1, V.G. Plotnichenko2,

A.F. Kosolapov2, E.M. Dianov2

1Institute of Chemistry of High-Purity Substances of RAS, 49 Tropinin Str, 603950,

Nizhny Novgorod, GSP-75, Russia, e-mail: [email protected]

2Fiber Optics Research Center RAS, 38 Vavilov Str, 119991, Moscow, Russia

Tellurite glasses have a wide transparency region, chemical stability, high nonlinearity and solubility of rare-earth elements and are promising for manu-facturing the fiber amplifiers. High-purity TeO2-ZnO-Na2O-Bi2O3 and TeO2-WO3-La2O3-MoO3 glasses were produced by fusion of batch mixture in platinum or gold crucible in hermetic chamber in the stream of purified oxygen. Glasses were prepared using high purity initial oxides. The total content of 3d transi-tion metals impurities, defined by atomic emission spectroscopy analysis, in initial oxides and produced glasses did not exceed 1 ppm. The level of absorption by hydroxyl groups in glasses was 0.02-0.008 cm-1

in the maximum of absorption band (λ ~ 3 mkm). On the basis of investigations of optical and ther-momechanical (coefficient of thermal expansion, DTA) properties for both glass-forming systems, the glass compositions for core and clad of fibers were selected characterized by absence of thermal effects of crystallization. Optical losses on absorption (at λ = 1.56 and 2.0 mkm) in the initial glasses, defined by the method of laser calorimetry, are in the range of 40-120 dB/km. From high-purity tellurite glasses the optical fibers were produced with losses at the level of several hundreds of dB/km.

Keywords: tellurite glasses, transition metals, hydroxyl groups, optical losses.

0384 | Rare earth doped sol-gel nano-glass ceramics:

upconversion fluorescence studyLuciano A. Bueno+, Artur da S. Gouveia-Neto,

Andréia F. da Silva, Diógenes S. Moura, Elias A. da Silva, Ernande B. Costa

Universidade Federal Rural de Pernambuco, Recife – 52171/900 – PE, Brasil, e-mail: [email protected]

There has recently been a great deal of inter-est in searching for new materials for application as hosts in infrared-to-visible light upconverters or optical amplifiers based upon rare-earth doped sys-tems. Some of their many applications include: color displays, high density optical recording, biomedical diagnostics, infrared laser viewers and indicators,



fiber lasers and amplifiers. Fluorosilicate based sol gel glass ceramics have recently emerged as auspi-cious candidates for such photonic devices applica-tions. These glasses are advantageous because they present low temperature of preparation, better me-chanical strength, chemical durability, and thermal stability than fluoride-based glasses. The present work involves the investigation of optical transitions and upconversion fluorescence spectroscopy of triva-lent lanthanide ions Er3+ codoped with Yb3+ in β-PbF2 nanocrystals dispersed in silica glassy matrix, excited with near-infrared diode lasers. The dependence of the upconversion luminescence upon diode laser power, and the upconversion excitation mechanisms involved are also investigated.

Keywords: upconversion, rare-earth, luminescence, optical properties, nano-glass ceramics.

0387 | Optical and structural properties of silver nanoparticles

in aluminosilicate glassesZ. M. Da Costa1, L. C. Barbosa2,

W. M. Pontuschka3, C. R. Da Costa3, V. Ludwig4, J. M. Giehl3, E. F. Chillcce2, A. C. Fonseca1,

P. E. R. Sangy1, J. E. Souza, Jr1.1Federal University of Juiz de Fora, Intitute of Exact

Sciences, Department of Physics, Juiz de Fora, Minas Gerais – Brazil, e-mail: [email protected]

2State University of Campinas, UNICAMP, Physics Institute, Campinas- Brazil

3State University of São Paulo, Physics Institute, São Paulo – Brazil

4Federal University of São João Del Rey, Ouro Branco, Minas Gerais – Brazil

Metal colloids or nanoclusters, embedded in glasses, have been found to introduce desired third-order optical non-linearities in the composites at wavelenghts very close to that of the characteristic surface-plasmon resonance of the metal clusters. Precipitation of silver metal and/or oxide of nano-clusters embeddead in thermally treated Ag-Na ion-exchanged soda-lime silicate (SLS) glasses was in-vestigated by Optical Absorption (OA), Electron Spin Resonance (ESR) and X-Ray Diffraction (XRD). The Lorentzian-adjusted OA curves of silver nanoparticles plasmon resonance were analyzed by Drude’s model approach. The XRD of a small amount of cristobalite particles, indicating a simmultaneous incipient devit-rification at 500 °C. We report the effect of femto-second laser irradiation conditions on precipitation of silver nanoparticles in SLS glasses. When a femto-second beam is focused onto a transparent mate-rial, the high peak power of the laser pulse induces multiphoton absorption and ionization process near the focal point of the laser beam inside the transpar-ent materials. Samples irradiated by a laser-beam exhibited the EPR spectra identified as OHC, E’ and

AlOHC centers. Emphasis is given to the comparison among existing approaches to the understanding of the chemical interaction in these system.

Keywords: nanoparticles ,nanoclusters, aluminosilicates,surface plasmon.

0389 | New tests of sinter-crystallization of spherical diopside

glass particlesRaphael M. C. V. Reis1*, Eduardo B. Ferreira2,

Edgar D. Zanotto3

1*Programa de Pós Graduação em Ciência e Engenharia de Materiais, PPG-CEM –

Laboratório de Materiais Vítreos, LaMaV – Universidade Federal de São Carlos, UFSCar,

São Carlos-SP, e-mail: [email protected] 2 Faculdade de Engenharia, UNESP – Universidade

Estadual Paulista, DMT, Guaratinguetá – SP 3Laboratório de Materiais Vítreos, LaMaV –

Universidade Federal de São Carlos, UFSCar, São Carlos – SP

Sintering with concurrent crystallization of glass powders is an alternative route for the development of glass-ceramics. One of the few models that de-scribe glass sintering with concurrent crystallization is the Clusters model. This model allows one to cal-culate the density of sintered compacts by knowing composition-dependent properties, such as viscosity, crystal growth rate and surface tension, and process-dependent parameters, such as particle size distri-bution, shape packing, and the density of surface nucleation sites, NS, where crystals will develop. Two modifications were recently proposed for the Clusters Model: i) the mathematical approach of surface crys-tallization during sintering was reevaluated leading to the development of a modified Clusters model and ii) a new mechanism in which the shrinkage of isolated pores causes an effective increase of NS was identi-fied leading to the Variable NS model. In this work compacts made of spherical diopside glass particles were isothermally sintered (in a heating microscope and via the traditional method) and characterized. The 3 different forms of the Clusters model were test-ed against experimental density data as a function of sintering time, and against saturation densities at different sintering temperatures. Additionally, to check the influence of crystallization on the sintering process, the crystallized fraction of the internal par-ticle surfaces at the end of the densification process was measured and compared to model predictions.

Keywords: sintering, crystallization, clusters model, glass-ceramics



0395 | Production of silica aerogel from rice hulls for dielectric application

José da Silva Junior*, Carlo Requião da Cunha1 Universidade Federal de Santa Catarina Carlos –

UFSC, Florianópolis-SC, Departamento de Engenharia Elétrica, e-mail: [email protected]

The Aerogel for dielectric use is produced from de silica extracted of the Rice hulls. Through a leaching process to remove the organic and inorganic compo-nents of the rice hulls, the silica obtained is submited to an alkaline solubilization and a neutralization to get a silicagel. A supercritical dryer is used to obtain aerogels that are submited to a electrical current-voltage setup to monitor the polarization, loss tan-gent and dielectric strenght of the devices at several frequencies.

Keywords: silica, aerogel, dielectric.

0402 | The influence of electromagnetic fields on the mecanical properties of

industrial glassesVasilii Sharagov, Ion Olaru*, Galina Lysenco,

Vitalie Botezatu, Olga Azarenco Balti State University “A. Russo” – USB, office 38, Pushkin str., MD 3121, Balti, Republic of Moldova,


The influence of constant, alternating and im-pulse magnetic fields on the mechanical properties of industrial glasses of different purpose has been investigated. The subjects of investigation were bottles and jars of colorless glass, bottles of green glass, sheet glass samples, ampoules made from medical glass, illuminating glassware made from transparent colorless and milk glasses. Mechanical properties of glassware were characterized by resis-tance to internal hydrostatic pressure, resistance to the compression in the direction perpendicular to the body walls and microhardness. Experiments on thermomagnetic treatment of glassware were held in laboratory and industrial conditions. Main regimes of the thermomagnetic treatment of glass samples and glassware were the following: temperature – between 300 and 600 °C, vector’s magnitude of the magnetic induction – up to 220 mT, duration – between 1 and 300 s. The electromagnetic treatment increases the mechanical strength of glass from 20 to 40%, at the same time the microhardness increases from 10 to 20%. The rise depends on the temperature and the duration of magnetic treatment, on the characteris-tics of magnetic fields and the position of magnetic lines of force relatively to the plane samples. The optimal regimes are determined and a technology of thermomagnetic treatment of industrial glassware is designed.

Keywords: industrial glass, thermomagnetic treatment, constant, alternating and impulse magnetic fields, mechanical strength, microhardness, optimal regimes.

0407 | Thickness dependence of the properties of magnetron sputtered

indium-tin oxide thin filmsLarissa R. Damiani1*, Ronaldo D. Mansano1

1Universidade de São Paulo – USP, São Paulo – SP, e-mail: [email protected]

Transparent conductive oxides (TCOs) are a class of ceramic materials that exhibits electrically conductive and optically transparent characteristics. Therefore, TCO coated glasses are used in many op-toelectronic devices, such as solar cells, organic light emitting diodes, smart windows and liquid crystal displays. Indium-tin oxide (ITO) is the most popular TCO due to its optimal combination of low electrical resistivity and high optical transmittance in the visible spectrum. ITO is a degenerate semiconductor mate-rial with high band gap (~3,7 eV) that exhibits n-type conductivity because of tin doping and intrinsic de-fects. These mechanisms provide free electrons to the conduction band, allowing the material to have high free carrier density. In this work, ITO films were obtained with different deposition times by radio frequency (RF) magnetron sputtering. Their optical, electrical, physical and chemical properties were in-vestigated. In order to perform all the characterization measurements, the ITO films were sputtered onto p-type silicon and optical glass (B270 Scotch) sub-strates. An ITO layer was deposited on the surface of each substrate using a high-purity (99,99%) ce-ramic indium-tin oxide target. Pure argon was used as sputtering gas, with 5 mTorr of process pressure and 75 W of RF power. The deposition times varied over the range 30–120 minutes, without intention-ally heating the substrates.

Keywords: Indium-tin oxide, ITO coated glass, optoelectronics, magnetron sputtering.

0408 | Performance analysis of automotive laminated glasses

Brunno S. Pimentel*1, Samuel M. Toffoli2, José Carlos Valério3, Gilberto Pereira1

1Centro Universitário da FEI – Campus São Bernardo do Campo – São Bernardo do Campo – SP, Brazil

2Escola Politécnica – Universidade de São Paulo – São Paulo – SP, Brazil

3Saint Gobain SEKURIT – Department of Engineering Methods and Processes – Mauá – SP, Brazil,

e-mail: *[email protected]

In this work, the main properties of different types of automotive laminated glasses were compared. Industrial experience shows that when maximizing one property, others can be degraded. For instance, improving the acoustic comfort by using the Acoustic Polyvinyl Butyral (PVB) layer can result in some loss in the impact resistance of the product. Therefore, a se-ries of comparative tests was performed to evaluate the acoustic, thermal, and impact resistance proper-ties of four different types of windshields available in the market. The variation of the same properties



along the time was also verified exposing samples to an aging test. The results indicated that the thermal windshield showed the best performance because of the Polyethylene Terephthalate (PET) layer, and the performance can be further increased when both the acoustic layer and the thermal layer were present in the windshield.

Keywords: windshield, performance, laminated.

0409 | Determination of light absorption coefficient and internal diffuse

reflectance of a dental porcelain by transmittance measurement

Humberto N. Yoshimura1*, Marcelo M. Pinto2,3, Erick de Lima3, Paulo F. Cesar3

1*Universidade Federal do ABC – UFABC – Santo André – SP, e-mail: [email protected]

2Universidade Nove de Julho – UNINOVE, São Paulo – SP

3Universidade de São Paulo – USP, São Paulo – SP

Bioceramic prostheses have been widely used in restorative dentistry due to their superior aesthetics. Data regarding their optical properties are scarce, despite the fact that they are necessary for modeling and predicting light interaction within a restoration. The aim of this work was to determine the optical behavior of a dental porcelain by transmittance mea-surements. A commercial glassy porcelain powder was vacuum sintered at 910 °C and disc shaped samples were successively polished to multiple thick-nesses (from 2.0 to 0.5 mm). The total and diffuse transmittances were measured in the visible light wavelength range using a double beam spectropho-tometer. The thickness dependence of transmittance followed the Beer-Lambert type equation, even for the highly light scattering porcelain. The determined apparent absorption coefficient (α) varied signifi-cantly with the light wavelength from 1.4 to 0.5 mm-1 (between 400 and 700 nm), while the transmittance for zero thickness (T0) had a smaller variation (0.59 to 0.56). This behavior was discussed based on the porcelain’s chemical composition. The internal dif-fuse reflectance (r2) was determined from the values of T0 and varied between 0.38 and 0.42. Though these values were close to the one calculated us-ing the equation proposed by Mudgett and Richards, they were different from that proposed by Judd.

Keywords: bioceramic, dental porcelain, dental prosthesis, optical properties, transmittance, absorption coefficient, internal diffuse reflectance.

0416 | Preparation of Bi-Sb-Te glasses and study of their some thermal and physical properties

Mônica A. S. Alencar1*, Younès Messaddeq1, Sidney J. L. Ribeiro1, Yannick A. G. Ledemi1

1Institute of Chemistry, UNESP, P.O. Box 355, Araraquara, SP 14801-970, Brazil,


The properties of Bi doped GeTe − Sb2Te3 have been identified to have short crystallization times (just 10ns) and are also well known phase change materials. Their properties have been investigated by a number of researches. However these promising results were reported for a limited number of com-positions.

In the present work, this problem has been simpli-fied to a Bi doped Sb-Te system.

Sputtered Bi-Sb-Te films were obtained and glass formation region and some thermal and physical properties were studied.

In the glass system Bi-Sb-Te the contents of the components were introduced in the quantitues (at.%) : Te – from 69 to 88, Sb- till 20, Bi – from 0 to 22. But there is a little information about optical properties of these glasses and about the composition of impurities that affect on their optical transmission in the infrared. The main optical absorption impurities that reduce their transmission were identified.

X-ray diffraction was performed on the deposited samples at room temperature and after annealing at 180 °C. The diffractograms shows that there is a clear dopant threshold between 13 and 15 atomic percent Bi at which point the material is crystalline at room temperature.

The crystallisation time for this material is reduced by an order of magnitude through the addition of Bi, making possible of use of Bi-Sb-Te glasses for data storage applications and rewritable technologies.

Keywords: Bi-Sb-Te glasses, short crystallization times, data storage.

0417 | Analysis of the sickle cell phase transitions using differential

scanning calorimetry (DSC)Antonio V Cardoso1*, Antonio Carlos V Alves1,

Arnaldo Nakamura Filho1, Pedro Henrique V. B. P. da Silva1,

João Carlos de Castro Pena1

1Rheology Laboratory, Cetec, Belo Horizonte – MG, Brasil

Theories of phase transitions in biomolecules and the vitrification of biological tissues have become a field of scientific interest mainly because: a- the Tam-mann/Kauzmann theory of glass transition seems to be helpful to explain the dynamics of proteins, poly-



saccharides and lipids inside the cell; b- the preser-vation of living cells in vitrified systems is better than in systems that crystallize during cooling or warming.

Many important issues in Medicine could ben-efit from the progress in calorimetry and the study of phase transitions in biological materials. For in-stance, sickle cell anemia was identified as a disease with molecular basis long time ago. But only recently the phase transitions involved in the symptomatology of the illness has been highlighted.

In this work we present the results of Differential Scanning Calorimetry (DSC) of samples of sickle cell erythrocytes as well as the DSC curves of red blood cell (RBC) from healthy donors and we discuss the nature of the thermal transitions that occur in these cells.

Keywords: glass transition, DSC, sickle cell, blood, vitrification.

0418 | Phase transitions of the mussel adhesive structures (byssus and plaque) studied by differential

scanning calorimetry (DSC)Antonio V Cardoso1*, João Carlos de C. Pena1,

Antonio Carlos V Alves1, Monica de Cassia S. Campos2,

Marcela D. Carvalho3, Maria Edith Rolla3, Helen Regina Mota3

1 Rheology Laboratory, CETEC, Belo Horizonte – MG, Brasil, e-mail: [email protected]

2 Water Resources Group, CETEC, Belo Horizonte – MG, Brasil

3CEMIG S.A., Belo Horizonte – MG, Brasil

Invasive species are a threat to native environ-ments as well as to the economic activities of the place that they manage to colonize. Among many, one known example is the disruption that mussels can do to the hydroelectric plant machines and pipes. Understanding the phase transitions of the mussel’s biopolymers responsible for the adhesive-ness can help to minimize the problem. In the pres-ent work the phase transitions (vitreous or crystalline transitions) of the byssus and of the adhesive plaque of the golden mussel (Limnoperna fortunei) and of the mussel Perna perna have been investigated using Differential Scanning Calorimetry (DSC).

Keywords: phase transition, DSC, mussel, Limnoperna fortunei, byssus, adhesive plaque, Perna perna

0419 | Photo-thermo-refractive glass for thick volume holograms

Larissa Glebova1,2, Julien Lumeau2, Vadim Smirnov1, and Leonid B. Glebov2

1OptiGrate Corp. 3267 Progress Dr. Orlando, FL 32826 2CREOL, The College of Optics and Photonics,

University of Central Florida, 4000 Central Florida Blvd, ORLANDO, FL 32816-2700,


Fabrication of holographic optical elements re-corded in a photo-thermo-refractive (PTR) glass was developed at University of Central Florida and production of this glass and holographic elements is successfully performing at OptiGrate Corporation. Photosensitivity of PTR glass is determined by ab-sorption of UV radiation by Ce3+ ions having a wide absorption band with maximum at 305 nm. This means that maximum thickness of a holographic op-tical element is determined by attenuation of record-ing UV radiation in a glass plate. The goal of this work is to develop PTR glass with lower concentration of the main photosensitive agent to provide increasing of a depth of recording. We have studied absorption spectra and refractive index change in a series of PTR glasses with different concentrations of Ce. Optimal concentration of Ce was determined. This glass en-abled hologram recording in thick layers up to several centimeters with low losses and acceptable refractive index change.

Keywords: photo-thermo-refractive glass, cerium, volume holograms

0422 | Glasses and glass-ceramics based on TeO2-WO3

Fabia Castro Cassanjes1* , Gaël Yves Poirier1, Camila Pereira2, Leonardo Henrique Silva2

*1*Universidade Federal de Alfenas – UNIFAL, Campus de Poços de Caldas, Poços de Caldas – MG,

e-mail: [email protected] 2Universidade Federal de Alfenas, Alfenas – MG

Tellurite glasses have scientific and technological interest due to their nonlinear refractive indice, n2, dielectric constants and low phonon energies. The values of refractive indice n2 make these glasses to be promising as non-linear optical materials. Low val-ues of phonon energies have at least two important consequences: improved infrared (IR) transmission (up to 6 mm) and low multiphonon decay rates for rare earths excited states as compared to silicate and phosphate glasses. Tellurite glasses are there-fore potential candidates for IR transmitting devices and also hosts for IR emitting rare earths. These properties make tellurite glass an excellent candidate for fabrication of fiber optic amplifiers.

Vitreous samples have been prepared and char-acterized in the binary system TeO2-WO3 and ternary system TeO2-WO3-M2O (M = Li, Na, K). The glass samples obtained showed high thermal stability against crystallization, high refactive index and good



optical properties. Samples in the ternary system show higher thermal stability. Large size samples can be obtained from this system.

With the main goal of obtaining glass ceramics bulk glasses have been submitted to heat treatments at different temperatures ranging from Tg to Tx. The glass and glass- ceramics were characterized using the follow techniques: Differential Scanning Calorim-etry (DSC) and X-ray powder diffraction.

Keywords: tellurite, glasses, glass-ceramic.

0423 | Nucleation of zirconia in a mas glass-ceramicOlivier Dargaud1,2*, Nicolas Menguy1, Laurent Cormier1, Georges Calas1,

Laurence Galoisy1, Cécile Jousseaume2, Gilles Querel3

1Institut de Minéralogie et de physique de la Matière Condensée, 140 Rue De Lourmel, Paris 75015, France, e-mail: [email protected]

2Saint-Gobain Recherche, 39 Quai Lucien Lefranc, Aubervilliers 93303, France

3Saint-Gobain Northboro Research and Development Centre, Goddard Road, Northborough 01532-512 MA, USA

A fundamental modeling of nucleation needs an accurate description of the structural changes occur-ring in the glass during the first steps of nucleation, especially when nucleating agents are used [1]. The results presented here aim at monitoring, at a medium/long range resolution, the structural role of ZrO2 in a MgO-Al2O3-SiO2 glass-ceramic.High-temperature DSC was used to define major stages of high-temperature phase transformations.

Transmission Electron Microscopy (TEM) and High Resolution TEM were used to determine crystallites appearing during the very first stages of nucleation/crystallization (about 100 °C above Tg). ZrO2 crys-tallites appear with a size of 1-3 nm and progres-sively grow up to 15 nm with increasing temperature. Precipitation of tetragonal nano-ZrO2 was identified by diffraction pattern simulation [2]. Scanning TEM at the atomic resolution demonstrates non random distribution of Zr in the homogeneous parent-glass. Medium range direct imaging (Z-contrast) indicates a medium range organization (as in [3]), showing that some organization of Zr preexists in the glass prior to any nucleation event. These data confirm the peculiar structural role of Zr illustrated in this system by X-ray absorption spectroscopy [4, Dargaud et al., this meeting].1. Fokin, et al. JNCS, 352, p. 2686, 20062. Dargaud, et al. Submitted, 20103. Neilson, J. of App. Phys., 43, p. 3728, 19724. Dargaud, et al. J. Am. Ceram. Soc., 93, 2, p. 342,

2010

Keywords: nucleation, TEM, STEM, HRTEM, zirconia.

0425 | Nanostructure and composition analysis of ferrimagnetic nanocrystals precipitated in oxide glasses by ASAxS

Armin Hoell1*, Vikram S. Raghuwanshi1, Sylvio Haas1, Dragomir Tatchev2, Ivailo Gugov3,

Ruzha Harizanova3, Christian Rüssel41*Helmholtz Zentrum Berlin, Glienicker

Strasse 100 -D-14109 Berlin – Germany, e-mail: [email protected]

2Institute of Physical Chemistry – Bulgarien Academy of Sciences – Sofia – Bulgaria

3Physics Department, University of Chemical Technology and Metallurgy – Sofia-Bulgaria

4Otto-Schott-Institut für Glaschemie, Friedrich-Schiller-Universität – Jena-Germany

The interest in glasses with high concentrations of transition metal ions is determined by their electrical and magnetic properties, which have many practical applications in electronics and medicine. Fundamen-tally, the estimation of the crystallization kinetics with respect to the evaluation of the crystallization rate, sizes and volume fraction of the crystals is interest-ing. In the system Na2O/MnO/SiO2/Fe2O3 the ratios SiO2/Fe2O3 and glass/Fe2O3 are varied, thus changing the acidity of the glass matrix and respectively, the redox-ratios of Fe-ions. After applying an appropriate heat treatment, nano-sized particles of a crystalline phase of type (MnII, FeII)O.(MnIII, FeIII)2O3 are pre-cipitated revealed by XRD.

The aim of this investigation is the study of struc-ture and composition of nanocrystals that means the size distribution; volume fraction and average dis-tance between the crystals, depending on the heat treatment by anomalous small-angle X-ray scattering.

The obtained results of an extensive ASAXS study at all accessible X-ray absorption edges (Mn-K and Fe-K) will be presented. The experiments have been carried out at the 7T-MPW-SAXS beamline at BESSY II in Berlin. All measured differential scatter-ing cross sections have been fitted by one structural model but varying scattering contrast caused by the anomalous scattering behavior near the absorption edges. The second step of the data analysis is the determination of the averaged composition of the two phases.

Keywords: anomalous small-angle X-ray scattering, nanostructure, glass-ceramics, crystallization, ferrimagnetic nanocrystals, iron and manganese oxide.



0426 | Near and mid-infrared luminescence Ge-Sb-(Se, Te) glasses

doped with rare earth ionsBozena Frumarova 1, Vaclav Parchanski2,

Jiri Oswald3, Miloslav Frumar2

1Institute of Macromolecular Chemistry of the ASCR, v.v.i., Czech Republic

2Res. Center and Dep. of Inorg. Chemistry, Faculty of Chem. Technology, University of Pardubice, Czech Rep. 3Institute of Physics of the ASCR, v.v.i., Czech Republic

Glasses of GeSe2-Sb2Se3 system doped with Yb3+ or/and Tm3+, Tb3+, Dy3+, Ho3+, Pr3+ were synthesized and studied. Part of Se ions was substituted by Te ions. The glasses were stable and homogeneous as confirmed by X-ray diffraction and electron micros-copy with high optical transmittivity from visible (red) region up to infrared region (~ 900 cm-1) depending on composition.

Luminescence of rare earth ions is dependent on the glass compositions. The influence of Te content on luminescent properties of studied glasses in near and mid-infrared spectral region was studied. The prepared glasses posses intensive luminescence in NIR and MID infrared region of spectrum and can be applied in chemistry, medicine and in environmental protection.

Keywords: chalcogenides, luminescence, rare earths.

0430 | Lithium borophosphate glasses: an example of the mixed glass former effect

Bérangère Raguenet, Gilles Silly, Annie Pradel, Michel Ribes

Institut Charles Gerhardt Montpellier, Equipe Physicochimie des Matériaux Désordonnés et Poreux (PMDP), CC 1503, Université Montpellier 2, Place E.

Bataillon, 34095 Montpellier Cedex 5, France

Borophosphate glasses are known to show the so-called “mixed glass former effect”. Indeed it has been proved that when two glass formers are pres-ent in a glass formulation, the substitution of one of these glass formers by the other one (with a constant rate of modifier) could lead to a non linear evolu-tion of some physical properties such as the glass transition temperature or the conductivity [1, 2]. The purpose of this study is to understand how the local structure of the glass is involved in this evolution.

The system 45Li2O – xB2O3 – (55 - x) P2O5 (0 < x < 40) has been investigated. Two series of compositions have been prepared using two different quenching methods: the classical air melt-quenching and the twin roller quenching. In the second tech-nique, the material under study is molten in an inert gas atmosphere and a small droplet falls between two rapidly rotating rollers. Heat is thus very rapidly

dissipated and the method allows achieving cooling rates of up to 106K/s. Glass films of about 100 mi-crometers in thickness are then obtained.

With the air melt-quenching method, although X-rays diffraction indicated the amorphous state of the samples up to 35 mol% of B2O3, SEM images revealed the presence of nanocrystallites (~300nm) in materials containing 20 mol% of B2O3 and more. The twin roller quenching was then used to get rid of these crystallites. Actually, even if reduced, the crystallites are still present in the glass.

A comparative study of these two compounds and those already reported in the literature will be reported. The influence of crystallites (presence, quantity and size) on the electrical conductivity has been investigated. A parallel study of the local envi-ronment by 31P and 11B NMR has been carried out in order to explain how the structure can influence the conductivity properties.1. T.Tsuchiya, T. Moriya, J. non Cryst. Solids, 38/39,

1980, 3232. S. Lee, J.Kim, D. Shin, Solid State Ionics, 178,

2007, 375 – 379

Keywords: borophosphate glasses, mixed formers effect, ionic conductivity, 31P and 11B NMR.

0431 | Nanotribological study using molecular dynamics simulations of

binary cu-zr bulk metallic glassCláudio José DaSilva1*, José Pedro Rino1

1 Departamento de Física, Universidade Federal de São Carlos – UFSCar, São Carlos – SP

Metallic glasses are amorphous structures that do not have a long range atomic order like crystalline materials do, but have pronounced short- and medi-um-range order at the atomic scale. Because of their high strength and high elastic modulus compared to those of their crystalline counterparts, their mechani-cal behaviors have received extensive interests.

We are performing atomistic simulation in order to characterize the nanodeformation of Cu-Zr bulk metallic glass through a nano-processing operation, which correspond to the indentation external load-ing process. This procedure enable us to determine the structural transformation, plastic flow and strain localization. The indenter is applied to both a perfect lattice and a glass structure of the material and is modeled by imposing a repulsive potential of spheri-cal shape to the sample. The indenter acts as a ma-terial of infinite stiffness with no surface friction. We are looking for how the metallic glass deforms initially and what kind of deformation events appear.

Keywords: metallic glass, molecular dynamics, nanotribology.



0432 | Micro-size tapered silica fibers for sensing applications

Enver F. Chillcce1, Roddy R. Gonzales1, Luiz C. Barbosa1,*

1 IFGW-Universidade Estadual de Campinas – Unicamp, Campinas – SP, Brazil, Zeferino Vaz s/n

Cidade Universitária-Barão Geraldo, e-mail: [email protected]

In this work we show results of controlled tapered fibers using a Vytran instrument. The tapered silica fibers were produced by pulling a 50 µm length by heating time. The minimum taper diameter was around 3 µm and the maximum taper length was around 600 µm. The evanescent field effect, in the near infra red (NIR) region, was observed to the tapers with diameter inferior to 15 µm. These micro-size tapers no modify the waveguide disper-sion spectra. This device could be used to splice a conventional fiber to photonic crystal fibers and also as liquid and gas sensors.

Keywords: Tapered silica fibers, sensing applications, evanescent field effect.

0433 | Effects of P2O5 content on microstructure and mechanical

properties of lithium disilicate glass-ceramics

Atiar Rahaman Molla, Sampad BiswasCentral Glass and Ceramic Research Institute, Council

of Scientific and Industrial Research (CSIR), India

Lithium disilicate (LDS) glass-ceramics finds use as transparent armour material and in restorative dentistry owing to their unique combinations of high strength and transparency. This paper investigates the effect of P2O5 content on the nucleation, crystal phase formation and microstructure of lithium disili-cate glass-ceramics (GCs) and analyzes the relation between microstructure and mechanical properties. The concentration of P2O5 has been increased from 0-3.2 wt% in the SiO2-Li2O-Al2O3-K2O-ZrO2-P2O5 sys-tem. FESEM micrograph shows plate-like Li2Si2O5 anisotropic crystals are present in the glass matrix and appears to form an interlocking pattern. Mi-crostructures of glass-ceramics containing varying amount of P2O5 show crystals of sizes in the range of 100 to 500 nm. Sizes of the crystals are indirectly proportional to the amount of P2O5 present in the GCs. It appears that P2O5 restricts the exaggerated grain growth. Hardness and Fracture toughness has been found in the range of 5.5-9.5 GPa and 0.6-2.45 MPa.m0.5 respectively determined by indenta-tion technique using 1 Kg load. LDS glass-ceramics shows high flexural strength in the range of 105-122 MPa and moderate elastic modulus of 49-52 GPa.

Hardness, flexural strength, fracture toughness and elastic modulus of the glass-ceramics increases with decreasing P2O5 content and increasing crystal sizes.

Keywords: glass-ceramics, armour, electron microscopy, mechanical properties, FT-IR, optical properties.

0434 | Characterization and thermal properties of JSC-1A lunar soil simulantS. T. Reis1, Jose R. Martinelli3, C. S. M. Partiti3,

R. Cohen3 C. S. Ray1, S. Sen4

1Materials Research Center, Missouri University of Science and Technology, Rolla, MO 65409, USA

2Energy and Nuclear Research Institute, São Paulo – SP, Brazil

3Institute of Physics, University of São Paulo, São Paulo – SP, Brazil

4BAE System, Marshall Space Flight Center, National Aeronautics and Space Administration,

Huntsville, AL 35812, USA

The space exploration mission of NASA requires human and robotic presence for long duration be-yond the low earth orbit (LEO), especially on Moon and Mars. Developing a human habitat or colony on these planets would require a diverse range of mate-rials, whose applications would range from structural foundations, (human) life support, electric power generation to components for scientific instrumenta-tions. A reasonable and cost-effective approach for fabricating the materials needed for establishing a self-sufficient human outpost would be to primarily use local (in situ) resources on these planets. Since ancient times, glass and ceramics have been playing a vital role on human civilization. A long term project on studying the feasibility of developing glass and ce-ramic materials has been undertaken using the new simulant from volcanic ash, designated as JSC-1A Lunar simulant as developed by Johnson Space Cen-ter. The first step in this on-going project requires de-veloping a data base on results that fully characterize the simulants to be used for further investigations. The present paper reports characterization data and thermal properties of JSC-1A Lunar simulants, with average particle size from 38 to 71µm, obtained via X-ray diffraction, particle size distribution, scanning electron microscopy, thermal analysis (DTA, TGA), chemical analysis, and Mössbauer Spectroscopy.

Keywords: lunar soils simulant, glass formation, XRD, DTA and Mössbauer.



0435 | Cadmium selenide/zinc sulfide quantum dots in

microstructured optical fibersRoddy E. R. Gonzales1,

Enver F. Chillcce1, Luiz C. Barbosa1

1Departamento de Eletrônica Quântica/ Instituto de Física, DEQ-IFGW, Universidade

Estadual de Campinas-UNICAMP, Campinas-SP, e-mail: [email protected]

The photoluminescence of CdSe/ZnS (core/shell) quantum dots inserted into the structure of the mi-crostructured optical fibers were characterized. First, the insertion process of colloidal quantum dots into the fiber structures was realized by using an Argon gas pressurized system. Second, the CdSe/ZnS pho-toluminescence was measured using a blue pump laser (473nm, 90mW) and an optical spectrum analyzer. Then, a photoluminescence band intense at 560nm was observed and analyzed.

Keywords: Colloidal quantum dots, photoluminescence, microstructured optical fiber.

0436 | Reuse of waste flat glass to obtain the ceramic stoneware

Valdênia de S. Porto1, Michelly F. da Silva1, Alderiza V. Albuquerque1,

Maria S. L. Cavalcante2, Crislene R. S. Morais1

1 Universidade Federal de Campina Grande – UFCG, Campus I, Campina Grande- PB

2Universidade Federal da Paraiba – UFPB, Campus III, Bananeiras – PB

The world-wide population has if come back to-ward the concepts of sustainability and thus some segments related to science and technology it comes searching alternatives to control or to minimize dam-ages caused by the indiscriminate consumption of raw materials and energy, beyond the high volume of generated residues. This work had as objective to study the possibility of the incorporation of plan glass residues, in ceramic masses for sanitary stone-wares in partial substitution to the feldspar. The raw materials were characterized through the assays of Chemical Analysis; Grain Sized Analysis and X-ray Diffraction. Were formulated ceramic masses with and without plain glass residues in the percentages of 5%, 7% and 10%, and posteriorly evaluated its rheological properties. The ceramic bodies were initially dried in heater at 110 ºC, and after burned at temperatures of 1000 ºC, 1100 ºC, 1200 ºC and 1250 ºC. We characterized the ceramic bodies through the following assays physicist-mechanics: water absorption and apparent porosity, all follow-ing the recommendations of Sousa Santos and the norms of the ABNT. The results evidenced that the ceramic bodies obtained with plain glass residues

presented physicist-mechanical properties that at-tend the recommended patterns for use in sanitary stonewares, being technologically viable its use.

Keywords: ceramic masses, glassy residues, physicist-mechanical properties, sanitary stoneware.

0437 | Optical characterization of fluorophosphates glass

samples at near-infrared regionLidiane M. Omena1, Nuccia C. A. de Sousa1,

M.V.D. Vermelho1, L.A. Bueno2, C.C. Santos3, I. Guedes3

1Universidade Federal de Alagoas – UFAL-AL-BRASIL 2Universidade Federal Rural de

Pernambuco – UFRPE-PE-BRASIL 3Universidade Federal do Ceará – UFC-CE-BRASIL

The development of opto-electronical devices, like optical amplifiers and lasers, gives direction to researches on the conceivement and enhancement of new host materials to this aim. As a marking ex-ample, we can cite the constant search for improve-ment of optical characteristics of host matrices, aiming the Dense Wavelength Division Multiplexing (DWDM) technology. This process has also a strong dependence on the rare earth host matrix composi-tion, having influence on the quality of the fluores-cence inhomogeneous broadening. In this work, we performed the optical characterization of Magnesium Fluorophosphate glass samples, the NaPO3 – PbO – MgF2 system, doped with Erbium ions, which con-centrations varying from 0.75 to 5.0 mol%, observing nonlinear effects of rare earth ions concentration raise on the emitting 1530 nm band. The character-ization of pumping wavelength efficiency, observing non-linear effects of energy Upconversion, was ac-companied by the utilization of Judd-Ofelt analysis to the determination of important spectroscopic pa-rameters to devices performance. The radiation life-time measurement in 1530 nm presented a strong reduction with the concentration increase, indicating how the energy transfer effects are a limiting factor of upconversion efficiency reduction. The maximum phonon energy of the glass samples were measured by Raman Spectroscopy technique, being its value measured as, approximately, 1100 cm–1.

Keywords: glass, earth rare, spectroscopy, optical.



0438 | Use of glassy material as a color modifier additive for ceramic tile massG.R. dos Santos1, A.R.Salvetti2, M.R. Morelli1

1Universidade Federal de São Carlos, DEMa – PPGCEM, Rodovia Washington Luis, Km 235,

CEP 13565-905, São Carlos – SP 2Universidade Federal do Mato Grosso do Sul,

Depto. de Física – CCET, Cidade Universitária s/n – Caixa Postal 549- CEP 79070-900, Campo Grande-MS, e-mail: e-mail: [email protected],

[email protected]

The presence of iron oxide in ceramics tiles con-tributes to the reddish color of the products, leading to a lower aggregate value, for not to be regarded as a “noble” ceramic. However, the use of raw ma-terials with low levels of chromophore oxides (Fe2O3 and TiO2) is sometimes economically impracticable in Brazil, since most of the deposits have iron com-pounds as principal contaminant. Thus, the study evaluated ceramic tile compositions, typically used in industries of ceramic tile pole of Santa Gertrudes-SP, with different additions of a viscous flow former material (previously obtained as a glassy phase) able to modify the color of the mass during the firing pro-cess. The results showed that the incorporation of the glassy material promotes some redox reactions during sintering making the final red color product a light color product. The understanding of these reactions can result in an alternative option to manu-facture porcelain stoneware tiles, allowing the use of clays with higher levels of iron oxides and lower cost.

Keywords: ceramic coatings, glassy phase, redox reaction, additive, porcelain stoneware tiles.

0439 | Influence of phosphorus precursors on the synthesis

of glassy and crystalline SiO2-CaO-P2O5 bioactive powdersRenato Luiz Siqueira*,

Oscar Peitl Filho, Edgar Dutra ZanottoUniversidade Federal de São Carlos – UFSCar,

Programa de Pós-Graduação em Ciência e Engenharia de Materiais – PPG-CEM,

Laboratório de Materiais Vítreos – LaMaV, e-mail: *[email protected]

Vitreous and crystalline bioactive powders of the system SiO2-CaO-P2O5 have been synthesized using the sol-gel process with different phosphorus precur-sors: phosphoric acid (H3PO4), triethyl phosphate (C6H15O4P), phytic acid (C6H18O24P6), and a solution prepared by dissolving phosphorus oxide (P2O5) in ethanol. The resulting materials were characterized by DSC/TG, XRD, FTIR, SEM and EDS and by in vitro bioactivity. These different phosphorus precursors significantly influenced the key steps of synthesis, such as the starting time of gel formation. The most outstanding influence of the precursors was verified during heat treatment (between 700 and 1200 °C) for the conversion of the gels into ceramics. Their

mineralization behavior were quite distinct, especially in the materials prepared with phosphoric acid, but all resulting materials are bioactive. Their bioactivity is strongly influenced by the temperature of heat treat-ment and by the existing crystalline phases. Bioactiv-ity is favored by the presence of wollastonite (CaSiO3) and alpha-tricalcium phosphate (α-Ca3(PO4)2). For the vitreous materials the bioactivity decreased with the temperature of gel stabilization.

Keywords: sol-gel method, phosphorus precursors, bioactive glasses and glass-ceramics, in vitro tests in SBF.

0441 | Cation effects on the structure of 0.45SiO2-(0.45-x)MgO-xK2O-

0.1(3CaOP2O5) glasses studied by 29Si MAS-NMR and FTIR spectroscopies

Carlos Araújo Queiroz1*1 VICARTE – Faculdade de Ciências e

Tecnologia – Universidade Nova de Lisboa – FCT/UNL, P-2829-516 Caparica, Portugal,


The silicate network structure of glasses with molar composition xK2O-(0.45-x)MgO-0.45SiO2-0.1(3CaOP2O5) (x ≤ 0.090) was investigated by 29Si MAS-NMR and FTIR, emphasizing alkali and alkaline-earth contribution. FTIR absorption suggests Mg2+ fa-vours octahedral coordination. Width of ~1050cm-1 band, mostly associated with bridging oxygens contri-bution at Q2 species, decreases with x. Is fair to infer that Q2 chains tend to become rigid as K joins com-position. Shoulder at ~950cm-1, strongest for x = 0 and weaker for x = 0.090, was mostly attributed to Q3 species influenced by Mg2+ and to Si-O- stretch-ing. ~765cm-1 band at the higher K-content glasses was ascribed to Q2 ring breathing while concomitant lack of absorption at ~805cm-1 suggests weaker Si-O-Si bending. NMR spectra show silicate network predominantly comprises Q2 and Q3. Q2 contribution increases with K while Q1 decreases. Q3 increases at lower K content, decreasing at K-richest glasses. Speciation was chiefly attributed to 2Q2↔ Q1+Q3 disproportionation, displaced toward left by K addi-tion, what is consistent with Mg2+ high field strength. K+ preferably locates at Q2; Mg2+ prefers Q3. Attack to Q4 accordingly 2Q4+ Mg2+ + O2-↔ 2Q3 governs phase separation at x = 0. O2- is probably mostly contributed by Q2 chains; either by depolymerization, extracting O2- and Si2O5

2- (Q3) from the oligomer; or by cyclization, generating a ring. Crystallization is noticeably influenced by glass structure, providing compatible evidence.

Keywords: glass structure, field strength, phase separation, crystallization, 29Si MAS-NMR, FTIR.



0443 | Structure and magnetic properties of the crystalline

phases in SiO2:Li2O:Fe2O3 glass-ceramics prepared via sol-gel method

M. A. Valente1, J.C. Lopes1,3, J. Monteiro1, M.P.F. Graça1,

S.K. Mendiratta1*, A.S.B. Sombra2

1I3N – Aveiro, Physics Department, Aveiro University, Campus Universitário de Santiago,

3810 – 193, Aveiro – Portugal 2Telecommunications and Materials Science and

Engineering Laboratory (LOCEM), Physics Department, Federal University of Ceará, Campus do Pici, Postal Cod

6030, CEP 60455-760, Fortaleza-Ceará-Brasil 3Physics Department, Faculty of Science and

Technology, University of Algarve, Campus de Gambelas, 8000-117 Faro, Portugal, e-mail: [email protected]

Kinetics of precipitation of crystalline phases in a glass is a theoretical problem and the data on kinet-ics is useful when we want to prepare a glass-ceramic with a desired crystalline phase and microstructure.

In this paper we present results on the pre-cipitation of crystalline phases in the silica glasses, prepared by the sol-gel, with Li2O and Fe2O3. We studied the crystallization as a function of tempera-ture of the heat treatment. We have used magnetic susceptibility measurements versus temperature, to characterise the nature of the magnetic crystal-line phases, scanning electron microscopy for the microstructure and X-ray diffraction for identifying the crystalline phases. The heat treatment was car-ried out at four temperatures (700, 800, 900 and 1000 ºC). The magnetic measurements indicate that the heat treated glasses at 700 ºC contain crystalline phases of silica, quartz and cristobalite, as well as hematite. The heat treatment at higher temperature leads to coarsening of iron containing crystalline phase. However for samples treated at still higher temperatures (900, 1000 ºC) a ferrimagnetic behav-iour is observed accompanied by the appearance of peaks corresponding to the lithium ferrite: Li Fe5O8 in XRD. A curious aspect of our observations is that the contribution of ferrite phase with the associated fer-rimagnetic behaviour is less at 1000 ºC than as com-pared to the contribution at 900 ºC. Further analysis and experiments are in progress to understand this phenomenon.

Keywords: glass ceramic, glasses, magnetic properties, sol gel route, structure.

0444 | Effect of the Dy2O3 addition on the structure, morphology and optical

properties of a SiO2:LiNbO3 glass prepared by sol-gel

M. A. Valente1*, C.C. Silva2, A.S.B. Sombra2, M. Peres1, C. Nico1, T. Monteiro1,M. P. F. Graça1

1I3N – Aveiro, Physics Department, Aveiro University, Campus Universitário de Santiago,

3810 – 193, Aveiro – Portugal 2Telecommunications and Materials Science and

Engineering Laboratory (LOCEM), Physics Department, Federal University of Ceará, Campus do Pici,

Postal Code 6030, CEP 60455-760, Fortaleza-Ceará-Brasil, e-mail: [email protected]

Lithium niobate (LiNbO3) has a great variety of ap-plications for the optics due to its properties, such as high electro- and acousto-optic coefficients, and the possibility of doping it to obtain laser action. The conventional LiNbO3 crystals preparation is difficult with high costs. The glass-ceramic method, with con-trolled temperature, atmosphere, is an alternative to prepare materials with desired particles shape and size. The sol-gel allows the synthesis of new glass, with less energy consumption, higher purity and ho-mogeneity.

The optical properties studies of dysprosium-doped matrices is by far less exhausting as compared to other rare earth ions. But, some reports indicate interest in activating optical glasses by Dy for the purposes of 1.3 mm band fiber telecommunication.

We present the preparation, by the sol-gel, of a transparent SiO2:Li2O:Nb2O5:Dy2O3 glass. The gel was heat treated (HT), in air, between 500 ºC and 800 ºC. The structure was investigated by X-ray pow-der diffraction (XRD), the morphology by scanning electron microscopy (SEM) and the optical properties by Raman, FTIR and by Photoluminescence.

The XRD patterns show SiO2 and LiNbO3 phases in the samples HT above 650 ºC. Besides the SiO2 and LiNbO3, DyNbO4 phase was detected in the samples HT above 750 ºC. The XRD and SEM show that the ratio between particles and glass matrix increases with the rise of the HT temperature. The optical prop-erties were related with the glass and glass-ceramics microstructure.

Keywords: glass ceramic, optical properties, sol gel route.



0445 | Dielectric properties of CCTO:TeO2 composite

F. Amaral1,2, L.C. Costa1, A.S.B. Sombra3, M. P. F. Graça1, M. A. Valente1*

I3N – Aveiro, Physics Department, Aveiro University, Campus Universitário de Santiago, 3810 – 193, Aveiro – Portugal

2College of Technology and Management of Oliveira do Hospital, 3400-124 Oliveira do Hospital, Portugal 3Telecommunications and Materials Science and

Engineering Laboratory (LOCEM), Physics Department, Federal University of Ceará, Campus do Pici, Postal

Code 6030, CEP 60455-760, Fortaleza-Ceará-Brasil, e-mail: [email protected]

Electroceramics with high dielectric constants (ε’) and low tan δ had increasing demand due to their applications in electronic devices. The CaCu3Ti4O12 (CCTO), presents an colossal dielectric constant, nearly constant in a wide temperature range. The high values of ε’ is an open question. Some researchers suggest that the dielectric behaviour is intrinsic, while others attribute this to extrinsic effects. It is believed that insulating surfaces are formed on semiconduct-ing grains, causing the electric charge accumulation at the grain boundaries. According to internal barrier layer capacitor model, the increase of the resistance of the grain boundaries contribute to the increase of the high ε’ in CCTO ceramics.

Changes in ε’ of the CCTO samples with the intro-duction of a material into the grain boundaries is one of the main objectives of this study. The effect of the addition of TeO2 glassy on the structure, morphology and dielectric properties of CCTO was investigated. TeO2 glass was chosen due to the low melting tem-perature. The composites xCCTO:(1-x)TeO2, with x = 0, 5, 10, 25 and 50 % (%wt) were prepared by solid state reaction and treated at 800 ºC and 1050 ºC. The structure was analyzed by XRD, Raman and FTIR spectroscopy. The morphology was studied by SEM and the EDS analysis was used to study the chemical distribution at the grains and the grain-boundaries. The dielectric constant was measured between 40 Hz and 110 MHz as a function of the temperature.

Keywords: dielectric relaxation, glass-ceramics, high dielectric constant.

0447 | 3-D thermal, hydrodynamic & magnetic modelling of elaboration of

glass by induction in cold crucibleE. Sauvage, P. Brun, A. Bonnetier, J. LacombeCEA/Marcoule, BP 17171, 30207 Bagnols-sur-Ceze,

Cedex, France, e-mail: [email protected]

The Vitrification of high-level liquid waste pro-duced from nuclear fuel reprocessing has been car-ried out industrially for over 30 years by AREVA, with two main objectives: containment of the long lived fission products and reduction of the final volume of waste. In parallel the French Atomic Energy Commis-sion (CEA) and AREVA (industrial Operator) have de-

veloped the cold crucible melter vitrification technol-ogy to obtain greater operating flexibility, increased plant availability and further reduction of secondary waste generated during operations.

The 3D numerical simulation of elaboration of glass by induction in cold crucible needs a coupled approach of the different phenomena: induction, thermal and hydrodynamic. Indeed, those three phenomena are strongly coupled because of the temperature dependence of the glass properties. The hotter the molten glass, the higher the electrical conductivity. In the present paper, we will focus on a full 3D simulation, when mechanical stirrer and bub-bling are stopped in the cold crucible melter. In this case, the convection is driven by two phenomena. First, buoyancy forces are modeled in the Boussinesq approximation. Second, thermocapillary convection at the surface is taken into account. This effect is due to the variation of the surface tension with the temperature. Hydrothermal waves appear at te free surface of the glass bath when the total Joule power injected reached a specific threshold.

Qualitative comparison of the aspect of free sur-face is performed with experimental.

Keywords: vitrification, induction, modeling, wastes immobilization.

0448 | Precious metal functionalizedsoda-lime silicate glasses

A. Simo*, K. RademannInstitut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany – anne,


Ion-exchanged glasses are excellently suited as host matrix for nanoparticles (NP) due to their out-standing stabilizing properties, metal functionalized surfaces of glass can play an important role in future bioanalytics, chemical and biological sensing and ca-talysis. In the present contribution we report on pre-cious metal functionalized soda-lime silicate glasses, namely Au, Ag and Cu NPs in the sub-surface region of glass and their application as long-term stable SERS (surface enhanced raman scattering) substrates (Figure). We developed an optimised technique con-sisting of a combined ion-exchange method and a subsequent reactive diffusion process in hydrogen atmosphere, that permits to introduce efficiently very high metal concentrations spatial localized in Raman spectra of an aqueous solution of adenine (10-4M)



mixed 1:1 with methanol as internal standard on a SERS-active glass substrate. The enhancement fac-tor can be quoted in the range of 106-107.

500 1000 1500 2000 25000

5001000150020002500300035004000450050005500

Ram

an in

tens

ity

wave number [cm-1]

A thin sub-surface layer of the glass. For a di-rected and controlled NP design a constitutive under-standing of mechanistic details is essential. Recently, it could be shown that Small Angle X-ray Scattering (SAXS) is a powerful tool to investigate the nucleation and growth processes of NPs. In this contribution we focus on systematic investigations of metal NP for-mation in soda-lime silicate glass using a coupling of methods such as EPR, SAXS, TEM and UV/VIS. New insights can be achieved using these methods providing information about the chemical state as well as the size, number and polydispersity of formed NP at one time. From the data the different phases of NP formation, nucleation and growth mechanism will be discussed.

Keywords: noble metal nanoparticles, nucleation and growth, small angle X-ray scattering, SERS.

0449 | Study of structural and dispersion of refractive index

of tellurite glassesWilson A. Capanema1, Keizo Yukimitu1, Salmo M. Sidel1, João C. S. Moraes1*, Otávio A. Sakai2, Antonio N. Medina2

1*Universidade Estadual Paulista – UNESP, Campus de Ilha Solteira, Ilha Solteira – SP,

e-mail: [email protected] 2Universidade Estadual de Maringá –

UEM, Maringá – PR

In this work the structural and linear optical prop-erties of 80TeO2-(20-x)Li2O-xTiO2 glass system with x = 0, 5, 10, and 15 mol% has been investigated. The analysis of the structural change with the glass composition of the sample was performed by FTIR spectroscopy. As optical properties it was studied the optical dispersion of refractive index through the interferometric measurements. The dispersion of linear refractive index was analyzed by Wemple’s model and the Sellmeier’s gap energy (Eo), disper-sion energy (Ed), and coordination number of cation nearest neighbor to the anion (Nc) of glasses were determined. The glass samples were prepared using a conventional melting-quenching method. The raw material reagent was mixed and melted at 850oC during 30min in a Pt-Au crucible. The samples were

annealed around the Tg temperature during 2h. For the refractive index measurements, slice of samples were prepared with 2.5mm of thickness and 1cm2 of surface. For FTIR spectra, the samples were prepared mixing powder of glass and KBr. The measurements were carried out in a Nicolet Nexus 670 spectrometer with 64 scans and resolution of 4cm-1. The refrac-tive index of the studied glasses increases when the amount of Ti is increased in the glass composition. This increase is due to Te coordination change from TeO3 tp to TeO4 tbp and the formation of TiO6 struc-tural units. This affirmation is supported by FTIR data analysis and by coordination number determined by Wamples’s relationship.

Keywords: tellurite glasses, optical dispersion, refractive index, gap energy, coordination number.

0450 | Physical-chemical characterization of fine powder waste

from polishing, hole and Edge cutting IN glass

Rosemary B. C. Sales1*, Fernando A. Sales2, Sebastiana L. B. Lana1, Nelcy D. S. Mohallem3,

Maria Teresa P. Aguillar3

1Universidade do Estado de Minas Gerais – UEMG – Escola de Design – MG, e-mail: [email protected]

2Centro Federal Educação Tecnológica de Minas Gerais – CEFET – Engenharia Mecânica – MG

3Universidade Federal de Minas Gerais- UFMG – Escola de Engenharia – MG

Nowadays, it is common to use waste content of amorphous silica as partial Portland cement replace-ment materials. The most usually waste materials for this application are granulated slag from blast furnace, silica fume, and fly ash. As an alternative another material with reactive silica is the glass waste, which is commonly used as raw material for the manufacture of new glasses. However, the fine powder waste from polishing, hole and edge cut-ting in glasses has dimensions around 2 µm, and it requires careful handling. However, if the waste has appropriate physical-chemical characteristics, it can be used in partial replacement of cement. Around 20 tons of glass powders are produced for months in the Brazil and they are usually disposed of in landfill.

In this work glass powder was characterized by gas desorption technique to evaluate the texture. Electron microscopy and microanalysis were used to access the morphology and composition, aiming to evaluate the use of this material in cement composi-tion.

Keywords: characterization of powder glass, composition of cement, recycled waste.



0451 | High modulus neodymium hydrosilicates synthesis and propertiesV. Baghramyan1*, A. Sargsyan1, R. Harutunyan1,

G. Petrosyan1, A. Chalyan1, G. Babayan1, C. Leonelli2

1“Stone and Silicates” SI&PCJSC, 40a, Acharyan Str., Yerevan, e-mail: [email protected]

2Universita’ degli Studi di Modena e Reggio Emilia, Via Vignolese 905/A, Modena, Itali

The investigations results of high modulus neo-dymium hydrosilicates synthesis from water solu-tions and main physico-chemical processes taking place at their thermal treatment are presented in the work. High modulus hydrosilicates synthesis by precipitation method from water solutions of so-dium silicates and soluble neodymium salts refers to a number of more prospective, producible and economical.NdCl3.6H2O of chemically pure grade and Na2O.nSiO2 (n = 1-3) sodium silicate solution were used for neodymium hydrosilicates synthesis. According to data of sediment (neodymium silicates) chemical analysis at SiO2:Na2O = 1 molar ratio in initial sodium silicate solution the synthesized solid phase has Nd2O3.3SiO2.mH2O composition, and at SiO2:Na2O = 2 and SiO2:Na2O = 3 molar ratio has Nd2O3.6SiO2.mH2O and Nd2O3.9SiO2.mH2O compositions accordingly. IRS investigations confirm the formation of chemical compounds. Intensive ab-sorption band at 1100 cm–1 characteristic for Si–O–Si bond is displaced to low frequencies direction due to Si–O–Nd bonds formation.It is shown, that at thermal treatment of synthesized neodymium silicates the phase transformations of initial silicates amorphous structure take place with crystalline phases forma-tion. On the basis of conducted differential-thermal, IRS, thermo gravimetric and x-ray phase analysis in-vestigations it can be stated that the chemical com-pounds with Nd2O3.nSiO2(n = 3-9) general formula are formed at neodymium silicates synthesis.

Keywords: silicate, modulus, neodymium, hydrosilicates, synthesis, structure, treatment.

0452 | Sol gel coating containing silica nanoparticles and cerium

salts on carbon steelIanina C. Santana, Andrés Pepe, Silvia Ceré*

INTEMA- Universidad Nacional de Mar del Plata – Buenos Aires, Argentina,


Carbon steel are widely used in industry, however their susceptibility to corrosion limits its applications. One strategy to minimize the corrosive attack is the application of coatings with rare earth (RE) salts as a valid alternative owing to its low toxicity and envi-

ronmental feasibility. The RE are employed to replace chromate treatments due their high toxicity which tends to their total elimination in the industry.

Sol gel process is a chemical method that al-lows the synthesis of glass and ceramic materials at temperatures much lower than the conventional methods and can be used to obtain coating which, in turn, may be functionalized.

This work evaluates the electrochemical behavior of carbon steel coated by sol-gel method. Hybrid or-ganic-inorganic silica sol-gel coatings were obtained by dip coating in an organically modified silica sol made from hydrolysis of 3-glicidoxipropyltrimetoxisi-lano (GPTMS) and tetra-orthosilicate (TEOS) as pre-cursors in acidic catalysis. The coatings were doped with cerium salts (Ce(NO3)3) and loaded with silica nanoparticles for improving the corrosion resistance of the coatings both by the inhibitory effect of the salt and by increasing the barrier effect. The coatings were obtained by dip coating onto AISI 1010 car-bon steel, producing a two-layer equally distributed homogeneous film without cracking. The corrosion behavior of the coated samples was characterized by electrochemical tests with various immersion times in NaCl 0.35%m/v.

Keywords: corrosion, sol-gel, cerium salts, carbon steel.

0454 | Study of doping profile of silica-titania glasses synthesized by the

synergy of VAD and ALD techniquesTarcio P. Manfrim*, Eduardo Ono, Eric Fujiwara,

Murilo F. M. Santos, Mirella N. O. Boery, Juliana S. Santos, Carlos K. Suzuki

Universidade Estadual de Campinas – Unicamp, Departamento de Materiais, Laboratório de Materiais e

Dispositivos Fotônicos, Campinas – SP, e-mail: [email protected]

This study aimed to synthesize and characterize glasses of high purity titania-doped silica for applica-tions in the field of high-performance photonics. In a first stage, using the vapor-phase axial deposition (VAD) technique, we synthesized two groups of pure silica porous boules, the first one with standard av-erage density (Sd) in order of 0.11 g/cm³ and the second group with variable average densities (Vd) in the range from 0.11 to 0.20 g/cm³. Afterwards, these boules were submitted to a cyclic process of impregnation with TiCl4 vapor and hydrolysis with deionized water vapor using the principles of atomic layer deposition (ALD) technique. The Sd boules were subjected to a variable number of cycles of impreg-nation (CI), while all the Vd boules were subjected to four CI. Finally, all the impregnated porous boules were consolidated at 1400 °C under a helium at-mosphere. Consolidated boules were characterized by X-ray scanning fluorescence technique in order to obtain the radial and longitudinal TiO2 doping profiles. We observed that the concentration and homogene-



ity of TiO2 are mainly functions of the number of CI and density. Furthermore, we estimated that the dop-ing rate for Sd boules is around 1.25 wt% TiO2/cycle for the first four cycles.

Keywords: silica-titania, flame hydrolysis, VAD, ALD, XRF, doping profile.

0455 | Glass and glass-ceramics prepared in the binary system SIO2-WO3

Roberto Bertholdo1, Felipe Silva Miranda2, Elivelton Alves Ferreira1, Camila Pereira1,

Fábia Castro Cassanjes1,2 and Gael Poirier1,2

1Departamento de Ciências Exatas – UNIFAL-MG, Campus de Alfenas, Alfenas-MG

2Departamento de Ciência e Tecnologia – UNIFAL-MG, Campus de Poços de Caldas, Poços de Caldas-MG,


Glass samples were prepared on the binary sys-tem (100-x)SiO2-xWO3 by the sol-gel process. TEOS (tetraethoxysilane) and tungstate precursors (WO2Cl2 and (NH4)10H2(W2O7)6.xH2O) were dissolved in etha-nolic solution and mixed for hydrolysis and condensa-tion. The final material was dried around 80ºC for a few days and heat-treated at 300ºC in order to prepare a transparent bulk sample. Amorphous state of the resulting samples has been checked by X-ray diffraction and thermal analysis. Thermal properties were investigated by DTA as a function of chemical composition. A detailed crystallization study of these tungstate silicate glasses has been performed to de-termine the crystallization mechanism, the possible crystalline phases and the possibility of obtaining transparent glass-ceramics containing WO3 nano-crystallites.

Keywords: sol-gel, tungsten, glass-ceramics, crystallization.

0456 | Preliminary study of selenium in commercial soda-lime glasses

Renata A. Kobayashi1, Samuel M. Toffoli2*

1,2Department of Metallurgical and Materials Engineering – Polytechnic School, University of

São Paulo, São Paulo – SP, e-mail: [email protected]

This paper reports a preliminary study of a re-search aimed at understanding the presence and ef-fect of selenium in glasses of the soda-lime system. Selenium is the element responsible for most of the pink or light red color in commercial glasses, but its effect is primarily dependent on the oxidation state of the element in the glass matrix. Besides, sele-nium is highly volatile at the melting temperatures found in an industrial glass furnace. Therefore, this paper presents a first evaluation of the presence of selenium in various selenium containing commercial glasses, by determining the chemical state of the se-lenium in the glassy matrix by XPS (X-ray photoelec-tron spectroscopy), by measuring the transmittance curve of the glass (and CIE L*a*b* coordinates) and

by observing the samples by TEM (transmission elec-tron microscopy), looking for the presence of crystal-line nuclei. The results obtained with the various in-strumental techniques are presented and discussed in an integrated manner.

Keywords: selenium, color, XPS, soda-lime.

0458 | Study of the influence of silver impurity on the linear and nonlinear refractive index of tellurite glasses

Júlia Maria Giehl1, Walter Maigon Pontuschka1, Luiz Carlos Barbosa2,

Sarah Isabel Pinto Monteiro do N. Alves1,3, Antonio Martins Figueiredo Neto1,

Niklaus Ursus Wetter4, Diogo Soga1, Zélia Maria Da Costa Ludwig5

1Instituto de Física da Universidade de São Paulo, São Paulo – SP, Brazil, e-mail: [email protected] 2Laboratório de Materiais Vítreos, UNICAMP,

Campinas-SP, Brazil 3Departamento de Ciências Exatas e da Terra,

UNIFESP – Campus Diadema, Diadema – SP, Brazil 4Centro de Lasers e Aplicações, IPEN,

São Paulo – SP, Brazil 5Departamento de Física ICE, Universidade

Federal de Juiz de Fora, Juiz de Fora – MG, Brazil

The tellurite glass system x AgO1/2. (100-x) (0,85 TeO2. 0,12 Nb2O5. 0,03 Na2O) mol%, where x = 0; 0.5; 2.0; 5.0 was investigated by OA, Z-scan and refractive index measurements using a coupled prism system. Refractive index data were used to calculate the linear susceptibility and dielectric con-stant using Wemple’s method and the optical gap was evaluated from AO. No significant changes were introduced with the addition of silver. However, the Z-scan plots showed an assymetric pattern for samples with added silver, which was analyzed with the aid of the models: Sheik-Bahae [1,2], thermal lenses [3], aberrant thermal lenses [3] and Lara [4], yieldind discrepant results. We attribute this assymetry to a multiphonon emission and a model based on Sumi [5] is proposed.

Keywords: tellurite glasses, silver, Z-scan, linear and nonlinear refractive index.

0459 | Distribution of sodim cations in the glass and glass fiber materials

Alexander A. Shubin, Konstantin V. Romanenko, Dzhalil F. Khabibulin, Olga B. Lapina

Boreskov Institute of Catalysis, pr.Lavrentieva 5, Novosibirsk, 630090, Russia, e-mail: [email protected]

NMR is one of the most informative methods for studying on the molecular level the structure of glass and glass fiber materials. It has been shown that fiber glass materials can be used as a support for the new generation of catalysts in environmental catalysis. Introduction of the active component to the



fiber glass matrix as well as the content of the active component in the fiber determines mainly by Na+ distribution in initial fiber glass.

Herein we demonstrate multinuclear solid state 23Na, 29Si and 1H NMR studies of the interrelation between the structure of initial glass and glass fiber material. It has been shown that Na+ distribution in fiber glass became less homogeneous than in initial bulk glass. Thus Na+ distribution in glass could be described by cation clastering, whereas in glass fiber large degree of cation clastering or even phase sepa-ration takes place.

This work partially supported by rfbr10-03-00667.

Keywords: glass fiber, NMR, multinuclear, distribution of Na+, cation clastering.

0460 | Multinuclear solid state NMR studies of sodium distribution in silica

fiferglass materials. Role of additives (Al, Zr)

Dzhalil F. Khabibulin, Andrey S. Andreev, Evgenii S. Papulovskii, Olga B. Lapina

Boreskov Institute of Catalysis, pr.Lavrentieva 5, Novosibirsk, 630090, Russia, e-mail: [email protected]

The silicate fiberglass materials for a long time are produced in industry and are widely used as perfect heat and electric insulators. At the same time these materials start to be known as catalyst supports hav-ing high thermal stability, high mechanical strength, improved hydrodynamic properties and the possibility to create the new flexible designs of catalysts and the catalytic reactors.

The fiberglass catalysts reveal unique catalytic performance in many oxidation reactions due to the ability of the glass to stabilize small nanoclusters or separate ions of transient metals in the bulk of fibers. It results in high catalytic activity and high catalyst resistance to poisoning and deactivation in aggres-sive reaction media. Notably, excellent catalyst per-formance is achieved at very low noble metal content (0.01-0.02% wt.) thus providing quite reasonable pricing for the catalyst.

The ability of fibreglass to stabilize the active sites is determined by the structure of the leached mate-rial, which is generated in accordance to the distri-bution of Na cations in initial fibreglass. Al and Zr additives significantly change the structure of Si net-work and the distribution of Na cataions. The present paper devoted to multinuclear solid state NMR study of molecular structure of silica network and cation distribution in silicate fiberglass materials promoted by Al and Zr.

This work partially supported by rfbr10-03-00667.

Keywords: glass fiber, NMR, multinuclear, distribution of Na+, cation clastering.

0462 | Determining the crystallization kinetic parameters

for the fresnoite glassA.M. Rodrigues1*, A.A. Cabral2

1Laboratório de Materiais Vítreos – DEMa – Univ Federal de São Carlos, São Carlos, SP, Brasil,

São Carlos – SP, Brazil, e-mail: [email protected] 2IFMA – Inst Federal do Maranhão,

Departamento de Física, São Luis – MA, Brasil, e-mail: [email protected]

Several analytical models have been widely ap-plied to determine the activation energy for crystal-lization, E, and the Avrami’s index, n. Nevertheless, it is well known that the non-isothermal models are more appropriated to provide the correct values of the activation energy. In this work, the parameters E and n for the crystallization of fresnoite (2BaO.TiO2.2SiO2) glass were calculated using isothermal models (Ozawa, Kissinger and Matusita and Sakka) and non-isothermal ones (Ligero). Bulk samples (≈ 36mg) were heated from room temperature up to 720oC (Tn) at 40oC/min, where they were kept for several times (tn = 0 – 110 min) at Tn in order to estimate the values of E and n through the isother-mal models. On the other hand, some samples were heated from the room temperature up to 1200oC under different heating rates (β = 3, 5, 8, 10, 12, 15, 20 and 25oC/min) in order to evaluate these ki-netic parameters from the Ligero model. Both experi-ments were carried out on a DSC furnace in argon atmosphere (20 ml/min), and using Pt crucibles. In an independent way, the evolution of the crystallized fraction with time was independently determined by X-ray diffraction to estimate the Avrami’s index. In this case, the samples were heat treated in a tubular furnace at 720oC for different times. The values of the activation energies obtained through the differ-ent models used varied from 700 to 940 kJ/mol. These results indicate that the activation energy for crystallization can be strongly influenced not only by the composition of the glass studied, but also on the choice of analytical models for the interpretation of the DSC/DTA experiments. DSC/DTA and XRD experi-ments provided a value of the Avrami’s index close to 4, which indicates that the fresnoite crystals are three-dimensional, where the growth is controlled by interfacial rearrangement, and the crystallization mechanism occurs simultaneously by nucleation and growth of crystals with constant rates.

Keywords: DSC/DTA, kinetic parameters for crystallization, fresnoite glass.



0463 | SiO2-K2O-MgO vitreous films doped with erbium and silver

nanoparticles for optical applicationsMaría Virginia Roldán1, Oscar de Sanctis1,

Nora Susana Pellegri1*1Laboratorio de Materiales Cerámicos, FCEIyA, IFIR, UNR, Av. Pellegrini 250, 2000 Rosario, Argentina,


The search for new glass compositions for films produced with high optical transparent throughout the visible spectrum from 0.5 mm to the near infra-red is important for wave guiding materials. On the other hand, Er3+-doped waveguides are fabricated for integrated optic amplifiers, but the increase of Er concentration has a cut-off due to the strength-ening of the ion-ion interaction. The co-doping of planar wave-guides (sol-gel films) with Er3+ and Ag0 nanoparticles is a way to avoid this inconvenient. The aim is to reinforce the fluorescence intensity by a resonant phenomenon between Er3+ and Ag0 nanoparticles, and the dielectric effect of the matrix.

In this work we present the preparation of SiO2-K2O-MgO vitreous sol-gel films to produce planar wave guides. The silver quantum dots were synthe-sized in continuous media by chemical reduction and isolation from media by anchoring chemical solution-compatible modifiers on their surfaces. We present the study of the preparation process and characterization of sol-gel matrices doped with Ag0 nanoparticles and Er3+ analyzing the role of the synthesis parameters and the optical properties, and comparing with other waveguide compositions such as PLZT and SiO2-B2O3

Keywords: waveguide, sol-gel, nanoparticles, films, erbium.

0468 | Use of red mud as a raw material for glass preparation

Heveline Vieira1*, Signo T. Reis1,2, Ulisses S. Prado1,3, José R. Martinelli1

1*Nuclear and Energy Research Institute, Sao Paulo – SP, Brazil, e-mail: [email protected]

2Missouri University of Science and Technology, Missouri, United States

3Lining, Representation, Consultancy, & Projects, Sao Paulo, Brazil

Nuclear waste vitrification is usually performed by melting and cooling glass frits and nuclear wastes. Glasses are prepared by mixing minerals and other chemical compounds which form particular glass structures. In the present work the use of red mud (a waste from the aluminum industry) is proposed to replace the conventional raw materials used in the glass production. It is intended to produce a glass which would be useful for a nuclear wasteform.

Glasses are prepared by the conventional pro-cessing method (melting and cooling) after mixing red mud, sand, and soda. The material is cast in

stainless steel molds, and finally annealed. Thermal analyses are performed to determine the glass tran-sition temperature and crystallization kinetics. X-ray diffraction is used to evaluate possible crystalline phases, and X- ray fluorescence spectrometry is used to determine the final glass composition. The glass chemical durability is evaluated by determining the dissolution rate in water at 90oC according to the MCP-1P standard.

Keywords: red mud, glass, vitrification and nuclear wasteform.

0469 | Glass matrices for solar cellsC. Kinowski1,2, J. Habinshuti1,3, S. Turrell1,

D. Stievenard3, B. Grandidier3, T. Xu3 and O. Cristini1,2

1LASIR (CNRS, UMR 8516), Bât C5, Université de Lille 1, 59650 Villeneuve d’Ascq, France

2PhLAM (CNRS, UMR 8523), Bât P5, Université de Lille 1, 59650 Villeneuve d’Ascq, France 3IEMN (CNRS, UMR 8520), Lab. Physique,

Université de Lille 1, 59650 Villeneuve d’Ascq, France, e-mail: [email protected]

The use of silicon as a solution for photovoltaic conversion has a multitude of drawbacks. Of these, the two most serious handicaps are first, the high expense of fabrication and secondly, the present-day relatively low conversion yields. In fact, actually the photovoltaic cell with a theoretical conversion limit of 30% cannot do better than 20% in the best of cases. Hence, at the present time one of the principle re-search aims is to determine a way of increasing this conversion yield.

Though several groups are working on the devel-opment of nanowire systems, our work possesses the originality of developing a hybrid structure in which Si nanowires are coupled with semiconductor nanoparticles (NPs). In this approach, after absorb-ing incident energy, the NPs can then transfer this energy to nearby Si nanowires. The result will thus yield a coupled efficiency. In this work, the NPs are deposited directly on the nanowires.

Evidently, such a system must be maintained in a package: the nanowires must first be supported in a non-conducting solid medium a few microns thick and this layer must be covered by an equally thin conducting layer. The design of the insulating layer for the nanowire/NP ensemble involved the use of sol-gel techniques for the preparation of amorphous systems, with a final choice going towards SiO2 or ZrO2 as the non-conducting material.

Keywords: Photovoltaic, nanowire, nanoparticle, sol-gel.



0474 | Perception of strategic marketing and new technological paradigms for

manufacturing glass productsVicente Cerqueira1

Doctor Science – Technology Management Materials, State University of Rio de Janeiro – UERJ,

Superior School of Industrial Design – Product Design Department, e-mail: [email protected],

Rio de Janeiro – RJ, Brasil

The history of glass show that these materials always stood in the manufacture of common prod-ucts. With scientific and technological development of glass industry achieved a privileged position in the manufacturing of commodity products (bottles, pack-aging and others), contributing to various sectors of the economy. In the second half of the 20th century, this industry segment glass begins to lose competi-tive strength, through of the adoption of emergent technologies on the market. In this context, the in-novations in the mass of glass and the improvement in processes were not sufficient to reduce the tech-nological and economic crisis in the product glass industry, which continues today.

The objective of this paper is to analyze the technological strategies for of commodities (press-ing, blowing and blowing-pressing) in the Brazilian market, identifying the factors that determined the decline in competitiveness and seek alternatives to recover their economic value. The study analyzed the business strategies in relation to marketing activities, as well the productive structures and programs of technological innovation. As a result, the research has show an example of “marketing myopia”, where management has always been a behavior tradi-tionally focused on the internal environment. It is therefore necessary to draw up strategic alternatives based on technological segments, with the objective of structures more flexible and dynamic in relation to the characteristics of products and markets.

Keywords: glass supply chain, marketing of technology, glass product design.

0475 | Optical studies of neodymium and praseodymium

doped phosphate glassesJ.A.Erwin Desa1*, Wilson Vaz1, Alka Sawaikar2,

P.R. Sarode1, and S.K. Mendiratta3

1Department of Physics, Goa University, Taleigao Plateau, Goa 403 206, India,

e-mail: [email protected] 2Marathwada Mitra Mandal’s College of Engineering, Karvenagar, Pune, India 3Department of Physics, University of Aveiro, Aveiro 3810-193, Portugal

Phosphate glasses incorporating oxides of lan-thanum, neodymium and praseodymium have been prepared. The molar concentrations of the rare earth oxides varied from 5 % to 15 % in a set of five samples as follows:

1. (La2O3)9.19(Pr6O11)0.99(Nd2O3)3.06(Al2O3)5.10 (P2O5)81.66

2. (La2O3)7(Nd2O3)8(Al2O3)5 (P2O5)80

3. (La2O3)10.73(Pr6O11)3.46(Al2O3)5.36(P2O5)80.43

4. (La2O3)10.56(Pr6O11)2.66(Nd2O3)2.29(Al2O3)5.28

(P2O5)79.21

5. (La2O3)9.19(Pr6O11)3.06(Nd2O3)0.99(Al2O3)5.10 (P2O5)81.66

UV and Visible spectroscopic data (190 nm to 900 nm) have confirmed the absorption spectra in the visible region to be due to 4f electronic transi-tions of the rare earth ions and shown them to occur at the same frequencies in all these samples.

Excitation at 445 nm of the rare-earth ions at room temperature led to emission in the 720-980 nm range. These data were used to measure the decay times. The fact that these times were similar to each other for all the glasses indicate that the levels involved in these emission are essentially unaffected by the detailed compositions of these glasses.

Raman spectroscopy on these glasses has also been made. The basic structures of these glasses have been reported earlier1. The present studies in-dicate that the 4f electronic levels of the rare-earth ions interact only weakly with each other and with the host structure of these phosphate glasses.1. Shikerkar, A.G., Desa, J.A.E., Krishna, P.S.R. &

Chitra, R. J. Non-Cryst. Solids, 2000, 270, 234- 246.

Keywords: phosphate glasses, rare-earth ions, UV-visible spectra, raman spectroscopy.



0476 | Production of glass wool from ornamental rock wastesJoner O. Alves*, Girley F. Rodrigues,

Denise C. R. Espinosa, Jorge A. S. TenórioDepartment of Metallurgical and Materials

Engineering, Polytechnic School, University of Sao Paulo, Sao Paulo-SP, Brazil, e-mail: [email protected]

Glass wools are mineral fibers composed of amorphous silicates. Due to their thermo-acoustic characteristics this material has a broad consumer market in the construction, automotive, and electric-electronics industries. This work studied the recovery of wastes from ornamental rocks (granite and marble) as partial raw materials in the production of the glass wool. The residues from granite and marble cuttings are industrial wastes with considerable production and limited applications. These wastes should be appropriately managed, because when discharged in rivers, lakes or watersheds, they can cause siltation. Also, these residues can cause serious human health problems, such as silicosis. In the experiments, mixtures were cast at temperatures of 1400, 1450 and 1500 ºC; the melted materials were quenched in water and also poured into a Herty viscosim-eter. Samples of produced materials with thickness smaller than 500 µm were characterized by chemical analyses, XRD, SEM, EDS and DTA. Results showed that the glass wools produced using granite or mar-ble wastes have important properties, especially the melting point. Therefore, this technique provides a decrease in the extraction of mineral resources, a profitable destination for ornamental rock wastes and economy in the glass wool production.

Keywords: glass wool, granite, marble, recycling, insulator.

0477 | Nanoindentation behaviors of SiO2–CaO–Na2O glasses with TiO2, ZrO2

and HfO2 under low temperatureMirabbos Hojamberdiev*, Harrie J. Stevens

New York State College of Ceramics, Alfred University, Alfred, NY 14802, United States,


The annealing treatment is of primary interest to estimate the ratio of densification to a total indenta-tion volume of soda lime silicate (SLS) glasses with TiO2, ZrO2 and HfO2 additives. The elastic properties, microhardness and density increased with increasing the amounts of additives (0, 1, 2, 4 and 8 mol.%) in the following order: SLS glass < SLS+TiO2 glass < SLS+ZrO2 glass < SLS+HfO2 glass. This is attributed to the packing ions present in the glass structure, the strength of the individual bonds, and higher atomic weight of additives, respectively. Nanoindentation experiments were performed using a Brinel1 indenter and scanned after predetermined annealing time us-ing a laser non-contact profilometer. The effects of 25 °C and 100 °C on the nanoindenations were stud-

ied as function of time up to 48 h. On the basis of the depth change of the ponds at low temperature, nanoindentation behaviors of glass samples was evaluated. The results showed that the rate of elastic response of the nanoindentations resulted from the gradual expansion of the structure took place in the following sequence: SLS glass > SLS+TiO2 glass > SLS+ZrO2 glass > SLS+HfO2 glass. Since annealing temperatures were low, we assume that the internal pressure raised by disentangling of structural ele-ments might play an important role in elastic recovery of the nanoindentations at low temperature. All the indented samples exhibited three main behaviors: elasticity, viscoelasticity, and permanent viscous flow.

Keywords: nanoindentation, silicate glass, elastic response, thermal treatment.

0478 | Does viscosity describe the kinetic barrier for crystal growth from the liquidus to the glass transition?

Marcio Luis Ferreira Nascimento1, Edgar Dutra Zanotto2*

1Institute of Humanities, Arts & Sciences, Federal University of Bahia, Rua Barão de

Jeremoabo s/n, PAF3, Ondina University Campus, CEP 40170-115 Salvador – BA, Brazil

2Vitreous Materials Laboratory, Department of Materials Engineering, Federal University of

São Carlos, CEP 13565-905, São Carlos – SP, Brazil, e-mail: [email protected]

An analysis of the kinetic coefficient of crystal growth, Ukin , recently proposed by Ediger and col-leagues indicates that the Stokes-Einstein / Eyring (SE/E) equation does not describe the transport con-trolling crystal growth rates in fragile glass forming liquids. Here we revisit this interesting finding consid-ering two other models: the screw dislocation (SD) and the two-dimensional surface nucleated (2D) growth model for nine undercooled oxide liquids, from slightly below the melting point down to Tg, cov-ering a wider viscosity range. We then propose and use normalized kinetic coefficients (Mkin) for the SD and 2D models. These new kinetic coefficients re-store the ability of viscosity to describe the transport part of crystal growth rates (Mkin ~ 1/η and ξ ~ 1) from low to moderate viscosities (η < 106 Pa.s), and thus the SE/E equation works well in this viscosity range for all systems tested. For strong glasses, the SE/E equation works well from low to high viscosi-ties, from the melting point down to Tg! However, for three fragile liquids [diopside, lead metasilicate and lithium disilicate] there are signs of a breakdown of the SE/E equation at higher viscosities. Our results demonstrate that viscosity data cannot be used to describe the transport part of crystal growth in fragile glasses in the neighborhood of Tg.

Keywords: glass, viscosity, crystal growth, stokes-einstein equation, diffusion.



0479 | Molecular-dynamics simulations of supercooled lithium disilicate melt

Luis G. V. Gonçalves1, José P. Rino2

1Federal University of São Carlos – UFSCar, São Carlos – SP, Brazil, e-mail: [email protected]

2Federal University of São Carlos – UFSCar, São Carlos – SP, Brazil

We performed simulations of lithium disilicate melt using classical molecular-dynamics (MD) tech-nique. The interaction forces used in this work is the Buckingham potential, with fitting parameters de-veloped by Habasaki and co-workers. This potential describes well the behavior of the material whether in the crystalline form or in the amorphous phase. The orthorhombic-liquid coexistence temperature calculated via MD is 1480K, in excellent agree-ment with the experimental value of 1360K. This is an indication of the robustness of this potential in describing the liquid state. The aim of this work is to evaluate element diffusivities and the shear viscosity in the supercooled regime down to Tg and check their temperature dependence. Diffusion was calculated using the slope of the mean square displacement. For T>1000K, Si and O diffusivities possess an Ar-rhenian behavior. Below that temperature, usual MD techniques are inefficient and more elaborate tools are required. The viscosity is equally challenging, given that near Tg it reaches 1012Pa.s, and standard MD gives erroneuos values. However, down to 1300K we could evaluate the structural relaxation time and check its temperature dependence. Until now, we found no evidence of the breakdown of the Eyring relation. Future work involves the application of tools based on the transition state theory to evaluate high viscosities. Also, we intend to apply accelerated dy-namics techniques to calculate diffusivities down to Tg.

Keywords: structural relaxation, viscosity, diffusion, decoupling, molecular-dynamics, lithium disilicate.

0480 | International collaboration on the strength of glasses

Charles Robert KurkjianUniversity of Southern Maine, Gorham,

Maine and Rutgers University, Piscataway, NJ, e-mail: [email protected]

At the present time there are many exciting activi-ties in the area of glass mechanics and the ‘strength of glass’. These are reviewed and new techniques/approaches/results are described. It is suggested that the time is right for serious international collabo-rations and mechanisms for such collaborations are suggested.

Keywords: strength, glass mechanics.

0481 | Luminescent property of metal doped high silica glass

Tomoko Akai, Masaki Murakam, Masaru Yamashita

National Institute of Advanced Industrial Science and Technology (AIST), – Ikeda, Osaka,

Japan, e-mail: [email protected]

Cu doped high-silica glass prepared by sintering porous glass at 1000-1100 °C shows intense lumi-nescence with UV irradiation [1]. This luminescent glass is an interesting target to study because it has other interesting optical properties such as multi-photon excited luminescence [2]. In this work, we prepared several metal doped high silica glass and studied their luminescent properties. It is found glasses with some species of metals (Ag, V, Sn, Mn) emit visible luminescence with UV irradiation at around 5eV. Broad excitation spectra between 230-300 nm are commonly observed for all of these glasses. From these results combined with our results on Cu doped glasses, it is speculated that charge-transfer mechanism may be a reason for the efficient UV excitation in glasses.1. Chen DP, Miyoshi H, Akai T and Yazawa T, Appl.

Phys. Lett., 86, 231908 (2005).2. Qiao YB, Chen DP, Liu XF, Ruan J, Qiu JR, Akai T,

IEEE, Photonics and Technology Letters, 20,13-16,1390 (2008).

Keywords: high-silica glass, luminescent property, Cu,V, Sn, Mn, charge transfer.

0482 | Vitrification process of steelmaking wastesJoner O. Alves*, Girley F. Rodrigues,

Denise C. R. Espinosa, Jorge A. S. TenórioDepartment of Metallurgical and Materials

Engineering, Polytechnic School, University of Sao Paulo, Sao Paulo – SP, Brazil,


The steelmaking slag and the slag of the FeS-iMn alloy production are wastes with considerable production and limited applications, therefore a large portion of industrial park space is occupied by these wastes, which raises disposal costs. This work studied the vitrification process of these wastes in the form of glass fibers with characteristics of thermo-acoustic insulation. Mixtures of the wastes and chemical reagents were casted at temperatures of 1400, 1450 and 1500 ºC, the melted materials were quenched in water and also poured into a Herty viscosimeter. Samples of produced materials with thickness smaller than 500µm were characterized by chemical analyses, XRD and SEM. Results showed that the produced materials have properties similar to glass, that is being translucent, fragile and brittle at room temperature. Therefore the fast cooling pro-cess was successfully performed.

Keywords: fiber glass, steelmaking slag, FeSiMn, recycling, insulator.



0484 | EPR of γ – Induced paramagnetic centers in tellurite glassesJ. M. Giehl1, W. M. Pontuschka1*,

L. C. Barbosa2, Z. M. C. Ludwig3, M. Navarro1

1Instituto de Física, Departamento de Física Geral, Universidade de São Paulo – USP, São Paulo – SP,

e-mail: [email protected] 2Instituto de Física, Gleb Wataglin,

Universidade de Campinas – UNICAMP, Campinas – SP 3Instituto de Física, Universidade

Federal de Juiz de Fora, Juiz de Fora – MG

Intrinsic paramagnetic responses were observed in the 60TeO2-25ZnO-15Na2O, 85TeO2-12Nb2O5-3Na2O and 85TeO2-15Na2O mol% glasses, after γ-irradiation at room temperature: (1) a very weak and broad (ΔH ~ 200G) pattern at g0 ~2.2; (2) a shoulder at g1 = g’’ = 2.02 ± 0.01 and an estimated g⊥⊥ ~ 2.0 attributed to tellurium-oxygen hole center (TeOHC); (3) a narrow resonance at g2 = 1.9960 ± 0.0005 related to the modifiers and (4) a resolved resonance at g3 = 1.9700 ± 0.0005 ascribed to a tellurium electron center (TeEC) of an electron trapped at an oxygen vacancy( VO

+) in a tellurium ox-ide structural center. The niobic tellurite glasses did not exhibited EPR on irradiation. It is suggested that the creation of (NBO-,VO

+) pair follows a mechanism where the modifier oxide molecule actuates as a catalyser. An additional model for the NBO radioly-sis produced by the γ-irradiation is proposed on the basis of the evolution of the g1, g2 and g3 intensities with increasing dose (KGy).

The extended manuscript will be published in Journal of Non-Crystalline Solids.

Acknowledgments – FAPESP, FAPEMIG.

Keywords: tellurite glasses, electron paramagnetic resonance, defect centers.

0486 | Termally stimulated depolarization current study

of sodium tellurite glassJ. M. Giehl1, W. M. Pontuschka1*, L. C. Barbosa2,

A. R. Blak1, M. Navarro1, Z. M. C. Ludwig3

1Instituto de Física da Universidade de São Paulo, 187 Rua do Matão – Travessa R, CEP 05508-090,

São Paulo – SP, Brazil, e-mail: [email protected] 2Laboratório de Materiais Vítreos, UNICAMP,

Box 6165, CEP 13083-970, Campinas – SP, Brazil 3Departamento de Física ICE,

Universidade Federal de Juiz de Fora, CEP 36036-330, Juiz de Fora – MG, Brazil

With the aim of a better understanding of the role of structure and defects involved in the polarization processes in the (85 TeO2 – 15 Na2O) mol% glass, the technique of thermally stimulated depolarization currents (TSDC) was chosen. The induced polariza-tion of the 1.4 mm thick sample was performed at the different applied d. c. voltages of 1200, 1500 and 2000 V, and a current peak was observed at the temperatures of 302, 309 e 296 K, respectively, be-

ing observed a small increase of intensity. An inverted peak was also observed at the temperatures 334, 343 e 340 K for the same voltages, respectively, with a considerable increase in intensity. After γ–irradia-tion with doses 25 and 50 KGy, respectively, for the sample with smaller dose occurred a decrease of de-polarization current peak. Otherwise, for the sample irradiated with 50 KGy, six TSDC peaks appeared at regular intervals of 50 K, in the temperature range of 100 and 300 K.

Acknowledgments – FAPESP and FAPEMIG for the financial support.

Keywords: tellurite glasses, gamma radiation, thermally stimulated depolarization currents.

0487 | Alternative boron oxide carriers in insulation and e-glass

batch model systemWidiya Jatmiko, Reinhard Conradt

Institute of Mineral Engineering, RWTH Aachen, GERMANY

Boron oxide, boric acid and borax are widely used as B2O3 raw material carriers in glass fibre production. However, the usage of those conventional raw mate-rials should be reduced according to REACH regula-tion (Registration, Evaluation, Authorisation, and Re-striction of Chemical) issued by the European Union in 2007. The main objective is to ensure the level of human health and the environment from the risk that can be posed by chemicals. An economic and feasible way to cope this situation is the substitution of conventional by alternative boron oxide carriers. In the present study, batch melting behavior in respect to batch-to-melt conversion and energy consumption of insulation fibre and E-glass batch is investigated by employing colemanite, ulexite, tincal, kernite and magnesium borate as boron oxide carriers. Based on results in laboratory tests ranging from the 10 mg scale (DTA-TG) to the 10 kg scale, the behavior of a batch in industrial furnace can be predicted in a reli-able way, as verified by industrial campaigns. Such laboratory tests on alternative boron containing batch suggest that alternative boron carrier can be used in industry without impairing glass melting.

Keywords: boron oxide, glass fibre, batch melting, borax pentahydrate, ulexite, colemanite.



0488 | The crystallization of calcium phosphate glass containing strontium

oxideDenise Stolle da Luz Weiss, João A. de Palma

Setti, Paulo Soares*Mechanical Engineering Department, Pontifícia Uni-versidade Católica do Paraná, PUCPR, Curitiba,PR,

[email protected]

Bioresorbable materials are desirable compo-nents for applications such as temporary implants. Phosphate based glasses have properties that allow them to be used as hard tissue substitutes with the advantage of being compositionally similar to the inorganic component of bones. Recent works have shown that incorporation of strontium in the PBG can increase the density, alters the bioactive prop-erties and the degradation rate of the glass. Stron-tium is currently used in bone therapies and it has been proved that it strengthens bone, reduces bone resorption and stimulates bone formation. Conse-quently, several studies have been conducted on the use of Sr in the composition of biomaterials. There are however limited studies on strontium-containing bioactive glass-ceramic. The aim of this work was to characterize new calcium phosphate glass-ceramic containing strontium oxide that would degrade in a controlled manner in the body environment. Glass with a molar composition of (CaO)3.(Na2O)2.(P2O5)5 and a SrO2 content of 2.5 mol% was prepared for the experiments. The crystallization was performed under isothermal conditions at T = 490 °C for periods of 1 to 8 hours. A heat-treatment schedule was obtained from DTA of this glass. The crystalline compounds were identified by using scanning electron micros-copy and X-ray diffraction techniques. The in vitro bioactivity of the glasses and glass-ceramics was conducted in simulated body fluid (SBF) at 37 °C for a period of 7 days.

Keywords: Glass-ceramic, Bioresorbable glass, Temporary implants, Phosphate based glass, Strontium.

0489 | Solar heat reflective glass by nanostructured sol-gel multilayer

coatingsZoulfia Nagamedianova1,2*, Miguel Arroyo1

1 Vitro Automotriz SA de CV, Carr. a Garcia km.10.3, Garcia NL, CP66000 Mexico

2 Facultad de Ciencias Quimicas, Universidad Autonoma de Nuevo Leon, Ave. Universidad s/n, Cd. Universitaria, San Nicolas de los Garza NL, CP66451 Mexico, znaga-

[email protected]

Solar heat reflective coatings on glass are inter-esting for automotive and architectural glasses due to important energy savings by air conditioning de-creasing if such glasses used on vehicles and build-ings. A Vitro project of sol-gel solar reflective films development is described. A new multilayer stacks of high heat reflective silica and titania based alternate

films are computer designed and prepared by immer-sion method. The interference layer stacks show high visible transmission with high near-infrared reflection indicating a high potential for practical applications.

Keywords: sol-gel coatings, interference filter, solar control glass

0491 | Impedance measurements of phosphate glasses and melts in the temperature range 300 – 1250 °C

Sylvia Flügel* & Doris EhrtOtto-Schott-Institut, Friedrich-Schiller-Universität Jena,

Fraunhoferstr. 6, D-07743 Jena [email protected]; [email protected]

Impedance measurements are important to de-termine the electrical conductivities of glasses and melts with high accuracy. Electrical conductivities depending on temperature provide a better under-standing of the structure and are important for new melting processes so-called ‘inductive skull melting technology’.

Phosphate glasses are of great interest for spe-cial applications in high performance optics, e.g. laser glasses with extremely high purity and optical homogeneity. Phosphate glass melts are very corro-sive against various crucible materials. With the skull melting technology a crucible is not necessary but special conductivities and crystallization behaviour of the melts.

Metaphosphate glasses M(PO3)2 with M = Mg, Ca, Sr, Ba were prepared and analyzed using imped-ance spectroscopy in a wide temperature range of 300 – 1250 °C and in frequency range of 1 – 6MHz with two different methods, for the solid glasses the “disk measurement” and for the melts the “im-mersion measurement”. Impedance spectra were analyzed using equivalent circuits and the electrical conductivities depending on temperatures were de-termined.

The conductivities and other determined proper-ties like viscosities and crystallization behaviour were interpreted and compared.

Keywords: impedance spectroscopy, phosphate glasses and melts, electrical conductivity.

Author Index

Author index


aAben, H............................................................30

Abreu, Wanderson M. de ....................................56

Abyzov, Alexander S. ................................93,94,95

Adamiv, V. ........................................................51

Adams, Brian ....................................................27

Affatigato, Mario .............................13,106,122,123

Agarwal, Anu ..................................................... 7

Aguillar, Maria Teresa P. ....................................161

Aitken, Bruce G. ................................................63

Akai, Tomoko ..................................................168

Akerman, Mauro ................................................. 9

Akkopru, Betul ..................................................27

Albuquerque, Alderiza V. ...................................157

Alencar, Mônica A. S. .......................................152

Ali, Sharafat .....................................................88

Allen, F. ............................................................68

Allix, Mathieu ....................................................45

Almeida, G. F. B. .............................................114

Almeida, Juliana M. P. de ..................................111

Almeida, Rui M. ............................................ 26,67

Alves, Antonio Carlos V. ..............................152,153

Alves, Joner O. ..........................................166,168

Alves, Rosa M. V. .............................................105

Alves, Sarah Isabel Pinto Monteiro do N. ....... 96,163

Amâncio, Carlos T. ............................................97

Amano, Masaru ...............................................124

Amaral, F. .......................................................160

Amis, A. ...........................................................93

Ananthanarayanan, A. ......................................102

Andersen, Mogens L. ..........................................56

Anderson, Troy ................................................... 7

Andrade, Luis H. C. ....................................120,121

Andreev, Andrey S. ..........................................164

Angel, J. A. .......................................................71

Anjos, V. ..........................................................33

Anjos, Virgilio de Carvalho dos ....................... 25,49

Antonello, Alessandro .........................................27

Aparicio, M. ......................................................28

Apel, E. ....................................................... 42,64

Araújo, Cid B. de ....................................21,97,119

Araújo, Eudes B.................................................98

Arroyo, Miguel .................................................170

Aso, Goro .......................................................130

Assumpção, Thiago A. A. ..................................116

Astrath, Francine B. G. .....................................111

Astrath, Nelson G. C. .................... 111,112,121,133

Aswal, V. K. ....................................................129

Austin, Stephen.................................................75

Avansi Júnior., W. ............................................114

Ayrinhac, S. ......................................................18

Azarenco, Olga ................................................151

bBabayan, G. ....................................................162

Baddour-Hadjean, R. .........................................12

Baesso, Mauro Luciano ............111,112,120,121,130

Baghramyan, V. ...............................................162

Baino, Francesco ...............................................66

Bal’zhinimaev, Bair S. ........................................74

Balaji, Subramanian ............................................ 6

Balogh, John .....................................................18

Balzaretti, Naira M. ..........................................109

Barbieri, Luisa ...........................................115,134

Barbosa, Anne J. .......................................132,147

Barbosa, Luiz Carlos ...............25,49,73,96,100,150,

156,157,163,169

Barboux, P. .......................................................95

Barboza, M. J. .................................................121

Barboza, Marcio J. ........................ 120,121,137,138

Bardez, Isabelle ......................................... 13,134

Basilio, Edson E. ................................................80

Baskov, Peter B. ................................................. 7

Batista Júnior, Edgard Dias..................................10

Battistella, Elisa ................................................64

Beckmann-Kluge, Martin ..................................136

Beerkens, Ruud .................................................34

Behrens, Harald ................................................50

Bell, M. J. V. ......................................................33

Bell, Maria José Valenzuela ............................ 25,49

Benino, Yasuhiko ................................................ 4

Bento, A. C. ....................................................121

Bento, Antônio C. ............................... 111,112,130

Berkowitz, Jack .................................................13

Berneschi, Simone ....................................22,47,50

Berthelot, Alice .................................................50

Bertholdo, Roberto...........................................163

Bertuzzi, P. .......................................................80

Bessada, Catherine ..........................................129

Bettinelli, Marco ................................................22

Betzen, Ashlea ................................................106

Beuneu, Brigitte ......................................... 61,138

Bhaktha, Shivakiran N. B. ...................................47

Bhatnagar, A. K. ..............................................132

Bialkowski, Stephen E. .....................................111

Bianchi, Claudia Letizia .......................................64

Bielecki, Sebastian ...........................................104

Biswas, Sampad ......................................... 48,156

Blak, A. R. ......................................................169

Blunn, G. ..........................................................68

Boccaccini, Aldo R. ............................................67

Bocker, Christian ...............................................60

Boery, Mirella N. de O. .....................................116

Boery, Mirella N. O. ..........................................162

Boery, Mirella O. ......................................... 55,139

Boldonalli, Aldario ............................................100

Author index


Bollino, Flavia ...........................................133,134

Bomfim, Joao Antonio ........................................81

Bonnetier, A. ...................................................160

Borczuch-Laczka, Maria ..............................130,131

Bordonalli, A. C. ................................................73

Borrero, Luis ...................................................139

Bosak, Alexey ...................................................18

Botezatu, Vitalie ..............................................151

Bouazaoui, Mohamed .................................... 28,47

Boulon, G. ......................................................121

Boulon, Georges ........................................120,121

Bourdonnais, Sebastien ......................................36

Brajato, P. ......................................................114

Brenci, Massimo ........................................... 22,50

Bretcanu, Oana .................................................64

Bretcanu, Xanthippi Chatzistavrou Oana ...............67

Brillant, L. ......................................................139

Brovarone, Chiara Vitale .....................................64

Brow, Richard K. ...............................................30

Brun, P. ..........................................................160

Brüning, Ralf ...................................................... 6

Buchenau, U. ....................................................18

Buchner, Silvio ................................................109

Buechele, Andrew ..............................................33

Bueno, L. A. ....................................................157

Bueno+, Luciano A. .........................................149

Bulatov, Lenar I. ................................................. 4

Bulla, Douglas ...................................................72

Burak, Ya. ........................................................51

Burch, Matt ....................................................122

cCabodi, Isabelle ................................................36

Cabral, A. A. .............................................. 48,164

Cacciari, Ilaria ...................................................50

Calas, Georges ........................11,14,15,17,138,154

Caldino, Ulises ..................................................22

Campo, Leire Del ...............................................19

Campos, Monica de Cassia S. ............................153

Candarlioglu, P. ............................................ 68,93

Canizarès, A. ............................................... 15,16

Capanema, Wilson A. .......................................161

Capoen, Bruno ............................................. 28,47

Cardoso, Antonio V. .............................. 56,152,153

Carlie, Nathan .................................................... 7

Carlos, Luis D..................................................147

Carmo, Alexandre Peixoto do ..............................49

Carvalho, Marcela D. ........................................153

Carvalho, Sandhra M. .......................................109

Cassanjes, Fábia Castro ........................ 47,153,163

Cassar, Daniel R. .............................................136

Cassinelli, Clara .................................................64

Castro, Y. .........................................................27

Catauro, Michelina ...........................................133

Caurant, D. .................................................. 12,95

Caurant, Daniel .......................................... 13,134

Cavalcante, Maria S. L. .....................................157

Cerqueira, Vicente ...........................................166

Cesar, Paulo F. .................................................152

Chalyan, A. .....................................................162

Chamma, Karima...............................................24

Champagnon, Bernard .................................. 50,71

Charpentier, T. ..................................................95

Charpentier, Thibault ................................... 13,134

Chaussedent, Stéphane ............................... 99,124

Cheng, Jinshu .................................................107

Chiasera, Alessandro ..................................... 22,27

Chillcce, Enver Fernández .................... 25,49,73,96,

100,150,155,157

Chilyasov, A. V. .......................................... 74,149

Chligui, M. ........................................................15

Chligui, Maggy Dutreilh-Colas Miriam ...................15

Cholewa-Kowalska, Katarzyna .............. 104,105,108

Cholewa-Kwalska, K. ........................................104

Chouard, N. ......................................................12

Chouard, Nolwenn ...........................................134

Chumakov, Aleksand I. .......................................18

Churbanov, M. F. ........................................ 74,149

Ciccotti, M. .......................................................70

Ciecinska, Malgorzata.................................126,127

Cincibusová, P. ..................................................53

Citti, Olivier ................................................. 34,36

Çivi, Özlem Aydin ..............................................75

Cobb, J. ...........................................................93

Cohen, R. .......................................................156

Coillot, Daniel ...................................................58

Comes-Franchini, Mauro ...................................133

Comez, Lucia ....................................................18

Conradt, R. .......................................................79

Conradt, Reinhard ...................................... 39,169

Conti, Gualtiero Nunzi ........................................50

Coqueiro, Crisneide R. da S. ..............................113

Cordeiro, Cristiano ...................................... 73,100

Cormack, Alastair ..............................................83

Cormier, Laurent ................ 11,14,15,17,61,138,154

Cornejo, Dr. Ivan A. ...........................................42

Costa, C. R. Da ...............................................150

Costa, Ernande B. ............................................149

Costa, L. C. ....................................................160

Costa, Z. M. Da ...............................................150

Costa, Zélia Maria Da .................................... 25,49

Courtens, E. .....................................................18

Courtens, Eric ...................................................19

Cramm, Sandra .................................................50

Crawford, Charles L. ..........................................31

Crichton, Wilson ................................................18

Cristini, O. ......................................................165

Author index


Cristini, Odile ............................................... 28,47

Crovace, Murilo C. .....................................108,112

Ctyroky, Jiri ......................................................50

Cunha, Carlo Requião da ..................................151

Currie, Stephen C. .............................................63

Czarnacki, Krzysztof ........................................103

dDaguano, Juliana K. M. F. ...........................136,137

Damiani, Larissa R. ..........................................151

Dantas, Sebastião A. dos S. ..............................113

Dargaud, Olivier .....................................11,15,154

DaSilva, Cláudio José .......................................155

David, Andreea .................................................95

Delevoye, Laurent .............................................. 5

Dericioglu, Arcan F. ............................................75

Desa, J. A. Erwin .......................... 126,127,129,165

Desai, Reshma R. ............................................126

Deschamps, Michael ..........................................45

Deschamps, Thierry ...........................................71

Deshpande, Rashmi .........................................126

Deubener, J. .....................................................42

Deubener, Joachim .............................. 41,44,46,50

Devreux, F. .......................................................95

Dianov, E. M. ............................................. 74,149

Dias, Luisa L. S. ..............................................109

Diniz, Geovanni S. ...........................................109

Djaoued, Yahia ................................................... 6

Domanická, Alena ..............................................98

Dongol, Ruhil ..................................................123

Donizetti, Carlos ................................................10

Dorofeev, V. V. ........................................... 73,149

Dressler, Martina ...............................................46

Drzewiecki, A. ...................................................51

Du, Jincheng .....................................................83

Dubcek, Alexander ............................................. 3

Dubinin, Nikolay E. ............................................. 8

Duca, Gheorghe ......................................... 70,128

Dugué, Aymeric.................................................11

Dulal, Prabesh ...........................................121,123

Dultz, Stefan ....................................................50

Dunkl, Dr. Michael .............................................88

Durán, A. .................................................... 28,43

Durán, Alicia .............................................. 56,102

Durucan, Caner .................................................27

Dussossoy, Jean-Luc .......................... 12,13,33,134

Dvoyrin, Vladislav V. ........................................... 4

eEberstein, Markus ..............................................44

Echegut, Patrick .....................................16,19,129

Eckert, Hellmut ............................................ 4,126

Ehrt, Doris ................................................. 41,170

Ek, Paul ...........................................................66

El-Amraoui, M. ................................................138

Engelaar, Erwin .................................................34

Enss, Christian ..................................................69

Ercole, P. ..........................................................80

Errapart, A. ......................................................30

Escaravage, Bruno .............................................36

Espinosa, Denise C. R. ...............................167,168

Evangelista, Luiz R. .........................................133

fFagerlund, Susanne ...........................................66

Falcone, R. .......................................................80

Fang, Zuo Ze ....................................................94

Farag, Mohamed M. .........................................116

Faria, Sabrina G. .............................................125

Farias, A. M. ...................................................121

Farias, Aline M. .........................................137,138

Faris, Cory ......................................................123

Fatome, J. ......................................................139

Favaro, N. ........................................................80

Felelgara, Henry ..............................................107

Feller, Heidi .....................................................106

Feller, Steve .............................. 13,55,106,122,123

Fernandes, Roger Gomes ....................................47

Fernie, J. A. ......................................................45

Ferrari, Maurizio .......................................22,27,47

Ferraris, Sara ....................................................64

Ferreira Neto, Elísio ...........................................95

Ferreira, Eduardo B. ..........................48,55,132,150

Ferreira, Elivelton Alves ....................................163

Ferreira, Fábio A. S. ...........................................86

Ferreira, Rute A. S. ..........................................147

Figueiredo Neto, Antonio Martins .......................163

Figueroa, Hugo ...............................................100

Filippov, Vladimir V. ............................................ 8

Fioretto, Daniele ................................................18

Flejszar, Aneta ..................................................41

Fletcher, Luke B. ................................................57

Flügel, Sylvia ............................................. 41,170

Fojud, Zbigniew ...............................................143

Fokin, Vladimir Mihailovich ............ 93,94,95,113,136

Fonseca, A. C. .................................................150

Fonseca, Fátima Roneiva Alves ....................113,114

Foret, M. ..........................................................18

Forler, Nina ........................................................ 5

Fourcade, Julien ................................................34

Fox, Kevin M. ....................................................31

Franco, Douglas F. .............................................93

Fredericci, Catia ..............................................107

Freitas, Alysson .................................................25

Frumar, Miloslav ..............................................155

Frumarova, Bozena ..........................................155

Fujiwara, Eric ..................................................162

Fujiwara, Takumi ........................................ 61,123

Author index


Fukasawa, Yasuji .............................................106

Füller, Alexandra ................................................35

Füller, Hermann .................................................35

Furusawa, Daisuke ............................................84

Futagami, Tsutomu ............................................77

gGaber, Martin ..................................................136

Gadret, G. ......................................................139

Gallo, Leonardo Sant’Ana ..................................113

Galoisy, Laurence ..........................11,14,15,17,154

Galusek, Dušan .................................................98

Gasparyan, L. A. .............................................148

Gaubil, Michel ...................................................36

Gedeon, Ondrej .................................................. 3

Gentili, Denis ..................................................133

Gentleman, E. .............................................. 68,93

George, M. .......................................................70

Gerasimenko, V. V. ...................................... 74,149

Gerdes, Thorsten ............................................5,35

Geža, Vadims ....................................................78

Gibim, Marcos H. ...............................................79

Giefers, Hubertus ..............................................18

Giehl, Júlia M. ...................................... 96,150,169

Giehl, Júlia Maria ....................................25,49,163

Glebov, Leonid B. ........................ 23,24,25,138,153

Glebova, Larissa .....................................24,25,153

Godoy, Ana L. E. ..............................................125

Golovchak, Roman .............................................99

Gomes, Anderson S. L. ...............................119,140

Gonçalves, Diniz Pereira ...................................140

Gonçalves, Luis G. V.........................................168

Gonçalves, M. Clara ...........................................26

Gonzales, Roddy E. R. ................................156,157

González-Leal, J. M. ...........................................71

Goodship, A. .....................................................68

Gorshkov, Alexander ........................................102

Goumeidane, Fayçal ...........................................88

Gouveia-Neto, Artur da S..................................149

Graça, M. P. F. ...........................................159,160

Grandidier, B. ..................................................165

Greaves, G. N. ............................................. 37,87

Greenman, Michael ....................................... 79,81

Greil, Peter .......................................................44

Grigorescu, Cristiana ........................................123

Grueneberg, Miriam .........................................136

Guedes, I. ......................................................157

Guglielmi, Massimo ............................................27

Gugov, Ivailo ..................................................154

Guignard, Marie ........................................... 11,61

Guimarães, Francisco E. G. .........................114,139

Guimarães, Marcio M. ........................................79

Guimbretiere, Guillaume .....................................20

Gula, Michal ....................................................136

Gupta, Amul .....................................................36

Gupta, Prabhat K. ......................................... 30,37

Gürer, Göksu.....................................................75

Gutzow, Ivan ....................................................13

Guyot, Yannick ..........................................120,121

hHaas, Sylvio....................................................154

Habel, Michael E. ...............................................80

Habinshuti, J. ..................................................165

Hacala, Amélie ................................................129

Hah, Jason .....................................................123

Hajek, Tomas K. ..............................................127

Halbedel, Bernd ................................................78

Hama, Shigenori ...............................................85

Hamzawy, Esmat M. A. .....................................116

Han, Won-Taek ........................................... 59,106

Hand, Russell J. ........................................29,31,33

Hannon, Alex C. ................................................61

Harizanova, Ruzha ...........................................154

Hartwig, Christina ..............................................76

Harutunyan, R.................................................162

Harutyunyan, Nora M. ......................................148

Hasegawa, Kazuo ............................... 103,115,125

Haung, Y. S. ............................................... 49,100

Hayakawa, Tomokatsu ........................................69

Hayashi, Akitoshi .......................................... 84,85

Hayashi, Kazutaka .............................................40

He, Xuan ........................................................... 7

Heffner, Bill .......................................................99

Heffner, William R. .............................................. 9

Hehlen, Bernard ................................................19

Heidrich, Roland ................................................36

Helebrant, Ales .......................................... 82,127

Helsch, Gundula ................................................41

Hernandes, Antonio C. ............... 62,86,111,112,139

Hernández-Figueroa, H. E. ..................................73

Hessenkemper, Heiko .................................... 35,75

Hoell, Armin ...................................................154

Hojamberdiev, Mirabbos .............................120,167

Höland, W. ................................................... 42,64

Holland, Diane ..................................................13

Holtappels, Kai ................................................136

Honma, T. ........................................................46

Honma, Tsuyoshi ...........................6,45,61,107,119

Horimouti, Newton K. T. ...................................110

Hornychova, Veronika ........................................82

Hotza, Dachamir ...............................................44

Hötzel, Mathias .................................................76

Hradecka, Helena ..............................................82

Hreglich, S. ......................................................80

Hruška, Branislav ..............................................98

Hu, Juejun ......................................................... 7

Hubrich, Michael ................................................35

Author index


Hughes, M. .....................................................103

Hughes, Mark A. ........................................115,125

Hugon, Isabelle .................................................32

Hupa, Leena ................................................ 65,66

Hupa, Mikko ................................................ 65,66

Hyatt, Neil C. ....................................................31

Hyre, Matthew R. ..............................................75

iIda, Kenji .......................................................... 4

Idalgo, Elio .......................................................98

Iezid, Mostepha .................................................88

Iida, Yuichi .......................................................39

Iihara, Junji ......................................................21

Imre, Attila R. ...................................................93

Inaba, Tadayuki ...............................................106

Inoue, Hiroyuki ................................. 21,55,85,128

Ioncea, Anghel ................................................123

Iseda, Toru .....................................................128

Iser, Ronald ......................................................78

Ispas, Simona ...................................................18

Ito, Danielle ....................................................105

Ito, Hiroshi ........................................ 103,115,125

jJ. Neto, Jonas ...................................................97

Jacinto, Carlos ................................................111

Jagerska, Jana ..................................................50

Jaglarz, Janusz ..................................................83

Jaime, Sandra Balan M. ....................................105

Jain, Himanshu ..............................................9,99

Jakovics, Andris ................................................78

Janetti, Paula Fernanda ....................................105

Jatmiko, Widiya ...............................................169

Jeandel, G. .......................................................77

Jebavá, M. ................................................... 52,53

Jensen, Martin ........................................... 76,125

Jeong, Seongmook ..................................... 59,106

Jiarawattananon, Mateekul .................................38

Jiemsirilers, Sirithan ..........................................38

Jitwatcharakomol, Tepiwan .................................38

Jochym, Pawel T. ...............................................18

Jones, Gerard F. ................................................75

Jones, Julian R. .................................................66

Jonson, Bo........................................................88

Joshi, Snehal P. ...............................................129

Jousseaume, Cécile ..................................... 15,154

Ju, Seongmin ............................................. 59,106

Jules, J. C. ......................................................139

Jurdyc, Anne-Marie ............................................50

kKabanskaya, Anastasia .....................................102

Kabashima, Shuji ..............................................52

Kajinami, Akihiko .............................................125

Kajita, Tetunori ...............................................140

Kalugin, V. V. ..................................................131

Kamihori, Toru ..................................................75

Kaminoyama, Meguru ........................................52

Kamitsos, E. I. ..................................................20

Kaneda, Kazuhiro ......................................101,119

Kaneko, Masashi................................................56

Karell, Radovan .................................................98

Kargl, F. ...........................................................87

Kargl, Florian ....................................................18

Karlsson, Kaj H. ................................................65

Karthikeyan, B. ...............................................111

Kassab, Luciana R. P. ............................ 97,119,140

Kassir-Bodon, Assia ...........................................71

Katarzyna, Bulat ..............................................143

Kato, Akihiro .....................................................28

Kato, Mitsuo ...................................................122

Kato, Yoshinari ..................................................69

Kawaguchi, Masataka .........................................77

Kawai, Hiroyuki .........................................115,125

Keding, Ralf ...................................................3,76

Kemp, Tom .......................................................13

Ketkova, L. A. ...................................................74

Khabibulin, Dzhalil F. ..................................163,164

Kii, Yasushi ................................................ 77,122

Kim, Cheol Jin ...................................................59

Kim, Jinhan ....................................................106

Kim, Su-Ah .......................................................59

Kim, Youngwoong ....................................... 59,106

Kimerling, Lionel ................................................ 7

Kinoswki, Christophe ..........................................28

Kinowski, C.....................................................165

Kinowski, Christophe ..........................................47

Kioka, Keitaro .................................................107

Kip, D. .............................................................42

Kitaoka, Kenji ...................................................40

Kleine, Guihlherme A. ........................................69

Klement, Róbert ................................................98

Kloužek, J. ........................................................52

Klyev, V. P. ......................................................136

Knowles, Jonathan C. .........................................65

Knyazev, Oleg A. ...............................................32

Knyazyan, K. B. ...............................................148

Knyazyan, Nikolay B. .......................................148

Kob, Walter.......................................................18

Kobayashi, Renata A. .......................................163

Kobayashi, William .............................................94

Kodama, Masao ...............................................119

Koepsel, Detlef ............................................. 54,89

Koike, Akio .....................................................106

Kojima, Seiji .............................................101,119

Kokoszka, J. ...................................................104

Author index


Kokshenev, Valery B. .................................... 98,99

Komatsu, Takayuki ................... 6,45,46,61,107,119

Kondo, Yuki ................................................. 38,40

Konno, Akiko ....................................................30

Konoshita, Satoko .............................................48

Kosmal, Magda................................................103

Kosolapov, A. F. .......................................... 74,149

Kotereva, T. V. ............................................ 74,149

Kothiyal, G. P. .................................................102

Koyo, Hirotaka ..................................................78

Kozyukhin, Sergey ............................59,99,101,102

Kraev, I. A. ................................................ 74,149

Krieger, Uwe .....................................................78

Krishna, P. S. R. ..............................................127

Kroeker, Scott .................................................106

Krol, Denise M. .................................................57

Kudoyarova, Vera ............................................101

Kumar, R. Raj ..................................................132

Kurachi, Junji ....................................................78

Kurkjian, Charles Robert ..........................30,69,168

Kustov, Evgeny F. ............................................... 4

Kwasny, Marek Nocun Slawomir ...................104,142

lLacombe, J. ....................................................160

Laczka, M. ......................................................104

Laczka, Maria ..................................... 104,105,108

Lahodny, Frantisek .............................................50

Lakshminarayana, Gandham ...............................28

Lambert, Julien ...............................................129

Lana, Sebastiana L. B. .....................................161

Lancellotti, Isabella ....................................116,134

Landfermann-Hessenkemper, Heide .....................76

Lapina, Olga B. .........................................163,164

Lawrence, Mathias B. .......................................128

Lebedev, Viktor ...............................................101

Lebedev, Vladimir V............................................32

Lebullenger, Ronan ............................................88

Lechenault, F. ...................................................70

Lechevalier, David ..............................................36

Ledemi, Yannick ......................................... 21,135

Ledemi, Yannick A. G. ......................................152

Lee, Yeong Seop ..............................................106

Legouera, Messaoud ..........................................88

Leite, Maria F. .................................................109

Lemos, Thiago ................................................140

Lenzi, Ervin K. .................................................133

Leonelli, C. .....................................................162

Leonelli, Cristina .............................33,116,133,134

Leonídio, Driely Aparecida...................................49

Lepienski, Carlos M. .........................................109

Leykam, Daniel .................................................. 5

Li, N. ...............................................................95

Licheron, Marina ........................................140,141

Lievre, Kevin A. .................................................80

Ligny, D. de ......................................................95

Ligny, Dominique de ................................... 71,141

Lima, .............................................................121

Lima, Erick de .................................................152

Lima, Sandro M. ........................................120,121

Limpt, Hans van ................................................34

Lin, Jian .................................................... 49,100

Lisiecki, R. ........................................................51

Liska, Marek ...................................................... 3

Liu, Qiming ........................................................ 7

Liu, Ye ...........................................................107

Lobanov, A. S....................................................74

Loiseau, Pascal ........................................... 13,134

Lomovskoy, Viktor ...........................................102

Lopes, Flávio Cavalcanti de Oliveira ......................11

Lopes, J. C. ....................................................159

Lotfibakhshaiesh, N. ..........................................93

Lousteau, Joris ..................................................65

Lower, Nathan P. ................................................30

Ludwig, V. ......................................................150

Ludwig, Zélia Maria Da Costa .............33,96,163,169

Lumeau, Julien ............................ 23,24,25,137,153

Luther-Davies, Barry ..........................................72

Luzinov, Igor ...................................................... 7

Lysenco, Galina ...............................................151

mM’Peko, Jean-Claude ................................... 62,139

Machado, Mariana Moura ..................................120

Magometbekov, El’dar P. ...................................114

Maia, Lauro J. Q. .............................................147

Majérus, O. .................................................. 12,95

Majérus, Odile ........................................13,17,134

Malacarne, Luis C. .....................................111,112

Maldonis, Jason ...............................................106

Malichova, Hana ................................................50

Mallinson, P. M. .................................................45

Mamiya, Seiichi .........................................101,119

Manea, Adrian .................................................123

Manfrim, Tárcio P. ...........................55,116,139,162

Manghnani, Murli H. ...........................................18

Mansano, Ronaldo D. .......................................151

Manzani, Danilo .................................... 21,134,135

Marra, James ....................................................33

Marra, James C. .....................................30,32,114

Martin, Steve W. ................................................13

Martinelli, José R. ............................... 110,156,165

Martinelli, José Roberto ....................................137

Martinet, Christine .............................................71

Martucci, Alessandro .................................. 6,27,81

Masai, Hirokazu .......................................... 61,123

Masaki, Shin-ichiro ..........................................115

Mascaraque, Nerea ..................................... 56,102

Author index


Mashinsky, Valery M. ........................................... 4

Massiot, Dominique ...........................................61

Mastelaro, V. R. ...............................................114

Masuno, Atsunobu ............................. 21,56,85,128

Matsubara, Masahiko .........................................18

Matsuda, Yu ..............................................101,119

Matsunaga, Masaya ...........................................97

Matsuoka, Jun .........................30,40,69,77,122,130

Matthewson, M. J. .............................................30

Matthias, A. ......................................................42

Matzen, Guy .............................................. 45,129

Mauro, J. C. ..................................................... XV

Mauro, John C. ..................................................15

Mazali, Italo O. ................................................100

McCarthy, I. ......................................................68

McConnell, Michael ............................................13

Méar, François O. ...............................................58

Medina, A. N. ..................................................121

Medina, Antônio N. .... 111,120,121,130,137,138,161

Mellott, Nathan P. ..............................................26

Melo, Francisco Cristóvão Lourenço de ................140

Mendes, Diego ..................................................79

Mendiratta, S. K. .......................................159,166

Mendonca, C. R. ..............................................114

Meneses, Domingos de Sousa ........................ 16,18

Menguy, Nicolas ................................ 11,15,61,154

Merkushkin, Alexei O. ......................................114

Meshaka, Y. ......................................................77

Messaddeq, Y. .................................................139

Messaddeq, Younés .............. 21,58,126,135,147,152

Meszaros, Robert .......................................... 44,68

Metcalfe, B. L. ...................................................45

Meyer, Andreas .................................................18

Meyer, Erich ......................................................63

Michaelis, Vladimir ...........................................106

Michon, Ulysse ................................................129

Mika, Martin...........................................33,50,127

Milanese, Daniel ................................................65

Miller, C. A. .......................................................68

Millot, Francis....................................... 45,140,141

Minaev, V. S. .............................................. 38,131

Minami, Keiichi ..................................................84

Miola, Marta ......................................................64

Miranda, Felipe Silva ........................................163

Misture, Scott T. ................................................27

Miura, Yoshinari ......................................30,77,122

Miyajima, Tatsuya ..............................................97

Mizuno, Kento .................................................115

Mizuno, S. ......................................................103

Mizuno, Shintaro .......................................115,125

Moesgaard, Mette ............................................... 3

Mohallem, Nelcy D. S. ......................................161

Moiseev, A. N. ............................................ 74,149

Molla, Atiar Rahaman .................................. 48,156

Monaco, Andrea ................................................18

Monaco, Giulio ..................................................18

Montagne, L. ..................................................102

Montagne, Lionel ............................................5,58

Montedo, Oscar R. K. .........................................44

Monteil, André ........................................... 99,124

Monteiro, J. ....................................................159

Monteiro, T. ....................................................159

Montorsi, Monia .......................................... 86,133

Montouillout, Valérie .......................61,129,140,141

Moraes, João C. S. ...........................................161

Morais, Crislene Rodrigues da Silva .............105,113,

114,157

Morand, Christel ................................................36

Moreira, Roberto .............................................109

Morelli, M. R. ..................................................158

Morra, Marco ....................................................64

Mosca, Tiago De Marchi ....................................113

Mota, Helen Regina ..........................................153

Moura, Diógenes S. ..........................................149

Mueller, R. ........................................................46

Mueller, Ralf ............................................... 44,136

Mugoni, Consuelo ....................................... 86,133

Muijsenberg, Erik H. P. H. .............................. 54,89

Mulvaney, Paul ................................................... 6

Muniz Júnior, Jorge ............................................10

Muñoz, F. .........................................................43

Muñoz, Francisco ........................................ 56,102

Murakam, Masaki ............................................168

Muranaka, Kouichi .............................................40

Mure, Sylvain ....................................................32

Myers, Tiffany ...................................................13

nNagakane, Tomohiro ..........................................45

Nagamedianova, Zoulfia ...................................170

Nagamine, K. ....................................................46

Nagel, Marcus ...................................................60

Nakamura Filho, Arnaldo ..................................152

Nakane, Shingo ...............................................125

Nakayama, Masanobu ........................................28

Nalbandyan, Karen A. ......................................148

Naldoni, Alberto ................................................64

Nalin, Marcelo ............................................ 58,110

Nanba, Tokuro ................................................... 4

Nardou, Eric .....................................................50

Nascimento, Marcio Luis Ferreira .... 136,142,148,167

Nasu, Hiroyuki ..........................................115,125

Navarro, M. ....................................................169

Negahdari, Zahra................................................ 5

Nemec, L. .........................................................52

Neumann, A. ....................................................79

Neuville, Daniel R. .....................................140,141

Author index


Newman, S. ......................................................93

Nguyen, Huy Phuc ...........................................101

Niciu, Daniela..................................................123

Niciu, Horatiu ..................................................123

Nico, C. ..........................................................159

Nieprzecki, Piotr ..............................................103

Nishida, Shinsaku ............................................125

Nishikawa, Yuki ...............................................122

Nishikubo, Yoshinori .........................................122

Nocun, Marek..................................................104

Nogami, Masayuki ........................................ 28,68

Nogueira, Ana C. .............................................130

North, Joseph .................................................105

Novajra, Giorgia ................................................65

Nunes, Luiz A. O. .......................................137,138

oO’Donnell, M. D. ........................................... 68,93

Ochkin, Alexander V. ........................................114

Oda, Kenji ........................................................51

Ofuchi, Hironori ...............................................125

Ohishi, Y. ........................................................103

Ohishi, Yasutake ................................... 21,115,125

Ohkawa, Hiroyuki ..............................................39

Ohtomo, Takamasa ............................................85

Ojha, C. B. .....................................................128

Ojovan, Michael I. .............................................37

Okajima, Toshihiro ...........................................125

Olaru, Ion.......................................................151

Oldenbourg, R. ..................................................30

Olejniczak, Zbigniew ........................................143

Oliva, Isaias ......................................................85

Oliveira, Agda A. R. .........................................109

Oliveira, Antonio P. N. de ....................................44

Oliveira, Luiz F. C. de .........................................93

Oliveira, Norma Maria Silva de ....................113,114

Omena, Lidiane M. ...........................................157

Ondracek, Frantisek ...........................................50

Ono, Eduardo .................................55,116,139,162

Ori, Guido ................................................. 86,133

Orlien, Pia V. .....................................................56

Ory, Sandra ...................................45,129,140,141

Osada, Minoru ...................................................61

Oskay, Sureyya ...............................................141

Oswald, Jiri ................................................ 50,155

Otuka, A. J. G. ................................................114

pPablos-Martín, A. de ...........................................43

Padlyak, B. .......................................................51

Pajkic, Zeljko ..................................................... 5

Pallares, G. .......................................................70

Pantano, Carlo G. ...........................................9,82

Papulovskii, Evgenii S. .....................................164

Parchanski, Vaclav ...........................................155

Parent, G. .........................................................77

Parker, John M. .................................................. 9

Parlinski, Krzysztof ............................................18

Partiti, C. S. M. ...............................................156

Pascual, M. J. ....................................................43

Pech, Stepan ....................................................82

Pedreira, Paulo R. B. ........................................112

Pedrochi, F. .....................................................121

Pedrochi, Franciana ....................................120,121

Peitl Filho, Oscar ................................ 108,112,158

Peitl, Oscar .................................. 107,108,120,147

Peláez, L. .........................................................28

Pellegri, Nora Susana .......................................165

Pelli, Stefano ....................................................50

Pena, João Carlos de Castro ........................152,153

Pereira, Camila ..........................................153,163

Pereira, Gilberto ..............................................151

Pereira, Marivalda M. .......................................109

Pereira, Rauber D. ...........................................110

Pereira, Vilany S. .............................................104

Pereira-Ramos, J.-P. ...........................................12

Peres, M. ........................................................159

Perezhilin, Vadim A. ............................................ 7

Peter Šimurka, ..................................................98

Petit, Laeticia ..................................................... 7

Petrosyan, G. ..................................................162

Piarristeguy, A. A. ..............................................87

Piatriková, Anna ................................................98

Piekarz, Przemyslaw ..........................................18

Pigeonneau, Franck ...........................................53

Pimenov, V. G. ........................................... 74,149

Pimentel, Brunno S. .........................................151

Pinet, Olivier .....................................................32

Pinto, Marcelo M. .............................................152

Pinto, Noel Nóbrega .........................................147

Pires, Clayton Antonio Pereira .............................49

Plotnichenko, V. G. ...................................... 74,149

Podor, Renaud ...................................................58

Poiret, Jeremy ...................................................36

Poirier, Gael ....................................................163

Poirier, Gaël Yves ........................................ 47,153

Polachini, F. C. ................................................139

Pontuschka, Walter Maigon .....25,49,96,150,163,169

Porto, Valdênia de S. ........................................157

Poulain, Marcel ..................................................88

Pradel, A. .........................................................87

Pradel, Annie ..................................................155

Prado, Miguel O. ..............................................132

Prado, Ulisses S.........................................110,165

Prè, Marta Dai ...................................................81

Prnová, Anna ....................................................98

Pulliam, Raevon M. ............................................75

Author index


Pushkin, A. A. ............................................ 74,149

Py, Xavier .......................................................129

qQueiroz, Carlos Araújo ................................ 62,158

Querel, Gilles ............................................. 15,154

Quintas, Arnaud ................................................13

rRademann, K. ............................................ 24,160

Radu, Dorel ............................................... 96,123

Raghuwanshi, Vikram S. ...................................154

Raguenet, Bérangère .......................................155

Raimboux, N. ............................................... 15,16

Ramm, Alexander ............................................106

Ramon, L. ........................................................80

Ramonda, M. ....................................................87

Ramos-Gonzales, R. E. .......................................73

Rancan, Karina ................................................135

Raszewski, Fabienne ..........................................33

Raulin, Katazyrna ..............................................28

Ray, C. S. .......................................................156

Reben, Manuela.........................................103,104

Reega, P. K. ....................................................129

Reinsch, S. .......................................................46

Reinsch, Stefan .................................................44

Reis, Felipe C. C. .............................................147

Reis, Raphael M. C. V. ................................132,150

Reis, Signo Tadeu ...................... 33,49,110,165,156

Renversez, G. .................................................139

Revel, B. ........................................................102

Rheinberger, V. M. .............................................64

Rheinberger, V. R. ..............................................42

Ribeiro, Sidney J. L. .........21,26,58,126,135,147,152

Ribes, M. ..........................................................87

Ribes, Michel ..................................................155

Richardson, Kathleen .......................................... 7

Richardson, Martin .............................................. 7

Ried, Peter .....................................................136

Righini, Giancarlo C. .................................22,47,50

Riley, Brian .......................................................33

Rimondini, Lia ...................................................64

Rinke, Matthias T. ............................................126

Rino, José P. ...................................................168

Rino, José Pedro ..............................................155

Ritzberger, C. ............................................... 42,64

Rocha, Wagner Farias da ..................................140

Rodrigues, Ana Cândida Martins ............ 10,112,113,

120,131,142,147,164

Rodrigues, Bruno P. ...................................108,112

Rodrigues, Girley F. ....................................167,168

Rohanova, Dana ..............................................127

Rohling, Jurandir H. ...................................137,138

Roitsch, Stefan ..................................................18

Roldán, María Virginia ......................................165

Rolla, Maria Edith ............................................153

Rolling, J. H. ...................................................121

Romanenko, Konstantin V. ................................163

Rosemann, Maik ................................................44

Rosin, Andreas ...............................................5,35

Rössel, Anne-Katrin ...........................................35

Rountree, C. .....................................................70

Roussel, Pascal ..................................................47

Roux, S. ...........................................................70

Rubio-Peña, L. ..................................................71

Ruedinger, Bernd ...............................................46

Rüffer, Rudolf ....................................................18

Rufflé, B. ..........................................................18

Rüssel, Christian ........................................ 60,154

Ryba-Romanowski, W. ........................................51

Ryota, A. ........................................................141

Rysiakiewicz-Pasek, Ewa .............................130,131

sSaito, Kazuya ..................................................124

Saito, Yoshihiro .................................................21

Sakaguchi, Koichi ..............................................78

Sakai, Otávio A. ..............................................161

Sakai, Tetsuo ....................................................45

Sakamoto, Akihiko ........................................ 45,48

Sakharov, Vyacheslav V. ...................................... 7

Sakida, Shinichi.................................................. 4

Sakuda, Atsushi ................................................84

Salaun, S. ......................................................139

Salavcova, Linda ...............................................50

Sales, Fernando A............................................161

Sales, Rosemary B. C. ......................................161

Salvetti, A. R. .................................................158

Sanctis, Oscar de ............................................165

Sangy, P. E. R. ................................................150

Santagneli, Silvia H............................... 58,126,135

Santalucia Júnior, Walter Minutti ..........................10

Santos, C. C. ..................................................157

Santos, Claudinei dos .................................136,137

Santos, Cristiane N. ...........................................16

Santos, Cristiane Nascimento ..............................19

Santos, G. R. dos ............................................158

Santos, Juliana S. ......................................116,162

Santos, Juliana S. dos ................................. 55,139

Santos, Marcos A. Couto dos .............................124

Santos, Murilo F. M. .........................................162

Sargsyan, A. ...................................................162

Sarode, P. R. ...................................................166

Sasai, Jun ........................................................39

Sato, Fumio ......................................................48

Sauvage, E. ....................................................160

Sawaikar, Alka ................................................166

Schiavon, Marco A. ..........................................125

Author index


Schirmacher, Walter ...........................................17

Schmelzer, Juern W. P. .......................................13

Schmelzer, Jürn W. P. ................................93,94,95

Schneider, José .................................................. 4

Schneider, José F. ............................................135

Sekiya, Edson H. .............................................124

Selkregg, Kevin .................................................36

Semanate, José Luis Narváez ............................131

Sen, D. ..........................................................126

Sen, S. ..........................................................156

Sen, Sabyasachi ................................................15

Sene, Frank F. .................................................110

Serbena, Francisco C. ......................................107

Setti, João A. de Palma ....................................170

Shackelford, James F. .......................................... 3

Shao, Long .....................................................106

Sharagov, Vasilii ................................... 70,128,151

Shatalov, Valentin V. ........................................... 7

Shen, Jun .......................................................112

Sherchenkov, Alexey ..........................................59

Shiiba, Hiromasa ...............................................69

Shimodaira, Noriaki ...........................................96

Shinde, A. B. ..................................................127

Shinoya, Kentaro ...............................................40

Shiryaev, Andrey A. .........................................114

Shojiya, Masanori ..............................................78

Short, Rick .......................................................33

Shpotyuk, Oleh I. ..............................................99

Shrivastava, A. K. ............................................128

Shubin, Alexander A. .......................................163

Shvetsov, Sergey Y. ...........................................32

Sidel, Salmo M. ...............................................161

Siligardi, Cristina ........................................ 86,133

Silly, Gilles ......................................................155

Silva Júnior, José da .........................................151

Silva, A. P. da....................................................33

Silva, Andréia F. da ..........................................149

Silva, C. C. .....................................................159

Silva, Davinson M. da ............................ 97,119,139

Silva, E. C. .....................................................130

Silva, Edna L. da .............................................105

Silva, Elias A. da .............................................149

Silva, Leonardo Henrique ..................................153

Silva, Maurício A. P. ...........................................89

Silva, Michelly F. da .........................................157

Silva, Pedro Henrique V. B. P. da ........................152

Simo, A. .................................................... 24,160

Simon, Guilhem ................................................19

Simon, P. ..................................................... 15,16

Singleton, Steve ................................................13

Siqueira, Renato Luiz .......................................158

Sitarz, Maciej ..................................................143

Skibsted, Jørgen ................................................. 3

Skibsted, Leif H. ................................................56

Skripachev, I. .................................................139

Skripachev, Igor ..............................................135

Smedskjaer, Morten M. .......................... 15,115,125

Smektala, F. ...................................................139

Smirnov, Alexey ..............................................101

Smirnov, Vadim ...............................................153

Smith, Anita .....................................................72

Smith, Charlene M. ............................................63

Smith, Mark ......................................................13

Smith, Mark E. ..................................................63

Smyrnov, O. .....................................................51

Snopatin, G. E............................................ 74,149

Soares, Paulo ............................................109,170

Soares, Vitorvani ...............................................63

Soares, Viviane O. ...........................................108

Soares, Viviane Oliveira ....................................107

Soga, Diogo ....................................................163

Soleilhavoup, Anne ............................................95

Sombra, A. S. B. .......................................159,160

Sonda, Yoshiyuki .............................................101

Soudre, L. ........................................................77

Souquet, Jean Louis ...........................................84

Sousa, Nuccia C. A. de .....................................157

Souza Filho, Nilson E. .......................................130

Souza, J. E. ....................................................150

Souza, José E. de ................................. 62,112,139

Souza, Seila R. de ................................ 62,112,139

Speghini, Adolfo ................................................22

Spirkova, Jarmila ...............................................50

Spriano, Silvia ...................................................64

Stara, Stanislava ...............................................50

Steagall Júnior, Washington ..............................137

Stefanovsky, Sergey V. ............................31,32,114

Steimacher, A. ................................................121

Steimacher, Alysson ............................ 111,120,121

Stevens, Harrie J. ......................................120,167

Stevens, M. M. ............................................. 68,93

Stievenard, D. .................................................165

Stoch, Pawel .............................................126,127

Stroescu, Hermine ...........................................123

Su, Yang ..........................................................75

Sudo, Takahiko ................................................122

Suezawa, Ryoya ................................................27

Sugawara, Toru ........................... 30,40,77,122,130

Suntsov, Dmitriy Y. ............................................32

Suzuki, Carlos K. ............................55,116,139,162

Suzuki, Futoshi .................................................60

Suzuki, Keiichiro ..............................................128

Suzuki, Paulo A. ..............................................136

Suzuki, T. .......................................................103

Suzuki, Takenobu ......................................115,125

Suzuki, Toshio ...................................................96

Author index


Suzuki, Yuichi ...................................................96

Svarcova, Silvie ...............................................127

Svecova, Blanka ................................................50

Swanton, Steve .................................................31

Szneler, Edward ..............................................104

tTadanaga, Kiyoharu ...........................................27

Takada, Akira ............................................... 12,14

Takahashi, Yoshihiro.................................... 61,123

Takashi, M. ....................................................141

Takenaka, Atsuyoshi ..........................................97

Tamitsuji, Chikaya .............................................39

Tamura, Takaaki ................................................27

Tanabe, Setsuhisa .............................................23

Tang, Zhongzhi .................................................30

Taraziuk, Tereza Helena S. Cavalcanti ...................11

Tasca, Abílio......................................................93

Tatchev, Dragomir ...........................................154

Tatsumisago, Masahiro ..............................27,84,85

Tavares, Albaniza A. .........................................105

Teider, Bruno Henrique .....................................113

Teixeira, Alexandra ............................................67

Tenório, Jorge A. S. ...................................167,168

Terczynska, Agnieszka......................................104

Terczynska-Madej, Agnieszka ......................105,108

Terra, Idelma A. A. ....................................137,138

Teslyuk, I. ........................................................51

Tholen, Kevin ....................................................13

Tian, Peijing ....................................................107

Tilocca, Antonio .................................................83

Timoshenkov, S. P............................................131

Toffoli, Samuel M. .............................. 9,79,151,163

Tomeno, Satoru .................................................40

Toporcov, Edison José ........................................10

Tran, Thanh V. ...................................................47

Travitsky, Nahum ...............................................44

Tricot, Grégory ................................................... 5

Trochta, Miroslav ...............................................81

Troles, J. ........................................................139

Troy, Neil ..........................................................57

Tscuchida, Jefferson ............................................ 4

Tsujimura, Tomoyuki ..........................................97

Tsunetomo, Keiji ................................................78

Tucci, A. ...........................................................80

Turrell, Sylvia .........................................28,47,165

Tweeton, Landon .............................................123

uUchoa, Catarina Maria Câmara ............................11

Ullrich, Jiri ........................................................89

Umesaki, Norimasa ..........................................125

Urata, Shingo ....................................................52

Utton, Claire .....................................................31

vVacher, R. .........................................................18

Vacher, René .....................................................19

Vaills, Y. ...................................................... 15,16

Valente, M. A. ...........................................159,160

Valério, José Carlos ..........................................151

Valverde, J. ......................................................71

Vander, Andrea..................................................68

Vargas, Helion .................................................130

Varshneya, Arun K. ............................................29

Vasconcelos, Filipe .............................................. 5

Vasiliu, Cristina ...............................................123

Vaz, Wilson ...............................................127,166

Verardi, Duilio ...........................................133,134

Verma, A. K. ...................................................128

Vermaut, Philippe ....................................... 13,134

Vermelho, M. V. D. ...........................................157

Verné, Enrica ............................................... 64,66

Véron, Emmanuel ....................................... 45,129

Vieira, Glauco Fioranelli ....................................137

Vieira, Heveline .........................................110,165

Vienna, John .....................................................33

Vitale-Brovarone, Chiara ................................ 64,66

Vitkala, Jorma ...................................................73

Vouagner, Dominique .........................................50

Vueva, Yuliya ....................................................67

wWang, Rong-Ping ...............................................71

Wasylak, Jan .............................................103,104

Watanabe, Kunio ...............................................39

Watanabe, Yasuhiro .................................... 56,128

Watekar, Pramod R. .................................... 59,106

Watson, Matthew J. ...........................................80

Weber, Rick ....................................................122

Wei, Wang Zong ................................................94

Weigand, Rolf ....................................................35

Weiss, Denise Stolle da Luz ...............................170

Wetter, Niklaus Ursus ............................ 97,119,163

Willert-Porada, Monika ....................................5,35

Williams, Quentin ..............................................18

Williams, Steve .................................................31

Wilsmann, W. ....................................................79

Wischnewski, A. ................................................18

Wisniewski, Wolfgang .........................................60

Witcher, Jonathan J. ...........................................57

Wolf, Hannes.....................................................35

Wondraczek, Lothar ...................................... 43,68

Wortmann, Gerhard ...........................................18

Wu, J. J. .................................................... 49,100

WushurHushur, Anwar ........................................18

Author index


xXu, T. .............................................................165

yYamaguchi, Naoko .............................................27

Yamamoto, Kiyoshi ...................................82,96,97

Yamamoto, Shigeru .........................................125

Yamamoto, Yuichi ..............................................82

Yamashita, Masaru ..........................................168

Yamauchi, Hideo ................................................45

Yamazaki, Hiroki ......................................... 69,125

Yasuo, H. ........................................................141

Yoko, Toshinobu ..............................................123

Yoon, Young Sik ..............................................106

Yoshida, S. .......................................................30

Yoshida, Satoshi ......................30,40,69,77,122,130

Yoshihara, Satoru ..............................................48

Yoshimura, Humberto N. ..................................152

Yu, Jianding ......................................................56

Yuan, James .....................................................94

Yue, Yuanzheng .............................3,15,76,115,125

Yuki, Ken ..........................................................45

Yukimitu, Keizo ...............................................161

Yung, H. W. ......................................................49

Yung, S. W. .....................................................100

zZanghi, Didier .................................................141

Zanotto, Edgar D. .XIV,10,48,55,94,107,108,112,113,

132,136,150, 158,167

Zdyrko, Bodgan .................................................. 7

Zelazowska, Elzbieta ........................................130

Zhao, Xiujian ..................................................... 7

Zheng, Weihong ..............................................107

Ziani, Nossair ..................................................124

Ziemath, Ervino C. ...........................................137

Zou, Meijing......................................................45

Zubavichus, Ian. V. ..........................................114

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