The 23rd International Congress on Glass

July 15, 2013 / Prague, Czech Republic

Book of Abstracts
www.icg2013prague.cz

The 23rd International

Congress on Glass
July 15, 2013
Prague, Czech Republic

Book of Abstracts

Content
Congress Committies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7
Plenary Talk, Gottardi Awarders Talk, Weyl Awarders Talk . . . . . . . . . . .9
Invited Speakers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13
Glass Science . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15
Glass Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Glass Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Other Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Optical Glass and Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .73
Glass Chemical Durability and Safety of Nuclear Power Plant . . . . . . . . .91
Computer and Structural Modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .97
Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Biomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .113
TC16 Nanostructured Sol-Gel glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . .121
TC6TC7TC8 Topological Principes in Glass Science . . . . . . . . . . . . .127
TC20 Photonic Glasses. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
TC17 Archaeometry of Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
TC05 Waste Glass Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .157
TC05 Waste Glass Structure and Characterization . . . . . . . . . . . . . . . .163
TC05 Waste Form Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
TC06 Indentation and Nanoindentation . . . . . . . . . . . . . . . . . . . . . . . . .175
TC26 Student Project Outcomes (ICG Summer School) . . . . . . . . . . . .181
TC11TC13TC14TC15TC18TC21 Glass Trend . . . . . . . . . . . . . . . 185
Refractory materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Melting Process Modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Melting Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
New Melting Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
Redox Equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
Batch Melting Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
Waste Glass Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
Combustion Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
Furnace Design and Waste Heat Recovery . . . . . . . . . . . . . . . . . . . . . . . . . 235
Glass Forming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
Analytical Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Poster Contributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .251
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .313

Congress Committies

Congress Chairman
A. Helebrant (Czech Republic)
International Advisory Board
R. Beerkens (The Netherlands)
R. Brow (USA)
G. Calas (France)
R. Conradt (Germany)
M. Choudhary (USA)
A. Duran (Spain)
N. Greaves (United Kingdom)
H. Inoue (Japan)
H. Jain (USA)

J. Matouek (Czech Republic)

F. Nicoletti (Italy)
J. M. Parker (United Kingdom)
D. Pye (USA)
U. Roger (Germany)
S. Tanabe (Japan)
E. Zanotto (Brazil)
X. Zhao (China)

Scientific Board
O. Gedeon (chairman, Czech Republic)
A. Duran (ICG, Spain)
M. Tatsumisago (ICG, Japan)
R. Vacher (ICG, France)

A. Helebrant (Czech Republic)

L. Koudelka (Czech Republic)
L. Nmec (Czech Republic)
M. Lika (Slovakia)

Local Organising Committee

A. Helebrant (chairman)
P. Bernek
O. Gedeon
V. Hota
S. Kasa

J. Klouek
J. Korek
L. Koudelka
J. Machek
P. imurka

Congress Secretariat
R. Koov, Event Manager, Icaris Ltd.
K. Lomeck, Event Manager, Icaris Ltd.

ICG Prague 2013 7

Plenary Talk,
Gottardi Awarders Talk,
Weyl Awarders Talk

ICG Prague 2013 9

 10

565

Glass and the nanotechnology paradigm

Pye L. D.
Dean and Professor of Glass Science, Emeritus,
The New York State College of Ceramics at Alfred University

The advent of the nanotechnology era or, more appropriately, nanoscale science and engineering, while not necessarily rising to the level of an abrupt Kuhn-type paradigm shift in science, has become arguably the foremost
conduit for focusing on how modern materials are viewed, fabricated, characterized, and utilized throughout
society. Paradoxically, some of the great milestones in glass science and engineering did not figure prominently
into to the emergence of this paradigm despite their impact on modern society. Among these milestones are microcrack theory, amorphous phase separation, photosensitivity, photonucleation, ligand field theory, controlled
crystallization, ion-exchange, and, of course, resolution of glass structure theory. Thus, our understanding of
glass at the nanoscale level has led to some remarkable applications in such diverse fields as energy, medicine,
photonics, architecture, transportation, communications, etc. Stated otherwise, glass is the quintessential nanotech material. With this perspective in mind, the origin and growth of the nanotechnology paradigm will be
examined with an intent to illustrate its connection to both historical and modern day glass science theory and
potential future applications of glass.

595

Stressed glasses: Effects of intermediate pressure

on the structure and properties of oxide glasses
Wondraczek L.
Otto-Schott-Institute, University of Jena, 07743 Jena, Germany

The freezing of asuper-cooled liquid to aglass may be achieved by rapid changes of temperature, pressure, composition, or all. This talk will review experimental approaches to non-isobaric as well as isothermal glass transitions in silicate and non-silicate oxide glasses at moderate pressure. The effects of fictive pressure on relaxation,
structure, structural heterogeneity and physical properties will be presented. It will be distinguished between reversible and inelastic pressure-effects, and the relation between continuous structural changes and the so-called
phenomenon of polyamorphism will be critically discussed.

593

Advanced glass substrates for spectral

conversion, light delivery and sensing
Wondraczek L.
Otto-Schott-Institute, University of Jena, 07743 Jena, Germany

This talk will discuss smart glass substrates and glass-based composite materials for spectral conversion, light
delivery and plasmonic sensing. Applications in manipulation and observation of microbial organisms will be
presented, i.e., anovel concept for versatile nanoporous coatings, photosynthetic solar energy harvesting and CO2
storage in algae reactors and high plants, nano-plasmonic sensing of biomolecular and microbial interaction and
novel concepts for light delivery within containments with low light transmittance.

ICG Prague 2013 11

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Invited Speakers
Beerkens R. (Netherland CelSian Glass and Solar)

197

Simulation of essential process steps in industrial glass melting

Deubener J. (Germany University of Technology Clausthal)

71

Nucleation kinetics in LAS glass-ceramics the missing Tammann

Ferrari M. (Italy CNR-IFN, CSMFO Lab.)

148

Glass-ceramics for photonics: Advances and perspectives

Girold C. (France Commission for Atomic Energy and Alternative Energies, Marcloule)

171

Academic research on glass and process development combined for nuclear waste vitrification progress

Heo J. (South Korea Pohang University of Science and Technology)

89

Novel glasses with PbS quantum dots

Lika M. (Slovakia Vitrum Laugaricio)

95

Kinetics and thermodynamics of glass fibrous insulation corrosion

by the coolant solution building akinetic model from experimental data

Nmec L. (Czech Republic Institute of Chemical Technology Prague)

210

Fundamental aspects of glass melting

Ojovan M. I. (UK Imperial College London)

17

Fragility characterisation from non-equilibrium thermodynamics of flow in oxide melts

Pascual M. J. (Spain Instituto de Cermica y Vidrio)

58

Glass sealing technologies for SOFC stack manufacturing

Richter R. (Germany Staatliche Museum Dresden)

153

Early glass engravings (c. 15851700) with focus on works

by Caspar Lehmann and by the Schwanhardt workshop in Nuremberg

Richardson K. (USA University of Central Florida)

148

Advanced chalcogenide glasses

Rouxel T. (France University of Rennes)

107

Elasticity and viscosity as probes of the structural stability of glass-forming liquids at high temperature

Salmon P. (UK University of Bath)

131

Density-driven structural transformations in network-forming glasses

Sierka M. (Germany University of Jena)

133

Crystalline and vitreous ultrathin silica fi lms: synergy between theory and experiment

Sundaram S. K. (USA Alfred University)

27

Terahertz spectroscopy and imaging of glasses

Tatsumisago M. (Japan Osaka Prefecture University)

54

Characterization of all-solid-state lithium rechargeable batteries withsulfide glass-ceramic electrolytes

Zwanziger J. W. (Canada Dalhousie University)

41

Glass structure-property correlations: Photelasticity, durability, and hardness

ICG Prague 2013 13

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Glass Science

ICG Prague 2013 15

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005

Fragility characterisation from non-equilibrium

thermodynamics of flow in oxide melts
Ojovan M. I., Lee W. E.
Imperial College London, United Kingdom

Oxide melts demonstrate adeviation from the Arrhenius type viscosity behaviour in which the activation energy
of viscosity changes from ahigh value at low temperature to alow value at high temperature. This change in activation energy with temperature can be used to classify network liquids as strong or fragile depending on the form
of the dependence of logarithm of viscosity versus reduced temperature 1/T. Their activation energy changes
only slightly with temperature for strong glass-forming liquids which demonstrate nearly Arrhenius temperature
dependence of viscosity. In contrast the activation energy of fragile glass forming liquids changes significantly
with temperature and their viscosity deviates significantly from Arrhenius behaviour. Doremus suggested acriterion for oxide melt fragility utilising the ratio of the activation energy at high viscosity to that at low viscosity.
We demonstrate that the Doremus criterion of fragility can be expressed in terms of non-equilibrium thermodynamic parameters of bond-breaking defects configurons which mediate viscous flow in the oxide melts:
RD=1+Hd/Hm, where Hd is the enthalpy of formation and Hm is the enthalpy of motion of such defects (see e.g.
M. I. Ojovan, W. E. Lee. Connectivity and glass transition in disordered oxide systems J. Non-Cryst. Solids, 356,
25342540 (2010). Hence the fragility of oxide melts is an intrinsic thermodynamic parameter of melts which can
be determined unambiguously by experiment.

006

On crystallisation driving force as glass forming

ability criterion for bulk metallic glasses
Roula A.
Jijel University, PNR-ANDRU-LIME, Eng. Sc. Fac., BP 98, Ouled Aissa, Jijel, 18000, Algeria

A review of the existing Glass Forming Ability (GFA) criteria for Bulk Metallic Glasses (BMGs) is given. This aptitude for glass formation is always and consensually discussed by the following criteria: the undercooled liquid
range, the reduced glass transition temperature, the critical cooling rate, and the driving force for the crystallization from the undercooled liquid. All of them are computed from data experiments and from thermodynamic
simulations/modelisations.
In this study, authors are discussing the crystallisation driving force criterion (DG/R.T; where DG, T and R are
Gibbs free energy change, temperature and the gas constant) as the most used criterion and amend it by using the
isobaric thermal capacity of the studied alloy instead of the universal gas constant.
The amended criterion (DG/Cp.T) does not invalidate the previous criterion but precise and confirm it; moreover,
it seems to be more comprehensive because taking in account an indispensable thermodynamic characteristic
that was omitted and replaced by R constant. It shows also aphysical sense while answering the question: why/
how do some metallic alloys form glasses?
The new computed values of this criterion for BMGs confirm the ability of known BMGs to form amorphous
structure materials (considering that the lower the value of this amended crystallisation driving force corresponds to the highest glass forming ability).

032

The results of application of Maxwell

relations in glass science
Nemilov S. V.
St. Petersburg National Research University of Information Technologies,
Mechanics and Optics, St. Petersburg, Russia

The First Part of the analysis covers the direct application of Maxwell equations to the events in glass transition
range, and to ionic migration in inorganic glasses. It is shown the existence of characteristic ratios of potential
barriers responsible for -, - and ionic relaxation. This is the evidence for essential role of local elastic deforma-

ICG Prague 2013 17

046

tions at these processes because -relaxation obeys Maxwell equation for viscous-elastic relaxation. It was shown
the efficiency of combination of Maxwell equation with classic relaxation theories of liquids for the finding the
precise relation between cooling rate of amelt and viscosity value at glass transition. It is shown the possibility of
precise calculation of the temperature of ionic internal friction peak for one-alkali oxide glasses directly from
Maxwell equation for conductivity of dielectrics and d.c. conductivity experimental data. The Second Part of
the review shows that common molecular modeling of elementary acts of viscous relaxation basing on Maxwell
equation results in simple equation permitting the calculation the volume of atoms overcoming the potential barrier from the value of this barrier, and instantaneous shear module of asubstance. Th is relation is true with high
precision for inorganic substances. The existence of universal relation between d.c. conductivity and viscosity for
the extremely wide temperature intervals (Littleton relation, 1933) is proved for silicate and phosphate melts. The
theory of this dependence is proposed; it uses just mentioned equation for viscous flow activation energy and the
similar one which is the generalized equation proposed by Anderson & Stewart (1954) for ionic conductivity. The
main reason of its existence is the similar dependences of activation energies for d.c. conductivity and Newtonian
viscosity on shear modulus; its temperature variation equally varies the both potential barriers. The paper generalizes the authors results published from 1968 up to date.

Chemical interactions of components

and glass structure formation and stability
Stoch L.
Institute of Ceramic and Building Materials Krakow Div.,
AGH University of Science and Technology, Krakow

055

Significance of chemical affinity as general tendency of atoms to binding and aggregate for the of glass structure formation and its stability is considered. Crystallochemical parameter, chemical bonds ionicity (iG) is used as the strength
and flexibility of bonds indicator. Ionicity of the MeO bond can be ameasure of the basicity of cation. Difference in
ionicity of cations forming oxygen bridge MeOMe (D iG) is taken as the measure of their mutual, local chemical affinity (A=(D iG)).Inorganic glasses are solids of nonstochiometric disordered structure which components are joined
by direction covalent, or covalent-ionic bonds and not directional ionic, Van der Waals or metlic bonds. Nondirectional bonds makes structure flexible what is the condition of disordered arrangement of atoms in amorphous structure
and glass existence. Formation of the middle range ordering clusters, differing in their chemical composition, is result
of the affinity attraction of elements, limited in the different degree by the their mobility ( diffusion rate D ) changing
with temperature and viscosity. The mechanism of crystallisation of glass, changes in relation to the growing mobility
of structure constituents with temperature increase. As aconsequence glass crystallization near the Tg temperature,
takes place through diffusive ordering of middle range order clusters according to their mutual chemical affinity. The
traditional mechanism of nucleation growth of crystals, limited by energy of interface surface formation, takes place
above the liquidus temperature (TL). This explains the phenomenon of glass nanocrystallization and nanoglass-ceramic formation. The of silicate, mixed layer phosphosilicate, borosilicate, oxy-fluoride oxy-nitride, halide glasses formation and crystallization confirming above considerations are presented.

Modified Adam Gibbs equation for glass viscosity

as a function of temperature and composition
Hrma P.
Pacific Northwest National Laboratory, Richland WA, USA;
Pohang University of Science and Technology, Pohang, Republic of Korea

Viscosity is aprominent property for glass processing from melting to forming and annealing. The knowledge of
viscosity () as afunction of temperature (T) and glass composition is of supreme importance. Therefore, such
afunction should represent the real behavior of glass as closely as possible. In addition, experimental data indicate that the viscosity equation, ln=A+B(T)/T, where B(T) is the temperature-dependent activation energy,
should meet the following assumptions: 1) the coefficient ais independent of composition; 2) glass viscosity is
independent of composition at the glass transition temperature, Tg; 3) when < 10^2 to 10^3Pas, depending

18 Glass Science

on the glass family and measurement accuracy, the activation energy is independent of temperature, and thus
B(T) = Bf = constant. The modified Adam Gibbs equation can be written in the form Y = [Bf /b()], where
Y=(lnA)/[ln(Tg)A] is the normalized logarithmic viscosity, =Tg/T is the normalized inverse temperature,
b=1(1Bf /Bg)^f is apower-law function of inverse temperature, Bg is the activation energy at Tg, and f is acoefficient, which is constant for afamily of glasses, such as float glasses or high-level waste glasses. The modified
Adam Gibbs equation meets the three assumptions stated above with a minimum number of temperature-independent coefficients. It represents the reality in an accurate and economical manner, i.e., it fits experimental
data for reasonably large composition regions with the minimum number of coefficients. With the Tg known as
afunction of composition, only one coefficient in the viscosity equation is afunction of composition to be fitted
to data. The validity of the modified Adam Gibbs equation will be demonstrated on glasses with alarge number
of components, both for commercial use and for nuclear waste immobilization.

082

On the ways reliable values of glass properties

should be prepared for publishing
Mazurin O. V., Priven A. I.
Scite Company, Petersburg, Russia

Every year hundreds of papers containing new data on glass properties are published. Corresponding efforts are totally justified if papers contain reliable data. However, if published data prove to be wrong, such publications will be
detrimental for anyone who tries to use them for practical or theoretical applications. Unfortunately, in most cases it
is difficult or even impossible to determine the quality of published data by analyzing the corresponding publication
itself. The authors of this paper show that an increase in deterioration of the quality of published glass property data
that started afew decades ago still persists, which is aserious danger for the future of glass science and technology.
The analysis of the main factors leading to such trend is given and the recommendations for both authors and journal editors that can be ahelp in improving basically the mentioned regrettable situation are formulated. It is shown
that if aproperty of aseries of glasses was measured by various authors in various countries and in various periods
of time, their total data are well approximated by the Gauss distribution, the centre of which always containing
the data obtained by the best scientists worked in the corresponding areas. For most studies one can select aglass
composition that is similar enough to the glasses meant for astudy and whose property of interest was previously
measured by quite anumber of scientists. At the beginning of the planned study the author should prepare such
glass and carefully measure its corresponding property. Then acomparison of found data with published ones is
made. Actually this will be similar to the well known Round Robin tests. If these data prove to be incorrect, it will be
necessary to find the reason and improve the experimental procedure. Thanks to the recently appeared possibilities
of finding the required information easily enough, such approach is practically quite realistic for any author. In the
paper anumber of specific examples of such approach are demonstrated.

Munoz-Senovilla L., Munoz F.

Ceramic and Glass Institute (CSIC), Madrid, Spain;

Phosphate glasses present lower glass transition temperatures and higher thermal expansion coefficients and transmission in the UV region compared with silicate glasses due to their particular structure, which is built-up of PO4
groups. These glasses may show excellent performance for their application as high power laser host materials, glass
fibres, glass-to-metal seals, biomaterials and matrices for the vitrification of nuclear wastes. In order to design new
glasses for specific applications, the knowledge of the viscosity as afunction of temperature and composition, as well
as the short and intermediate range order structure, is important for the melting and forming of glasses. In general,
phosphate based glasses present ahigher change of viscosity with temperature above their glass transition compared
with silicate glasses, which classifies them as fragile, based on Angells kinetic fragility of liquids.
In this work the fragility of different phosphate glasses has been studied through experimental viscosity measurements by beam-bending and rotational viscometry methods. The fit of the experimental viscosity data in

ICG Prague 2013 19

099

Viscosity behaviour of phosphate glasses through

their short and intermediate range order structure

156

phosphate glasses has shown to be more complex than in silicate ones. The highest discrepancy is found in high
temperature data. It has been seen that the ionic field strength of the modifier cations and the polymerization degree of the phosphate network, determine the fragility behaviour of the glasses, as proved through the structural
characterization carried out by means of Raman and Nuclear Magnetic Resonance spectroscopy. Furthermore,
the activation energy of the viscous flow depends not only on the temperature but also on the composition of
the glasses through their different structural features. This behaviour suggests that the viscous flow might be
controlled by different mechanisms.

Drying of water glass dependence on drying

conditions and structure characterisation
by thermal analysis and atomic force microscopy
Roggendorf, H., Roth, R., Fischer, M., Godehardt, R.
Institute of Physics, Halle (Saale), Germany

173

Water glass is acommon name for dissolved alkaline silicate glasses. They are liquids with high concentrations of
silica. Their structure can be described as colloidal suspensions or sols. The solutions can be dried to amorphous
and transparent solid materials. Modified materials of this type are used as intumescent layers for fire resistant
glazings. Sodium silicate solutions with amolar SiO2:Na2O ratio of 2.2 to 3.8 were dried in controlled climates for
up to 90d at temperatures between 30 and 80C and partial H2O pressures between 4.7 and 19kPa. The residual
water contents were determined gravimetrically. Scanning calorimetry, hot stage and optical microscopy, and
atomic force microscopy were applied for characterisation. agradual solidification of the solutions during drying
is observed. Under appropriate drying conditions amorphous and transparent materials were obtained. Relations
between drying conditions, structure and properties of the materials are discussed. The colloidal structure of the
dried materials is demonstrated by atomic force microscopy. The process of solidification is interpreted as immobilisation of colloidal aggregates due to the extraction of water which reduces the distances between the colloidal
particles. Structures formed in that way can be addressed as dense gels or colloid glasses which is aterm applied
for random close packed colloids. The influence of temperature on structure and properties of the materials is
discussed. Different thermal analysis tools (thermal analysis under hydrothermal conditions, conventional calorimetry) have been applied to characterize the intumescing behaviour.

Low-frequency inelastic light scattering

in alkali and alkaline-earth silicate glass
Nakamura K.1, Takahashi Y.1, Osada M.2, Ihara R.1, Fujiwara T.1
1

Department of Applied Physics, Tohoku University, Miyagi, Japan;

International Center for Materials Nanoarchitectonics,
National Institute for Materials Science, Ibaraki, Japan

Inelastic light scattering could provide detailed observations of the structural relaxation and rearrangement of
the glassy/supercooled-liquid state [Y. Takahashi et al., Sci. Rep. 2, 714 (2012).]. In amorphous matter, an asymmetrical broad band is observed in the low-wavenumber region of the spectra and is termed as the boson peak
[V. K. Malinovsky and A. P. Sokolov, Solid State Comm. 57, 757 (1986).]. The boson peak is known to be related to
transverse acoustic-phonon, which is able to give information about elastic property (e.g., transverse sound-velocity) [H. Shintani and H. Tanaka, Nat. Mater. 7, 870 (2008).]. However, relation between the boson peak and elastic
properties is not fully understood yet. Therefore, in order to elucidate the issue above-mentioned, we conducted
the spectroscopic observation in binary alkali and alkaline-earth silicate glasses. As aresult of the boson-peak
measurements, an intriguing relation between boson-peak position (BP) and transverse sound velocity was discovered, and will be introduced in the presentation. In addition, we also found agood correlation between BP
and mean atomic volume. Furthermore, we considered the high-wavenumber region (9001,200cm-1) in the obtained spectra to discuss how glass structure affects boson-peak features.

20 Glass Science

179

Analogy between stress relaxation in glass

and growing the parameters of engineering systems
Priven A. I.1, Kynin A. T.2
1

Institute of Theoretical Chemistry, Newton, USA;

St. Petersburg State Polytechnic University, Russia

Glass science often borrows the ideas and mathematical models from other knowledge areas. In particular, the
models of stress and structural relaxation in glass borrowed the basic ideas from simulations of chemical (Le
Chateliers principle) and electrical (Kohlrauschs equation) phenomena. The authors try to go in opposite direction: to extend known model of stress relaxation in glass to describe the process of growing main parameters of
engineering systems, such as strength and density of fibers, or speed and fuel efficiency of cars, in process of their
evolution. The authors consider the difference between customers expectations and actual value of aparameter
as astressful factor (or driving force) of the evolution process, and the difference between the actual value and
physical limit as an analogue of mobility (or fluidity) of the system, i.e. the ability of its developers to match
customers expectations of growing main parameters. The model was validated by using the historical data for
multiple engineering systems (transport, energy, electronics etc.) and artificial materials (fibers, tissues etc.). In
this paper, we consider an example concerning glass industry: growing the complex parameter of glasses for flat
display panels from the end of 1980s to now, by using the SciGlass Information System as adata source. Some
predictions for the near future are made concerning the improvement of physical properties of these glasses.

182

Structure and properties of thin glass layer

prepared by Pulsed Laser Deposition
Montagne L., Castanie S., Mear F., Desfeux R., Saitzek S., Blach J. F.
University Lille Nord de France, UCCS UMR-CNRS 8181, France

In arecent paper, authors reported on atwo-dimensional silica glass deposited on agraphene sheet [Nano Lett.,
2012, 12 (2), pp 10811086, DOI: 10.1021/nl204423x]. They observed through ADF-STEM (atomic-resolution annular dark-field scanning TEM) that the positions of silica and oxygen atoms are in close accordance with the
principles of Zachariasen published in 1932 [J. Am. Chem. Soc. 1932, 54, 38413851]. The authors claimed that
their silica glass layer can be simulated as asingle bilayer of silica tetrahedra, without interaction with the underlying graphene sheet. We generated thin glass layers by Pulsed Laser Deposition (PLD) on various substrates,
much thicker than in the previous study (in the range of afew nanometers, measured by ellipsometry), but still
thin enough to be considered as non-bulk glasses. They are also much more complex than pure silica glass, since
they contain 4 to 6 oxides; hence they are classified as modified glasses in Zachariasens terminology. Our aim is
to investigate if such modified glasses in thin layer obey to the same structural rules than bulk ones. We analysed
the glass layer compositions with XPS and TOF-SIMS, and the optimisation of experimental PLD conditions
enables to obtain the same compositions than bulk ones. Structural data were collected with diff use reflectance
Infra-Red spectroscopy, which showed that the structure of thin glass layer differs somewhat from bulk one, but
thermal annealing treatment decreases the difference. Our final aim is to produce with PLD alternated thin layers
of glass and vanadium boride, in order to obtain self-healing glass coatings [Advanced Functional Materials 2010,
20 (24), 43714374. doi/10.1002/adfm.201000147/abstract].

229

Modelling of oxide glasses with required

structure and properties
Prokhorenko O. A.1, Pevzner B. Z.1, Chistokolova M. V.1,Prokhorenko S. O.2
1

Laboratory of Glass Properties, LLC St. Petersburg, Russia;

Ecole Centrale, Chtenay-Malabry, France

Very often an experimental glass or aseries of glasses with unique combinations of physical, and chemical properties are needed. Having such objects available one can investigate some specific features of the glass structure
and/or study its physico-chemical behaviour or find candidates for new practical application(s). Selection of glass

ICG Prague 2013 21

232

compositions includes aset of routines, such as, formulation of trial glasses, melting, and testing their physical
properties till the target composition is found. Sometimes, the authors use additive schemes for calculation of
properties by composition. Compositional search is, usually, based on systematic study of properties as functions
of composition, which is an iterative process. anumber of glasses in each series, and anumber of iterations depend on amount of available literature data, and effectiveness of the modeling tools. The present paper describes
an efficient method of formulation of new experimental glasses, which uses the following four parts of compositional search together. Determination of structural groups responsible for given physical properties by using
available data on the glass structure and Molecular Dynamics. 2. Development (based on the results of part 1) of
reliable structure-properties correlations within wide compositional ranges. 3. Multidimensional global optimization for finding glasses with required combinations of properties, and containing target structural groups. 4.
Express and precision glass synthesis followed by reliable testing methods to validate the results of modeling. All
four parts are the elements of anew methodology. The methodology represents an iterative process, which allows
one to perform systematic search to narrow the compositional range till the target glass(es) are found.

Self-organization of chemical bonds

in glass-forming substances
Chechetkina E. A.
Institute of General and Inorganic Chemistry, Moscow, Russia

300

Glassy state is considered as aresult of self-organization in the chemical bond system. There are three general
conditions for self-organization: (1) the open character of the system under consideration; (2) amany-stable, at
least two-stable, nature of the elements constituting the system; and (3) afeedback between the elements. These
conditions are fulfi lled in glass in the following way. (1) When glass is under preparation, it is always an open
system, just due to the thermal flow through the cooling liquid. In addition, the pressure gradients must be
applied to the softening glass in order to obtain the article of adesired form. (2) Chemical bonds constituting
structural network of glass is not necessarily the same that those in arelated crystal. The same covalent bonds
(CB) constitute classical continuous random network, which is unstable without additional soft bonds that
link covalent fragments together. Dembovsky has shown that low-energy hypervalent bonds can be formed from
covalent bonds using lone-pair electrons located on the electronegative atoms of chalcogen, oxygen or halogen
it is arelevant model for alternative bonds (AB), at least in inorganic glasses. (3) When elementary acts of bond
exchange CBAB are correlated in time and space, one obtains afeedback in the form of BOND WAVE.
The bond wave model concords fairly with glass features, such as the first sharp diff raction peak (the true Bragg
reflex from the wavefronts the layers populated with ABs), non-Arrhenius viscous flow (collective reconstruction of bonding network by means of bond waves), and characteristic fracture (discovery of fractal surface formed
by the wavefronts). Finally, glass transition can be considered as the dimensional transition: from the 3D bond
wave above Tg to the 2D bond wave(s) below Tg, within the frozen wavefronts/layers.
Thus, glass in NOT adisordered material, and the process of glass transition versus crystallization in supercooled
liquid can be considered as acompetition and inter-transformation of two types of long-range order (LRO): the
dead translational LRO of crystal and the living bond-wave LRO of glass. The original experiment of crystallization of Se-X glasses in ultrasonic field shows how one can manage bond waves.

Structural and vibrational aging

of a glass at a constant temperature
Kobayashi H.1, Ohtake Y.2, Hirata S.2, Morinaga A.2
1

Natinal Institute of Advanced Industrial Science and Technology, Osaka, Japan

Science University of Tokyo, Chiba, Japan

We presented that the glass transition is the self-organization of the intermediate-range orders, by which the glass
state has adissipative structure, on the basis of the relaxation time theory developed by Adam and Gibbs and the
dissipative structure theory developed by Prigogine (J. Chem. Phys. 132, 104504 (2010)).The time dependence of
the configurational entropy of aglass is zero, whereas that of its vibrational entropy has anegative and constant

22 Glass Science

value according to the theorem of minimum entropy production presented by Prigogine. This means that the
volume of aglass at aconstant temperature decreases at aconstant time rate through the spontaneous vibrational
aging while radiating heat in an isostructural state, which results in breaking of the timesymmetry. The vibrational contraction in the volume of aglass is caused by the irreversible displacement of its molecules due to their
inelastic and random configuration. In aglass, the amplitudes of vibrations of their molecules decrease while
maintaining the constant frequencies of their vibrations at a constant temperature. a spontaneous and linear
decrease in the length of aglass (ULE, Corning) was experimentally observed as afrequency drift of the laser
stabilized to aresonance line of the ULE cavity from aCalcium frequency standard. The result shows aconstant
decrease in the length given by L(t)=100mm4.6x10-10mm/dayxt(days), after 340 days where the structural aging
is over. The rate of alinear decrease in the length is 4.6x10-12/day at 3.6C.

345

Vitreous silica distends in helium gas

Weigel C.1, Polian A.2, Kint M.1, Ruffl B.1, Foret M.1, Vacher R.1
1

Universit Montpellier 2, CNRS UMR 5221, Montpellier, France;

Universit P. et M. Curie Paris 6, Paris, France

Vitreous silica (v-SiO2) has been extensively studied over large pressure (P) and temperature (T) ranges. Several
anomalous physical properties were discovered. In particular, the bulk modulus B does not show the P and T dependencies observed in most solids. As P is increased at room T, the modulus first decreases to reach aminimum
around 2GPa and it increases thereafter. The variation with T is also anomalous. It increases as T increases above
ambient up to the glass transition temperature. These anomalies are related to the flexibility of the structural
network of v-SiO2. It relies on the existence of asufficiently large free volume allowing strong structural modifications with T and P. Here, we present Brillouin light-scattering measurements of the elastic moduli of silica
as afunction of P up to 6GPa in noble gas atmosphere. It is found that the anomalous minimum in the pressure
dependence of B is almost completely suppressed by helium atoms incorporation into the silica network. It seems
likely that the helium atoms dissolve in the voids and hinder the flexibility of the network in SiO2 glass. An estimate of the amount of He entering v-SiO2, based on measurements of refractive index, is as much as 1.5mol per
mole of SiO2 glass at 6GPa. Another apparent bulk modulus can be calculated from the measured relative change
of volume under P. The huge difference between this static and the acoustic B indicates that the amount of incorporated helium still increases above 6GPa. Similar results are obtained in the case of silica pressurized with neon
gas atoms. The kinetics of the adsorption desorption process is presented.

Machado M. M.1, Rodrigues A. C. M.2

1

Basell Polieolefinas Ltda, Pindamonhangaba, S. P. Brazil;

Federal University of So Carlos, So Carlos, Brazil

We present experimental data on the evolution over time of the electrical conductivity of soda-lime-silicate glasses, at atemperature near the glass transition. Samples were first stabilized at different temperatures (T=530C)
above and below (T=560C) the glass transition temperature (Tg=553C), thus leading to different fictive temperatures. The variation in isothermal electrical conductivity was then measured at an intermediate temperature
of 530C. The electrical conductivity was found to decrease or increase over time, when the fictive temperature
was, respectively, above or below the temperature at which the electrical conductivity was measured. In both
cases, the electrical conductivity tended toward the same value. The change observed in electrical conductivity
is attributed to structural relaxation. Data were fitted with aKohlrausch equation assuming aMaxwell fluid behavior for the glassy phase, allowing for the determination of the relaxation time. The results are compared with
relaxation times extracted from density variations.

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357

Effect of structural relaxation on the electrical

conductivity and density of a window glass

393

Glass forming ability and crystalline

phases in system Na2O-CaO-Nb2O5-P2O5
Stunda-Zujeva A., Krieke G., Vecstaudza J., Berzina-Cimdina L.
Institute of General Chemical Engineering, Riga Technical University, Riga, Latvia;

396

Glass forming ability in system Na2O-CaO-Nb2O5-P2O5 with 8mol% Na2O was studied. Batch were melted in
electrical furnace at 1,000C for 30min. Melt was quenched between two steel plates.
One glass forming range is at 30mol% P2O5 and various niobia content and second at 10mol% Nb2O5 and various
phosphate content. Batch was not melted and even poorly sintered at compositions with no CaO. For glasses
with 30mol% P2O5 niobium gives yellow to brownish colour, depending on the amount (1060mol%), indicating
ahigher oxidation state Nb5+. Glass with 10mol% Nb2O5 and increasing the amount of P2O5 becomes dark blue,
indicating the presence of Nb4+ in the structure due to phosphate reductive effect. With increasing amount of
niobium glass transition temperature increased this indicates that niobium has involved in glass network as
glass former. Glass stability decreases from 127C till 40C with increasing amount of niobia from 20 to 60mol%.
There are calcium niobates forming at the phosphate poor area where P2O5 is less than 30mol% and niobophosphates at the calcium poor area where CaO is 30mol% and less.
The phase diagram can be divided in five overlapping regions according to obtained crystalline phases formed during
reheating till complete crystallization of powdered samples: CaNb2O6, Na4Nb8P4O32, Na2Nb6P4O26, NbPO5 and Ca2P2O7.

Mathematical modelling for nuclear

waste glass viscosity
Miller J. A.1, Hand R. J.1, Travis K. P.1, Bankhead M.2
1

University of Sheffield, Yorkshire, United Kingdom;

National Nuclear Laboratory Limited, Greater Manchester, United Kingdom

453

Viscosity is an important process parameter in vitrification, but it can be adifficult property to measure for the
full range of compositions and temperatures of aglass. Mathematical modelling is used to help augment and
extrapolate experimental viscometry studies.
The Vogel-Fulcher-Tamman (VFT) equation is the most prevalent model used by industry for approximating the
viscosity / temperature relationship of glasses. VFT was initially developed as an empirical relationship, without
reference to any mechanistic rationale for viscous flow. More recently, various new proposals about the microscopic underpinnings of rheological processes have given rise to alternative viscosity equations. In this presentation we explore some of the current theoretical developments, and compare and contrast the efficacies of their
fits to experimental data. In particular we concentrate on the superior interpolative and extrapolative properties
of contemporary models with respect to nuclear waste glasses. We also examine correlations and composition
dependencies in the parameters of the MYEGA model.

Glass formation behavior in different binary

and ternary tellurite glass systems
Ersundu A. E., Celikbilek M., Aydin S.
Istanbul Technical University, Istanbul, Turkey

Tellurite glasses have become acutting-edge research topic in glass science due to their outstanding properties, such
as relatively low-phonon energy, high refractive index, good infrared transmissivity, low crystallization ability, good
thermal and chemical stability. Recently considerable attention has been focused on the investigation of different
tellurite-based glasses which can be used in various technological fields, such as fiber optics, laser hosts, optical data
storage, sensors, spectroscopic and chromogenic applications. Unlike classical glass forming oxides, TeO2 does not
form glass under normal quenching conditions without addition of asecondary component, such as alkalis, heavy
metal oxides and halogens, etc. Combination of TeO2 with two or more secondary components yields stable glasses
and provides control of the desired properties. Since the nature and concentration of the constituent oxides in mul-

24 Glass Science

ti-component systems substantially determine the thermal, physical and structural features of glasses, in the present
study different oxide components (WO3, CdO, B2O3, ZnO, Li2O, Na2O, K2O) were used to investigate the glass formation behavior of different binary and ternary tellurite glass systems. aconventional melt-quenching technique
was used for the synthesis of the glasses. Thermal, physical and structural investigation of glasses were realized
according to the changing composition by using DTA, DSC, XRD, Raman and FTIR techniques.

454

Thermodynamic and kinetic investigation

of alkali containing tungsten-tellurite glasses
Celikbilek M., Ersundu A. E., Aydin S.
Istanbul Technical University, Istanbul, Turkey

Physical and structural properties of glass forming liquids change through the glass transition region with
changing temperature; therefore it is important to thermodynamically and kinetically investigate the glass
transition region in detail. To investigate the kinetic nature of the glass transition reaction, the activation energy of the transition from glass to supercooled liquid was determined in alkali oxide containing tungsten-tellurite glasses by astrong heating and cooling rate dependence of the glass transition temperature using differantial scanning calorimetry (DSC). Modified Kissinger equation which was originally introduced to determine
the kinetics of chemical reactions and widely used to calculate the activation energy of crystallization was applied in the present study to determine the glass transition activation energy from the non-isothermal kinetic
investigations. Kinetically estimated fragility from the glass transition activation energy and calculated values
of C parameter, viscosity and reduction in viscosity at afew selected temperatures near the glass transition
reaction were investigated according to the changing alkali oxide content. Heat capacity measurements in the
glass transition region was realized in terms of the heat capacities in glass and liquid states (Cpg and Cpl). Heat
capacity change (Cp) and the ratio of heat capacities (Cpl/Cpg) were determined to thermodynamically defi ne
the fragility of glasses depending on alkali oxide content.

463

Oxide glass structure as the additive

sum of the middle range order structures
according to vibrational spectroscopy
Bogdanov V. N.1, Markova T. S.2, Maksimov L. V.3,
Polyakova I. G.4, Tagantsev D. K.3, Yanush O. V.2
1

Saint-Petersburg State University;

Saint-Petersburg State Technological University of Plant Polymers;
3
Saint-Petersburg State Polythechnical University;
4
Institute of Silicate Chemistry, Saint Petersburg, Russia
2

In the early 1980s it was shown that the vibrational spectra of glasses can be represented as the additive sum of
small quantity of constant spectral forms (principal spectral components, PSCs) belonging to the middle range
order structures, so called Constant Stoichiometry Groupings (CSG). These CSGs are the stable products of the
interaction of initial oxides. The composition dependences of intensities of PSCs, i.e. the concentrations of CSGs,
afford an opportunity to determine their stoichiometry, explain, calculate and even predict the composition dependences of refractive index, density, the fractions of B, Ge and Al in different coordination and other properties
of binary and ternary glasses in agood agreement with experimental data even for glasses with anomalous composition dependence of properties. Currently more than 30 glassforming systems have been investigated. The advancement of the CSG concept is the possibility to design low scattering glasses built from CSGs of asingle type
(i.e. without concentration fluctuations), in which scattering level is lower than that in silica glass, and also glasses
with the record value of Kerr coefficient which are interesting for photonics technology. Vibrational spectra of
CSGs are often similar to those of the corresponding crystals, but usually shifted by tens of cm-1. However, in
many cases they are fundamentally different, which indicates the existence of unknown compounds. Thus, new
compounds (Na2O8B2O3, Na2O4SiO2, TeO22PbO2P2O5, TeO2PbOP2O5, and others) have been predicted and

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504

then found. The CSG concept is based only on experimental data with the appropriate mathematical treatment as
opposed to more speculative approaches dealing with assumptions on glass structure. The study was supported
by RFBR (Grant 10-03-00323).

Atomic diffusion in glasses studied by X-ray

photon correlation spectroscopy
Ross M.1, Leitner M.1,2, Stana M.1, Sepiol B.1
1

University of Vienna, Department of Physics, Strudlhofgasse 4, 1090 Vienna, Austria;

FRM-II, Technische Universitt Mnchen, Lichtenbergstrae 1, 85747 Garching, Germany

531

Solids can be categorized by their microscopic structure into crystals and amorphous materials. Knowledge of
diff usion processes on the atomic level can play acrucial role in the understanding of many properties of these
materials. In our group, we applied anew method which allows to measure dynamics on atomic length scales,
in contrast to the typically applied macroscopic methods. We extended X-ray photon correlation spectroscopy
(XPCS) to the sub-nanometer range utilizing the most brilliant X-rays generated by high energy synchrotron
sources and measuring in the diff use regime of scattering.
One of physics unsettled questions is the dynamic behavior of amorphous materials, especially that of ionic
glasses. Having shown how to observe atomic dynamics with XPCS in acrystal model system, we extend our
method to the physically interesting case of non-crystalline materials. In particular, we investigated lead-silicate
glasses, where the network formation is governed by the interplay of SiO4 tetrahedra and PbOx polyhedra. As both
components can act as network formers, the composition of them is apromising candidate for studying diff usion
in glasses with XPCS. Our analysis allows to draw conclusions on physical properties like the mean distance of
ionic motion and thus to shed light on the processes which govern glassy dynamics. I will give an overview on
our recent results obtained from measurements at the synchrotrons ESRF and PETRA III and discuss the consequences for our picture of the atomic dynamics in glasses.

Structural relaxation and crystal

growth kinetics in Se-Te glasses
Mlek J.1, Svoboda R.1, Bartk J.1, Kol P.2
1

Department of Physical Chemistry, Fac. Chem. Technol., University of Pardubice, CR;

Department of Inorganic Technology, Fac. Chem. Technol., University of Pardubice, CR

Understanding the structural relaxation, and crystal growth kinetics in glass-forming systems is currently seen
as one of the most important challenges in in materials science. These phenomena are essential for large scale
production of conventional silica-based glasses as well as for advanced non-crystalline materials used for optical
and electrical data recording devices based on chalcogenide systems.
For asystematic study it is convenient to select material that can be prepared in the form of bulk, powder fractions
with defined particle size distribution as well as thin films such as Se-Te system. There are three topics related to
this system that will be addressed in this contribution. First topic is related to the structural relaxation study in
the glass transition range measured by dilatometric as well as by calorimetric techniques and their description
within Tool-Naraynanaswamy-Moynihan and Adam-Gibbs-Scherer model. Second topic is related to viscosity behavior of Se-Te undercooled liquids measured by penetration, parallel plate method and rotation cylinder
method. The applicability of Adam-Gibbs theory is tested and discussed with respect to structural relaxation
models. The third topic is associated with kinetic studies of crystal growth processes in bulk, powders and thin
fi lms of Se-Te materials. These processes are studied by DSC calorimetry, optical and IR microscopy, electrical
conductivity, and other complementary experimental methods.
Our research attempts to get more detailed information about complex kinetic processes aiming to develop suitable models for the description and prediction of structural relaxation, viscosity behavior and crystal growth
kinetics under selected experimental conditions needed for advanced materials R&D.
The financial support from the Czech Science Foundation under grant No. P106/11/1152 is gratefully acknowledged.

26 Glass Science

Sundaram S. K.
Kazuo Inamori School of Engineering and The New York State College of Ceramics,
Alfred University, Alfred, NY 14802, United States of America

The terahertz (THz) spectroscopy and imaging covers the 0.110 THz frequencies linking the infrared and microwave bands of the electromagnetic (EM) spectrum. As THz waves are non-ionizing in nature, they can be used
to probe and image matter safely, including glasses. THz spectrometers available commercially cover different
frequency ranges, resolutions, and data quality. arecent example is the THz time-domain spectrometer (THzTDS) that measures the real and imaginary parts of the dielectric constant without the use of the Kramers-Kronig
(KK) relations. These tools have advanced over the past couple of decades. They show promise as glass characterization tools. Many rotational and vibrational spectra of liquid and gas molecules lie within the THz frequency
band, enabling identification of their molecular structures. THz spectroscopy can be used for identifying unique
resonances e.g., vibrations suggesting medium-range order in non-oxide glasses. Early attempts to correlate glass
compositions to THz properties and some universality have been reported in the literature. Measurement of THz
properties of broad range of glass chemistries is critical to generate adatabase that will be useful for realizing
the full potential of glasses for application in passive, active, and integrated optical components and devices. As
glasses generally transmit THz waves to different extents and metals reflect them mostly, these families of materials can be combined to build photonic structures that guide the THz waves efficiently. THz imaging can be used
for non-destructive examination of glasses, e.g., modified surface layer. As water absorption is strong in the THz
region, the imaging can be used to view deeper hydroxyl layers as afunction of depth. This talk will present an
overview of literature in this area, highlight the THz facilities (T-Lab) at Alfred University, and summarize recent
key results. Future prospects of these tools in advancing glass science and engineering will also be discussed.

ICG Prague 2013 27

570

Terahertz spectroscopy and imaging of glasses

 28

Glass Structure

ICG Prague 2013 29

 30

042

Structure determination in chalcogenide

glasses using anomalous X-ray scattering
Pilgrim W.-C.1 , Hosokawa S.2 , Koura A.2 , Shimojo F.2 , Brar J.-F. 3
1

Philipps-University of Marburg, Germany;

Kumamoto University, Kumamoto, Japan;
3
CNRS/UJF, Grenoble, France

The application of Anomalous X-ray scattering to determine microscopic structural correlations in multi-component
disordered systems has received considerable advancement over the past decade. Especially, the combined use of AXS
with Reverse Monte Carlo Simulations (RMC), to analyse the measured differential scattering laws, allows aprecise
visualization of microscopic structural features and hence the access to difficult questions where physical properties
depend on very small structural variations. ashort overview on the AXS/RMC-technique will be given and its applicability will be demonstrated by means of two scientific investigations on well-known vitreous chalcogenide systems:
Data from an AXS/RMC-investigation on aso called Phase-Change Material will be presented which is commercially
used for data storage on rewritable optical media. Data storage is thereby accomplished by the ability of these materials
to switch reversibly between acrystalline and avitreous phase on the nanosecond scale, accompanied by achange in
optical properties. While the crystal structure is well known from conventional XRD-investigations clear structural
information of the vitreous phases of these ternary systems is still amatter of controversial debate. We will present
aclear-cut picture of the vitreous structure for one of these materials which complies well with other theoretical and
experimental studies. In the second example we will present AXS/RMC-data of As2Se3 glass questioning the universality of the so called 8N bonding rule, which was originally introduced by N. F. Mott. This rule has been questioned
before in the past on basis of calorimetric data but adirect structural proof was still missing. We will present very accurate structural data obtained from an AXS/RMC-study which supports this reasonable doubt. The structural findings
are in very good agreement with recent ab initio MD-simulations which we will compare with our experimental data.

076

Structural study of caesium silicate glasses

and melts by Raman spectroscopy
Osipov A. A., Osipova L. M.
Institute of Mineralogy UB RAS, Miass, Russian Federation

The structures of binary caesium silicate glasses and melts with Cs2O content ranging from 17 to 37mol% were
studied by Raman spectroscopy. The band deconvolution procedure of the high-frequency region of Raman spectra was carried out as asuperposition of the Gaussian lines in order to estimate the fractions of various Q species.
It was found, that the structure of glasses consists of Q4 and Q3 units at Cs2O content >25mol% and Q2 units
appear at the higher concentrations of the modifier oxide contents. At the same time, the Q2 units exist in the
SiO2-rich melts. The formation of Q2 units in the melt structure is accompanied by decrease in concentration of Q3
units and increase in fraction of Q4 species. It could be explained by the shift of 2Q3 Q4 + Q2 equilibrium reaction to the right as the temperature increases. The enthalpy of this reaction was found to be equal to 53 7kJ/mol
and does not depend on the melt composition at Cs2O content ranging from 27 to 37mol%. The value of enthalpy
decreases at lower caesium oxide contents. Based on concentrations of Qn species, the glass and melt structures
were analyzed in terms of different type of Qn-O-Qj bonds and Qn,a1,a2,a3,a4 groupings (ai=0.4). It was found that
both the Qn-O-Qj and Qn,a1,a2,a3,a4 distributions strongly depend both on glass composition and temperature.

Osipova L. M., Osipov A. A.

Institute of Minaralogy UB RAS, Miass, Russian Federation

Glasses and melts of the xBaO-(100-x)B2O3 (20 x 67mol%) composition were studied by high-temperature Raman spectroscopy. The analysis of the Raman spectra has shown that the local structure of the barium borate glasses

ICG Prague 2013 31

077

Structure of glasses and melts

in the BaO-B2O3 system: The Raman scattering data

101

is qualitatively similar the structure of alkali borate glasses and mainly consists of B3 symmetric triangles and
[B4] teterahedra at BaO content less than 40mol%. At relatively low concentrations of BaO (x < 30mol%), no significant changes in the SRO (short range order) structures depending on temperature were found. The transformations in the IRO (intermediate range order) structures are the dominant process in this compositional range. These
transformations are caused by destruction of various borate rings and lead to increase in fraction of the so-called
independent basic structural units in the melt structure. The temperature induced structural changes are not limited by the destruction of IRO structures but are also related to the reduction of boron coordination from 4 to 3 at
higher (up to 40mol%) concentration of the modifier oxide. Such changes can be explained by the shift of [B4]
B2O equilibrium to the right with increase in temperature. For x > 40mol%, BO22 pyroborate units are formed
and BO33 orthoborate anions appear in the melt structure with the highest BaO content (60 and 67mol%). It was
found that arole of structural reorganizations with [B4] tetrahedra gradually decreases at x > 40mol%. For the
given compositions, 2B2O B3 + BO22 disproportional reaction is adominant mechanism of changes in the
SRO structures. This equilibrium is shifted to the right as the temperature increases.

Selective and collective behaviour

of iron in oxide glasses: A multi-spectroscopic study
Bingham P. A.
Materials and Engineering Research Institute, Sheffield Hallam University,
City Campus, Sheffield S1 1WB, UK

122

The local structural environment and oxidation state of multivalent elements in oxide glass can strongly affect
their physical properties and hence it is important to gain adetailed understanding of the factors governing their
behaviour. Here, the behaviour of Fe in oxide glass matrices has been considered since iron is almost ubiquitous
in practical glasses, yet its behaviour is far from fully understood.
The effects of bulk glass composition and iron concentration, and the presence of iron in multiple valences and
multiple coordinations can be barriers to obtaining adetailed and quantitative understanding of its behaviour in
glasses as functions of glass composition and preparation conditions. Here these barriers have been partially removed by studying Fe2+ and Fe3+ separately and in isolation and the results show clear differences in the behaviour
and local structural ordering of Fe2+ and Fe3+, termed collective and selective behaviour, respectively.
Results from acombination of spectroscopic methods, chiefly Fe K-edge XAS, of measurements on silicate glasses
doped with 0.2mol% Fe2O3 (broadly indicative of technical silicate glasses) are discussed. Whilst Fe2+ exhibits collective behaviour and can be auseful probe ion for investigating average or bulk glass structure, Fe3+ exerts strong
local ordering effects, exhibiting selective behaviour, and may be less useful for probing bulk compositional effects.
This local ordering of Fe3+ takes the form of atransition from [4]Fe3+ to [6]Fe3+ as functions of alkali and alkaline earth
cation type. For the first time, this transition has been measured and quantified by XAS in terms of average coordination and Fe-O bond lengths and the results are consistent with the model for selective behaviour of Fe3+ ions.

Structure of novel zinc phosphate glasses

for bone cement applications
Kanwal N.1 , Abrahams I.1 , Karpukhina N.2
1

School of Biological and Chemical Sciences, Queen Mary University of London,

London, United Kingdom
2
Dental Physical Sciences Unit, Barts and The London School of Medicine and Dentistry, Queen Mary
University of London, London, United Kingdom

Glass ionomer cements are acid base cements, where traditionally the base is an acid soluble calcium aluminosilicate
glass and the acid is apolyalkenoic acid or acopolymer of different alkenoic acids. The resulting product is asalt hydrogel which acts as abinding matrix. Various modifications of aluminosilicate glass have been made to optimise the
strength and biocompatibility of the resultant cements. Silica to alumina ratio is very crucial in these glasses, since aluminium works as network intermediate which chelates polymeric chains and strengthens the network. However there
is aconcern over the neurotoxicity of aluminium leached into the body fluid, particularly if the cement is to be used as

32 Glass Structure

abone cement. We have attempted to develop and investigate the structure of aluminium-free zinc containing phosphate glasses for potential use as abase component of glass ionomer cements. Since phosphate glasses are more closely
related to those of natural bone. In addition the properties of phosphate glasses can readily be tailored by changing the
composition. We have attempted to investigate the structural role of zinc in aseries of phosphate glasses using different
techniques such as 1-D and 2-D 31P MAS-NMR, 67Zn NMR and neutron diffraction. 67Zn NMR is anovel technique
which we have used here to probe the structure of disordered solids. The results confirm that Zn acts as anetwork intermediate with both octahedral and tetrahedral coordination for Zn. Careful analysis of the 1-D and 2-D NMR data have
been used to guide analysis of the neutron diffraction data and provide amodel of the structures in these amorphous
solids. The resulting structures are correlated with the solubility behaviour of the glasses and hence their bioactivity.

123

Structural studies of lead borophosphate glasses

modified by tungsten oxide with the application
of 11B MAS NMR and Raman spectroscopy
Koudelka L.1, Rsslerov I.1, Moner P.1, ernoek Z.1, Montagne L.2, Revel B.2, Tricot G.2
1
2

University of Pardubice, Faculty of Chemical Technology, 532 10 Pardubice, CR

University of Lille, 59655 Villeneuve dAscq, France

Borophosphate glasses reveal better thermal stability and chemical durability than phosphate glasses. Their doping
by heavy metal oxides shows promising electronic applications. In this contribution lead borophosphate glasses of
the composition (1-x)[50PbO-yB2O3-(50-y)P2O5]-xWO3 with 060mol% WO3 and with 1525mol% B2O3 were synthesized and their structure was studied by 11B MAS NMR and Raman spectroscopy. The effect of composition on
the properties of these glasses and the relations between composition, structure and properties were evaluated. The
addition of tungsten oxide to borophosphate glasses increases their thermal stability, glass transition temperature
and chemical durability. Structural studies were devoted to the investigation of changes in boron coordination in
the dependence on changes of WO3 content and of the B2O3/P2O5 ratio in the lead borophosphate glasses. aspecial
attention was devoted to the formation of mixed structural units B(OP)4-x(OW)x in the studied borophosphate glasses revealed from 11B MAS NMR spectra. 11B DQ NMR spectra revealed complex connectivity scheme between tetrahedral and trigonal units showing on the formation of BO4 units with B-O-P, B-O-W, B-O-BIV and B-O-BIII bonds.

142

Low-energy ion scattering

spectroscopy of silicate glasses
Almeida R. M.1 , Hickey, R.2 , Jain H.2 , Pantano, C. G. 3
1

Instituto Superior Tcnico, Lisboa, Portugal;

Lehigh University, Bethlehem, USA;
3
Pennsylvania State University, State College, USA

The nature of glass surfaces is of fundamental importance as it determines properties like mechanical strength,
hardness, chemical durability, wetting behavior, coating adhesion and optical reflectivity, among others. While
optical reflectivity probes the glass surface down to several microns, RBS (Rutherford Backscattering spectroscopy) is asub-micron analytical technique and XPS (X-ray photoemission spectroscopy) probes the glass composition to within ~27nm below the surface, Low-Energy Ion Scattering (LEIS) spectroscopy is atechnique with
aunique sensitivity to the composition of the glass surface top atomic layer. One of the issues which LEIS may
address is whether the composition of the top surface layer of aglass coincides with its average bulk composition
and whether the same holds for the surface created upon glass fracture under high vacuum.
LEIS measurements of binary and ternary silicate glasses (di- and tri-silicates modified with Na2O, Cs2O, CaO,
SrO and BaO) have shown that the compositions of the free air surface and the in-vacuum fracture surface often
differ. While the air surface is usually depleted in alkali ions (Na+ or Cs+) compared to the nominal (batch) glass
composition (probably due to their evaporation from the melt), there is often strong accumulation of the same
mobile cations on the fresh fracture surface and, curiously, its composition, after prolonged sputtering cycles,
often fails to tend to the nominal composition with respect to the modifier cations (Na+, Cs+, Ca2+, Sr2+ or Ba2+).

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During depth profi ling, however, the tendency towards stoichiometry might go in parallel with preferential sputtering. In the presence of sufficient concentrations of divalent modifier cations (Ca2+, Sr2+ or Ba2+), the movement
of the more mobile monovalent ones (Na+ or Cs+) is blocked and these are no longer found to be preferentially lost
by melt evaporation. The Si/O ratio does not usually deviate much from stoichiometry.

Structural characterization of sodium containing

ionomer glasses by MAS-NMR spectroscopy
Zainuddin N.1 , Karpukhina N2 , Hill R. G2 , Law R. V3
1

Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, Malaysia;

Unit of Dental Physical Sciences, Institute of Dentistry, Barts and The London School of Medicine
and Dentistry, Queen Mary University of London, Mile End Road, London E1 4NS, UK
3
Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ, UK
2

196

The structure of sodium containing Ca aluminosilicate glasses was studied by 29Si, 27Al, 31P and 19F MAS-NMR
spectroscopy. The glass compositions studied were based on 1.5SiO2. 1.0Al 2O3 0.5P2O5. 1-XCaO.0.5CaF2 XNa 2O
where X=0.1, 0.2, 0.3 and 0.4. The 29Si spectra showed that all glasses have apredominant Q4(3Al) and Q4(4Al)
structure, which means there are few or no NBOs on the SiO4 tetrahedra. It is suggested that the Si tetrahedral
network has not changed with the sodium content. The 27Al MAS-NMR spectra of sodium containing glasses
showed amajor peak at around 52.0 to 53.0ppm that is attributed to an Al(IV) site. The chemical shift below
60.0ppm suggesting the presence of Al-O-P species. The introduction of sodium in the glass composition does
not change the 27Al chemical shift simply because it is influenced more by the Al:P and the Al:Si ratios, rather
than by sodium. The chemical shift of 31P MAS-NMR moved to amore positive value which suggested mixed
sites of Ca and Na charge balancing cations around the pyrophosphate tetrahedra. 19F MAS-NMR spectra
showed the presence of F-Ca(n), F-Ca/Na(n), Al-F-Ca(n) and Al-F-Na(n) species in these sodium glasses. The
reduction in the glass transition temperature is not due to Na cations are disrupting the Si network but is due
to the ability of Na cations to disrupt the phosphate and fluorine environments due to the existence of mixed
Ca/Na sites from 31P and 19F MAS-NMR.

Structure-density correlations in bioactive glasses

Brauer D. S.1 , Karpukhina N.2 , Doweidar H. 3
1

Otto Schott Institute of Materials Research, Jena University, Jena, Germany;

Dental Physical Sciences, Queen Mary University of London, London, United Kingdom;
3
Glass Research Group, Dep. of Physics, Fac. of Science, Mansoura University, Mansoura, Egypt

Bioactive glasses are used as implant materials for bone regeneration, and a good understanding of their
structure-property relationship allows for designing new compositions to meet clinical requirements. Fluoride-containing bioactive glass monoliths (SiO2-P 2O5 -CaO-Na 2O-CaF 2; CaF 2 = 0 to 25.5mol%) were prepared by amelt-quench route. Glass density was determined using Archimedes principle, using deionised
water as the immersion fluid, and showed an increase in glass density with increasing CaF 2 content from
2.699 ( 0.003) to 2.812 ( 0.003)g/cm-3. Glass structure was analysed using 29Si, 31P and 19F magic angle
spinning nuclear magnetic resonance (MAS NMR) spectroscopy. amodel was developed for the density and
molar volume of such bioactive glasses on the basis of MAS NMR results. This model correlates the glass
density with the concentration and volume of the structural units forming the glass (Q2 and Q3 silicate units
associated with sodium and calcium ions, orthophosphate charge balanced by sodium and calcium ions and
CaF4). The volume of CaF4 in the studied glasses is about 1.02% greater than in the CaF 2 crystal. Calculated
density and molar volume show good agreement with the experimental data. Because of constant network
connectivity of the silicate network, the increase in both the density and molar volume is related only to
the increase in the concentration of CaF4 units. The density model shows that such bioactive glasses can be
described as mixtures of various matrices (silicate, phosphate and CaF 2).

34 Glass Structure

210

MnO cluster formation and ensuing structural

changes in borate and borosilicate glasses
probed by EPR, IR and Raman spectroscopy
Mncke D. 1 , Winterstein A.2 , Kamitsos E. I. 3, Wondraczek L.1
1

Otto-Schott-Institute, Friedrich-Schiller-University Jena, Germany

Max Planck Institute for the Science of Light, Erlangen, Germany
3
Theoretical & Physical Chemistry Institute, National Hellenic Research Foundation, Athens, Greece

Low alkaline borosilicate (BS) and Sr-borate glasses were doped by MnO, with doping levels in the BS glass series being
restricted to 4mol% where phase separation sets in. Also, quenching allowed to prepare glasses in the xB2O3xSrO
(12x)MnO glass series with the highest MnO content being 60mol%, at aB2O3 content as low as 20mol%.
Exchange narrowing of the EPR signals indicates the formation of clusters containing edge or even face-sharing
MnO6-octahedra in both glass systems. MnO addition to low alkaline BS glasses results in an increased population of [B4] groups ( denotes bridging oxygen atom). However, instead of abetter mixing between borate and
silicate tetrahedra, the [B4] groups act preferentially as ligands to Mn-ions and, therefore, accumulate around
the MnO-clusters and enhance phase separation.
In the borate glass series, addition of increasing amounts of MnO leads to progressive transformation of metaborate entities into pyroborate dimers and orthoborate monomers. IR and Raman spectra of the glass with the highest MnO content confirm the presence of [B2O2]3 tetrahedral units, which are an isomeric form of the trigonal
(BO3)3 groups. The presence of [B2O2]3 units explains the observed increase of the transition temperature Tg
and the decrease of density for the sample left with only 20mol% B2O3, which goes against the general trend of
these properties within the glass series.

319

Property and structural characterizations

of low dielectric glass fiberfor new printed
circuit board base materials
Li H.1 , Eng D.1 , Charpentier T.2 , Ollier N. 3
1

Fiber Glass, PPG Industries, Inc., Pittsburgh, USA;

CEA, IRAMIS, SIS2M UMR CEA/CNRS 3299, F-91191 Gif-sur-Yvette cedex, France.
3
LSI/IRAMIS-CNRS-Ecole polytechnique, Palaiseau, France

Standard printed circuit board (PCB) base material is composed of woven fabric of E-Glass fiber and FR-4 epoxy resin.
E-Glass fiber has ahigher dielectric constant (Dk) than the resin. As aresult, the laminate composite PCB material
exhibits local spatial Dk nonuniformity due to the presence of the woven fabric geometry. To minimize the spatial
nonuniformity, new glass fibers with lower Dk are thought to be one of the key solutions for PCB base material for
applications at computing speed greater than 10GHz. This paper will cover glass physical, electrical, and mechanical
properties relevant to the development of low dielectric fiber and PCB applications. The structure of fibers produced
at various temperatures was investigated using both magic angle spinning nuclear magnetic resonance (MAS NMR)
triple quantum MQMAS and confocal microRaman spectroscopic methods. The structure investigation focused on
local environment of Al, B, and Si as afunction of fiber drawing temperature.

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340

MAS-NMR study of sodium aluminosilicate

glasses with lanthanum fluoride
Calver A.1 , Karpukhina N.2 , Law R. V.1 , Hill R. G.2 , Sroda M. 3
1

Imperial College London, London, United Kingdom;

Queen Mary University of London, London, United Kingdom;
3
AGH University of Science and Technology, Krakow, Poland

341

Oxyfluoride glasses and heat-treated glasses from the system SiO2-Al2O3-Na2O-LaF3 have been studied by multinuclear 19F, 27Al, 29Si, 23Na MAS-NMR spectroscopy and X-ray diffraction. This system has been previously studied using DSC/DTA, IR and Raman spectroscopy. The effect of the compositional changes, in particular change
in SiO2 content, on glass structure and crystallisation of the lanthanum fluoride will be discussed. The findings
will be summarised and compared with the other oxyfluoride systems studied by the authors and the design rules
for forming the nano-sized crystals in oxyfluoride glass-ceramic will be reviewed.

Magnesium and zinc substitution for calcium

in fluoro-phospho-alumino-silicate glasses
Kusumoto H.1 , Karpukhina N.2 , Hill R. G.2 , Law R. V.1
1
2

Imperial College London, London, United Kingdom;

Queen Mary University of London, London, United Kingdom

360

Three series of glasses were produced by substituting calcium by magnesium and zinc in the base glass composition,
LG26 [4.5SiO23.0Al2O31.5P2O53.0CaO2.0CaF2]. These glasses were characterised by XRD, 19F, 31P, 27Al, and 29Si
MAS-NMR spectroscopy, and DSC. The mixed cation effect on glass transition temperatures for the glasses in
all three series was observed on the DSC. The MAS-NMR spectra have shown some structural changes upon the
substitution of calcium by magnesium in the Ca-Mg series and by zinc in Ca-Zn series. The gradual substitution of
calcium resulted in the steady change of the chemical shift in the 31P MAS-NMR spectra indicating the replacement
of charge balancing cations on NBOs of phosphorus from Ca2+ to Mg2+ in Ca-Mg series and from Ca2+ to Zn2+ in
Ca-Zn series. In addition, the 31P MAS-NMR spectrum of the fully magnesium substituted glass LG26Mg exhibited
apossible formation of magnesium pyrophosphate, Mg2P2O7, as well as Al-O-PO33 species. The substitution for
calcium in both series revealed increase in the formation of Al(V) species from the 27Al MAS-NMR spectra. The
chemical shift in the 29Si MAS-NMR spectra decreased with the substitution which indicated the decrease in the
number of Al around each SiO4 tetrahedra and the increase in the number of BOs on the Si. Despite similar charge
to size ratio of Mg2+ and Zn2+ some differences have been revealed from the 19F MAS NMR spectra. In the Ca-Mg
series, the 19F MAS-NMR spectra showed the formation of F-Mg(n) species starting in the middle of the series at
the expense of F-Ca(n) and Al-F-Ca(n) species which is consistent with the higher field strength of the Mg2+ cation.
However, in Ca-Zn series the 19F MAS-NMR spectra showed mostly the presence of F-Ca(n) and Al-F-Ca(n) species.

Structure and properties

of alumino-boro-silicate glasses and melts
Neuville D. R.1 , Florian P.2 , Cadars S.2 , Massiot D.2
1
2

Gochimie & Cosmochimie, CNRS-IPGP, Sorbonne Paris Cit, 1 rue Jussieu, 75252 Paris
CEMHTI-CNRS, 1D av. Recherche Scientifique, 45071 Orlans cedex 2, France

The relationship between physical properties and structure of glasses and melts in the system MO-T2O3-SiO2
(with M=Na2, Ca and T=Al, B) are technologically and geologically important, in particular to understand the
microscopic origin of the configurational thermodynamic properties. The connection of these network former is
fundamental to understand the physical properties of magmatic liquids.
The configurational properties of melts and glasses provide fundamental information needed to characterize
magmatic processes. aprincipal difficulty, however is to link the macroscopic configurational entropy with the
structure of melts. This has been done by combining viscometry with Raman and NMR spectroscopy studies.

36 Glass Structure

From the viscosity measurements at low and high temperatures, we have obtained the configurational entropy,
Sconf (log =Ae + Be/TSconf, were is the viscosity, T the temperature and Ae, Be two constants).
Silicon, aluminum, and boron are 3 network formers playing different role on the silicate network, whereas Si
is the strongest network former in coordination 4, 5 or 6 as afunction of T, P; Al can play different function as
anetwork former in 4- or 5-fold coordination and probably as anetwork modifier in 6 fold coordination. Boron
observed in 3 or 4 fold coordination is always anetwork former but for very fragile glasses.
For the glass the Al/B substitution produce asmall decrease of the molar volume while this substitution produced
astrong decrease of viscosity and glass transition temperature while the fragility of the network is less affected by
this chemical change. Raman spectra show significant change in the D1 and D2 bands. NMR spectroscopies show
also significant change as afunction of chemical change and temperature. All this observations will be discussed
and interpreted in order to link microscopic versus macroscopic changes.

371

Anisotropic property and structure

of alkali metaphosphate glass
Ito S.1 , Inaba S.1 , Endo J.2
1
2

Tokyo Institute of Technology, Yokohama, Japan;

Asahi Glass Co., Ltd, Yokohama, Japan

Glass is generally known to be isotropic, although some glasses have anisotropic properties showing birefringence. We investigated the relation between anisotpropic property, composition and structure of metaphosphate
glasses. The thin rod-like glass samples of 0.10.5mm in diameter were prepared by being drawn directly from
melt at near Tg and cooled to room temperature under tensile stress. We found that multi alkali metaphosphate
glasses showed unique anisotropic behaviours, compared to single alkali metaphosphate glasses. The former type
metaphosphate glass of (Li, Na, K, Cs)PO3 showed alarge birefringence comparable to quartz crystal. The anisotropic glass showed ahuge shrinkage of about 35% in adirection of parallel to the rod axis without volume change,
when it was heat-treated over Tg and its anisotropy was released. Raman and NMR spectra revealed that the glass
had highly oriented P-O-P chain structure. The unusual anisotropic properties will be discussed in terms of the
chain structure of the glass.

394

Mixed-ion effect in phosphate glasses:

Local order and cation distribution
Schneider J. 1 , Tsuchida 1 , Eckert H.1,2 , R. R. Deshpande2
1
2

Instituto de Fsica de So Carlos, Universidade de So Paulo, So Carlos, Brazil;

Institut fr Physikalische Chemie, Westflische Wilhelms-Universitt Mnster,
Mnster, Germany

The mixed-ion effect (MIE) is the dramatic non-linear variation in the values of transport properties in glasses
due to restriction in ionic mobility upon mixing. asatisfactory explanation of this phenomenon has been elusive
during decades. Metaphosphate glasses A xB1-xPO3 with two mobile monovalent cations A+ and B+ are archetypical examples of MIE in d.c. conductivity. The deepest known reduction in conductivity is observed in Rb-Li
metaphosphates, attaining 8 orders of magnitude. In contrast, reductions of less than 1 order of magnitude are
observed in Ag-Na metaphosphates. acomprehensive analysis of local order and the alkali distribution in mixed
metaphosphatesis presented here, covering A-B pairs as Na-Li, Na-Ag, Na-K, Na-Rb, Na-Cs, and Li-Rb, Li-Cs,
Ag-Cs. The aim of this study is the identification of segregation or random mixture of cation species and their
possible dependence with their size mismatch or differences in ionic potential. abroad set of Nuclear Magnetic
Resonance (NMR) techniques was applied: 31P, 23Na, 7Li and 133Cs high-resolution NMR, 109Ag-NMR, 23Na Triple-Quantum-MAS, REDOR/SEDOR between 31P- 23Na, 7Li-6Li, and 7Li-133Cs, 87Rb quadrupole Carr-Purcel-Meiboom-Gill, and 23Na-NMR spin-echo decay. The structural picture emerging from these results reveals that each
cation site retains its structural specificities, as in single cation glasses. acommon structural adjustment on the
cation environment was detected: the compression of the O environment around the smaller cation of the pair as
its concentration is reduced. The mixture of cations species at atomic scale is generally random, even in glasses

ICG Prague 2013 37

421

having the biggest cation mismatch as Li-Cs, but sizable deviations are observed for Na-K, Na-Cs and Na-Rb,
indicating short range like-cation preferences. These findings support recent structural approaches developed to
describe MIE, indicating the possibility to extend this description to other systems.

Mixed network structure of tin boro-phosphate

glasses studied by advanced 1D/2D solid
state NMR and infrared spectroscopy
Takebe H.1 , Saitoh A.1 , Tricot G.2
1
2

Ehime University, Matsuyama, Japan;

University of Lille 1, Lille, France

441

Tin boro-phosphate (TBP) glasses have features of low glass transition temperature, good water durability, high
refractive index and low photoelastic constants. TBP glasses are attractive for fiber and precise mold optics. Binary tin phosphate (TP) and ternary TBP glasses with compositions of 67SnO(33x)P2O5xB2O3 where x=0, 3,
5, 7 and 10mol% were prepared by aconventional melt quenching method. The structures of TP and TBP glasses
were analyzed by Nuclear Magnetic Resonance (NMR) performed at very high static field (18.8 T). In addition
to standard 1D 31P and 11B experiments that probe the local order, the presence of P-O-B linkages was analyzed
through the edition of 2D 11B/31P correlation spectra (obtained with the D-HMQC technique) and the existence of
B-O-B bonds involving both tetra and tri-gonal borate units was highlighted by the recently developed 11B DQSQ technique. Infrared spectroscopy results in the existence of phosphate Q1 and Q0 species, BO3 and BO4 units,
and relating chemical bonds. The mixed network structure evaluated by NMR was considered in correlation with
borate and phosphate anion species and chemical bonds due to infrared spectroscopy. The glass structure was
also related to the dissolution behavior of TBP glasses in hot water.

Structure of low-Tg ZnO-Bi2O3-P2O5

glass by X-ray diffraction
Kitamura N.1 , Fukumi K.1 , Kohara S.2 , Ohara K.2 , Nishii J. 3
1

National Institute of Advanced Industrial Science and Technology, Osaka, Japan;

Japan Synchrotron Radiation Research Institute, Hyogo, Japan;
3
Research Institute for Electronic Science, Hokkaido University, Sapporo, Japan

Bismuth phosphate glasses, which have high refractive index and low deformation temperature, are candidate
materials for producing optical components having sub-wavelength periodic structures, such as high performance compact lenses and diff ractive optics, by anano-imprinting process. It is of interest that azinc bismuth
phosphate glass system has two distinct glass-forming regions; orthophosphate and isolated phosphate structures
are dominant in the region of O/P>3.5 (called low-P2O5 region) and metaphosphate and pyrophosphate structures
are dominant in the region of O/P<3.5 (called high-P2O5 region). Especially it is interesting that the glass in the
low-P2O5 region shows refractive indices higher than 1.8 and shows lower absorption edge energy in the lowP2O5 glass. In our previous work, the presence of aRaman band at 160cm-1 in the low-P2O5 glass, which was not
observed in the high-P2O5 glass, suggested the differences in the Bi-O bonding state, which was related with the
difference in absorption edge energy between two glasses. In the present study, we report results of High-energy
X-ray diff raction measurements on these glasses in order to obtain information on the difference in the local
structure around bismuth ions. Bi-O bond length for the glasses in the low-P2O5 region, 2.1, was shorter than
that for the glasses in the high-P2O5 region, 2.3. The Bi-O bond lengths suggested the origin of the differences
in refractive index and absorption edge energy.

38 Glass Structure

476

Inelastic X-ray scattering: a tool to study the structure

of glasses and melts around low Z-elements
Lelong G., Cormier L., Ferlat G.
Institut de Minralogie et de Physique des Milieux Condenss,
Universit Pierre et Marie-Curie, CNRS, Paris, France

The local structure around low-Z elements in glasses and melts is not well known, since conventional synchrotron
X-ray absorption spectroscopy is limited by the low energy of the incident X-rays. As aconsequence, only the
near-surface of the sample can be probed in an ultra-high vacuum environment. Th is can be circumvented by using inelastic X-ray scattering (IXS) and hard X-rays, amethod recently emerging on synchrotrons. This technique
allows to measure low-Z elements XANES spectra of excellent quality in complex sample environments.
Here, we will focus on two in situ IXS scattering spectroscopy experiments probing: (i) the O K-edge of vitreous
GeO2 at high pressure1, and (ii) the B K-edge in alkali borate glasses and melts using alevitation device in order to
probe the local structure in both the solid and liquid states. These examples will show all the potentialities of IXS
in the study of atomic configurations in glasses placed under extreme conditions.
1

Lelong, G., Cormier, L., Ferlat, G., Giordano, V., Henderson, G. S., Shukla, A. and Calas, G. Phys. Rev. B 2012,85, 134202

478

Why are obsidian black? Evidence of coloring clusters

Chasse M., Galoisy L., Calas G., Menguy N.
IMPMC, Pierre et Marie Curie University, 4 place Jussieu 75005, Paris, France

Speciation of iron in obsidians (shiny, black volcanic glasses) from various localities has been determined using
X-ray Absorption spectroscopy (XANES), Optical Absorption Spectroscopy and Transmission Electron microscopy
(TEM). Optical absorption spectra were measured over awide range of temperatures (from 10K to 1,073K). XANES
measurements show variable Fe2+/Fe3+ ratio depending on formation conditions and provenance of the obsidian.
Optical absorption spectra show aspectacular temperature-induced evolution. This is interpreted as arising from
the coexistence of distinct absorption processes due to different Fe-speciations. Isolated Fe2+ is located in aregular
octahedral site, alocal environment unknown in silicate glasses, whereas isolated Fe3+ is found in both tetrahedral
and octahedral coordinations, in the structure of the glassy matrix. The presence of iron intervalence charge-transfers processes is evidenced through the temperature dependence of the intensity of associated bands.
The specific coordination of Fe2+ together with the charge-transfer bands are related to the existence of iron oxide
clusters (<5nm), in the glass evidenced using TEM. These clusters (amorphous or crystalline), show aspecific
arrangement around iron in the glass and may be precursors of crystalline nanophases of iron oxide (titano-magnetite, magnetite or maghemite). The existence of these clusters and their nature seem to be related to the conditions of formation of the investigated obsidians. The high temperature measurements show an evolution of the
structure around iron in these glasses compatible with are-dissolution of Fe-clusters in the glassy matrix.

479

The role of chameleon elements

on the structure and properties of glasses;
Calas G., Cormier L., Galoisy L., Lelong G.
Institut de Minralogie et Physique des Milieux Condenss,
Universit Pierre et Marie Curie and CNRS, Case 115, 75252 Paris, France

More disordered than nanomaterials, amorphous solids such as glasses and gels have recently benefited from molecular scale approaches, which have provided at the same time adeeper knowledge of their structural organization
as well as giving potential tools to predict their properties. Glass stability is required for environmental applications,
including the development of insulating materials or nuclear waste matrices. On the other hand, nanophase crystallization is favored in glasses to form glass ceramics. It is interesting that the same glass components, such as Zr,
B or Fe are used to develop such different properties. We will summarize recent data obtained by acombination of
structural approaches (EXAFS, neutron and X-ray diffraction), and of numerical modelling/simulation tools.

ICG Prague 2013 39

499

Zr decreases the solubility of simulated nuclear glasses. In these glasses, Zr occurs in octahedral coordination
and has anetworking role. At the glass-water interface, Zr coordination may change or nor not depending on
alteration conditions, and Zr may provide or not aprotective role. In Mg- or Li-aluminosilicate glasses in which
higher field strength cations increase the disorder of the glassy network, Zr is used for enhancing the nucleation
of nanocrystals. Zr occurs in apeculiar local surrounding, explaining its structural instability during thermal
treatment. Other structure-property relationships will be illustrated on the influence of Fe3+-clustering on optical
and magnetic properties of glasses, or of B-coordination on radiation and thermal-dependent properties. They
show that bond valence rules and principles governing mineral crystal chemistry are active in glasses emphasizing the interdependence between the local surrounding and chemical state of the various glass components.

Spectroscopic and structural properties

of Fe3+ in silicate glasses
Vercamer V.1,3, Lelong G.1 , Galoisy L. 1 , Hijiya H. 2 , Kondo Y. 2
1

Institut de Minralogie et de Physique des Milieux Condenss, Universit Pierre et Marie-Curie, Paris, France
Research Center, Asahi Glass Co., Yokohama, Japan
3
Asahi Glass Co., France

508

Silicate glasses are the major components of flat glasses (e.g. automotive glazing, building industry, solar energy
solutions and specialty products). They contain iron (Fe2+ and Fe3+) as an impurity or intentionally introduced for
improving glass functionality. In this study, we present spectroscopic properties of Fe3+ in silicate glasses containing
less than 1wt% of Fe2O3 and synthesized under different redox conditions. We will compare the optical absorption
spectra with new data on electron paramagnetic resonance (EPR) at X- (9.8GHz) and Q-band (34GHz) frequencies.
This will shed light on the chemical dependence of the environment of Fe3+ in silicate glasses.

Structure/property correlations in mixed-network

former glasses studied by solid state NMR
Eckert H. 1,2 , Larink D.1
1
2

Institute fr Physikalische Chemie, WWU Mnster, Germany, Paris, France;

Institute of Physics in Sao Carlos, University of Sao Paulo, Brazil

Non-linear changes in the physical properties of glasses containing more than one type of network former species
are often exploited for optimizing the technological performance of glasses for optical and electrical applications.
Issues at the structural level concern the identification of the coordination polyhedra arising from the specific interactions between the network former species involved, their connectivity distribution, and the competition of both network formers for the network modifier species. Modern solid state nuclear magnetic resonance
(NMR) techniques present anew element-selective, inherently quantitative approach to this problem, as NMR
is not affected by the absence of periodicity. Specifically, we have developed the site-resolved measurement and
quantitative analysis of internuclear magnetic dipole-dipole interactions, which can be translated into distance
information in astraightforward manner. Using this approach we have studied the mixed network former effect
in avariety of borate and phosphate based glass systems, providing astructural rationale for the compositional
dependence of glass transition temperatures and ionic conductivities.

40 Glass Structure

523

In situ investigation of the Fe3+ and Fe2+

surroundings in soda-lime silicate melts
Michel F.1,2, Cormier L.2, Calas G.2, Galoisy L.2
1

Saint-Gobain-Recherche, 39, quai Lucien-Lefranc BP 135, 93303 Aubervilliers Cedex, France

Institut de Minralogie et de Physique des milieux condenss, Universit Pierre et Marie Curie, CNRS
UMR7590, 4 place Jussieu, 75005 Paris, France
3
SaintGobain Chantereine R&D Center, 60777 Thourotte, France

Fusion is the first step for glass production and is mainly done by radiative transfer in furnaces. amajor concern
is the optimization of the way this heat is transferred to the glass melt. To achieve this goal, glass optical properties have to be known precisely in situ in the temperature range operating in furnaces, mainly in the middle and
near infrared domain. We obtained in situ near infrared absorption spectra for different compositions of glasses/
melts. One of the most spectacular changes being observed in most compositions concerns the main Fe2+ absorption bands, the intensity of which decreases from glass to melt, in addition with significant shape modifications.
Moreover, major modifications for Fe3+ are also observed in the visible spectral range.
The structural understanding of the evolution with temperature of the local structure around Fe3+ and Fe2+ in
silicate melts has been investigated in soda-lime compositions from room temperature up to 1,500C. Previous
results indicate possible modification of Fe3+ coordination with temperature. Fe2+ K-edge XANES and EXAFS
spectra were investigated in situ in the melts using afurnace setup allowing acontrol of the atmosphere to prevent Fe-oxidation and preventing element volatilization from the melt. The evolution of pre-edge features and
EXAFS-derived Fe-O distances indicates asignificant modification of the surrounding of Fe2+. These data will be
discussed with the evolution measured on the optical absorption spectra in the same temperature rang and the
processes acting on radiative heat transfer efficiency within silicate melts.

588

Glass structure-property correlations:

Photelasticity, durability, and hardness
Zwanziger J. W.
Department of Chemistry, Dalhousie University, Halifax, Canada

The combination of local structure probes, including NMR, Raman, and EXAFS spectroscopies, and bulk measurements of mechanical and optical properties lead to useful understanding and predictive structure-property
correlations in glass. Here we will illustrate these points with anumber of recent studies in our lab, incluidng
photoelastic response, durability and strength, and surface hardness.

ICG Prague 2013 41

 42

Glass Surfaces

ICG Prague 2013 43

 44

228

Al2O3 coating by atomic layer deposition (ALD)

on various glass substrates
for surface strength improvement
Arai Y.1,2 , Pantano C.1
1
2

Materials Research Institute, The Pennsylvania State University, University Park, PA, USA
Central Research Center, Asahi Glass Co., Ltd., Yokohama, Kanagawa, Japan.

The modification of surface cracks on glass by coating to modify the crack-tip geometry, to provide aclosure
force and to protect the surface is apromising technique for realizing practical strength improvement. We focused on atomic layer deposition (ALD) which can coat high aspect ratio surface features such as cracks with
precise and conformal layers. In this study, we investigated the effect of an Al2O3 coating on surface strength for
soda-lime-silicate glass, fused silica glass, and borosilicate glass. We characterized the coating and its microstructure by TEM observation. We evaluated the surface strength based on cone-crack-initiation loads (CIL) measured
by Hertzian indentation, and then calculated the Weibull modulus. The surface Youngs modulus and contact
area were estimated by in-situ observation of Hertzian indentation.
The Al2O3 was deposited on polished float glass by ALD without any obvious pinholes and cracks. It showed an
amorphous interface layer in contact with the glass and extending several nm, and then atransition to the alumina crystal structure; ie, ~100 atomic-layer depositions were crystalline to yielded atotal fi lm thickness of 10nm.
In addition, no alkali was detected at the coating surface by XPS measurement for this soda-lime-silicate glass
substrate. The Al2O3 coated samples showed ahigher CIL than the bare substrate although the surface Youngs
modulus did not change due to the coating. CIL increased with coating thickness from 5 to 50nm, and slightly
decreased for coatings greater than 50nm. The degree of improvement in CIL and Weibull modulus with coating
thickness depended on the glass substrate composition. This suggests that the nature of the damage passivated by
the ALD coatings is different amongst the various glass substrates.

272

Oxide glasses irradiated by electrons

Gavenda T.1 , Gedeon O.1 , Jurek K.2
1
2

Faculty of Chemical Technology, Institute of Chemical Technology, Prague, Czech Republic;

Institute of Physics, Academy of Sciences of the Czech Republic, Prague, Czech Republic

Three glasses (float, borosilicate glass and optical glass Schott D263) were irradiated with an electron beam of
50keV. Irradiated glasses undergo changes in the structure, that result in volume changes and changes in surface
roughness. These changes were quantified using AFM method. The incubation period (characterizes the change
of transport mechanism and anticipates depleting of alkali ions from the surface layer) was measured for all types
of glasses. Glasses were consecutively irradiated by the series of electron doses within the range 0.21318.5kC/m2.
Lower doses created depressed areas indicating some structural changes leading to the volume compaction. For
higher doses, acreation of abump in the middle of the exposed area was identified. The bump was rising continuously with adose and at last exceeded the original surface. It is suggested expansion can be contributed by
the creation of new rings including O-O bonds and requiring larger space. Nevertheless, in borosilicate glass the
expansion was not observed. The increase of the surface roughness with an increasing dose was documented for
all three glasses and can be explained on base the surface structural relaxation.

Hork M.1 , Novotn F.1 , Panchartek Z.2 , Star M.1

1
2

Technical University of Liberec, Liberec, Czech Republic;

Sklopan Liberec, a. s., Liberec, Czech Republic

Current requirements to the glass treatment with minimal ecological impact turn the attention to new modern
mechanical processes, which represent new technology. Typical chemical processes are connected with fluoride

ICG Prague 2013 45

292

New trends of flat glass surface mechanical treatment

295

impact and sanding with dustiness. Recently patented glass matting method is one of current examples of this
trend. It disposes of considerable potential for future application in production. This method has awide range of
design modification and it finds its use in the interior as well as in the exterior of modern architecture.
The article submits the theoretical analysis of the new flat glass matting technology. It considers the matting by
abrush mechanism with composite hair enhanced by synthetic diamond. It summarizes results of theoretical
analysis, which deals with interaction of each fibre and glass surface during the dynamical process with impacts.
Subsequently ageneralization of main brush parameters was done, considering the multiple actions to the glass
surface. Finally results of the glass matting experiment are presented and the surface quality is evaluated.

Principles of twofold nucleation

and crystallization in glasses to develop
glass-ceramics with special properties
Hland W. 1 , Beall G. H.2 , Schweiger M.1 , Ritzberger C.1
1
2

Ivoclar Vivadent AG, Li-9494 Schaan, Principality of Liechtenstein

Corning Inc., Research and Development, Corning, NY, 14831, USA

303

The presentation demonstrates main results of basic principles of twofold nucleation and crystallization in glasses shown in the textbook glass-ceramic technology 2nd edition, written by W. Hland and G. H. Beall and
published by Wiley in 2012. These principles of twofold nucleation and crystallization are focused on multicomponent systems of glass-ceramics. The authors report on the possibility to control these mechanisms as parallel
solid state reactions. The system SiO2Al2O3K 2OCaOP2O5F allows the formation of two, chemically different
phases, asilicate phase of leucite-type and aphosphate phase of fluoroapatite-type. The important principle is to
control the surface nucleation on the one hand and the internal nucleation on the other hand.
In contrast to surface and internal nucleation, the authors also demonstrate the principles of twofold nucleation
of both internal-internal and surface-surface nucleation and crystallization mechanisms.
The glass-ceramics show special mechanical properties or controlled CTE. The processing methods of sintering,
molding and machining were applied. Technical products and biomaterials for dental restorations are the most
preferred applications of these products.

Evaluation of corrosion behaviour of structural

ceramics as a material for harnessing geothermal
heat under hydrothermal conditions
Galuskov D.1, Hnatko M.2, Galusek D.1 ajgalk P.2
1
2

Joint Glass Center of the IIC SAS, TnU AD, FChPT STU, and RONA, j.s.c., Trenn, Slovak Republic;
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Bratislava, Slovak Republic

Exploitation of geothermal heat represents an ecologic and renewable source of energy. During drilling process
the hydrostatic pressure increases with the depth of borehole, eventually reaching the critical conditions, if water is used as adrilling fluid. Geothermal water is often saline, with avery high content of mineral salts. More
extensive utilization of geothermal energy is thus prevented by severe scaling and corrosion of structural parts
of drilling rig. Corrosion damage in geothermal systems can be minimized by proper selection of corrosion resistant materials. Liquid phase sintered alumina and silicon nitride ceramics were therefore studied as potential
candidates for the mentioned applications, with respect to their chemical durability under hydrothermal conditions in aqueous sodium chloride solution. Dissolution of the non-oxide ceramics occurred through attack on
the Si-N bonds resulting in ammonia release and formation of the layer of corrosion products. Corrosion effect
augments with time and temperature. Pitting corrosion was observed at the surface in the initial time period of
dissolution. Ytrium oxynitride glassy phase at the grain boundaries remained resistant to attack of the aqueous
solution, while the matrix silicon nitride grains dissolved. The chemical durability of the liquid phase sintered
alumina ceramics at temperatures up to 300C was controlled by corrosion resistance of the grain boundary

46 Glass Surfaces

glass. In this respect the corrosion of model glasses with compositions close to those found at grain boundaries
in liquid phase sintered alumina ceramics was also studied. Experiments with the model calcium aluminosilicate
glasses revealed that increased concentration of calcia had only negligible influence on their corrosion durability
in aqueous environment, especially at temperatures below 290C. Under the conditions of the tests the liquid
phase sintered alumina ceramic was found to be more corrosion resistant than the studied non-oxide ceramics.

315

Formation and properties of an antireflective

glass surface for use in solar energy conversion
Nielsen K. H. 1 , Koynov S.2 , Orzol D. 3, Hultstein E. 3, Carney S. 3, Wondraczek L.1
1

Otto Schott Institute, Jena, Germany

Walter Shottky Institute, Munich, Germany
3
Linde AG, Munich, Germany

For cover glasses used in solar energy conversion, high optical transmission is important for increasing the energy output. Optical transmission of glasses used in photovoltaic modules may be improved through the use of high
purity raw materals and by alteration of the glass surface to reduce reflection losses. Anti reflective thins fi lms of
low refractive index are widely applied for this purpose. For such anti reflective thin fi lms, important properties
include cost as well as mechanical and chemical durability. This work concerns an alternative wet chemical means
of creating such an antireflective thin fi lm and the properties of it.

335

Properties and applications of mixed

alkali bismuth silicate glasses
Jonson B.1 , Karlsson S.1 , Messing M.2 , Wallenberg R.2
1
2

Linnaeus University, Vxj, Sweden;

University of Lund, Lund, Sweden

Unleaded glasses expected to exhibit high densities and low glass transition temperatures enamels have been explored within aglass system in general terms described by the mole fractions 0.25 R 2O 0.16 (RO+R2O3) 0.59
SiO2 where R=Li, Na, K; R=Ba, Zn and R=B, Bi. This correspond to glasses containing up to more than 40%
of weight of Bi2O3.
The thermal expansion coefficient (20300C) within the system ranges from 1114*106K-1 and the glass transition temperatures (Tg) between 410460C. These quantities could be fitted to the chemical composition by
multiple regression analysis with correlation coefficients around 0.9. The determined glass densities were up to
4g/cm3 or even higher.
A possible application of these glasses is the use as enamels in decorated glassware of crystal and lead crystal
stemware products.
Some glass compositions were doped with cerium oxide or cerium compounds in order to investigate the potential of using these dense glasses as candidate scintillating material by monitoring their optical properties in terms
of transmission, emission and luminescence.

354

Glass-metal historical object corrosion

Greiner-Wronowa E.
AGH-Technical University of Science and Technology Faculty of Materials Science and Ceramics,
Department of Glass Technology and Amorphous Coating, Krakw, POLAND;

Corrosion of joint materials are dependent on many parameters. Their degradation is analysed separately for each
component. But their mutual reactions must be taken into consideration. This research is focused on investigation of corrosion products on historical object. Moreover environmental condition influence on their exposition

ICG Prague 2013 47

382

were analysed. Some pieces of old jewellery have been chosen. They were originated from excavated works under
the Main Market Square in Krakw and from Czermno (close to Lublin in Poland). All of them are in different
stage, pointed very advanced technology of glass as well as metal parts. To predict negative environmental influence on object stage some induced corrosion on glass sensors have been done. The originate samples, and corroded sensors were analysed by the following methods: SEM, EDS, SIMS, RS, metallurgical microscopy. Obtained
data from non-destructive methods will inform conservators and help preserve these vulnerable materials in
continued storage and display under ambient circumstances.

Frozen capillary waves on glass surfaces:

The impact of a flow
Brun C.1 , Ciccotti M.2 , Tessier G. 3, Vandembroucq D.1
1

Laboratoire de Physique et Mcanique des Milieux Htrognes (ESPCI), Paris, France;

Laboratoire de Physico-chimie des Polymres et des Milieux Disperss (ESPCI), Paris, France;
3
Institut Langevin (ESPCI), Paris, France

519

The roughness of melted glass surfaces is extremely low, typically below the nanometer range when measured over
amicrometric scale. This roughness has been attributed to the freezing of capillary waves of the liquid interface
in the glass transition temperature range Tg. In this scenario, the amplitude of the roughness is controlled by the
ratio Tg/ where is the interface tension and the height spatial correlations are characterized by adecay in k2
in the spatial frequency space. Moreover, this long-range correlated regime is expected to extend down to alower
cut-off about an interatomic distance and up to an upper cut-off, the capillary length which typically amounts to
afew millimeters in oxide glasses. Surface capillary waves result from the competition between thermal noise and
surface tension in aliquid at equilibrium. We thus wonder if the breaking of this equilibrium conditioned by the
introduction of aflow modifies the spectrum of the surface fluctuations.
Studying industrial soda-lime glass surfaces obtained by float process, we shown that the roughness of glass surfaces frozen under moderate tension i.e. close to the mechanical equilibrium can be quantitatively accounted for
by frozen capillary waves. Indeed, using atomic force microscopy and differential profi lometry we obtained the
expected roughness spectrum with agood agreement for the ratio Tg/.
To highlight the impact of the flow, we measured the roughness of the inner surfaces of capillary fibres obtained
by fibre drawing process. Using AFM we find that the high frequency part of the roughness spectrum is in agreement with the surface capillary waves scenario. Looking for an upper cut-off smaller than the capillary length, we
developed an oil-immersion technique using our differential profi lometer. Results obtained are used to develop
astrategy of loss reduction in holow core photonic bandgap fibres.

Research on the corrosion mechanism

of ECR-glass fibers in acid environment
Jun Xie1 , Xin Mu 1 , Jianjun Han 1 , Kaiwen Hu 1 , Lixiong Han 2 , Yuan Yao2
1
State Key Laboratory of Silicate Materials for Architectures,Wuhan,China
2
ChongQing Polycomp International Corp,Chongqing,China
Glass fiber has aseries of outstanding characteristics, is one kind of structural materials and functional materials. Its
filament diameter is between afew microns and tens of microns. It has been applied to construction, transportation
and other fields due to its good corrosion resistance, high mechanical strength, good insulation and heat resistance.
At present, ECR-glass fiber is drawing more and more attention not only because it does not contain boron and fluoride in its composition, but also it has abetter performance than those of traditional E-glass. In this paper, we investigate the corrosion of ECR-glass fibers in different acids and at different times. By the analysis methods of weighing,
SEM (scanning electron microscopy), AAS (atomic absorption spectroscopy) and EDX (energy dispersive X-ray), we
get the results of weight loss, leaching of cations, surface morphology and surface composition of ECR-glass fibers
and etc. The corrosion mechanism of ECR-glass fibers in acid environment will be explained.

48 Glass Surfaces

Other Properties

ICG Prague 2013 49

 50

031

Atomic mobility in silicate glasses and melts

Claireaux C.1 , Chopinet M. H.1 , Toplis M. J.2 , Roskosz M. 3
1

UMR125 CNRS-Saint-Gobain, Laboratoire Surface du Verre et Interfaces, Aubervilliers, France;

UMR5277 IRAP, Observatoire Midi-Pyrnes, Toulouse, France;
3
Unit Matriaux et Transformations, Universit Lille 1, Lille, France

At many stages of the glass making process and subsequent application, atomic mobility is a key factor. It is
particularly critical during the melting of raw materials to form aliquid and during the cooling leading to glass
formation. Thus, aclear understanding of the factors affecting cation mobility in molten silicate matrices would
help both in optimizing glass composition and synthesis conditions. Here we study this mobility through the
juxtaposition of glasses of contrasting compositions, treated for variable duration at high temperatures. These
experiments have been performed using six pairs of pre-synthesized polished glass plates centred on 63% SiO2,
13% Na2O, 12% Al2O3, 11% CaO. Diff usion couples were designed such that for agiven pair, only two oxide components had initial and opposing step-shaped differences in composition, the other two oxide components being
of constant concentration across the sample. With time spent at high temperature, the compositional step is modified by chemical diff usion, resulting in compositional gradients. The diff usion profi les measured at 1,200C will
be presented together with the resulting diff usion matrix, which describes not only the diff usion of an element in
its own concentration gradient, but also diff usion of agiven element in response to aconcentration gradient in
another element (leading to phenomena such as up-hill diff usion). In this respect, special attention will be paid to
the diff usive coupling between Al and Ca, the latter probably being the charge-compensating cation of alumina
tetrahedra at such temperatures. This approach has the potential to highlight structural interactions present in
heterogeneous molten system that are not easily accessible by spectroscopic methods.

Mascaraque N.1 , Duran A.1 , Munoz F.1 , Seo I.2 , Martin S. W.2
1
2

Ceramic and Glass Institute (CSIC), Madrid, Spain

Materials Science & Engineering (Iowa State University), Ames, united states of america

In the last years, solid state electrolytes have gained much attention for their application in rechargeable lithium
batteries. Solid electrolytes possess several advantages compared to liquid ones, such as being non-contaminant,
do not have flammable organic compounds and aseparator is not needed to prevent physical contact between
both electrodes. Bates and co-workers developed a new amorphous lithium phosphorous oxynitride (LiPON)
suitable to be used as electrolyte in thin-film lithium secondary microbatteries. It has been proved that the nitrogen for oxygen substitution produces an increase of the electrical conductivity as well as an improvement of the
chemical and mechanical stability of the fi lms. Similarly, the nitridation of lithium phosphate glasses gives rise to
the increase of their electrical conductivity.
This work presents astudy on the synthesis of lithium phosphorous oxynitride glasses with variable lithium and
nitrogen contents. Li2OP2O5 glasses with composition between 40 and 55mol% Li2O have been nitrided through
thermal treatment under anhydrous ammonia flow at 750C. The results showed that the increase of conductivity for agiven nitrogen depends on the lithium content, where the conductivity improvement diminishes for
increasing lithium in the glass. Based on the obtained results, lithium phosphate glasses and their nitrided ones
have been selected for their preparation as thin-fi lms through RF magnetron sputtering. The results have demonstrated that the deposition of oxynitride glasses is more difficult to achive and that the highest ionic conductivity
values are obtained in thin-fi lms obtained from lithium phosphate glasses deposited in Argon gas.

ICG Prague 2013 51

039

Processing of thin-film solid electrolytes by RF

magnetron sputtering of lithium phosphate glasses

045

New ferroelectric glass-ceramics

with high dielectric parameters on the basis
of the BaO-B2O3-2AlF33LaF3 system
Nalbandyan K. A., Harutyunyan N. M., Knyazyan N. B.
Institute of General and Inorganic Chemistry of NAS RA,Yerevan, Armenia

058

We theoretically substantiated and experimentally confirmed the possibility of obtaining of ferroelectric glass-ceramics (FGC) with a polar structure and high dielectric parameters on the basis of investigated
BaOB2O32AlF33LaF3 system. As aresult of structural and physico-chemical studies it was revealed that for obtaining of FGC, the most optimal set of properties has the glass with BaLa3Al2B6(O10, F15) composition located in
the field of crystallization of BaLa3[F4/AlB3O5]2F7 compound. For the monophasic crystallization of glasses twostage heat treatment has been chosen, without entering additional catalyst for crystallization. It was revealed that
the maximum values of dielectric constant have glass-crystalline samples, the degree of crystallization of which
is 85%, and the duration of heat treatment is 30 hours. Based on the results of X-ray diffraction and IR-spectroscopic studies of BaLa3[F4/AlB3O5]2F7 compound, the possible dimensional structural model of this compound is
suggested. Designed glass-ceramics have high values of dielectric constant (~10,000), wide temperature range of
the phase transition (T~150C) and relatively low temperature of ferroelectric phase transition (TC4255C) in
comparison with known analogues (TC520540C). anew type of ferroelectric glass-ceramics synthesized on
the basis of alow-melting system have highly reproducible properties, asmall residual polarization, which creates
an opportunity for their widespread use in electronic equipment.

Self-healing glass coating for high

temperature applications
Castanie S.1,2 , Mear F. O. 1 , Podor R.2 , Saitzek S.1 ,
Blach J. F.1 , Ferri A.1 , Desfeux R.1 , Montagne L. 1
1
2

Universit Lille Nord de France, UCCS UMR CNRS 8181, Villeneuve dAscq, France
Institut de Chimie Sparative de Marcoule, UMR 5257 CEA-CNRS-UM2-ENSCM, Marcoule, France

Glass-ceramics are atechnological solution to achieve efficient materials to operate at high temperatures, such as
for enamel protective coatings applications. To overcome cracking of the glass when subjected to thermal cycles,
self-healing is shown to be apromising solution. The self-healing property is defined as the capacity of amaterial
to recover its mechanical integrity and initial properties after destructive actions of external environment or
under internal stresses. Coillot et al. [Coillot et al., Adv. Funct. Mater., 2010] have shown that the self-healing
processing can be obtained in two different ways: autonomous or non-autonomous.
Based on the non-autonomous processing, an innovative approach is to develop self-healing glassy thin films for
protective coating applications such as in the aerospace field. The present study is based on the heterostructure
deposition of glass-ceramics and active particles layers by Pulsed Laser Deposition (PLD). The properties of the
deposited fi lms depend on many parameters during growth such as: number of pulse, frequency, energy density,
atmosphere, temperature of the substrate, target-substrate distance, etc We have shown that highly homogeneous layers of about 100 to 200nm are obtained under high vacuum, at room temperature, using apulse energy
of 225mJ, with atarget-substrate distance varying from 3.5 to 5.5cm.
The characterization of the multi-layers fi lms has been studied using different techniques: (i) film thickness by
ellipsometry, ToF-SIMS, AFM, Castaing microprobe; (ii) homogeneity by Castaing microprobe, XPS; and (iii)
structural characterization by ATR-FTIR spectroscopy. The efficiency of the self-healing effect is demonstrated
by an in-situ experiment performed into an environmental scanning electron microscope (HT-ESEM).

52 Other Properties

148

Chalcogenide glasses and glass-ceramics

in the Cu-As-Te system:
Toward new thermoelectric materials?
Vaney J. B.1,2, Delaizir G. 3, Alleno E. 4 , Piarristaguy A.2 , Monnier J.4 ,
Godart C. 4 , Ribes M.2 , Pradel A.2 , Gonalves A.5, Lopes E. B. 5 , Godart C. 4 , Lenoir B. 1
1

Institut Jean Lamour (IJL), UMR 7198 CNRS Universit de Nancy, ENSMN, France
Institut Charles Gerhardt (ICG), UMR 5253 CNRS-Universit Montpellier 2, France
3
Sciences des Procds Cramique et de Traitement de Surface (SPCTS), UMR CNRS 7315,
Centre Europen de la Cramique, Limoges, France
4
Institut de Chimie et des Matriaux de Paris Est (ICMPE), UMR 7182 CNRS, CMTR, Thiais, France
5
Instituto Tecnolgico e Nuclear, Instituto Superior Tcnico,
Universidade Tcnica de Lisboa, Sacavm, Portugal
2

We report on the thermoelectric properties at room temperature for glass and glass-ceramics with different crystalline fraction in the Cu-As-Te system. Our approach is different from the one conventionally used during the
last ten years and which consists in reducing subsequently the thermal conductivity from existing crystalline materials. Here, we start from materials with very poor thermal conductivity characteristic of chalcogenide glasses
and we undertake to improve their transport properties through the addition of metallic elements (Cu, Ag, etc)
and the creation of nano-crystals through glass-ceramics.
Glass-ceramics including metastable -As2Te3 crystalline phase have been obtained in the Cu-As-Te system
through the Spark Plasma Sintering (SPS) experiments from amorphous powder. Th is non-conventional technique shows recent interesting results about the reduction of treatment time.
Preliminary results indicate that the thermoelectric performances increase as the crystallization proceeds. The
highest power factor of 260W.K-2.m-1 at T=300K has been found for the highest crystalline fraction leading to
amaximum dimensionless thermoelectric figure of merit ZT~0.1.

166

Measurement of the phonic thermal

conductivity of molten glass
Schick V.1 , Remy B.1 , Degiovanni A.1 , Meulemans J.2 , Lombard P.2
1
2

LEMTA/CNRS UMR 7563 Universit de Lorraine, Vandoeuvre-les-Nancy, France;

Saint Gobain Research, Aubervilliers, France

A laser pulse method is implemented to measure the phonic thermal conductivity of molten glass between 1,100C
and 1,500C. aheat flux stimulation controlled in energy and time is generated on the front face of an experimental
cell through ashuttered continuous CO2 laser beam (=10.6m). The temperature rise is measured on the rear
face of the cell by using acooled fast InSb infrared multi-spectral camera (1.55.1m). The liquid sample is placed
in aparallelepipedic hollow cell of 40mm*40mm*6mm (wall thickness of 1mm) made of Platinum/Rhodium (10%).
The choice of the measurement cell geometry is fundamental to be able to estimate both the thermal diffusivity and
the specific heat of molten glass by an inverse method. The 3D numerical model developed for the inversion takes
into account the coupled heat transfer modes (conduction and radiation) that can occur during the experiment, particularly the thermal conductive short-cut through the lateral walls of the cell and the radiative heat transfer within
the molten glass by using aPN (P1) approximation method. In our case, the natural convection in the measurement
cell can be neglected due to the low Rayleigh number. The model is implemented in FlexPDE coupled with Matlab in
order to identify the thermal conductivity of molten glass. First measurements were performed on acell filled with
water at ambient temperature in order to validate the parameters estimation procedure. In asecond time, measurement of the phonic thermal conductivity of amolten glass sample is presented.

ICG Prague 2013 53

175

Preparation of sulfide glass-ceramic electrolytes

for all-solid-state sodium rechargeable batteries
Hayashi A., Noi K., Tanibata N., Nagao M., Sakuda A., Tatsumisago M.
Osaka Prefecture University, Osaka, Japan

176

All-solid-state sodium rechargeable batteries are expected as next-generation energy storage devices with high safety, low
cost and high energy density. Development of solid electrolytes with high Na+ ion conductivity is needed to realize the
batteries. Sulfide glassy materials are promising solid electrolytes because of their high conductivity. However, sodium ion
conducting sulfide electrolytes have not been widely researched so far, compared to lithium ion conductors. Recently, we
have reported sulfide glass-ceramic electrolytes in the system Na2S-P2S5. The precipitation of cubic Na3PS4 phase by heating of the mother glass increased conductivity and the prepared glass-ceramic electrolyte showed an ambient-temperature
conductivity of 10-4 S cm-1. The glass-ceramic exhibited awide electrochemical window of 5 V. All-solid-state Na-Sn/TiS2
cells with the Na3PS4 electrolyte were cycled as asecondary battery at room temperature. To improve cell performance, the
increase in conductivity of solid electrolytes is apriority issue to be solved. In this study, compositions and crystallization
conditions of glass-ceramic electrolytes were examined for achieving higher conductivity. All-solid-state sodium-sulfur
batteries was assembled and characterized as an ultimate high-energy density battery.

Characterization of all-solid-state lithium rechargeable

batteries with sulfide glass-ceramic electrolytes
Tatsumisago M., Nagao M., Aso K., Sakuda A., Hayashi
Osaka Prefecture University, Osaka, Japan

181

Recently, sulfide solid electrolytes with high Li+ ion conductivities of 10-3-10-2 S cm-1, which are comparable to those of
organic liquid electrolytes, have been developed. Sulfide glass-ceramics in the system Li2S-P2S5 are promising solid electrolytes for all-solid-state lithium cells because of their high conductivity and wide electrochemical window. Sulfide
electrolytes have another merit of achieving intimate solid/solid contacts by only cold-press without high-temperature
sintering. All-solid-state lithium batteries using sulphide electrolytes are expected as anext-generation battery with
high safety and reliability. The possible use of active materials with high capacity such as sulfur positive electrode and
lithium negative electrode, which are difficult to use in aliquid electrolyte cell, is another advantage of all-solid-state
batteries. In this study, characterization of electrochemical performance and reaction mechanism for all-solid-state
cells with the combination of sulfide glass-ceramic electrolytes and several kinds of active materials was examined.
Several approaches to forming afavourable electrode-electrolyte interface will be demonstrated.

Fabrication of TiO2-crystallized glass

for photocatalytic material
Yoshida K.1 , Masai H.2 , Takahashi Y.1 , Ihara R.1 , Fujiwara T.1
1
2

Tohoku University, Sendai, Japan;

Kyoto University, Uji, Japan

From viewpoint of both energy and environment, establishment of the production method of clean hydrogen
energy is one of the most important subjects. Since photocatalytic materials can split water into hydrogen and
oxygen by light absorption, photocatalysts are expected as novel hydrogen source. For practical use, an ideal
material has visible light reaction, high photocatalytic activity, and good chemical durability. Especially we
have focused on improvement of catalytic activity by using porous glass which is fabricated by phase separation
and chemical etching of glass. Because photocatalytic reaction occurs at the surface of material, porous glass with
high specific surface area has an advantage of catalytic reaction.
Recently, we have succeeded in preparing Sr0.5Ba0.5Nb2O6 (SBN50)-precipitated glass by acid etching via aglass-ceramic process using SrO-BaO-Nb2O5-B2O3-ZnO-SiO2 glasses. Also, we have found that the SBN50-precipitated
ceramic exhibits photocatalytic activity, which is the first report on the activity of SBN50.

54 Other Properties

If porous glass is applied to TiO2-crystallized glass, we can fabricate novel bulk photocatalyst which has high catalytic activity equal to powdered TiO2 photocatalyst. In this study, we have prepared TiO2-crystallized glass using
TiO2-B2O3-ZnO-Al2O3 glasses. Crystallized samples were etched by HCl solution at room temperature. We discuss
the relationship between inner structure and chemical durability, photocatalytic properties of prepared samples.

197

Impedance spectroscopy of zirconia

containing silicate glasses
Plko A.1, Zemanov V.1, Faturkov K.2, Lissov M.1, Pagov J.3, Lika M.2, Karell R.2
1

Alexander Dubek University of Trenn, Trenn, Slovakia;

Vitrum Laugaricio Joint Glass Center of IIC SAS, TnUAD, FChPT STU, and RONA, Trenn, Slovakia;
3
Faculty of Industrial Technologies, Alexander Dubek University of Trenn, Pchov, Slovakia

The glasses which are significant dielectrics are widely used in electronic industry. For these applications, it is necessary to understand not only the relation between dielectric properties of glasses and their composition but also
the relation between the given property and temperature. We have studied glasses from SiO2-Na2O-CaO-ZrO2 and
SiO2-Na2O-ZnO-ZrO2 systems. Amount of ZrO2 in both systems was changed, as follows: 0, 1, 3, 5 and 7mol.%, respectively. Dielectric properties were measured by the impedance spectroscopy at the temperatures ranging from
laboratory temperature to 450C. The frequency was changed in the range from 50Hz to 1MHz. First, the measured
spectra were evaluated by using equivalent circuits. Then the activation energies of relaxation processes were calculated from temperature dependences. Results were discussed from the aspect of glass compositions.
Acknowledgement: This work was supported by the Grant Agency of the Slovak Republic Grant No. 1/0006/12,
project APVV-0487-11 and the project PVTECHSKLO, ITMS code 26220220072, of the Operational Program
Research and Development funded from the European Fund of Regional Development.

248

Tellurium-based thermoelectric bulk glasses

Lucas P.1 , Conseil C.2 , Hao Q.1 , Bureau B.2 , Boussard-Pledel C.2 , Caillaud C.1,2
1
2

University of Arizona, Tucson Az, USA

University of Rennes I, Rennes, France

Telluride glasses are usually of interest for the development of infrared optical materials due to their good transparency to long wavelengths. More recently, several types of fully stable bulk telluride glasses with an unusually
high electrical conductivity were synthesized for the development of electrophoretic optical elements. In the
present study, the application of these glasses for the production of high efficiency thermoelectric material is investigated. These glasses combine high electrical conductivity and particularly low thermal conductivity because
of their highly disordered structure as well as the relatively low phonon energy resulting from heavy atoms like
Te. The conductivity can be tuned by doping and alloying with metallic elements in order to optimize their thermoelectric properties. The combination of high electrical conductivity and low thermal conductivity shows good
promises for the development of high-efficiency, low-temperature thermoelectric devices.

262

Influence of GeO2 on lithium ion transport

in lithium borophosphate glasses
Mogu-Milankovi A.1 , Sklepi K.1 , Blaanovi H.1 , Moner P.2 , Vorokhta M.2 , Koudelka M.2
1
2

Ruer Bokovi Institute, Department of Chemistry, Zagreb, Croatia

University of Pardubice, Faculty of Chemical Technology, Pardubice, Czech Republic

The frequency and temperature dependences of the electrical conductivity and dielectric permittivity of the Li2OB2O3-P2O5-GeO2 glasses have been investigated in the 0.01Hz to 1MHz frequency range and over the temperature range from 183 to 523K. The observed increase in dc conductivity with addition of GeO2 is aresult of the

ICG Prague 2013 55

293

depolymerisation of phosphate chains and incorporation of Ge atoms into network which enables formation of
the continuous channels for an easier migration of lithium ions. The frequency dependent ac conductivity was
described using Jonschers power law. The temperature dependent behaviour of the frequency exponent (s) suggested that the correlated barrier hopping model was the most appropriate to explain the electrical transport in
studied glasses. The dielectric properties have been analyzed in the framework of complex dielectric permittivity
and complex electrical modulus formalisms. The evolution of the complex permittivity as afunction of frequency
and temperature has been investigated. The thermal activated relaxation mechanism dominated the observed
relaxation behaviour. The activation energy associated with dielectric relaxation was almost identical to that of
dc conductivity suggesting that the similar energy barriers are involved in both processes.

Electrical properties of phosphate glasses

containing Cu nanoparticles
Mugoni C.1 , Montorsi M.1 , Siligardi C.1 , Jain H.2
1
2

Department of Engineering Enzo Ferrari (DIEF), University of Modena and Reggio Emilia, Italy
Department of Materials Science and Engineering, Lehigh University, Bethlehem, Pennsylvania (USA)

310

Glassy nanomaterials rapidly gained an increased research interest during the last few years, due to their wide spectrum of different technological uses, mainly as optical non-linear materials for optical, switching, and computing applications. The This work focuses on the preparation of metal copper nanoparticles in lithium phosphate glass matrix,
in order to obtain metal nano-composites with multi-functional properties. Lithium phosphate glasses doped with
copper (Cu2O) and tin oxide (SnO) were prepared by the melt quench method. 50Li2O50P205mol% glass system was
used as matrix, and Cu2O and SnO, at 3 and 5mol%, were selected as the redox couple, the latter acting as the reducing
agent. The batch materials were melted in platinum crucibles and the obtained glass samples were treated at different
temperatures and times. The addition of SnO and the subsequent heat treatments were exploited to convert some of the
copper ions into metal copper nanoparticles. The mechanism of electrical conduction in such novel nano-composites
was explored by means of impedance spectroscopy as afunction of temperature. Different characterization techniques
such as X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and
UV/VIS spectroscopy were performed to accurately examine the presence of metal copper nanoparticles. Size, shape
and the degree of dispersion of nanoparticle the glassy matrix were deeply investigated. Finally, the effect of structural
changes (which largely depend on the thermal treatments employed) on the electrical conductivity was determined.

Methodic aspects on hydrogen permeability

Ried P. 1 , Gaber M. 1 , Mller R. 1 , Meyer R. 1 ,
Grschl Ch. 1 , Schmidtchen U. 1 , Pflaum S. 2 , Deubener J. 2
1
2

BAM, Federal Institute of Material Research and Testing;

Technical University, Clausthal

Hydrogen is acapable energy carrier to store the electrical energy surplus resulting from energy production by
wind and solar energy in chemical energy due to its high gravimetric energy density. Corrosion stable, pressure
resistant glasses offer apromising opportunity for long term hydrogen storage e.g. at high pressure in glass capillaries. ahigh efficiency and compared to conventional pressure vessels, the light weight and safe handling are the
key advantages. Until now the development of such energy storage devices is limited to commercial compositions.
In this context, investigations of hydrogen permeation and diffusion can provide important fundamental knowledge to evaluate the applicability of avariation of glass compositions.
Different sample geometries as bulb shaped, capillaries, as well as powders can be used as measurement methods. The experimental operability and the sensitivity of each geometry were evaluated. Limiting factors are e.g.
wall thickness of small glass bulbs, availability of glass capillaries and adefined grain of powders. High pressure
hydrogen charging was applied to enhance the sensitivity of the vacuum hot extraction coupled with MS. The
obtained results are compared emong each other as well as with literature data. Additionally, the applicability of
glass capillaries to store high pressure hydrogen was evaluated by high pressure bursting tests.

56 Other Properties

324

Influence of doping on the properties

of Ge-Sb-Te glassy thin films
Sherchenkov A. A. 1 , Kozyukhin S. A.2 , Babich A. V.1 ,
Lazarenko P. I.1 , Nguyen H. P.2 , Veres M. 3, Chigirinsky Yu. I.4
1

National Research University of Electronic Technology, Moscow, Russia;

Kurnakov Institute of General and Inorganic Chemistry
of the Russian Academy of Sciences, Moscow, Russia;
3
Institute for Solid State Physics and Optics, Wigner Research Centre for Physics, HAS, Budapest, Hungary;
5
Scientific-Research Physicotechnical Institute at the Nizhnii Novgorod State University,
Nizhnii Novgorod, Russia
2

Despite the successful application of chalcogenide glassy semiconductors of Ge-Sb-Te system in phase change memory (PCM) devices, PCM technology is needed to be improved. The aim of this study is to investigate the influence
of In, Ti, Sn, and Bi doping on the thermal, electrophysical and optical characteristics, and cyclability of Ge2Sb2Te5
glassy thin films used in PCM devices. The glassy thin films were deposited by two different methods: the thermal
evaporation of synthesized materials in vacuum and using RF-magnetron sputtering. The composition and phase
state of thin films were studied by different diagnostic techniques. Differential scanning calorimetry was used to
study the thermal properties of the materials. Raman scattering spectroscopy ( = 30450cm-1) and spectral ellipsometry (=3801,050nm) were used to study the optical properties. Doping of Ge2Sb2Te5 with In, Ti, Sn, and
Bi impurities can change phase transition temperature, thermal, electrophysical and optical characteristics, and
sufficiently improve stability during thermal cycling of the chalcogenide glassy semiconductors. The existence of
two concentration ranges with different doping mechanisms, and the influence of dopants on the properties of thin
films were established. Anomalous deviations of properties from main tendencies were observed in the range of low
concentrations (0.51.0 wt.%). This effect is explained using of percolation theory: there is an impurity concentration
at which will be formed acluster of finite size. The increase of concentration leads to the increase of the size of cluster
accompanied by the creation at critical concentration and appearance of the infinite cluster consisting of overlapping
spheres. The formation of infinite cluster is accompanied by critical phenomena.
This work was supported by Ministry of Education and Science of RF (SCs 8437, 7086) and RFBR (11-03-00269).

Ramesh K., Gopal E. S. R.

Department of Physics, Indian Institute of Science, Bangalore, India.

A unique electrical switching behaviour has been observed in bulk Cu x As30Se70-x glasses prepared over awide
range of composition (0 x 35). For x < 15, the glasses do not exhibit switching, whereas glasses in the range
15 x < 25 show athreshold type switching. An unusual switching from low resistance to high resistance state is
observed for the glasses in the range 25 x < 30. When the concentration of Cu is 30, the glasses are found to
show memory switching. These glasses were thermally crystallized in two ways to understand the different kinds
of switching behaviour observed. First the glasses were crystallized by annealing at their respective crystallization temperatures (Tc). Second the glasses were heated up to their melting temperatures (Tm) under vacuum and
cooled back to room temperature. Samples annealed at Tc, shows the formation of Cu3AsSe4 phases only for the
entire range of composition. On the other hand samples crystallized by melting showed Cu3AsSe4 for the composition range 0 x 20 and for 25 x 35, Cu3AsSe4 and Cu3AsSe3 phases were observed.
Normally, the memory switching is explained by the models based on thermally induced transitions and threshold switching is explained by the models based on the electronic transitions. The present studies provide aunique
way to understand both the threshold and memory switching based on the thermal model and fi lament formation. This study also indicates that the crystalline phases formed from the melt state are responsible for switching.
Hence, at the time of switching the sample in between the electrodes undergo the phase change by glass melt
crystal transformation and not by the direct glass crystal transformation.

ICG Prague 2013 57

481

Unique electrical switching in Cu-As-Se glasses

561

Electrical field assisted viscous flow accompanied

by electrical conductivity and photoemission
in a sodium aluminosilicate glass
Scipioni U.1 , Sglavo V. M. 1 , Ito S.2 , Raj R. 3
1

University of Trento, DIMTI, Trento, Italy;

Tokyo Institute of Technology, Yokohama, Japan;
3
Department of Mechanical Engineering, University of Colorado, Boulder (CO), USA

569

It is shown that the application of modest electrical fields, in the 100300V/cm range, has adramatic influence
on the fluidity of asodium aluminosilicate glass at temperature below the nominal softening temperature. The
nature of this viscous flow also differs from the conventional one and the glass becomes abruptly fluid. Moreover,
this phenomenon is accompanied by ahighly non-linear increase in electrical conductivity as well as by intense
photoluminescence. The luminescence has a distinct peak near or at the Na doublet, superimposed on white
emission. The possible ways of explaining the underlying physics of this new finding will be discussed.

Glass sealing materials and technologies

for SOFC stack manufacturing
Pascual M. J.
Instituto de Cermica y Vidrio (CSIC), C/Kelsen 5, Campus de Cantoblanco, 28049 Madrid, Spain

One of the major challenges for the commercialization of planar solid oxide fuel cells (SOFC) is the development of reliable sealing materials suitable for separating the anode and cathode chambers and maintaining the
gas-tightness of the system at high temperatures, 6001,000C. The sealants are applied to the cell edges, between the interconnects and the electrolyte and/or electrodes, depending on the type of design, and also to the
gas manifolds to join them to the sintered cell. The crucial requirements of the sealants are thermo-mechanical
and chemical stability, negligible physical and electrochemical gas leaks during cell operation, and a thermal
expansion coefficient similar to that of the other components (9-13x10-6K-1). Several approaches have been used,
including rigid bonded, compressive and compliant bonded sealings. The most common approach is the use of
rigid vitreous or glass-ceramic seals. The processing of these materials normally implies the sintering and crystallization of glass powders. The compositions of the BaO-Al2O3-SiO2 (Pacific Northwest National Laboratories,
USA) and CaO-BaO-Al2O3-SiO2 systems (RWTH and Jlich Research Centre, Germany) are notable examples.
apromising combination of physical-chemical properties was also obtained in the ZnO-MgO-BaO-B2O3-SiO2
system in the CSIC (Spain). However, given that these materials are inherently fragile, metal, metal-ceramic and
ceramic-ceramic sealants of both types rigid and compressive have also been studied. The use of multi-phase
sealants makes it possible to enhance wetting capacity, adapt the interphases and eliminate tensions, as well as
improving gas-tightness and stability. In the last decade, numerous papers and reviews of this topic have been
published and this work will initially analyze these highlighting present studies and advances.
In addition to the design of new glass sealing materials, for example glass-ceramics without BaO, the main
current goal is the improvement of the mechanical and self-healing properties of already developed materials,
and the characterisation of the sealing ability and durability in fuel cell simulators. Post-mortem study of the
joining allows the reactivity between materials, as well as the performance in working conditions, to be characterised. It is still necessary to optimize the processing of materials, stability on long-term thermal cycling,
chemical compatibility with the components (particularly metal interconnect plates) and atmospheres, and
gas-tightness behaviour. The applicability of laser-induced glass welding for proper sealing and/or repairing
purposes, especially for lightweight stacks, is also of increasing interest. All these aspects will be discussed for
the glass-ceramics materials developed in the CSIC.

58 Other Properties

Crystallization

ICG Prague 2013 59

 60

029

Isothermal and non-isothermal

crystallization of a fresnoite glass
Rodrigues A. M.1 , Mercury J. M. R. 1,2 , Leall V. S. 3, Cabrall A. A.4*
1

Postgraduate Program in Materials Engineering

Department of Chemistry DAQ, Federal Institute of Maranho IFMA
3
Department of Mechanical and Materials Engineering DMM, Federal Institute of Maranho IFMA
4
Department of Physics DEFIS, Federal Institute of Maranho IFMA,
65030-001 So Luis, MA, Brazil, *aluisio_cab@yahoo.com.br
2

Several analytical models have been widely applied to determine the activation energy of crystallization, E, and
the Avrami index, n. In this work, the parameters E and n for the crystallization of fresnoite (2BaOTiO22SiO2)
glass were calculated using different approaches (Ozawa, Kissinger, and Matusita & Sakka). Monolithic glass
samples ( 36mg) were heated in aDSC furnace from room temperature to 650C at 40C/min, and held at that
temperature for 5min. To induce the formation of new nuclei mostly in the nucleation zone, these samples were
heat-treated in the temperature range of 650C to 750C at heating rates of 10C/min and 20C/min. They were
then reheated at different heating rates (c=6, 8, 10, 15 and 20C/min) until they became completely crystallized.
The experiments were carried out in aDSC furnace under an argon atmosphere (20ml/min), using Pt crucibles.
Additionally, to confirm the Avrami coefficient and the predominant crystallization mechanism, the evolution
of the crystallized fraction over time was determined independently by powder X-ray diffraction of the fresnoite
glass. In this case, the samples were heat-treated in atubular furnace at 720C for different lengths of time. The
Avrami index obtained by the non-isothermal DSC and XRD experiments are in excellent agreement and demonstrate that fresnoite crystallizes predominantly in the volume and occurs by simultaneous crystal nucleation
and growth. The activation energy of crystallization predicted by Kissinger and Matusita & Sakkas models was
EC=(68822)kJ/mol, and ECK=(94070)kJ/mol, respectively.

050

Laser bonding of sapphire wafers

using a fresnoite-glass sealant
De Pablos-Martin A. 1 , Ebert E.1 , Lorenz M.2 , Grundmann M.2 , Hche T.1
1
2

Fraunhofer Institute for Mechanics of Materials IWM, Halle, Germany

Institut fr Experimentelle Physik II, Universitt Leipzig, Linnstr. 5, 04103 Leipzig, Germany

The development of micro electromechanical systems, MEMS, is on-going. Novel reliability requirements particularly affect basic assembly processes. Localized bonding and hermetic sealing of materials (e.g. after patterning) is asignificant issue in several microsystems-technology applications, for example, for electrically insulating
hermetic seals, sealants in solid oxide fuel cells (SOFC), or new applications including low-temperature bonding
of dissimilar wafers for BioMEMS, e.g. in ambient assisted living applications.
Glass-ceramics offer excellent properties for sealing applications. While in the past, sealings based on glass-ceramics have been based on very slowly crystallizing glasses, rapidly crystallizing glasses are looked for in the
context of local, transient heat generation. Prime candidate glasses are fresnoite (BTS) based glasses, since they
possess an extremely high nucleation rate, which leads to avery fast crystallization process.
BTS thin fi lms of about 2m thickness were grown on asapphire substrate by pulsed laser deposition (PLD) using
aKrF excimer laser (248nm).
One sapphire substrate was placed over aBTS-coated sapphire substrate, and laser direct writing was performed
by focusing apulsed Nd:YAG laser (1.064nm) on the fresnoite thin film surface between both substrates. By varying the laser parameters (power, scan speed, passes, etc.), the optimization of these experimental parameters was
carried out, in order to promote energy accumulation in the focal point. It is shown that the laser irradiation leads
to alocal heating which melts the fresnoite glass, sealing both sapphire substrates upon cooling.
The structure and morphology of the written patterns were characterized by SEM and EDX. The quality of the
obtained bonds was proofed by Scanning Acoustic Microscopy (SAM).

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067

Nano-crystalline tin phosphate glass

for lithium-ion battery anode
Yamauchi H., Nagakane T., Ohji M., Sakamoto A.
Nippon Electric Glass, Otsu, Japan

085

Lithium-ion rechargeable batteries (LiBs) mainly consist of cathode, anode, electrolyte and separator. To realize
safe and compact batteries with high energy density, which are required for automobiles and large scale energy
storage, development of new electrode materials with improved performance is necessary. We have developed
atin phosphate glass for the anode of LiBs as areplacement of conventional graphite anode. This glass is converted to apolycrystalline material with tin nano-crystals by electro-chemical reaction during the first charge
process. In the course of charge/discharge process, the nano-crystals act as reversible occlusion sites for Li ions.
This material exhibits larger capacity and better low-temperature performance than those of existing graphite
anode as well as long-term stability. The structure and property of this material and the performance of the LiB
fabricated with this material will be presented.

New transparent strontium aluminate and gallate

ceramics: Synthesis and characterisation
Al Saghir K.1,2 , Alahrache S.1,2 , Chenu S.1,2 , Ocana Jurado M. 3, Matzen G.1,2 , Allix M.1,2
1

CEMHTI laboratory, CNRS UPR 3079, 1D Avenue de la Recherche Scientifique,

45071 Orleans Cedex 2, France;
2
Faculte des Sciences, Universite d Orleans, Avenue du Parc Floral, 45067 Orleans cedex 2, France;
3
Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Avenida Americo Vespucio s/n,
Isla de la Cartuja, 41092 Sevilla, Spain

089

Transparent ceramics obtained by full crystallization from glass are an emerging class of photonic quality materials competing with single crystal technology, especially for optical properties applications, due to their great
capacity to combine the easy shaping, high density and low cost synthesis. In this work, we show that we have
succeeded to prepare transparent Sr3Al2O6 and Sr3Ga2O6 ceramics by full crystallization from the parent strontium aluminate (75SrO-25Al2O3) and strontium gallate (75SrO-25Ga2O3) glasses synthesized by aerodynamic
levitation coupled to laser heating devices. Tg and crystallization temperature were determined using differential
scanning calorimetry, powder X-ray diff raction was used to study the nature of the crystallized phases and the
microstructures of the transparent ceramics were studied by transmission electron microscopy. No porosity, thin
grain boundaries and micron scale size of the crystallites were observed. The high transparency (>80%) of the
ceramics is then discussed from these results. As an example of the diverse optical properties of these materials,
we show that the as-prepared Sr3Al2O6 and Sr3Ga2O6 ceramics can exhibit tunable luminescence emissions depending on the doping agent used.

Laser patterning of optical active crystals with high

orientation in glasses and crystal growth mechanism
Komatsu T., Suzuki F., Ogawa K., Honma T.
Nagaoka University of Technology, Nagaoka, Japan

Laser irradiation to glass has been regarded as aprocess for spatially selected structural modification and/or crystallization in glass. The laser-induced crystallization method was applied to pattern optical active crystals such
as nonlinear optical -BaB2O4 (-BBO) and ferroelastic -Gd2(MoO4)3 crystals in glasses. For instance, -BBO
crystals were patterned in the inside of bulk plates and fibers (diameter: 450m) of 8Sm2O3-42BaO-50B2O3 glasses,
in which the focal position of continuous wave Yb:YVO4 fiber lasers (power: 0.9~1.0W, scanning speed: 2m/s)
with awavelength of 1,080nm was moved from the surface to the inside. It was confirmed from second harmonic
intensity measurements and transmission electron microscope observations that -BBO crystals patterned are
highly oriented, i.e., c-axis orientation, along the laser scanning direction. The present study proposes the direct

62 Crystallization

and simple processing for the fabrication of glass fibers consisting of optical functional crystal cores, in which
it is not necessary to draw fibers with core and clad structure prior to crystallization. The curved and bending
-BaB2O4 crystal lines were also patterned by just changing the laser scanning direction. The crystal growth
mechanism in laser-induced crystallization is proposed, in particular, from the points of temperature gradient
and its movement induced by laser heating.

091

Synthesis and laser patterning of Bi2ZnB2O7 crystal

and their morphology in ZnO-Bi2O3-B2O3 glasses
Inoue T., Honma T., Komatsu T.
Department of Materials Science and Technology, Nagaoka University of Technology, Japan

ZnO-Bi2O3-B2O3 glasses have received much attention because of their unique properties such as low melting
temperature and high refractive index (large optical basicity). In addition, the crystallization behavior is also
interesting. For their practical applications, it is of important to clarify their thermal stability and crystallization behavior. However, crystallization behavior of ZnO-Bi2O3-B2O3 glasses has been studied only alittle. It is
known that Bi2ZnB2O7 crystal (BZB) synthesized by asolid-state reaction exhibits alarge second harmonic (SH)
intensity. In this study, we attempted to synthesize nonlinear optical BZB crystals through the crystallization
of ZnO-Bi2O3-B2O3 glasses and to pattern crystal lines consisting of BZB by laser irradiation. Furthermore, the
morphology of laser patterned crystal line was observed directly by transmission electron microscope (TEM).
Glasses with the compositions of 33.3ZnO-33.3Bi2O3-33.3B2O3 and 50ZnO-20Bi2O3-30B2O3 were prepared by melt
quenching technique using platinum crucible and were heat-treated at around crystallization temperature. It was
found from X-ray diff raction analyses that both glasses show asurface crystallization behavior and the main
crystalline phase is BZB. The laser patterning of BZB crystals on the surface of Sm2O3-ZnO-Bi2O3-B2O3 glasses
was succeeded by irradiations of Yb:YVO4 fiber laser (wavelength: 1,080nm). The orientation and morphology of
BZB in the patterned lines was confirmed from the Azimuthal dependence of SH intensity and TEM observation.

Honma T., Sato A., Togashi T., Ito N., Komatsu T.

Nagaoka University of Technology, Japan

Recently, poly-anion based LiFePO4 has been much attracted because of its remarkable electrochemical storage
properties for the next generation lithium ion second battery. LiFePO4 has superior thermal and electrochemical
stability compared with conventional LiCoO2, LiMn2O4 cathode materials. The capacity of battery package in electrical vehicle (EV) requires over than 10kWh, therefore pretty much lithium resources will be required. However,
lithium resources contain only 20ppm in the earths crust. In near future the problem concern about materials cost
must be happening. On the other hand the other alkaline and alkaline earth ion based second batteries are proposed. In especially sodium ion is being just under the lithium in periodic table and exhibits higher voltage (2.7V for
Na/Na+) after lithium ion (3.03V for Li/Li+). By using crystallization process of glass materials, it is easy control
crystal morphology and size distribution from uniform glass matrix. We are proposing unique technique to fabricate phosphate based cathode materials such as olivine LiFePO4 and NASICON Li3V2(PO4)3 ceramics by crystallization process from glass precursor. Precursor glass has very homogeneous compositional distribution hence we
obtained any ferromagnetic byproduct free LiFePO4 which working even in the high current density condition.
We found new cathode candidate Na 2FeP2O7 triclinic P-1 crystal that fabricated by glass-ceramics process.
In this study we discuss the crystallization behaviour and electro-chemical performance on Na 2FeP2O7 glass
ceramics-carbon composites.

ICG Prague 2013 63

115

Na2FeP2O7/C glass-ceramics for sodium ion batteries

136

Physical-chemical research of glass formation

and crystallization in the ZrF4-SnF2-NaPO3-MF3,
ZrF4-BaF2-NaPO3-MF3 (M = Ga, In, Bi) systems
Alexeiko L. N.1 , Kavun V. Ya.2 , Kharchenko V. I.1,2 ,
Maslennikova I. G.2 , Yaroshenko R. M.2 , Telin I. A.2 , Goncharuk V. K.2
1
2

Far-Eastern Federal University, Vladivostok, Russia;

Institute of Chemistry, FEB RAS, Vladivostok, Russia

153

Systematic research of aglass formation was carried out in the ZrF4-SnF2-NaPO3-MF3 and ZrF4-BaF2-NaPO3-MF3
(M=Ga, In, Bi) systems. It was found that glasses were obtained in these systems in awide range of trifluoride
concentrations. Physical-chemical study of processes at the glass-nanocrystal-polycrystal transition was fulfilled
in some of the obtained glasses. Using DSC, DTA, X-ray diffraction and electron microscopy data, the conditions
were determined for aformation of transparent glass-ceramic materials. aseries of physical-chemical studies of
changes in the structure and thermal properties of glasses was carried out in the temperature range from the glass
transition temperature to the crystallization temperature. XRD data showed that after heat treatment, depends
on the treatment temperature and duration, avariety of micro-crystals were formed which composition was determined. Nano-sized crystallites were obtained by controlled crystallization of glasses through inhomogeneous
nucleation and growth during reheating.Using thermal analysis, XRD and transmission electron microscopy,
the phase separation was studied as afunction of composition of the glass precursor and heat treatment.The
processes were studied of introduction and distribution of optically active additives (Rear Earth elements) in the
glass matrix. NMR and impedance spectroscopy was used to research amobility of fluoride ions.

Nucleation in lithium aluminosilicate

glass-ceramics (LAS) studied by optical spectroscopy
Donfeu T. R.1 , Pfeiffer T.2 , Ruedinger B.2 , Deubener J. 1
1
2

Institute of Non-Metallic Materials, Clausthal, University of Technology, Germany;

Research and Technology Development, Schott AG, Mainz, Germany

171

The efficient development of glass ceramics with homogeneously dispersed and nanograined crystals depend on the
detailed understanding of nucleation rates and its dependence on time, temperature and chemical environment. In
the past, spectroscopic and imaging methods like Raman spectroscopy, XANES or HRTEM helped to characterize
the nucleation process of zircotitanate (ZrTiO4) in ZrO2- and TiO2-bearing LAS glass-ceramics. In this work it will
be demonstrated that the nucleation of ZrTiO4 can also be quantified and by analysis of spectroscopic data from the
UV-Vis-region. In this analysis both the scattering power of the nuclei as well as their absorptive properties were
determined. Thus, alink between the number of newly formed nuclei and its kinetic parameters can be deduced.

Photo-structural transformations
in photo-thermo-refractive glass
Glebova L.1 , Klimov M.2 , Chamma K. 3, Glebov L. B. 3
1

Optigrate Corp., Oviedo, FL, USA

AMPAC, University of Central Florida, Orlando, FL, USA
3
CREOL, University of Central Florida, Orlando, FL, USA

Photo-thermo-refractive (PTR) glass is a multicomponent silicate glass that shows refractive index change after
exposure to UV radiation followed by thermal treatment at temperatures exceeding Tg. This feature is successfully
used for volume holographic optical elements fabrication. It is known that refractive index change is caused by mechanical stresses produced by precipitation of crystalline phase of NaF in the areas exposed to UV radiation. This
work is directed to study the structural transformations occurred in PTR glass at different stages of optical and thermal treatment. Transmission electron and optical microscopy, X-ray diffraction, differential scanning calorimetry,

64 Crystallization

secondary ion mass spectroscopy, and optical spectroscopy were used for this study. Structural transformations of
UV exposed and original glasses under high voltage electron beam were investigated at different stages of optical
and thermal treatment. Special efforts were directed to development of reliable measurement techniques applicable
to photosensitive multicomponent glass where structure could be easily modified by electron or ion beams or by
ionizing radiation. The shape, sizes, volume, and composition of crystalline phase along with transformations of
vitreous phase were detected at different stages of optical and thermal treatment. It was found that initial shape of
nanocrystals is pyramidal with length about 80nm and aspect ratio about 5. The study of these features was combined with the investigation of induced absorption and refractive index at different stages of the treatment. The role
of structural transformations in formation of stable refractive index change is discussed.

245

Why does single-domain crystal form in

nonstoichiometric glass?: Micro and nanoscopic
study in fresnoite glass-ceramics
Takahashi Y., Yamazaki Y., Yamaoka K., Ihara R., Fujiwara T.
Department of Applied Physics, Tohoku University, Sendai, Miyagi, Japan

Glass-ceramics (GC) is material obtained from the crystallization of functional phases in glass. To synthesise stable
precursor glass, the composition is often selected from systems in which typical glass-forming oxides are added
to afunctional (e.g., ferroelectric) phase, resulting in nonstoichiometric glass. On the other hand, the nonstoichiometric precursors apparently form uniform crystalline domain texture, which is sufficient for light propagation
via annealing/laser-irradiation. However, these facts give asimple question; how does GC permit the presence of
residual glass phase resulting from the addition? In order to clarify this issue, we prepared perfectly surface-crystallized GC consisting of single phase of fresnoite-type Sr2TiSi2O8 from anonstoichiometric glass and performed
texture/morphology observations. As aresult, we demonstrated that numerous SiO2-rich binodal-like nanoparticles (~10nm) were parasitic on the fresnoite single-crystal domains. The parasitic texture is considered to form via
the following process, i.e., (i) binodal-type phase separation into stoichiometric fresnoite (matrix) and SiO2-rich
phases (amorphous nanoparticles) followed by (ii) single-domain formation by surface crystallization in the matrix
through geometrical selection process. Usual transparent GCs have astructure that the nanocrystalline phase embedded in the glass matrix. The resulting GC in this study differs from the GCs to date, i.e., inverse GC.

258

Synthesis of Xenotime (YPO4) via

reaction with glass frits
Morena R., Lamberson L.
Corning Incorporated, Corning, NY 14831 USA

The rare earth orthophosphate xenotime (YPO4) is notable for its refractoriness (Tmelt=2,150). Its close-packed
structure with alternating PO4 and YO8 groups bonded together in an edge-sharing configuration suggests excellent creep resistance and potential as ahigh temperature structural ceramic. However, synthesis of phase pure
xenotime with adense microstructure is difficult by both the standard ceramic route because of high processing
temperatures, and by the glass-ceramic route because of high liquidus temperatures for glasses with the xenotime
composition. (It is also unlikely that abinary 50% Y2O3-phosphate mixture would form astable glass). This paper
describes the synthesis of xenotime via reaction with a glass frit using a schema (reactive-ceramming) that
consists of reacting alow temperature precursor glass frit with 1 or more reactants to achieve the stoichiometry
of the desired, much higher refractory phase, i.e.:
frit + reactant(s) desired crystalline phase.
Precursor Y2O3-P2O5 glasses for reactive-ceramming were prepared by melting glasses in the low liquidus (1,200
1,300), high P2O5 (8085mol%) portion of the binary using reagent grade phosphorus pentoxide and yttrium oxide
as raw materials. The compositions formed nice, fluid glasses that cooled without any evidence of stickiness or other
signs of hydroscopicity. Frits were prepared from the glasses by standard dry ball-milling techniques to give apowder with d50=510m. Following ball-milling, the frits were mixed with additional reagent grade yttrium oxide to

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attain the YPO4 stoichiometry. Phase pure xenotime was successfully prepared using the reactive-ceramming route
from the precursor frits. Xenotime began to form over abroad temperature range beginning at 850. At 1,200 it
constituted the major phase, with just asmall amount of unreacted Y2O3 present. Phase pure xenotime was obtained
at temperatures as low as 1,400, without any evidence of unreacted Y2O3, or residual glass (there were, however,
three unidentified very minor XRD peaks which persisted throughout the entire thermal process; these essentially
disappeared when the stoichiometry was adjusted to be slightly P2O5-enriched). Extremely dense microstructures
with very coarse grain size (1025m) were obtained by iso-pressing the reactive-ceramming mixture and then
firing. Flexural creep measurements made at 1,250 on these samples showed very low creep rates (1.0-1.5x10-7/hr),
attesting to the promise that xenotime holds as ahigh temperature structural material.

High temperature X-ray diffraction study

of crystallization of aluminate glasses
Galusek D. 1 , Prnov A.1 , Klement R.1 , Smrok .2
1

Vitrum Laugaricio Joint Glass Center of the IIC SAS, TnU AD, FCHTP STU and Rona, a.s.,
tudenstsk 2, SK-911 50 Trenn, Slovak Republic
2
Institute of Inorganic Chemistry, Slovak Academy of Sciences,
Dbravsk cesta 9, 845 36 Bratislava, Slovak Republic

260

Aluminate glasses are often reported as ideal host matrices for optically active dopants. Due to their low phonon
energies, in comparison to common silicate glasses, radiative transitions are favoured over non-radiative losses,
and high intensity emission in visible region can be achieved. They can also accommodate much higher levels of
optically active dopants than crystalline aluminates. Moreover, the wavelength of emitted light, especially in the
case of doping with optically active d-elements, can be deliberately influenced by changes of chemical composition of the host glass, or by the change of coordination sphere of optically active ions, e.g. by controlled crystallisation of glass. In the present work high temperature flame synthesis was used for preparation of aluminate glasses
in the form of microspheres with diameters up to 40m. High temperature XRD measurements were carried out
in the temperature interval 7501,200C and the crystallization of glasses and phase development were studied
in-situ. On the basis of XRD analysis heating schedules facilitating preparation of samples with controlled phase
compositions were proposed, and materials containing crystalline phases dispersed in residual glassy matrix
were prepared. The influence of chemical composition, degree of crystallinity, and phase composition on luminescence properties was evaluated.

Evidence for a breakdown between viscous flow

and crystal growth kinetics in inorganic glasses
Cassar D. R., Rodrigues A. M., Baldin J. M. C., Zanotto E. D.
PPG-CEM, LaMaV, Federal University of So Carlos UFSCar, So Carlos, Brazil

The correlation between the diffusion coefficients obtained via viscosity and crystal growth kinetics (using
the Eyring equation) is well established for inorganic glasses from small to medium undercoolings. However, some theoretical and (little) experimental evidence suggests that this correlation may cease to exist (i.e.,
there is abreakdown) below acertain decoupling temperature range somewhat above the glass transition,
Tg. In order to shed definitive light into this behaviour, we measured viscosity and crystal growth rates
in a wide temperature range for three stoichiometric glass compositions: diopside, lithium diborate and
barium disilicate. The data were analysed via the VFT and MYEGA viscosity models and by the classical
crystal growth theory. All the three glasses revealed adecoupling temperature near 1.1Tg (in agreement with
a recent report of our group for lithium disilicate glass). Therefore, our findings provide support for the
generalization of the breakdown phenomenon in inorganic glasses.

66 Crystallization

265

Crystallization behavior of glass-ceramics

in the BaO-TiO2-SiO2 system
Boulay E. 1 , Idrissi H.2 , Godet S.1
1
2

ULB, 4MAT Department, CP194/3, 50 Avenue FD Roosevelt, 1050 Brussels;

EMAT, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerpen

Glass ceramics are of growing interest due to their enhanced properties compared to the base glasses. The control
of microstructures is consequently amajor challenge in those systems. aglass with the stoichiometric composition of fresnoite (Ba2TiSi2O8) has been reported by Cabral et al. to show avery large nucleation rate leading to
the formation of nanometric crystals. Komatsu et al. reported that transparent nanocrystallized glasses exhibit
blue/white photoluminescence by UV excitation, demonstrating that fresnoite has asignificant potential as luminescent material. Furthermore, it was recently reported by Hijiya et al. that non stoichiometric compositions
included inside the miscibility gap in the phase diagram allow enhancing the photoluminescence properties; the
heterogeneous crystallization is finer, providing an enhancement of the fluorescence effect.
The possible role of aprior Amorphous Phase Separation (APS) on the subsequent crystallization has been the topic
of vigorous debates over the last decades and has not yet been clarified. This study proposes to focus on the interplay
between APS and the crystallization of fresnoite by comparing the crystallization behavior of the stoichiometric
composition with two non-stoichiometric ones, one outside the miscibility gap and one inside. The crystallization
mechanism is studied using Differential Scanning Calorimetry. It reveals that interfaces created by the APS have no
effect on the crystallization mechanism since both non-stoichiometric compositions exhibit surface crystallization.
The evolution of the microstructure is investigated by conventional Scanning Electron Microscopy (SEM). It confirms the surface crystallisation mechanism and the very limited role of APS. However, the final microstructures
depend on the compositions investigated. The size of the crystals become finer when the silica content is increased
and the composition falls inside the miscibility gap. Two possible scenarios are proposed to explain the formation
of oriented but finer microstructures: the presence of amorphous silica-rich droplets or ahigher viscosity, both disturbing the dendritic growth of fresnoite observed for the non-stoichiometric composition. In order to explore those
hypotheses, the microstructures of bulk samples with prior APS are investigated more deeply by coupling SEM to
local crystallographic orientation mapping using Electron BackScatterred Diffraction techniques to scrutinize the
local orientation around the droplets at the early and final stages of crystallization. High Resolution Transmission
Electron Microscope coupled with Electron Energy Loss Spectroscopy is also used in order to characterize the
nanoscale composition gradients at the interface between the matrix and the droplets both in the amorphous state
and after the crystallization of fresnoite. In order to minimize the effect of composition and the associated viscosity
change, two specific glass compositions are further investigated. They are chosen such that they are very close but
fall respectively inside and outside the miscibility gap. Their final microstructures are compared.

266

Study of thermal properties

of yttrium-aluminate glasses
Prnov A.1 , Klement R.1 , Galusek D. 1 , Bodiov K.2 , imon P. 3, Smrok .2 , Migt M. 3
1

Vitrum Laugaricio Joint Glass Center of the IIC SAS, TnU AD, FCHTP STU and Rona, a.s.,
tudentsk 2, SK-911 50 Trenn, Slovak Republic
2
Institute of Inorganic Chemistry, Slovak Academy of Sciences,
Dbravsk cesta 9, 845 36 Bratislava, Slovak Republic
3
Faculty of Chemical and Food Technology, Slovak University of Technology,
812 37 Bratislava, Slovak Republic

Yttrium-aluminate binary glasses containing 62.6, 76.8, and 81.8mol.% of Al2O3 were prepared by flame synthesis
in the form of glass microspheres and characterised by X-ray diff raction (XRD), high temperature X-ray diff raction, and differential scanning calorimetry (DSC). The high temperature XRD measurements were carried out in
the temperature interval 7501,200C with the step 5C. The temperature dependence of phase composition was
determined. The XRD data were confronted with the results of DSC measurements. The onset and crystallization
peak temperatures were determined by the DSC technique in the temperature range between 35 and 1,200C at
the heating rates 5, 10, 15, 20 and 25C/min, and used for determination of kinetic parameters describing the
nucleation period and crystal growth in studied glasses. The relationship between composition, structure and

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kinetic parameters of nucleation and crystallisation are evaluated and discussed in terms of better understanding of thermal stability of these glasses. The possibility of preparation of bulk glasses by hot-pressing of glass
microspheres without crystallization in the temperature interval between the glass transition and the onset of
crystallization temperature is tested.

The effect of titanium dioxide

and calcium oxide addition on the nucleation
and crystallisation of alumino-silicate glasses
Almuhamadi J., Karpukhina N., Hill R., Cattell M. J.
1

Institute of Dentistry, Barts and The London School of Medicine and Dentistry;
Queen Mary University of London, London, United Kingdom

273

Objectives: The objectives of the study were to investigate the effect of titanium dioxide (TiO2) and calcium oxide
(CaO) addition on the nucleation and crystallisation of apotassium alumino-silicate glass.
Methods: Experimental glasses were designed (using Appen Factors) with the addition of 0.5, 1, 2 and mol% TiO2/CaO
content (B0.5, B1, B2, and B3). Glass compositions were heated in an electric furnace, quenched, ball milled and reheated to produce glasses. Glasses were ball milled and sieved through 45, 125 and 300m sieves, then characterised using
Differential Scanning Calorimetry and Dilatometry. Two step heat treatments were next carried out. Glass/Glass-ceramic samples were characterised using Scanning Electron Microscopy and X-ray Diffraction (XRD).
Results: Glass transition temperatures and activation energy of crystallisation were increased with TiO2/CaO ratio increases. XRD indicated glasses were amorphous and glass-ceramics contained Tetragonal leucite. The Mean
crystal size (SD) for glasses after three hour nucleation /1hour crystallisation holds were: B0.5: 0.652(0.666), B1:
0.988(1.153), B2: 2.650(3.716) and B3: 3.627(5.524). Glasses with 3mol% TiO2/CaO content exhibited asignificant
(p<0.05) increase in mean crystal size after 3 hour nucleation/1hour crystallisation holds. Glasses with the smallest
amount of added TiO2/CaO produced the highest crystal number and smallest crystal size after crystallisation holds.
Crystal coalescence and increased crystal growth was found with glasses with higher TiO2/CaO content (3%).
Conclusions: The addition of TiO2/CaO to apotassium alumino-silicate glass led to changes in the crystal number and morphology. ahigh area fraction of tetragonal leucite crystals was produced with minimal matrix micro-cracking which may enhance mechanical properties.

Crystal orientations in surface crystallized SiO2 glass

Wisniewski, W., Berndt, S., Muller, M., Russel, C.
Otto-Schott-Institut, Jena University Jena, Germany;

Vitreous silica has many commercial applications, e.g. as laboratory glassware, as amaterial for microlithography
or as optical fibers. The use for high-temperature applications, however, is limited by the crystallization of the
glass which is accompanied by aphase transition during cooling and may lead to spalling or mechanical failure.
Pure SiO2-glass crystallizes via the surface crystallization of cubic high cristobalite which transforms to tetragonal low cristobalite during cooling. This phase transition is accompanied by avolume reduction of about 5%,
introducing tensions to the material. It will be shown that these tensions are relaxed by cracking, twinning, and
texture formation with respect to the nearest surface.
Two textures are detected close to the untreated surface of crystallized samples using Electron Backscatter Diffraction
(EBSD) and X-Ray Diffraction (XRD). While XRD-results indicate arandom orientation of crystals further from the
surface, local texture differences around major cracks may be detected using EBSD. Hence it may be concluded that the
surface textures result from astress induced non random phase transition with respect to crystal orientations.

68 Crystallization

294

Long-term stability of glass-ceramic sealants

in the SiO2-B2O3-BaO/SrO-MgO-ZnO system for SOFC
Rodrguez-Lpez S., Durn A., Pascual M. J.
Instituto de Cermica y Vidrio (CSIC), C/Kelsen 5, Campus de Cantoblanco, 28049 Madrid, Spain

This work is focused on the design and development of optimised glass-ceramics, with self-healing properties
and high mechanical resistance for sealing low-weight solid oxide fuel cells (SOFCs). The SiO2-B2O3-BaO/SrOMgO-ZnO system has been chosen for this investigation and different processing routes have been employed for
the sealing application (sintering-crystallization from glass powder, laser assisted-welding). The role of boron
oxide addition in the studied system has been explored from thermal and structural data of the base glasses and
final glass-ceramics. The crystallization kinetics, crystalline phases and microstructures have been characterized
by DTA, XRD and electron microscopy, respectively. adetailed study of the thermo-mechanical behavior of the
glass-ceramics as well as the degradation mechanism in the working conditions of the SOFC and the characterization of the reaction interphases due to the chemical reactivity with the cell components and atmospheres
are provided. In addition, the sealing capability, effects of thermal cycling and the gas-tightness after extended
periods of time have also been evaluated.

299

Crystal formation in modified

fluor-miserite Kx(Ca, Ce)5-xSi8O22F2 glasses
Hamzawy E. A. M. 1 , Ferrari A. M. 2 , Leonelli C. 2
1
2

Department of Glass Research,National Research Center, Dokki, Cairo Egypt;

Department of Engineering Nzo Ferrari, University of Modena and Reggio Emilia, Modena, Italy;

Different ratios of K 2O/CaO were investigated in aK x(Ca,Ce)5-xSi8O22F2 fluor-miserite glass composition to find
their effect on crystallization process. Xonotlite, tokkoite, fluorite and cristobalite were developed in all crystallized glasses; however, miserite was only identified in Ce-containing samples. Increase of K 2O/CaO ratio, in
Ce-free sample, enhanced the formation of tokkoite K2Ca4Si7O17(OH,F)2, and reduced the contents of xonotlite
Ca6Si6O17(OH,F)2 and fluorite CaF2. Rietveld evaluation on XRD spectra allowed the quantification of phase percentages. On the other hand, in Ce-containing samples, an increase of K 2O/CaO ratio promotes the formation of
miserite crystallized with or without cerium in the structure. The cerium containing miserite lattice parameter
were also evaluated. The microstructure of Ce-free glassceramics was relatively coarse and characterized by
presence interlocked flakes, rods; however, it became unpronounced in the sample of highest K 2O/CaO ratio. In
Ce-containing glass-ceramics, irregular fine growths were spread as nanosize in cryptocrystalline groundmass,
such fineness increase with increasing K2O/CaO ratio. The CTE values of the present glasses and the corresponding glass-ceramics varied from 10.305 to 11.053 and from 7.524 to 9.840 x 10-6 C-1 respectively. The CTE of Ce-free
glass-ceramics was lower than Ce-containing ones. Densities of the glass-ceramic samples varied from 2.652 to
2.856g/cm3 and the samples containing miserite show larger densities.

309

Effects of milling on sinter-crystallization

of alkaline earth silicate glass powders
Reinsch S., Rothe S., Mller R., Erfurt D.
BAM Federal Institute for Materials Research and Testing, Berlin, Germany

Glass powders obtained by milling of pre-melted glass frits can be applied for various ceramic shaping technologies like cold-pressing, extrusion, slip and tape casting in manufacturing sintered glass-ceramics or glass
matrix composites e.g. for structural or architectural applications, for seals and solders, for dental applications,
and Low Temperature Co-fired Ceramics. Densification often proceeds via viscous sintering, which must be
completed prior to crystallization if dense products are required. In these cases, due to the related moderate
process temperature, glass powder properties like e.g. particle size and shape, surface roughness, and milling impurities may largely control sintering and crystallization. Especially in case of isochemically crystallizing glasses

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with strong nucleation tendency, sinter crystallization is known to be essentially influenced by powder preparation. However, this effect is rarely reported for multicomponent glass powders of less pronounced crystallization
tendency, which are more frequently in use. Against that background, the influence of powder processing on the
sintering and crystallization behaviour of alkaline earth silicate glass powders will be discussed.

Study of nanosized ZrTiO4 crystals

in lithium alumosilicate glass by Anomalous
Small Angle X-ray Scattering (ASAXS)
Raghuwanshi V. S.1, 4 , Tatchev D.2 , Ruessel C. 3, Hoell A. 4
1

Humboldt University of Berlin, Berlin, Germany;

Institute of Physical Chemistry, Sofia, Bulgaria;
3
Friedrich-Schiller-University of Jena, Jena, Germany;
4
Helmholtz-Zentrum-Berlin for material and energy, Berlin, Germany
2

399

Crystal nucleation and growth control is critical in the development of glass ceramics microstructures from glass.
Glass ceramics with low thermal coefficients are widely used for various scientific, industrial and daily applications. We present here SAXS and ASAXS experiments for studying the formation of ZrTiO4 nanocrystals in lithium alumosilicate glass (LAS). The glass under study has the composition 7.6Li2O-0.16Na2O-0.13K 2O-1.85MgO0.33BaO-1.2ZnO-12.73Al2O3-72.58SiO2B-2.11TiO2-0.9ZrO2-0.39As2O3. After heat treatment at 750C for variable
time intervals; there is aprecipitation of ZrTiO4 nanocrystals in LAS glass system. XRD confirmed the formation
of ZrTiO4 nanocrystals after the heat treatment.
The ASAXS measurements were performed near the absorption edges of five different elements Ti, Zr, Ba, Zn and As
present in the system. ASAXS investigation helps to determine the size, shape, volume fraction, and distribution of
the ZrTiO4 nanocrystal in glass. In earlier studies, it was reported that the quantity of crystalline ZrTiO4 increases
with increasing time of thermal treatment, while the formation of ZrTiO4 nanocrytsals upon heat treatment is accompanied by the formation of adiffusion barrier surround the precipitate. Alumina enriched layer was observed by
EELS at the interface of the ZrTiO4 nanocrystal and the residual glass, which is also preventing the further growth
of the nanosized crystals. The outcome of the ASAXS measurements supports in understanding the crystallization
kinetics and crystal growth with respect to the evaluation of the crystallization rate, average size and volume fraction of the crystals depending on the role of the zirconia and titania used as nucleation agent in LAS glass system.

Nanocrystallization of oxy-fluoride glass

ceramics studied by Anomalous Small
Angle X-ray Scattering (ASAXS)
Hoell A. 1 , Raghuwanshi V. S.1,2 , Varga Z.3, Bocker C.4 , Ruessel C. 4
1

Helmholtz-Zentrum-Berlin fuer Material und Energie, Berlin, Germany;

Humboldt Universitaet zu Berlin, Berlin, Germany;
3
Institute of Molecular Pharmacology, Budapest, Hungary;
4
Friedrich-Schiller-Universitaet, Glas-Chemie, Jena, Germany
2

Glass ceramics containing fluoride crystals such as BaF2 or CaF2 with crystallite sizes in the range from 5 to
100nm are potential candidates for numerous photonic applications. They also have the ability to draw fibers and
considered as fiber amplifiers. The size distribution plays an important role and often anarrow size distribution is
required for photonic applications. In the last years ahindered growth effect leading to amore narrow size distribution was observed during the crystallization of BaF2 and CaF2 crystals in some oxy-fluoride glasses.
The aim of this study is adetailed quantitative structural and nano-chemical analysis of the formation of BaF2 and
CaF2 in two glass ceramics by ASAXS to understand the mechanism of hindered growth.
Nanocrystals of BaF2 precipitate during heat treatment of asilicate glass with composition 69.6SiO2-7.52Al2O315.04K 2O-1.88Na2O-4BaF2-2BaO (mol%). X-ray diffraction measurement proved the formation of BaF2 crystals

70 Crystallization

in the glass matrix. High resolution transmission electron microscopy measurement shows the formation of
spherical particles of sizes in range from 1040nm surrounded by alayer enriched with SiO2.
SAXS curves for the as prepared sample and the samples annealed for different times and temperatures. SAXS reveal
the growth of the particles with annealing time and temperatures. ASAXS experiments are done at four energies
close to the Ba-L3 X-ray absorption edge (5,247eV). The ASAXS curves for the sample annealed at 540C for 20h that
could be fitted by aspherical core-shell model. It turned out that the layer surrounding the BaF2 crystals are enriched
with SiO2. Sizes and compositions of these layers are analyzed quantitatively. Furthermore, the ASAXS analysis reveals the presence of very small nucleates of size of about 3nm in the as prepared glass sample already.
A precipitation of CaF2 nanoparticles takes place during heat treatment of glasses of composition 7.65Na2O
7.69K 2O10.58CaO12.5CaF25.77Al2O355.8SiO2 (wt.%) up to 40 hours. SAXS experiments and especially
ASAXS near the Ca-K edge proves the formation of CaF2 nanoparticle surrounded with SiO2 enriched layers,
quantitatively. The ASAXS effect is very pronounced at this untypical low energy for ASAXS studies at the Ca-K
edge. The ASAXS result reveals crystal sizes between 1020nm.

410

Effect of ZrO2 on the crystallization kinetics

of multi-component lithium disilicate
glass-ceramics for dental application
Krger S.1, Ritzberger C.2, Hland W.2, Deubener J.1
1
2

Institute of Non-Metallic Materials, Clausthal University of Technology, Germany

Ivoclar Vivadent AG, Schaan, Principality of Liechtenstein

The addition of ZrO2 to multi-component lithium disilicate based glass-ceramics was studied to control the crystallization kinetics for dental restorative application. amulti-methodology approach was used combining DSC,
SEM, XRD and viscometry to determine the crystallization sequence, fractions of lithium metasilicate and disilicate crystals as well as their steady-state nucleation and crystal growth rates. In particular differences in the
crystal number density determined by XRD (Scherrer) and relict structures (SEM) of HF etched surfaces indicate
partitioning of diff usion and early nucleation processes of phosphate and silicate phases. Positive correlation
of viscosity with ZrO2 content (strengthening role on the glass network) shifts nucleation rate curves to higher
temperatures which results in aZrO2 independent mobility of structure units (assuming Stokes-Einstein is valid)
for nucleation processes. Reduction of the work of nuclei formation due to early phase separation is discussed.

469

Nucleation kinetics in LAS glass-ceramics

the missing Tammann curve
Deubener J.
Institute of Non-Metallic Materials, Clausthal, University of Technology, Germany;

Temperature dependent crystal nucleation and growth rate curves were pioneered by Tammann in the beginning of the last century, quickly become textbook knowledge and provided the basis for manufacturing
glass-ceramics by controlled crystallization of glasses using his two-stage development method. For several
glass-ceramic systems Tammann curves were derived from theory and determined experimentally. However,
for the commercially most successful system, i.e. lithium aluminosilicate (LAS) glass-ceramics, the stationary
nucleation rate curve is still lacking. Thus, the paper aims in addressing this problem. Thermoanalytical data
as well as results from microscopy and X-ray diff raction studies were analyzed to show new paths, which allow
the detection of fast crystal nucleation in LAS glasses catalyzed by different nucleation agents. In conclusion,
it can be seen that Tammann curves of multi-component LAS glasses show arelative strong overlap typical for
the heterogeneous nature of the involved nucleation process.

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Preparation and optical properties

of aluminosilicate glass-ceramics with fluorite
and pyrochlore-type crystalline phases
Alekseeva I.1 , Dymshits O.1 , Khubetsov A.1 , Tsenter M.1 ,
Zhilin A.1 , Golubkov V.2 , Skoptsov N. 3, Malyarevich. A. 3, Yumashev K. 3
1

NITIOM Vavilov State Optical Institute, Saint-Petersburg, Russia;

I. V. Grebenschikov Institute of Silicate Chemistry, Russian Academy of Sciences, Saint-Petersburg, Russia;
3
Institute for Optical Materials and Technologies, Belarus National Technical University, Minsk, Belarus

529

Transparent glass-ceramics based on nanosized crystals of titanates and titanates-zirconates of yttrium, transition metal and rare-earth ions with fluorite and pyrochlore structure were prepared in LAS, MAS and ZAS
systems. Liquid phase separation of parent glasses and precipitation of crystals with defect fluorite structure
and their transformation to crystals with pyrochlore structure was studied using electron microscopy, X-ray
diff raction, SAXS and Raman spectroscopy. Absorption spectra, spectra and kinetics of luminescence in near IR
spectral range and up-conversion luminescence were studied for parent glasses and glass-ceramics obtained by
different heat-treatment schedules. Structure peculiarities and spectral-luminescent properties of glass-ceramics
based on crystals of titanates and titanates-zirconates with different contents of TiO2 and ZrO2 were compared.

Nanocomposite and glass ceramics as solid-state

electrolytes: Processing, microstructure, and properties
Berbano S. S., Mirsaneh M., Lanagan M. T., Randall C. A.
Center for Dielectric Studies, Millennium Science Complex, Materials Research Institute,
The Pennsylvania State University, University Park, PA 16802

Solid-state electrolytes are broadly applicable for energy storage. We discuss current work in our lab and review
future questions, challenges, and opportunities. Thin (200m) glass-ceramic membranes of lithium phosphates
were made by melt-quenching, crystallization, and tape casting and characterized using impedance spectroscopy.
Lithium thiophosphate glasses and glass-ceramics were made by mechanical milling and pressure-forming. Percent relative densities up to 94% of the x=0.70 crystalline phase Li7P3S11 were obtained without detectable crystallinity in the X-ray diff raction patterns. As relative density increased from 72% to 94%, the frequency of the imaginary electrical modulus (M) peak increased approximately one order of magnitude for agiven temperature. The
existence and relative coincidence of M and imaginary impedance (Z) peaks indicates enhanced bulk (rather
than surface) ionic transport in compacts prior to crystallization. These results indicate that in denser compacts,
ionic conductivity does not simply scale with mobile ion concentration, but may also be mobility enhanced.

72

Optical Glass
and Optical Properties

ICG Prague 2013 73

 74

013

Optical properties of PbS quantum dots

in oxyfluoride glass-ceramics
Liu C.1, Zhao X. J.1, Heo J.2
1

State Key Laboratory of Silicate Materials for Architectures (Wuhan University of Technology),
122 Luoshi Road, Hongshan, Wuhan, Hubei 430070, China;
2
Center for Information Materials, Department of Materials Science and Engineering,
Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk 790-784, Korea

Quantum confinement effect endows glasses containing quantum dots with tunable optical properties. For lead chalcogenide quantum dots with narrow bandgap energies, their absorption and photoluminescence can be tuned in awide
wavelength range, covering the important transmission window of silica fiber. Therefore, lead chalcogenide quantum
dots doped glasses are considered to have potentials for broadband fiber-optic amplifiers, lasers, etc. However, most of the
quantum dots formed in the glasses are lack of passivation of the surface defects, leading to the low quantum efficiency,
which hindered the applications as various light sources. All inorganic passivation of surface defects of quantum dots is
one of most successful routes to increase the quantum efficiency. In our recent studies, it was found that it is possible to
form similar core/shell structured quantum dots in the glasses, leading to the passivation of surface defects of quantum
dots and enhancement of photoluminescence efficiency. In this work, PbS quantum dots were synthesized in oxyfluoride
glass-ceramics containing lead fluoride nanocrystals, which has compatible crystal structure with PbS. X-ray diffraction
patterns indicated that PbS quantum dots can promote the formation of PbF2 nanocrystals. Formation of PbF2 nanocrystals in the glass not only affects the absorption and photoluminescence wavelength, but also the photoluminescence
efficiency of the PbS quantum dots. All these results indicated that formation of PbF2 nanocrystals has important effect on
the optical properties of PbS quantum dots in the glass-ceramics. Details will be discussed in this talk.

Avakyants L. I.1, Arbuzov V. I.2, Babina T. O. 1, Fyodorov Yu. K. 2,

Ignatov A. N. 1, Krekhova E. Yu. 1, Pozdnyakov A. E. 1, Shashkin A. V. 2, Surkova V. F.1
1
2

Lytkarino Optical Glass Plant, Lytkarino, Region Moscow, Russia

Research and Technological Institute of Optical Material Science, Saint-Petersburg, Russia

Neodymium phosphate glasses find a wide application in production of rod and disc active elements of different standard sizes. Phosphate glasses of the KGSS 0180 type with neodymium concentration from 0.4*1020
to 5.0*1020cm-3 (RTIOMS), as well as glasses KNFS-1 and KNFS-3 with 3.5*1020cm-3 (LOGP) are developed in
Russia in recent years. The above glasses considerably surpass in their parameters glasses of the old brands
(GLS21 (1.4*1020cm-3, GLS22 (2.0*1020cm-3) and GLS23 (3.6*1020cm-3)). On the basis of the KGSS 0180/35 glass
(3.5*1020cm-3), the four-channel amplifying facility Luch with 18 disc active elements (DAE) with sizes of
475*240*40 mm in each channel was built in Russia very early in the 21st century.
One of the main operations in production of neodymium glasses is glass melt dehydration for the purpose of
bringing the luminescence quantum yields to limiting values (qlim). In the process of water removal from glass
melt, qlim increases to 76 % in new glasses with neodymium concentration of 3.5*1020cm-3, and to 90 % in glasses
with smaller (from 0.4*1020 to 0.8*1020cm-3) activator concentrations. As for old glasses, their values of qlim do not
exceed 74 % for the GLS21 and GLS22, and 60 % for the GLS23. Lower limiting luminescence efficiency at comparable neodymium concentrations, as well as higher value of anonlinear refraction index n2 (1.65*10-13cm2V-1 of
old glasses instead of values of new glasses that does not exceed 1.19*10-13cm2V-1) exclude possibility of use of old
glasses as amaterial for DAE of high-pick-power/high-energy lasers.
A release of inverse population density in the ensemble of excited activator ions and as aresult of this areduction of radiation energy that is amplifying in the necessary direction can take place in aDAE because of the
phenomenon of super-luminescence. To suppress this phenomenon, plates of copper containing glass (cladding)
are pasted by special glue to lateral sides of the DAE.
Russia now turns to building the 192-channel amplifying UFL-2M facility with the output energy in 2 MDzh
that will be used for the aims of laser controlled thermonuclear synthesis. The LOGP is going to produce serially

ICG Prague 2013 75

041

Phosphate glasses for making rod

and disc active elements of lasers
and high-pick-power/high-energy radiation amplifiers

071

DAEs with the sizes of 810*460*40mm, and the RTIOMS glasses for cladding plates and the glue. The glass
for DAEs should be characterized by ahigh optical homogeneity, the absence of birefrigence (5nm/cm), ahigh
quantum yield (not less than 75%), ahigh damage threshold (more than 20J/cm2 for pulse duration at the level of
35ns), alow decimal coefficient of inactive absorption at the lasing wave length (<0.001cm-1), and the absence of
inclusions and bubbles with diameters more than 0.3mm.

Mid-infrared emission properties

of rare-earth doped oxyfluoride glass-ceramics
Zhiyong Zhao, Bing Ai, Ying Huang, Chao Liu*, Haizheng Tao, Xiujian Zhao
State Key Laboratory of Silicate Materials for Architectures (Wuhan University of Technology),
122 Luoshi Road, Hongshan, Wuhan 430070, China.

072

In recent years, mid-infrared (25m) emission from rare-earth doped glasses has attracted alot of attention,
and efficient mid-infrared wavelength range has been reported from rare-earth doped chalcogenide and fluoride glasses due to the low-phonon energy of the host matrices. Besides these two kinds of glasses, oxyfluoride
glass-ceramics have been considered to be good host matrices to realize efficient upconversion and near-infrared
emission from rare-earth ions. Mid-infrared emission in 23m wavelength range has been reported, however,
no emission in 35m wavelength range has been found in rare-earth doped oxyfluoride glass-ceramics. The
main obstacle is the low transparency of the host glasses, since most of them are based on silicates or borosilicates.
When fluoride nanocrystals doped with rare-earth ions were precipitated in oxyfluoride glass-ceramics based
on germinates or tellurites, efficient mission in 35m wavelength range may be achievable since these glass-ceramics can be highly transparent in 36m. In this work, rare-earth doped oxyfluoride glass-ceramics based
on GeO2-PbO-PbF2-CdF2 were prepared through conventional melt-quenching method and subsequent thermal
treatment at temperature near to the glass transition. Precipitation of PbF2 nanocrystals were confirmed by X-ray
diff raction and transmission electron microscope analysis. Incorporation of rare-earth ions into these fluoride
nanocrystals were confirmed by absorption spectra and electron energy loss spectroscopy analysis. 2.7m and
4.3m emission from Er3+ doped oxyfluoride glass-ceramics were observed upon 980nm laser excitation. These
results indicate that rare-earth ions doped oxyfluoride germinate glasses are good host materials for the mid-infrared emission from rare-earth ions.

Valence states of co-activators

in photo-thermo-refractive glasses
and their contributions to the UV absorption spectra
Efimov A. M., Ignatiev A. I., Nikonorov N. V., Postnikov E. S.
St. Petersburg State University of Information Technologies, Mechanics, and Optics,
St. Petersburg, Russian Federation

Photo-thermo-refractive glasses are anew class of materials for recording phase holograms and developing avariety
of devices for the integrated optics, which is why understanding the physical nature of the glasses and of processes
involved is of special interest. Specific properties of such glasses originate from the presence, in their compositions,
of co-activators such as cerium, silver, and antimony. Each of these activators is capable of occurring, in glasses, in
various valence states that contribute substantially to the total glass absorption in the 28,500 to 51,000cm-1 region.
Experimental UV spectra of photo-thermo-refractive matrix glass samples doped with each of these activators and
also with their pair combinations were recorded and processed with the dispersion analysis method based on Convolution model for the complex dielectric function. Individual spectral components related to various valence states
of the above activators were deconvoluted and the numerical magnitudes of their inherent frequencies, relative
intensities, and parameters responsible for the bandwidths were computed. It was shown that, in photo-thermo-refractive matrix glasses containing the pair combinations of various activators, the Ce(IV) valence state plays the role
of an oxidizer with respect to both atomary silver and trivalent antimony. As aresult, cerium and silver in the co-activated photo-thermo-refractive glasses occur almost completely in the Ce3+ and Ag+ valence states. Estimates for the

76 Optical Glass and Optical Properties

total molar absorptivities of different valence states of the activators were obtained. The reliability of the estimates
was confirmed by the fact that their use (together with data on the parameters of photo-thermo-refractive matrix
electronic transitions) allowed for calculating, with reasonable accuracy, the UV absorption spectrum of standard
commercial photo-thermo-refractive glass co-doped with all three activators.

088

Rare earth ions for the controlled nucleation

of PbS quantum dots in glasses
Won Ji Park1, Woon Jin Chung2, Jong Heo1
1

Department of Materials Science and Engineering and Division of Advanced Nuclear Engineering,
Pohang University of Science and Technology (POSTECH), San 31, Hyoja-dong, Nam-gu, Pohang,
Gyeongbuk 790-784, Republic of Korea
2
Institute for Rare Metals and Division of Advanced Materials Engineering Kongju National University,
Cheonan, Chungnam 330-717, Republic of Korea

It is important to control the size of quantum dots (QDs) precisely if one were quantum confinement effect. Previously, it was necessary to change the heat-treatment temperature and time if one were to control the quantum
dots size precipitated in glasses. We have investigated the influence of rare-earth ions on the control of nucleation
and growth of the semiconductor nanocrystals in silicate glasses. Glasses containing different rare-earth contents
were prepared through conventional melt-quenching methods, PbS quantum dots (QDs) were precipitated in
glasses by heat treatment method. The peak positions of the absorption from PbS QDs moved to short-wavelength
side as the concentration of rare-earth ions in glass increased under the same heat-treatment condition. For examples center wavelengths of the absorption bands decreased from 1,230nm for aglass with 0.2mol% of Er2O3
to 944nm at Er2O3 content of 0.8mol%. The center wavelengths of the PL spectra also moved from 1,277nm to
1,035nm as rare-earth oxide concentration increased.
It appeared that rare-earth ions facilitated the nucleation of PbS QDs in glasses. Absorption, photoluminescence
and TEM analysis decrease in PbS quantum-dot size with increasing rare-earth ion concentration. Lifetimes of
rare-earths were also analyzed to understand the changes in the environment induced by the precipitation of QDs.

Kondo Y., Hijiya H., Kobayashi T., Arai Y.

Research Center, Asahi Glass Co. Ltd., Yokohama, Japan

When fabricating glass products industrially, we have to pay attention to Fe2O3 because it is contained in raw
materials as contamination. This contamination affects optical property of products. Optical absorption due
to Fe2+ is mainly in near infrared wavelengths region, and that due to Fe3+ is mainly in ultraviolet wavelengths
region. Since absorption coefficient of Fe2+ is larger than that of Fe3+, Fe2+ has more influence on transmittance
and color. It is well known that absorption spectral shape, its peak wavelength and molar absorption coefficient
of Fe2+ are dependent on mother glass composition. It has already been reported that molar absorption coefficient
of Fe2+ in Na2O-SiO2 glass shows much larger than that in Na2O-B2O3 glass. Commercially soda-lime silica glass
is applied for automotive and architectural field, and alkali-free glass for display field. To our knowledge, there
is no detailed study on molar absorption coefficient of Fe2+ in soda alkali-earth silicate glass and alkali-free glass.
In this study, we investigate the molar absorption coefficient of Fe2+ dependent on glass composition using various
silicate glasses. Glass samples doped with 0.5 wt% of Fe2O3 were obtained after melting under air atmosphere. Absorbance spectra were measured in wavelengths range from ultraviolet to near infrared. Reflectance spectra were
calculated from refractive index dispersion fitted by Sellmeiers dispersion formula using refractive indices of
glass samples at more than seven wavelengths. Internal absorption was calculated by subtracting the reflectance
from the transmittance. Concentration of Fe2+ was measured by wet chemical analysis. We have found that the
molar absorption coefficient of Fe2+ in soda-alkali earth silicate glass shows larger than that of alkali-free glass
and is dependent on constitution of alkali-earth.

ICG Prague 2013 77

098

Molar absorption coefficient of Fe2+ ion

in soda-alkali earth silicate glass and alkali-free glass

103

Highly transparent infrared glass-ceramics made

by mechanical milling and Spark Plasma Sintering
Calvez L.1*, Petracovschi E.1, Hubert M.1, Delaizir G.2, Zhang X. H.1
1

Equipe Verres et Cramiques, UMR 6226 Sciences Chimiques de Rennes, Campus de Beaulieu,
Avenue du Gnral de Gaulle, 35042, Rennes, France
2
Laboratoire Sciences des Procds Cramiques et Traitements de Surface (SPCTS, ENSCI),
Centre Europen de la Cramique, 12 rue Atlantis, 87068 Limoges, France

132

Chalcogenide glasses are widely used for infrared applications. The presence of oxygen during their synthesis
process leads to the presence of detrimental absorption bands on the transmission spectra. To avoid this phenomenon, these glasses are synthesized using expensive and single use silica tubes sealed under vacuum. The low thermal conductivity of silica also limits the quenching rate, and thus the size of the samples produced. In this study,
we present anew synthesis way for chalcogenide glasses and glass-ceramics without use of silica tubes. aglass
powder is produced by mechanical milling of the raw starting elements and is then sintered using Spark Plasma
Sintering technique. Bulk glasses and glass-ceramics with higher dimensions and transparent in the infrared
region have been produced. This process paves the way of anovel approach for the production of chalcogenide
glasses at alower cost. Moreover, anti reflections coatings were deposited onto the chalcogenide glasses leading to
atransparency higher than 90% in the third atmospheric window between 8 and 12m.

Structural, mechanical and nonlinear optical

properties of glasses within the TeO2-TiO2-ZnO system
Ghribi N.1, Dutreilh-Colas M.2, Carreaud J.2, Duclre J.-R.2, Hayakawa T.3,
Rebai R.1, Kabadou A.1, Chotard T.2, Dublanche-Tixier C.2, Thomas P.2
1

Sciences des Matriaux et de lEnvironnement Laboratory, Sfax University,

Route de Soukra km 4, 3038 Sfax, Tunisia.
2
Science des Procds Cramiques et de Traitements de Surface laboratory UMR7315 CNRS,
Limoges University, European Ceramic Center, 12 rue Atlantis, 87068 Limoges Cedex, France
3
Nagoya Institute of Technology, Gokiso-cho, Showa-Ku, Nagoya, Aichi 466-8555, Japan

141

TeO2-based glasses are now well known as promising materials for telecommunications devices (they have shown
nonlinear refractive indices in arange from 20 up to 50 times larger than that of SiO2 [1]).
In the present study we investigate the influence of both ZnO and TiO2 addition to such glasses.
They are expected to show high nonlinear optical properties due to the presence of TiO2 which inhibits the depolymerisation of the glassy network [2], and ZnO which should improve the thermal stability of the samples [3].
alarge glass-forming domain has been evidenced. Physical (density, thermal stability), structural (Raman and
IR spectra, lattice dynamic calculations), optical (transmission spectra, linear and non linear refractive indices),
elastic (Young modulus, Coulomb modulus and Poisson ratio) and mechanical properties (Young modulus, hardness, elastic recovery ) of the glasses have been determined and discussed with respect to the TiO2 or ZnO content.
The relations between the structure and the properties of these glasses are discussed.

Optical properties of bismuth active centers

in germanate glasses and fibers
Firstov S. V.1, Pynenkov A. A.2, Panov A. A.2,
Firstova E. G.1, Bufetov I. A.1, Nishchev K. N.2, Dianov E. M.1
1
2

Fiber Optics Research Center Russian Academy of Sciences, Moscow, Russia;

Ogarev Mordovia State University, Physics and Chemistry Institute, Saransk, Russia

The bismuth ions embedded into glass matrix result in formation of active centers having peculiar emission properties. Materials containing bismuth centers are attracting some interest because of their luminescence covers
spectral region from 1,150 to 1,500nm where rare-earth ions do not have any the optical transitions.

78 Optical Glass and Optical Properties

In present work we report comparative study of luminescent properties of bismuth doped germanate glasses and
fibers prepared with crucible technique and modified chemical vapor deposition (MCVD) process correspondingly.
Results indicated that emitting centers formed in glass doped with alow bismuth concentration (less 0.01mol%)
similar to ones in fibers (aluminosilicate, silicate and germanosilicate fibers) with approximately the same bismuth
concentration. The luminescence spectra of glasses with higher Bi concentration (~0.110mol%) differed essentially
from the glasses with low level doping. Apparently, the observed transformations of emission spectra were due to
an appearance of complexes like dimers or other clusters. The presences of bismuth complexes and structural host
changes in glass with an increasing of bismuth content were investigated by Raman spectroscopy.

154

High refractive index glasses

for self-sensing composites
Hand R. J., Wilson P. R., Bailey P., Hayes S. A.
Department of Materials Science & Engineering, University of Sheffield, Sheffield, United Kingdom

The increasing use of polymer matrix composites in safety critical applications highlights the need for reliable
damage assessment techniques for these materials. One class of techniques involves the use of self-sensing elements to detect either mechanical damage or chemical degradation. Glass fibre reinforcements could potentially
act as the sensing element, for at least of the former of these applications. However conventional reinforcing fibres
(e.g. E-glass) have refractive indices (RI) that are either similar to, or below that of the epoxy matrix (typically
RI~1.6 in the visible), thus preventing light guiding in the fibres. We have therefore investigated two classes of
glasses with high refractive indices as sensing elements germanium antimony lead sulphide glasses and silicate
glasses modified with niobium. The former have the advantage of good infra-red (IR) transmission and RI values 2 in the IR regime and have been shown to work as chemical sensing elements using fibre evanescent wave
spectroscopy. The RI values of the latter vary with composition but in the best cases are ~1.7 in the visible regime;
these glasses are also more compatible with existing reinforcing fibres and we are currently undertaking amore
extended study of these niobium silicate glasses. The optical, mechanical and durability properties of the glasses
developed have been assessed and will be reported. Their use as sensing elements will also be considered.

167

Optical properties of rare-earth ions

in TeO2-WO3-PbO-Lu2O3 glasses
Reben M.1, Burtan B.2, Cisowski J.2, Lisiecki R.3, Wasylak J.1
1

AGH University of Science and Technology, Faculty of Materials Science and Ceramics,Cracow, Poland;
Institute of Physics, Cracow University of Technology, Cracow, Poland
3.
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Wrocaw, Poland.

The goal of this work was to investigate the influence of rare earth ions doping on the optical properties of tellurite-tungstate glasses, containing luthetium. These glasses possess high photothermal stability and resistance
against crystallization during reheating. The optical studies of the glasses comprised spectrophotometry (reflectance and transmittance) and spectroscopic ellipsometry. The spectrophotometric measurements yield anumber
of narrow absorption bands which correspond to characteristic transitions between the ground and consecutive excited states of rare-earth ions. From ellipsometric studies, in turn, the dispersion of the refraction coefficient has been obtained. The glasses containing RE ions were studied experimentally at 77 and 293K using
spectroscopic methods. The JuddOfelt intensity parameters were derived from the absorption spectra and used
to calculate the radiative lifetimes and branching ratios.

ICG Prague 2013 79

180

Phosphor-in-glass (PiG) color converter for high

power white LED using Pb-free silicate glasses
Woon Jin Chung1, Yl Kwon Lee1, Won Bin Im2, Jong Heo3
1

Division of Advanced Materials Engineering, Kongju National University, Cheonan, Republic of Korea
School of Materials Science and Engineering, Chonnam, Gwangju, Republic of Korea
3
Department of Materials Science and Engineering and Division of Advanced Nuclear Engineering,
Pohang University of Science and Technology, Pohang, Republic of Korea

195

Phosphor in glass (PiG) is asintered mixture of glass frits and phosphor materials and has been recently suggested as astrong candidate for inorganic colour converter in high power white LED applications. It can effectively
solve the problems induced by conventional organic or silicone based resins allowing long-term stability with its
improved thermal and chemical properties. However, proper glass frit materials should be provided which have
good viscosity at reasonable sintering temperature along with high transparency. Sintering temperature should
be low enough to avoid thermal degradation of phosphor materials. In this study, we investigated SiO2-B2O3-RO
(R=Ba, Zn) system as aPb-free glass frit material to compose PiG structure. Various compositions based on SiO2B2O3-RO were examined and successful sintering at 750C was achieved with high visible transmittance of 70 %
after sintering. When the glass was mixed and sintered with YAG:Ce3+ yellow phosphor, it showed good wetting
property to the phosphor without any noticeable interaction. Successful white light emission was observed when
the PiG was mounted on blue LED with centre wavelength of ~450nm. Colour coordination could be easily varied via controlling thickness or glass to phosphor ratio of PiGs. Enhanced thermal quenching property was confirmed when the PiG was compared to conventional silicone resin for high power white LED. In order to improve
colour rendering index, red phosphor has been mixed and patterned structure of PiG has been also examined.

Occurrence and formation mechanism

of scattering centres in photonic crystal fibres
Keding R., Drschner S., Frosz M., Russell P. St. J.
Max-Planck Institute for the Science of Light, Erlangen, Germany

227

We study the appearance of strong scattering centres in solid core photonic crystal fibres produced from glassy SiO2
using the stack and draw technique. The fibre was characterised using OTDR, microscopy, absorption measurement
and side-scattering observations. asmall number of strong scattering centres were detected in the fibre by optical
time-domain reflectometry. Side-scattering measurements revealed that each centre was between 2 and 25m in
extent along the fibre axis. Cleaving the fibre at one of the scattering points permitted us to image it directly on
asurface perpendicular to the fibre axis. Particles with diameters between 0.5 and 1m were seen on the cleaved face
close to the holes, smaller particles ~0.2m diameter being present at agreater distance from the holes. Additionally,
the inner surface of the holes in the scattering centre itself were covered by small particles. In an attempt to identify
the origin of the scattering centres, the fibre preform was baked at 900C while varying the atmosphere between N2
and N2 + Cl2; no significant change in the occurrence of scattering centres was seen in the drawn fibre.
Detailed investigations of the particles and the layer coating the interior of the hole are on-going and should allow
us to identify their composition and propose aformation mechanism.

The effect of tin in the float glass

surface on its optical properties
Bretschneider J.1, Brokmann U.2, Mika M.1,3, Nekvindova P.3, Raedlein E.2, Stanek S.3
1

Members of the ICG-TC10 Subgroup Chemical Effects on Optical Properties of Glass;

Technische Universitaet, Ilmenau, Germany;
3
Institute of Chemical Technology, Prague, Czech Republic

In the float glass production process the properties of the glass are influenced by the uptake of tin from the float
bath. Tin migrates into the surface of the glass which is in contact with the molten tin. Literature about the chem-

80 Optical Glass and Optical Properties

ical effects and several physical properties is available but there is still lack of information on its optical properties
especially for newer applications like solar glass or sophisticated coatings.
The members of the ICG-TC10 subgroup Chemical Effects on Optical Properties of Glass have recently started
measurements with aset of float glass samples including low-iron glass types having different tin concentration in the glass surface with the following goals:
to quantify the effect of the tin on the transmittance of the float glass
to measure the spectral fluorescence induced by the tin
to study the wave-guiding effects of atin containing layer
The measurements with the spectrophotometers show clearly that the transmittance is reduced by the tin in the float glass
surface but there is no simple relationship between the reduction in transmittance and the amount of tin that was measured by XRF. Equally, the spectral fluorescence does not linearly depend on the total amount of tin in the glass surface. The
wave-guiding effect has been observed on the tin side of the float glass and the properties of this waveguide were measured.

251

Low birefringent ZnO-SnO-P2O5 glass:

Optical and thermal properties
Saitoh A., Takebe H.
Ehime University, Matsuyama, Japan

Ternary ZnOSnOP2O5 (ZSP) glasses provide with features of low melting temperature, low and/or zero photoelastic constants (PECs). The ZSP glass having zero PEC is acandidate material for next optical fibre-typed
current transducer (present fibre made by flint glass) based on the Faraday effect, which is utilized for current
monitoring for supervision and protection in facilities sustaining industry and community.
The optical current transducer made by non-flint glass such as the ZSP glass is now needed because it satisfies
both environmentally harmlessness and zero stress-induced birefringence which is known as photoelasticity. At
fibre forming temperature estimated by viscosity, precipitation of microcrystal in fibre-core glass should be prevented since it might degrade an optical transmittance.
The obtained ZSP glasses, with general formula of xZnO(67-x)SnO33P2O5 (x=030) in molar ratio, by conventional
melt quenching technique were cut to arbitrary forms and polished to its surfaces. The PECs were determined for disk
shaped forms by applying uniaxial load using an optical heterodyne technique with astabilized 633-nm transverse Zeeman laser. Minimum absolute value of PEC with 0.04 10-12Pa-1 was obtained when x=18.5mol%. Temperature dependences of viscosities from 107 to 1011Pas were measured by apenetration method using athermo-mechanical analyser and
an insert pin of SiO2 with adiameter of 1 mm. In conclusion, the ZSP glass in x ~20mol% having very low PEC could
possess sufficient transparency without notable crystallization heat-treated at viscous temperature not above 400C.

Masuno A., Yoshimoto K., Inoue H., Watanabe Y.

Institute of Industrial Science, The University of Tokyo, Japan

Transparent and high refractive index La 2O3-WO3 glasses were prepared in bulk form by containerless processing
with an aerodynamic levitation furnace. The glass forming region was determined and the thermal and optical
properties of the glasses were investigated. The glass transition temperature, crystallization onset temperature,
and melting temperature 0.2La2O3-0.8WO3 glass were rather lower than those of other network former-free high
refractive index glasses such as TiO2- and Nb2O5-based glasses, indicating that the glass can be pressed into
shapes easily. The lower glass transition temperature is agreat advantage for amolding process because it can
decrease the molding temperature without breaking the mold. The glass was colorless and widely transparent, in
the visible to infrared region. The transparency is evidence that the valence state of the W ion was 6. The refractive
index was 2 in the visible range, and the Abbe number estimated from the Drude-Voigt relationship was 24. From
the optical parameters obtained by the analyses on the basis of the Lorentz-Lorenz equation, the oxygen ions in
the glass exhibited acomparatively large polarization and existed in adensely packed state. Both these features
are characteristic of glasses prepared by containerless processing. These results indicate that the La2O3-WO3 glass
would be useful for optical applications in the visible to infrared region.

ICG Prague 2013 81

252

Transparent and high refractive index La2O3-WO3

glasses prepared by containerless processing

304

Cooperative luminescence of Yb3+ ions

in fused and unfused silicon dioxide
Golant K. M.1, Shikin A. S.1,2, Savelyev E. A.1
1
2

Kotelnikov Institute of Radio-engineering and Electronis of RAS, Moscow, Russia;

Moscow Intsitute of Physics and Technology (State University), Moscow, Russia

307

The presence of profusion stage on technological route of optical fiber fabrication influences uniformity of Yb3+
ions distribution in silica glass causing the increase of ions portion aggregated in clusters. In the clusters the distance between neighbor ions shortens and probability of cooperative luminescence associated with simultaneous
deactivation of two closely spaced ions from excited states accompanied by one photon emission with duplicate
energy becomes greater. It is already demonstrated that intensity of cooperative luminescence is reversely proportional to interionic distance in apair to the power of six. At distances 35 probability of this process becomes
high enough for registration of the luminescence signal in the visible band, and thus its intensity could serve as
ameasure of active centers clustering. With the help of SPCVD we fabricated two sets of Yb doped silica samples:
preforms subjected to profusion and slices of substrate silica tubes with deposited on their inner surface unfused
Yb-doped silica layers. The results of comparison study of infrared and cooperative luminescence spectra as well
as decay kinetics at wavelengths of 998nm and 500nm excited by 975nm diode laser are presented. Influences of
various technological factors on Yb clusters formation in fused and unfused silicon dioxide are discussed.

Cooperative effect of P2O5 and Al2O3 introduction on the

physical, thermal, optical, luminescence and structural
properties of erbium-doped borosilicate glasses
Bourhis K.1, Massera J.2, Petit L.3, Ihalainen H.3, Fargues A.4,
Cardinal T.4, Hupa L.2, Hupa M.2, Dussauze M.5, Rodriguez V.5, Ferraris M.1
1

Politecnico di Torino, DISAT, Istituto di Ingegneria e Fisica dei Materiali, Torino, Italy
nLIGHT Corporation, Lohja, Finland
3
Process Chemistry Centre, bo Akademi University, Turku, Finland
4
CNRS, Universit de Bordeaux, ISM, Talence, France
5
CNRS, Universit de Bordeaux, ICMCB, Pessac, France
2

308

Erbium-doped borosilicate glasses with various silica content up to 60 % have been co-doped with P2O5 and Al2O3.
We evidence that the luminescence properties strongly depend on the P/Al ratio. The spectroscopic variations are
tightly related to structural modifications of the borosilicate network, in particular to the depolymerisation of the silicate network and to the transformation of neutral borate groups to charged species. The phenomenon taking place is
acharge compensation mechanism in order to equilibrate the negative charges born by the PO4 and AlO4 groups. This
phenomenon is minimized when the ratio Al/P is equal to 1 since neutral AlPO4 is formed. AlPO4 has been confirmed
to enhance the spectroscopic properties, especially the fluorescence intensity. Its effect on the spectroscopic properties
is very noticeable in the high-silica content glasses. Regarding the 4I13/2 level lifetime, it is greatly increased by the introduction of P2O5 while it is reduced in Al2O3-rich glasses. The quantum efficiency of the 4I13/2 4I15/2 transition is strongly
influenced by the Al/P ratio. It is maximal for the glasses containing only P2O5 and is diminished by afactor 2 to 3 when
only Al2O3 is present. For 1.5 mm stimulated emission, acompromise has to be found to get the best quantum efficiency
(P-rich glasses) and the highest stimulated emission intensity (Al/P=1 glass).

On the bismuth interstitials responsible

for near infrared luminescence in silica glass
Bazakutsa A. P.1, Golant K. M.1
1

Kotelnikov Institute of Radio-engineering and Electronics of RAS, Moscow, Russia;

Experimental data is discussed to clarify the origin of the species responsible for near infrared (NIR) luminescence in Bi-doped silica. Particular attention is paid to photoluminescence spectra and kinetics in 0.71.6 micron

82 Optical Glass and Optical Properties

wavelengths band at temperatures of 300900K. Bi-doped additive free SiO2 and SiO2/Al2O3 samples synthesized
by means of plasma chemical deposition under reduced-pressure microwave-induced discharge are investigated. In as deposited unfused Bi-doped silicon dioxide abroad luminescence band centered at the wavelength of
1,420nm with decay time of about 0.6ms dominates in along wavelength part of the spectral band under investigation regardless the presence of aluminum in the material. Profusion of plasma-deposited alumosilicate material
causes shift of the center of this band to 1,100nm wavelength, while profusion of Al-free material does not significantly affect the structure of the spectrum. Our observations favor interstitial species rather than substitutional
impurity bonded to the glass network as luminescent centres responsible for NIR luminescence in silica. The rate
of such species formation at agiven temperature depends on glass viscosity, which is affected by additives used to
shape refractive index profi le of fiber preforms. At high concentrations under reducing conditions and elevated
temperature, bismuth interstitials can aggregate to nanoclusters embedded in silica matrix. According to above
reasoning, there should be an upper limit for Bi content, providing atradeoff between concentrations of species,
which are able to operate as activators for NIR light amplification, and their counterparts, which can only absorb
and/or scatter light. Obviously, this upper limit depends on the mobility of bismuth atoms in melted high silica
glass, which in turn strongly depends on the additives manipulating glass softening temperature. It is clear that in
this case temperature regimes during preform consolidation and fiber drawing become extremely critical.

338

Evaluation of optical homogeneity in the zinc-silicate

glasses containing erbium and ytterbium
Stank S., Nekvindov P., vecov B., Mka M., pirkova J.
Faculty of Chemical Technology, Institute of Chemical Technology, Prague, Czech Republic

For optical glasses that are used in the photonics agood homogeneity is the key property. However, it is quite difficult
to determinate it quickly and accurately. In this paper, anew easy way how to check the glass homogeneity was described. Moreover our attention was paid also to the relationship between technology of the erbium and ytterbium
containing zinc-silicate glass fabrication and homogeneity, which glass according to our previous research showed
as avery promising for using as optical amplifier matrix. Three types of the glasses containing up to 6at.% of rare
earths with different ratio between erbium and ytterbium were melted by several different ways. The samples wafers
were obtained from the bulk glasses by cutting them into rectangular parallelepipeds and polishing both sides to optical quality. Values of the substrate refractive index in several glass wafer points were measured by Metricon Prism
Coupler at 633nm. The obtain results were statistically analysed and compared with measurement of commercially
available type of IOG optical glass. It was found that homogeneity of our glasses is equal or better than value of IOG
glass depending on the melting process and subsequently thermal treatment.
The research was supported by the grant P 108/12/6108 GAR.

Yang G.1, 2, Dussauze M.1, Cardinal T.2, Rodriguez V. 1, Fargin E. 2,

Deepak K. L. N. 3, Charmasson L.3, Grojo D.3, Uteza O.3, Delaporte P.3
1

Univ. Bordeaux, ISM, CNRS UMR 5225, F-33400 Talence, France;

Univ. Bordeaux, ICMCB, CNRS UPR 9048, F-33600 Pessac, France;
3
Laboratoire LP3, 163, Avenue de Luminy, Case 917, 13288 Marseille cedex 09, France.

Fabrication of micro-structure with nonlinear optical properties in amorphous materials has agreat potential for
many applications in photonics. It is well known that thermal poling is an efficient method to induce second harmonic generation (SHG) responses in glassy materials. However, efforts are needed in order to control the effect
of poling at the micro-meter scale aiming the conception of glasses with locally structured second order optical
properties. In the present work, our strategy was to use micro patterned anode electrode as part of an imprinting
thermal poling process. Notably, we have used as electrode silicon substrates with sub-micron size micro-craters
which were obtained from an innovative irradiation technique using UV photonic nanojets from glass microspheres. The structural and optical properties of the poled glasses have been characterized by micro-Raman

ICG Prague 2013 83

348

Imprinting periodical micro-structure with second

harmonic generation on glass by thermal poling

350

spectroscopy, AFM and KFM techniques (i.e. Kelvin Force Microscopy for surface potential characterization)
and micro-SHG measurements. After the imprinting thermal poling process, glass surface topology as well as
SHG responses have been founded to be periodical with asub-micron period. Moreover, this imprinting process
was successfully apply to glass composition exhibiting large second order optical susceptibility ((2)> 1.0pm/V).
The periodical SHG responses obtained have been related to internal electric field implementation mechanisms.

Spectroscopic studies of Co2+ in oxide glasses

Hunault M., Calas G., Cormier L., Galoisy L., Lelong G.
Institut de Minralogie et de Physique des milieux condenss, Universit Pierre et Marie Curie,
CNRS UMR7590, 4 place Jussieu, 75005 Paris, France

359

Coloring glasses using cobalt impurities has been used since centuries in glassmaking, giving the well-known
intense blue coloration of glasses. Alkali borate glasses containing cobalt are compared to silicate glasses using
optical absorption spectroscopy. We pay special attention to the variations in the molar extinction coefficient, in
order to get quantitative information on the local surrounding of Co2+ cations in these glasses. The influence of
the nature of the alkali (Li, Na, or K) on coloration for agiven alkali content is also investigated.
In borate glasses, the concentration of 4-coordinated cobalt increases with the alkali content and with the size
of the alkali ion. The evolution of the absorption spectra agrees well with the literature. However, the amount of
tetrahedrally coordinated cobalt reaches only the half of the cobalt concentration in the glass. This indicates that
most Co2+ behave then as asilent species in borate glasses.
X-ray absorption spectroscopy (EXAFS and XANES) data indicate that alkali-poor borate glasses contain mostly
octahedral Co2+ occurring within regular sites. These data are discussed in the light of Ni-bearing alkali borate
glasses. Silicate glasses have been investigated in abroad range of soda-lime glasses used for designing modern
stained-glasses. This comparison confirms the importance of silent Co2+ species in the coloration of oxide glasses.

Glass-compositional dependence of Tm3+ blue

up-conversion photoluminescence for Tm3+/Yb3+
codoped TeO2-TlO0.5-ZnO glasses
Hayakawa T.1, Uchida M.1, Shimoda M.1, Duclre J. R.2, Thomas P.2
1
2

Nagoya Institute of Technology, Japan;

SPCTS, University of Limoges, France

Tm3+ ions can emit blue up-conversion photoluminescence (UCPL) via three-steps energy transfer from Yb3+
ions as asensitizer. In this study, we synthesized (99.4-x-y)TeO2-xTlO0.5-(19.4-y)ZnO-0.1Tm2O3-0.5Yb2O3 (x=10,
20, 30, y=0, 10) glasses by amelt-quenching method [1], and estimated their energy transfer rate (ETR) d5 for
blue Tm3+ UCPL. From optical absorption spectra of the glasses in interest, Judd-Ofelt parameters were calculated and then radiative transition probabilities of emissive levels of Tm3+ ions were theoretically obtained. Based
on the UCPL intensities of 1G4-3H6 (blue) and 3H4-3H6 (near-IR) photoluminescence, the energy transfer rate
for the third one from Yb3+ to Tm3+ was estimated [2] as afunction of the glass compositions. As aresult, the
optimized Tm3+/Yb3+ concentration ratio was firstly examined so as to be found to be 1/5 for TeO2-TlO0.5-ZnO
system. It was also found that the energy transfer rate d5 was decreased with an increase in TlO0.5 content for
the fi xed Tm3+/Yb3+ ratio, meaning that TlO0.5 possibly made glass network longer and the rare-earth ions could
not be dispersed with enlonged glass-network.

84 Optical Glass and Optical Properties

364

Mid-infrared luminescence from modified lead

chalcogenide quantum dots in silicate glasses
Zhang J., Heo Jong
Center for Information Materials and Department of Materials Science and Engineering,
Pohang University of Science and Technology (POSTECH), San 31, Hoyja-dong, Pohang,
Gyeongbuk 790-784, Republic of Korea

The semiconductor quantum dots made of lead chalcogenide have attracted lots of intention for their tuneable
infrared luminescence, due to quantum confinement effect. However, the photoluminescence efficiency dramatically decreases with their radii increase. Its difficult to get mid-infrared luminescence (>2m) from lead chalcogenide quantum dots. In this report, the infrared luminescence properties of Sn-modified PbSe quantum dots in
silicate glass matrix were investigated. The size of quantum dots could be controlled by different thermal treatment temperature and duration. The peak of absorption band shifted from near infrared to mid-infrared region.
Except near infrared luminescence from PbSe quantum dots, mid-infrared emission from PbxSn1-xSe quantum
dots were observed simultaneously. The influences of Sn addition content on luminescence were also discussed.
The structure of PbSe and PbxSn1-xSe quantum dots were analysed by X ray diffraction and transmission electron
microscopy. The luminescence difference between PbSe and PbxSn1-xSe quantum dots with similar size originated from the band gap energy change. The Sn addtion could change the energy structure of quantum dots. The
efficiency of mid-infrared luminescence was calculated. The results showed that Sn-modified PbSe quantum dots
could be promising candidate for efficient mid-infrared emission.

369

Preparation and study of waveguiding

and luminescence properties of new
silicate glasses containing Er and Yb
Stank S.1, Nekvindov P.1, vecov B.1, Mka M.1, Oswald J.2,
Mackov A.3, Malinsk P.3, Kubeek V.4, Szotkwski P.4
1

Faculty of Chemical Technology, Institute of Chemical Technology, Prague, Czech Republic

Institute of Physics, Academy of Sciences of the Czech Republic, Prague, Czech Republic
3
Nuclear Physics Institute, Academy of Sciences of the Czech Republic, Rez, Czech Republic
4
Faculty of Nuclear Sciences and Physical Engineering, CTU, Czech Republic
2

Nowadays photonics is adynamically developing modern discipline, which significantly contributes to development of telecommunication systems. Increasing demands on data volume, their transfer speed and processing
leads to search for new suitable materials with useful properties. Our previous research showed that avery promising matrix for laser active ions is the zinc silicate glass doped with rare earths.
Th is research is focused on luminescence properties of the prepared glasses as well as on the possibility to
influence the luminescence properties by modification of glass composition or by presence of silver. Glasses
containing up to 6at.% of rare earths with different ratio between erbium and ytterbium and also with different
zinc content were melted. Based on the prepared samples we evaluated influence of rare earths or zinc on the
properties of the substrates from the point of view of their utilization in photonics. Refractive index values and
also dispersion of glass substrates were measured by Metricon Prism Coupler using five different wavelengths
in the range from 473nm to 1,552nm. Basic passive characteristics of the glasses like absorption and luminescence were examined as well. To achieve Ag particles containing thin fi lms on the substrate surfaces we used
Ag+ Na+ ion exchange or ion implantation technique and measured their waveguiding, spectroscopic and
lasing properties as well as the silver concentration depth profi les.
The research was supported by the grant IGA UJEP 532221500030. Some parts of this research were realised at the CANAM (Centre of Accelerators and Nuclear Analytical Methods) infrastructure and under the project SPIRIT No.227012.

ICG Prague 2013 85

385

Linear and non-linear optics and FTIR characteristics

of borosilicate glasses doped with NdF2 ions
Marzouk S. Y.
Basic and applied science, Faculty of engineering, Arab Academy of Science and Technology, Al-Horria,
Heliopolis, Cairo, Egypt, (samir_marzouk2001@yahoo.com)

404

Borosilicate glasses have been prepared using the high-temperature melt components of ingredients NdF2
doped borosilicate glasses. FTIR spectra were measured in the wavenumber range (4,000400cm-1) to explore
the influence of Nd+3 ions in the structure of the glasses. Data indicated to; B2O3 noticeable as network formers
(BO3) and (BO4) are structural units whereas the Nd ions playing the role of the network modifier in these
glasses. Optical transmission spectra were recorded in the range 1902,500nm and different optical parameters such as the direct and the indirect optical band gap, Urbach energy, refractive index and optical dielectric
constant, have been determined. The molar refraction, electronic polarizability and the optical basicity results
have been determined using the measured glass refractive indices. Nd-doped borosilicate glasses effected on
different several of optical parameters.

Impact of irradiation on optical properties

of Yb-doped oxide glasses
Pukhkaya V.1, Ferrier A.2, Goldner P.2, Ollier N.1
1
2

Laboratoire des Solides Irradis, Ecole Polytechnique, Palaiseau, France;

Laboratoire de Chimie de la Matire Condense de Paris, Chimie-Paristech, CNRS UMR 7574,
Universit Pierre et Marie Curie, Paris, France

406

Yb-doped optical fibers are well-known materials for IR lasers. In case of their use for communication in satellites, the
active fibers will be submitted to radiation from space and it is thus important to better understand how the optical
properties evolve under radiation. In particular, we are interested in the influence of RE initial environment on its
luminescent properties under ionizing irradiation in aluminosilicate (AS) and phosphate glasses. The Yb-doped AS
glasses with same concentration of Yb2O3 show different intensity of cooperative luminescence and lifetime values of
Yb3+ excited state 2F5/2 IR and CL, indicating different amount of cluster. The presence of more Yb clusters is found for
glasses with higher Al content and thus less Non Bridging Oxygens. Under electron- or gamma-irradiation, we observe
the decrease of cooperative luminescence intensity as well as lifetimes IR and CL. In order to analyse the role of defects
on the decrease of both cooperative emission and lifetime, some annealing treatments are undertaken. Concerning the
evolution of both properties within time, it is worth to notice that the Yb cluster amount plays an important role: in
glasses with higher Yb cluster amount, the lifetime IR and cooperative luminescence decrease is stable for months after
the irradiation whereas with less Yb clusters the value of lifetime IR slightly increases. This trend is not correlated with
the behaviour of paramagnetic point defects which amount decreases in two months after the irradiation [Pukhkaya,
JNCS 2013]. In phosphate glasses the decrease of lifetime IR is not as crucial as in aluminosilicates and it reaches its
initial value of before irradiation after four months of relaxation. In conclusion, the Yb cluster seems to be very efficient
for trapping excitons and decrease the relaxation of properties evolution under radiation.

Influence of thermal treatment on the optical

and structural properties of heavy metal oxide glasses
Valle P. S., Nalin M.
LaViE Department of Chemistry. UFSCar, So Carlos, Brazil

Heavy metal oxide glasses have been broadly studied due to their interesting photonic properties, such as high,
linear and nonlinear refractive indexes. Other studies have shown that the presence of both metallic nanoparticles and rare-earth ions within such matrices can add new properties to the material allowing their application
as near infrared broad band emission devices with potential beyond that of conventional Er3+ doped systems.
Considering these factors, our research have been made based on the glass system 100-x-y (0.4GeO2 0.3Bi2O3

86 Optical Glass and Optical Properties

0.2PbO 0.1TiO2) xAgCl yRE, (RE=Eu2O3, Tm2O3 and Nd2O3), with 0 < x < 5 and 0 < y < 1 (in mol%). After
preparing samples using the melting-quenching methodology, selected samples were submitted to heat treatment
in order to induce growth of the nanoparticles. The samples have been studied by DSC, UV-Vis spectroscopy
(insitu), X-ray diff raction, transmission electron microscopy, Raman and luminescence spectroscopy. The results
have shown that compositions with different contents of Ag present different kinetics of crystallization. Studies
carried out by DSC have suggested that the crystallization is homogeneous, while X-rays diff raction has been
used to identify the crystalline phases. We have been observed that controlling the thermal treatment conditions,
metallic silver nanoparticles may be obtained. The presence of the nanocrystals has been confirmed by both
transmission electron microscopy and in situ UV-Vis spectroscopy. Preliminary studies of luminescence have
shown that different concentrations of Ag and different times of heat treatment influence the luminescent properties of the samples containing Eu3+. Further studies are under consideration.

414

Heavy metal oxides glasses containing rare earth ions

Mugoni C.1, Gatto C.2, Siligardi C.1
1
2

Department of Engineering Enzo Ferrari (DIEF), University of Modena and Reggio Emilia, Italy
Italian Institute for Nuclear Physics (INFN), Napoli

Heavy metal oxide (HMO) glasses are currently attracting great attention due to their interesting properties such
as non-linear optical behavior and high radiation hardness. This work is focused on the development and the
study of transparent HMO glasses as host materials for rare earth oxides in order to obtain heavy scintillating
glasses, which can be used in applications of high-energy physics (HEP), homeland security and radiation detection. Since they posses both high density and high transparency over ultraviolet and visible regions, barium
bismuth borate glasses of 20BaO-xBi2O3-(80-x) B2O3 systems (10 x 55mol%) were selected and doped with
dysprosium and praseodymium oxides. The glasses were synthesized by the melt quench method and characterized in terms of physical (density and molar volume) and optical properties (ultraviolet and visible transmission
spectra together with luminescence properties). Particular attention was dedicated to explore both the effect of
composition and type of RE ion to the UV absorption mechanisms The scintillating properties under UV and
X-ray excitation were studied with aUV-Vis Spectrophotometer and an high energy electrons and ions beam
at Fermilab Test Beam Facility (FTBF). The emitted scintillating light was recorded by aphotodetector (either
aPMT or an SiPM) and the intensity and time structure of the signal was retained for further study.

415

Gallate glasses as candidates for optical

applications in the near infrared
Hee P.1,2, Ledemi Y.2, Dussauze M.3, Adamietz F.3,
Wren J. E. C4, Kroeker S.4, Messaddeq Y.2, Cardinal T.1, Fargin E.1
1

ICMCB-CNRS, Pessac, France;

COPL, Qubec, Canada;
3
ISM, Talence, France;
4
Department of Chemistry, University of Manitoba, Winnipeg, Canada;
2

The demand of adapted glass compositions for optical applications in the near infrared (NIR) spectral region is
continuously rising. The processing issues of novel exotic glass preparation and their incorporation in photonic
and opto-electronic devices are becoming less and less challenging. Silicate, phosphate and aluminate glasses
have been widely investigated for that purpose but few systematic studies have been devoted to glass matrices
with heavy metal oxides such as gallate. Gallate glasses represent good candidates for applications in the NIR
region, since they offer low phonon energy and could offer wider transparency compared to classical oxide glass
compositions. Thanks to the significant polarisability and hyperpolarisability of Ga 2O3, these materials are also
promising for applications based on nonlinear optical properties. The linear and nonlinear optical properties of
new gallate glasses have been investigated. Second-order nonlinearity was highlighted by thermal poling. Structural investigations were conducted using IR, Raman and NMR spectroscopies. Correlations between composition, structure and optical properties of these glasses will be presented.

ICG Prague 2013 87

437

Long persistent luminescence

in transparent glass ceramic phosphors
Tanabe S.1, Nakanishi T.2, Ueda J.1
1
2

Kyoto University, Kyoto, Japan;

Hokkaido University, Sapporo, Japan

505

Transparent glass ceramics (GC) containing SrAl2O4:Eu2+,Dy3+ microcrystals were developed, which show long
and intense persistent luminescence. Glasses in the system of SrO-Al2O3-B2O3 doped with Eu2O3 and Dy2O3 were
prepared by melting under various oxygen partial pressures, pO2 from 10-1 to 10-22atm. Obtained GCs were almost
transparent, being composed of SrAl2O4 (SA) crystalline phase and Sr-rich borate glass phase, the refractive index
difference between which was 0.02. They showed broad green luminescence from Eu2+ ions in the SA microcrystals and sharp fluorescence bands from Eu3+ and Dy3+ mainly in the borate glass phase under uv or blue excitation.
The color of the GC and intensity ratio of the Eu2+ to (Eu3+,Dy3+) fluorescence bands were varied with pO2. After
stopping uv irradiation, only the broad green afterglow from the SA crystals were observed, with very long persistence, especially for the sample melted under pO2=10-8atm (GC-8). GC samples prepared under too strong
reducing condition (GC-22, GC-19) looked yellow due to the presence of Eu2+ ions also in the glass phase, which
prevent efficient excitation of the active Eu2+ in the SA phase and thus kill its persistent luminescence. The sample
GC-8 showed slow change in photoluminescence color for 60s because of electron charging process, as well as
excellent afterglow through large volume and penetration depth, the persistent time of which is 24h, longer than
the best commercial powder phosphor.

Optical properties of glass self consistent

UV-Vis-NIR multi-angle spectrophotometric reflectance,
transmittance and absorptance measurements
Burt T. C., Comerford J., Hind A., Death D.
Agilent Technologies, Melbourne, Australia.

Spectroscopic measurements of transparent, non-scattering samples are shown to a high level of photometric
accuracy using arecently developed spectrophotometer system. In this paper self consistent sets of reflectance,
transmittance and absorptance data of silica and glass samples are presented spanning the ultra-violet, visible
and near infrared wavelength range from near normal incidence through to grazing angles. Spectroscopic data
is obtained without altering the incident illumination onto the sample, or the samples physical position during
analysis, permitting close correlation between predicted and measured spectra.
The multi-angle spectral photometric measurements were performed using an advanced double beam UV
VISNIR-type spectrophotometer system. The system uses alinearly polarized beam to illuminate the sample
in transmission or, by moving the detector assembly in aplane at aconstant radius from the sample, in reflectance. The range of measurement angles is limited by the sample width and thickness since both the main
transmitted beam, and at least the second double internal reflection (in transmission), or the main reflected
beam and fi rst reflection from the back face (in reflection) need to be unobstructed and included in the measurement. a photolithographic wire grid polarizer, two colour UV-Vis/NIR detector and direct sample view
optical design enabled uniform detection over alarge optical aperture, typical of an integrating sphere, but
without the physical bulk and optical losses making data collection faster.

88 Optical Glass and Optical Properties

535

Effect of glass composition on the optical

properties of colour conversion glasses for
white LED in BaO-ZnO-B2O3-SiO2 glasses
J. Hwang.1, C. Huh.1, J. H. Kim.1, M. J. Lee.1, T. Y. Lim.1, J. S. Yoo2, T. H. Park2
1
2

Korea Institute of Ceramic Engineering &Technology, Seoul, Korea;

Particlogy Co., Limited, Asan, Korea

To investigate the effect of glass composition on the properties of colour conversion glasses for white LED, five
BaO-ZnO-B2O3-SiO2 glasses, comprising different mol% of each four component, were tested. There is one glass
as areference, comprising 25mol% of each component and other four glasses, comprising 40mol% of one component and 20mol% of other three components in BaO-ZnO-B2O3-SiO2 glasses. Melted glasses were pulverized to
make glass frit of small particle size. Five colour conversion glasses were made by sintering the mixture of these
glass frits and YAG phosphor. The content of YAG phosphor of colour conversion glasses was kept at 5wt% and
the sintering temperatures of them were adapted with the consideration of softening temperature of each glass.
Characteristics of colour conversion glasses, such as Luminous efficacy, luminance, CIE (Commission Internationale de IEclairage) chromaticity, CCT (Correlated Colour Temperature) and CRI (Color Rendering Index)
were analyzed according to PL spectrum. Luminous and colour characteristics were dependent on the ratio of
each component in BaO-ZnO-B2O3-SiO2 glasses. Colour conversion glass, comprising 40mol% of BaO, showed
the best luminous efficacy and luminance but those characteristics of glass, comprising 40mol% of ZnO, showed
the worst result among five. But colour conversion glasses which showed good luminous efficacy and luminance,
showed yellowish chromaticity and low CCT values of under 6,000K because of their strong peak intensity around
550| |. Instead, colour conversion glasses which showed bad luminous efficacy and luminance showed white colour characteristics of CIE chromaticity, CCT. CRI values also showed similar tendency with CIE chromaticity,
CCT. Finally, YAG phosphor distribution in the colour conversion glasses was analyzed by XRF mapping and the
state of YAG phosphor in glasses was analyzed by XRD peak intensity variation of YAG phosphor.

539

Novel glasses with PbS quantum dots

Heo J.1, Xu K.1, Liu C.2
1

Department of Materials Science and Engineering and Division of Advanced Nuclear Engineering,
Pohang University of Science and Technology (POSTECH), Pohang, Republic of Korea
2
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology,
Wuhan, Hubei, P. R. China

Glasses doped with PbS quantum dots (QDs) can absorb and emit light at wavelengths that can be controlled from
~0.7 ~2.0m by adjusting QDs size from ~2 to ~10nm. They have possible applications as solid-state saturable
absorbers for mode-locked lasers and as fiber-optic amplifiers in optical communication. The average size of PbS
QDs and their size distribution inside glasses can be tailored by carefully controlling the temperature and duration
of thermal treatment. This process, however, normally results in an uncontrolled spatial distribution of QDs in the
glass matrix. Ion-implantation and femto-second laser irradiation techniques were used to realize space-selective
formation of QDs for micro and nano-photonic devices. Doping of rare-earth ions was found effective to control
the size of quantum dots. Using Ag nano-particles (NPs) as nucleating agents to realize accurate control of PbS QD
precipitation in glasses also has been investigated. Adding Ag+ ions allowed control of the size and size distribution
of PbS QDs together alarge increase of absorption and photoluminescence (PL) intensities.
This work reviews the several methods applied to control the size, shape and spatial distribution of quantum dots
in inorganic glasses. Glasses with anominal composition (mol%) of 50SiO2 35Na2O 5Al2O3 8ZnO 2ZnS
doped with 0.8mol% of PbO was prepared using melt-quenching. Precipitation of PbS quantum dots (QDs) in
silicate glasses controlled by heat treatment, rare-earth ion concentrations and Ag+ ion diff usion was investigated.
Radii of PbS QDs were controlled from 1~4nm with their photoluminescence wavelengths of 1~2m range that
match the fiber-optic telecommunication window. Rare-earths and Ag+ ions seem to provide sites for the heterogeneous nucleation of QDs

ICG Prague 2013 89

573

Optimizing composition of full-colour

luminescence glasses for white LED
Mika M.1, Hujova M.1, Nekvindova P.1, Lahodny F.1, Oswald J.2
1
2

Institute of Chemical Technology, Prague, Czech Republic;

Institute of Physics AVCR, Prague, Czech Republic

Novel glasses optimized to exhibit afull-colour luminescence spectrum can be used for the development and
production of highly efficient white light emitting diodes, W-LEDs. Recently, these diodes have been gaining an
increasing importance as advanced lighting sources with lower energy consumption and longer lifetime. The
advantage of the luminescent glass over common phosphors is mainly in their easier production resulting in
lower production costs. In our work, we developed the full-colour luminescence glasses for the LED chip emitting very intense blue light with the maximum at wavelength =460nm with the bandwidth FWHM=18nm.
We focused on alkalizincaluminosilicate and alkalialuminoborosilicate baseline glass systems. To achieve the
required full-colour luminescence, we doped the glasses with the oxides of rare earth elements Ce, Pr, Sm, Eu, Tb,
Dy, and/or Ho. We measured their transmittance and luminescence spectra with afibre UV-VIS spectrometer
in the range 300800nm and excitation spectra in the range 200900nm. For the glasses containing Ce, Ho or
Pr, we observed astrong absorption in the blue region and asignificant broadening of the transmitted excitation
light to the green region up to 560nm; for the glasses containing Tb or Dy, we observed the emission in the green
region; and for the glasses containing Eu or Sm, we observed the emission in the red region of the visible spectrum. To quantify the effects of composition, we plotted the colour of the emitted light in the CIE XYZ 1931 and
CIE 1976 L*, a*, b* chromaticity diagrams. Applying the multiple regression in combination with optical basicity
theory, we calculated the glass components effects on the chromaticity coordinates and developed corresponding
composition-property models. With this approach, we were able to optimize the glass composition and achieve
the required white full-colour luminescence spectrum for the blue LED.

90 Optical Glass and Optical Properties

Glass Chemical Durability

and Safety of Nuclear Power Plant

ICG Prague 2013 91

 92

151

Chemical durability of sodium silicate glasses

in neutral and alkaline aqueous solutions
Dathe M., Roggendorf H.
Martin-Luther-Universitt Halle-Wittenberg, Institute of Physics, Halle, Germany

The dissolution behaviour of two sodium silicate glasses (composition Na2OxSiO2, with x=2 and 3.3) were investigated in corrosion experiments. These experiments were done in static and dynamic set-ups. Corrosion values in
apH value range from 7 to 14 were gained for temperatures between 25C and 160C. Different corrosion media
were used (sodium hydroxide solution in different concentrations, de-ionized water, SiO2 containing solutions
and potassium hydroxide solution).
The corrosion solutions were analyzed with respect to dissolved parts (Na2O, SiO2). The altered glass was characterized. Therefore, scanning electron microscopy was performed in order to analyze the surface structure after
corrosion experiments. In addition, energy dispersive analysis was combined with SEM for information about
elemental depth profiles. Furthermore, reflective infrared spectroscopy and Raman microscopy were used for
information about the band assignments in the altered glass compared to the untreated glass samples. In-situ
investigations of the corrosion process showed, that crack formation occurs already during the corrosion.
The experimental data were compared with established corrosion models, which regard well known corrosion
mechanisms of silicate glasses, like ion exchange, network dissolution and developing of amodified surface. But
the effect of the crack formation was neglected in these models. The quantification of the crack formation process
was tried to be included in the corrosion modelling.

157

In-situ surface characterisation by optical

microscopy during corrosion tests of some
glasses differences and similarities
Pfeiffer Th., Dathe M., Roggendorf H.
Martin-Luther-Universitt Halle-Wittenberg, Institute of Physics, Halle, Germany

A standard method for the production of sodium water glass is the dissolution of sodium silicate glass, which was
investigated here. Besides corrosion processes like ion exchange or network dissolution, crack formation and spilling
were observed at the sample surfaces after standard corrosion tests. In order to exclude sample preparation as cause
of this phenomenon (drying for weighing during longer experiments), microscopic in-situ measurements of the
sample surface were accomplished. aspecial experimental set-up was developed with abinocular loupe (magnification 10X to 100X) for surface characterisation. This set-up was applied for in-situ measurements under varying test
conditions during static and dynamic corrosion tests. Corrosion processes were documented during aperiod of up
to four days. Surface alterations, glass dissolution and crack formation can be observed in fast motion videos. The
composition of the sodium silicate glasses investigated here was Na2OxSiO2, with x=2 and 3.3. Furthermore aslag
glass from copper processing was observed and analyzed. The avarage chemical compositon of the slag glass was
(major components only, in mass %): 47SiO2, 19CaO, 14Al2O3, 8MgO, 4K2O, 4Fe2O3, 1Na2O, 3 others.
Parameters like leachant (water, sodium hydroxide solution) and temperature were varied. The materials surviving short-time corrosion tests, the altered glass and the solution, were analysed. The solutions were characterized
by measuring pH value and concentrations of the dissolved components (Na2O, SiO2). Selected samples were analyzed by scanning electron microscopy with energy dispersive analysis in order to gain elemental concentration
profi les. The results were compared for similarities and differences with each other.

ICG Prague 2013 93

222

Spray dried glass for flame sprayed

coatings onto concrete
Zhang L., Prange A., Conradt R.
Department of Glass and Ceramic Composites, Institute of Mineral Engineering,
RWTH Aachen University, Aachen, Germany

279

Glass is an attractive coating material applied onto concrete against chemical attack. Flame spraying is afast and
commercial technique to produce the glass coating. Two differently prepared float glass powders were used as the
coating materials: sprayed dried powders and ball milled ones. The obtained results showed that the properties
of glass powder (morphology and particle size distribution) exhibit aclose relationship with the feedstock during
flame spraying, and further the microstructure of the as-sprayed float glass coatings. The effect of spray drying
process on the consequent coatings was also determined on the base of their tensile bonding strengths to the
substrate, and anti-corrosion performance, compared with the coatings from the ball milled glass powders. It
indicates that the characteristics and the properties of the flame sprayed glass coating depend not only on the
operating conditions but also on the powder feedstock.

Zn2+ adsorption on soda-lime silicate

and borosilicate glass and consequences
on their dissolution kinetics in water
Tourni A.1, Majrus O.1, Lefvre G.2, Manolescu G.1, Caurant D.1, Barboux P. 1
1

Laboratoire de Chimie de la Matire Condense de Paris site Chimie Paristech,

CNRS UMR 7574, Chimie Paristech, 11 rue P. et M. Curie, 75005 Paris, France;
2
Laboratoire d'Electrochimie, Chimie des Interfaces et Modlisation pour l'Energie,
CNRS UMR 7575, Chimie Paristech, 11 rue P. et M. Curie, 75005 Paris, France

283

Chemical durability of silicate glasses is akey issue in glass industry and in other fields such as the management of high
level nuclear wastes, which are immobilized in glass wasteforms, and the conservation of ancient glasses. The basic
dissolution processes of alkali silicate glasses consist in glass hydration, ionic exchange (Na+/H+) and hydrolysis of the
Si-O-Si bonds, the latter being the surface-controlled, rate-limiting step. Thus, the dissolution kinetics may be strongly
dependent on surface species that may modify the activation barrier to hydrolysis. In this work, we investigate the
effect of Zn2+ ions present in aqueous solution, on the dissolution kinetics of asoda-lime silicate glass and of asodium
borosilicate glass, using static conditions at low S/V (0.1cm-1) and ICP-AES analysis. Solutions were buffered (pH=7.5,
TRIS/HCl) or not, and the Zn2+ ions were provided as ZnCl2 salt at different concentrations. Zn2+ sorption experiments
demonstrate that Zn2+ cations have astrong affinity for surface silanol sites and allow quantitative assessment of the
surface complexation. Beside, astrong decrease of the Si dissolution rate is observed in both glasses, while the pH
stays at aconstant or even slightly acidic value due to the surface complexation. In particular, the borosilicate glass
dissolution is considerably slowed down, indicating that the surface complexation also contributes to stop hydrolysis
of the borate component of the network. Near-surface characterization of altered glass plates by TOF-SIMS confirm
the bonding of Zn2+ cations at the surface. Consequences on the chemical gradients in the altered layer are analysed.

Corrosion of IZOMER TT carded E-glass

fibers in Borate Water Solution
Soltesz V.1, Vlckova P.2, Faturikova K.2, Kankova H.2, Chromcikova M.2, Liska M.2
1
2

VUEZ a.s., Hviezdoslavova 35, Levice, SK;

Vitrium Laugaricio Joint Glass Center of IIC SAS, TnU AD, FChPT STU and RONA, a.s.;
Studentska 2, Trencin, SK

IZOMER TT carded E-glass fibers are commonly used as thermal insulation in nuclear power plant. In case of LOCA
(Loss of Coolant Accident) these fibers can be strongly corroded by particular cooling solution. The pH value of coolant

94 Glass Chemical Durability and Safety of Nuclear Power Plant

solution is stabilized by H3BO3/KOH buffering systems. Therefore the chemical durability of IZOMER TT fibers was
tested in present work. The static and flow-through leaching tests were realized in isothermal conditions. The glass
dissolution was followed by OES ICP and the corroded surface of glass fibers was studied by SEM/EDS.
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project ZDESJE, ITMS code 26220220084, of the Operational Program Research and Development funded
from the European Fund of Regional Development.

444

Kinetics and thermodynamics of glass fibrous

insulation corrosion by the coolant solution
building a kinetic model from experimental data
Liska M.1, Chromcikova M.1, Kankova H.1, Vlckova P.1, Faturikova K.1, Soltesz V.2
1
2

Vitrum Laugaricio Joint Glass Center of IIC SAS, TnUAD, FChPT STU, and RONA, Trencin, Slovakia;
VUEZ, a.s., Levice, Slovakia

Glass fibrous insulation is commonly used in the nuclear power plants. In case of aLoss of Coolant Accident the
chemical durability of the insulation plays acrucial role for solving the critical situation. The present contribution presents amethod of nonlinear regression analysis treatment of experimental data represented by the time evolution
of leaching solution chemical composition obtained from static leaching tests. The PHREEQC software is used to
calculate the quasi-equilibrium solution composition after dissolving of particular amount of glass in distilled water
or in the coolant solution. Various specific assumptions are taken for the possible crystallisation of oversaturated
crystalline phases. Simultaneously the solution composition is calculated after its stabilisation (e.g. by adjusting pH
by addition of nitric acid) performed before its quantitative analysis by Inductively Coupled Plasma Optical Emission
Spectroscopy. The Aagaard Helgeson kinetic equation is used for calculation of glass dissolution rate in the solution
of particular composition. The sum of squares of deviations between experimental and calculated composition of
leaching solution is minimised with respect to the parameters of Aagaard Helgeson kinetic equation and with respect
to undertaken assumptions of the crystallisation of oversaturated crystalline phases.
Acknowledgement
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project ZDESJE, ITMS code 26220220084, of the Operational Program Research and Development funded
from the European Fund of Regional Development.

494

Volatility control of borate from high

temperature sealing glass
Ihara R., Takahashi H., Takahashi Y., Fujiwara T.
Department of Applied Physics, Tohoku University, Miyagi, Japan;

In recent years, sealing glass materials were used as part of the solid oxide fuel cell (SOFC) and thermoelectric
conversion elements with high temperature state. For example, in the case of SOFC that operating temperatures are around 600 to 1,000C. Therefore, electrical power generation devices were negatively-affected by
volatilized elements from sealing glass materials such as boron and alkaline. In such instances, temperature
programmed desorption (TPD) techniques are important methods for the determination of volatile elements
and thermal property of glass. In this study, we investigated and controlled volatilization of borate from glass
to use the crystallization of glass at high temperature.
We have prepared Bi 2O3-ZnO-B2O3 glass systems. The volatility of elements were measured by Temperature
Programmed Desorption (TPD type V, Rigaku Corp., Japan). The samples were heated in vacuum at room temperature to melting temperature under various conditions. At the same time, mass spectra were obtained until
m/z=150. As aresult of TPD measurement, volatility of borate was related to glass transition temperature, and
inhibited by crystallization of glass.

ICG Prague 2013 95

 96

Computer
and Structural Modeling

ICG Prague 2013 97

 98

021

A study on CeO2 containing glass

discoloration by -ray irradiation
Nishida S., Choju K., Ohji M.
Nippon Electric Glass Co., Ltd., Otsu, Japan

Compositional effect on discoloration by -ray irradiation of CeO2 containing glass was investigated. It is well
known -ray irradiated glass is strongly discolored due to color center formation, which results from trap of
excited and isolated hole and/or electron by certain ions. It is also well known addition of CeO2 weakens glass
discoloration by -ray irradiation and its effect is reported to be mainly determined oxidation state of Ce ions.
Although glass composition would affect both color center formation and oxidation state of Ce ions, compositional effect on CeO2 containing glass discoloration by -ray irradiation is not understood well.
In this work, optical absorbance was measured before and after -ray irradiation to quantitatively evaluate glass discoloration by -ray irradiation changing glass composition such as Al2O3, B2O3 and alkaline oxide. Glass samples were
exposed to -ray equivalent to 25kGy in absorbed dose. Changes of optical absorbance and wavelength at which optical
absorbance peak was observed were examined and compared each other. Molecular dynamics calculations were also
carried out to discuss the relationship between optical absorbance changes and short range glass structure.

Kohara S.1, Akola J.2, Ohara K.1, Fujiwara A.1, Weber J. K. R.3, Benmore C. J.4
1

Research & Utilization Division, Japan Synchrotron Radiation Research Institute/SPring-8

1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan;
2
Department of Physics, Tampere University of Technology, P.O. Box 692, FI-33101 Tampere, Finland;
3
Materials Development, Inc., 3090 Daniels Court, Arlington Heights, IL 60004, USA;
4
Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439, USA

Understanding atomic structure and bonding upon glass formation is one of the most important scientific topics
in glass science. We have recently combined the reverse Monte Carlo (RMC) modelling technique with density
functional theory (DFT) simulations, to reveal the relationship between the atomic/electronic structure and glass
forming ability in several oxide glasses. The overarching advantage of this combination is that the RMC method
can produce alarge atomic configuration that is consistent with the measured diff raction and extended X-ray
absorption fine structure (EXAFS) data, while DFT simulations can optimize the RMC configuration to provide
electronic structure information through the use of asupercomputer. We have successfully applied this approach
to MgO-SiO2 glass in order to discuss the relationship between atomic/electronic structure and glass forming
ability, with aspecial focus on the concept of topological order/disorder proposed by Gupta and Cooper. Furthermore, we address the discrepancy in Mg-O coordination between our RMC model and recent NMR data reported
by Shimoda et al. and Sen et al. We will also present our recent results on CaO-Al2O3, in which we discuss the
formation of an electride glass as reported by Kim et al.

ICG Prague 2013 99

023

Atomic and electronic structure of oxide

glasses revealed by a combination of reverse
Monte Carlo method and DFT simulation

024

Determination of the intermediate length

scale structural motifs in mixed network
phosphate glasses by 1D/2D correlation NMR
Tricot G.1, Raguenet B.2, Silly G.2, Ribes M.2,
Pradel A.2, Vezin H.1, Wegner S.3, Van Wllen L.4.
1

Universit de Lille, Sciences et Technologies, 59655 Villeneuve dAscq, France

Institut Charles Gerhardt UMR CNRS 5253, Universit de Montpellier 2, 34095 Montpellier, France
3
Bruker Biospin GmbH, solid state NMR application, Silberstreifen, 76287 Rheinstetten, Germany
4
Institut fr Physik, Universitt Augsburg, 86135 Augsburg, Germany
2

025

P2O5 based based glasses have attracted much attention over the last decades because of the low Tg, the high
thermal expansion coefficients, the UV transparency and the high oxide acceptation ability associated to the
phosphate network. Nevertheless, P2O5 based glasses are also known for their poor stability that strongly limits
the number of applications they are involved in. asolution to develop stable phosphate glasses is to combine P2O5
with another glass former oxide (GFO). If the 1D 31P solid state NMR spectroscopy has proven to be avaluable
technique for the characterization of the simple phosphate glasses (where the network is only formed by interconnected phosphate tetraedra), it appears that the 31P 1D spectra of the mixed network phosphate glasses do not
provide such interesting information. The 1D spectra are composed of very broad resonances resulting from the
superimposition of several signals with close chemical shifts. No structural information can be extracted from
the 1D analysis and the real structure of the mixed networks has remained in many cases uncharacterised. We
show in this communication how the use of 1D/2D NMR correlation techniques (CP-HETCOR, D-HMQC, DQSQ, REAPDOR, REDOR, J-RESolved) can be used to overcome the poor quality of the 1D analysis. The strategy
has been successfully applied to alkali boro-, vanado and alumino phosphate in the 45Li2O xB2O3 (55-x)
P2O5, 50Na2O xV2O5 (50-x)P2O5 and 50K 2O xAl2O3 (50-x)P2O5 systems. At the light of these results, the
impact of the glass composition on the Tg property has been re-investigated and the nature of the mixed units
governing the evolution of Tg has been discussed in the three systems.

Formulation and characterization of phosphate based

glasses with low-Tg and high thermal stability
Rajbhandari P., Montagne L., Tricot G.
Unit de Catalyse et de Chimie du Solide, UMR CNRS 8181, USTL-ENSCL, Universit de Lille 1,
Villeneuve dAscq F-59652, France.

Phosphate based glasses are involved in awide variety of technological applications including biomaterials, sealing glasses, antioxidation coatings or confining matrices for special nuclear waste material, all of which benefit
from the lower thermal characteristics, higher thermal expansion coefficient or high oxide-acceptation ability.
Thus the subsequent interest in phosphate glasses stemmed as potential alternatives to silicate glasses, especially
for many low temperature applications. However the pure phosphate glasses suffer from poor chemical and thermal stability that severely hinders their straightforward applications. In this work, we present the first results of
aproject dedicated to the improvement of the thermal stability of low-glass transition temperature (Tg) (< 350C)
glasses. apyrophosphate composition which was first formulated in the (66.6-x)MO xN2O 33.4P2O5 system
where M=Zn, Pb, Cd, Cu and N=Li, Na, K. Then, the influence of the insertion of small amounts (15%) of B2O3
on their thermal stability was assessed employing the Angell parameter (K A =Tx-Tg) and the resistance against
crystallization after isothermal treatments. The effect of doping on the pyrophosphate glass structure was also
investigated with 1D/2D advanced solid state NMR (11B/31P D-HMQC, D-INEPT, REAPDOR, 11B & 31P DQ-SQ
techniques) in order to understand how the doping elements enter into the network and how it interacts with the
phosphate network to finally change the macroscopic material properties.

100 Computer and Structural Modeling

133

Molecular dynamics simulation

of sodium borosilicate glasses
Takada A.1,2
1
2

Research Center, Asahi Glass Co., Ltd, 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Japan;
University College London, Gower Street,, London, United Kingdom

Borosilicate glasse is industrially important material with low thermal expansion coefficients and high resistance
to thermal shock. However, due to the mixture of two network formers, SiO2 and B2O3, its structure and properties behave in avery complex way. The Molecular Dynamics method was applied to investigate the atomic structures of sodium borosilicate glasses. In this study the change in glass structure was analyzed in asystematic way
when two important compositional ratios, R (=Na2O/B2O3) and K (=SiO2/B2O3) were varied. First, it was found
that the ratio of 4-fold to 3-fold boron atoms could be reproduced reasonably in harmonic with the NMR measurements and thermodynamic calculations. Moreover, the local structures were analyzed in terms of structural
balance between SiO4 units and BO3/BO4 units. The crystal structure and its corresponding glass structures were
also compared in terms of chemical ordering and geometrical topology.
Second, the structures in the well-known phase-separation regions were investigated. It is still very difficult to reproduce phase-separation phenomena by atomistic simulation. No clear indication of phase separation was observed
by using normal simulation techniques. On the other hand, several new techniques were applied to enhance phase
separation in glasses. In some extreme cases new features in either statistic or dynamic structure were observed.
Finally, the whole picture on sodium borosilicate structure speculated from the calculated results was discussed.

189

Structural characteristics of cation mixing

in SiO2-Na2O-RO (R = Ca, Mg) glasses
by computer simulations
Tanaka A., Hijiya H., Matsunaga M., Kondo Y., Fukasawa Y.
Research Center, Asahi Glass Co., LTD. Yokohama, Japan

Extent of cation mixing in soda-lime silicate glasses has long been studied, because of the technical and scientific
importance of these systems. The quantification of atomic disorder in silicate glasses is essential for understanding the microscopic origin of optical properties. Yet the details of atomic-scale disorder among network modifier
cation such as Ca, Na and Mg in the glasses are far from being understood.
Disorder of cation distribution has been investigated in several systems. The results can be divided between glasses showing arandom mixing and those showing anonrandom mixing. Recent neutron diffraction experiments
on soda-lime silicate glasses have shown anon-random distribution of cation, with the prevalence of cation pairs.
Cationcation interactions and cation coordination numbers are important structural parameters that could
affect strongly optical properties. However, experimental results indicate nearest neighbour atomic distance and
coordination, it is difficult to analyze condition of 2nd and 3rd neighbour atom and evaluate aggregation structure
compose of cation. In the past decade, with the advent of powerful computers to implement atomistic computational techniques such as Reverse Monte Carlo (RMC) modelling and molecular dynamics (MD), computer
experiments were carried out extensively to study cation distribution.
In this work, we performed RMC modelling and MD simulations to provide characteristic structural information
on several different compositions of soda-lime glasses, 74 SiO2-16Na2O-10RO (R=Ca, Mg) (mol%). The distribution and local strcture of cation in the glasses by RMC and MD method showed the critically interesting structures. These results would be allowed to infer some conclusions for revealing significant structural properties of
the glass composed of several cations.

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203

Structure of MgO-SiO2 system using empirical

molecular dynamics simulations
Inoue H., Masuno A.
Department of Materials and Environmental Science, Institute of Industrial Science,
The University of Tokyo, 4-6-1, Komaba, Meguro-ku, Tokyo, Japan

253

The structural models for MgSiO3 and Mg2SiO4 glasses have been prepared by means of the molecular dynamics
technique. Total correlation functions for X-ray and neutron diffraction are calculated from the models and they
are agreed with the observed ones. In the structural models for both glasses, there are MgOn (n=4, 5, 6) polyhedra and the average coordination numbers of Mg ions are about 4.8. The average coordination numbers of Si ions
are 4.0. The obtained proportion of the Qn species are substantially agreed with those obtained from 29Si NMR
and Reverse Monte Carlo simulations. The average bridging oxygen for SiO4 tetrahedra is 2.4 in the structural
model for the MgSiO3 glass. The Mg2SiO4 composition glass with low glass-forming ability has been synthesized
using arapid quench method or containerless processing. There are from Q0 to Q2 species in the structure models
for the Mg2SiO4 glass and the average bridging oxygen is 1.0. It indicates that the number of oxygen, which is
connected with only Mg ions, increased.

Essential structural features of 'stuffing' alkali

accommodation in ion-exchanged silicate glasses
from molecular dynamics simulations
Kreski P. K.1,2, Varshneya A. V.1,2, Cormack A. N.1
1
2

Alfred University, Alfred, New York, United States;

Saxon Glass Technologies, Inc., Alfred, New York, United States

296

Molecular dynamics simulations have been used to elucidate the essential features of the structural accommodation of stuffing ions (via ion exchange) in sodium silicate, soda-lime silicate, and sodium aluminosilicate glasses.
The structural differences between these compositions governing their stuffing alkali accommodation characteristics, and ultimately their compression generation after ion exchange, are highlighted. In particular, attention
is focused on network topology and the contrast in features of alkali sites associated with non-bridging oxygens
versus those associated with tetrahedral alumina groups.

Molecular dynamics simulations

of phosphate-based bioactive glasses
Christie J. K., Ainsworth R. I., de Leeuw N. H.
Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK.

Biomaterials which play an active role in tissue regeneration are used increasingly widely in arange of biomedical
applications. Among these, phosphate-based bioactive glasses (PBGs) are of considerable interest, due to their
unique properties. PBGs dissolve in physiological surroundings, with a rate of dissolution which can vary by
several orders of magnitude depending on the precise glass composition, which allows the tailor-made design of
these glasses for specific applications. One potential application is their use in the targeted delivery and controlled
release into the body of drugs, antibacterial agents, nutrients and other substances, which require low doses at
specific locations. Optimisation of PBGs for these applications requires detailed knowledge of their atomic structure which, due to their amorphous nature, can be difficult to achieve experimentally. We use first-principles and
classical molecular dynamics simulations to create atomistic models of PBGs, made up of different compositions
of P2O5, Na2O and CaO and other dopant species. We describe our recent simulations on the structure of PBGs,
including how the formation of different structures at the medium-range length scales around different modifier
ions (e.g. Na and Ca) affect the dissolution rate. We also show the effect of the addition of Ti into the glass and the
consequences for the structure and dissolution rate.

102 Computer and Structural Modeling

442

Role of alkali elements on the rheology

and the structure of aluminosilicate melts and glasses
Le Losq C.1, Neuville D. R.2
1

IPGP-CNRS, Gochimie et Cosmochimie, 1 rue Jussieu, 75005 Paris, France, lelosq@ipgp.fr

Alkali elements are present at high concentrations in industrial glasses, ceramics and vitroceramics as well as in
natural (volcanic) glasses. They affect properties and structure of silicate and aluminosilicate glasses and melts.
Furthermore, in those compositions, the mixing of different alkali elements impact also glass and melt structure,
viscosity and thermodynamical properties (Le Losq and Neuville, 2012, Chemical Geology). Therefore, the study
of the role of alkali elements on the rheology and the structure of aluminosilicate melts and glasses is of prime
importance in order to understand their impact on glass-making processes and on geological processes.
In this communication, we will present our results on the properties of lithium, sodium and potassium aluminosilicate melts and glasses. We will show that the viscosity of alkali aluminosilicate melts depends strongly on the
alkali element that is present in the aluminosilicate network. To go further and as rheological properties are directly linked with structural properties, we will present our first results obtained by Raman and NMR spectroscopy. These last ones provide important structural pieces of information on the polymerization state of glasses and
melts, and also on the environment of tetrahedrally coordinated cations. The data show that the largest the alkali
element is, the highest the viscosity is and the highest the intertetrahedral mean angle is. Furthermore, potassium
glasses contain ahigh proportion of small membered tetrahedral rings in comparison to the lithium or sodium
glasses. It appears that the presence of large alkali cations in an aluminosilicate amorphous network extends the
structuration at the middle range order of this network. This results in anon-random mixing of alkali elements
in aluminosilicate glasses and melts, which affects strongly and non-linearly their properties.

540

Structure and dynamics of ZnO-MoO3-P2O5

glass: A molecular dynamics study
Machacek J.1, Liska M. 2, Sulcova J. 2, Gedeon O.1
1
2

Department of Glass and Ceramics, Institute of Chemical Technology, Prague, Czech Republic;
Institute Vitrum Laugaricio Joint Glass Center of Institute of Inorganic Chemistry SAS, Alexander
Dubcek University of Trencin and RONA Lednicke Rovne, Trencin, Slovak Republic

The ab initio molecular dynamics simulation of ZnO-MoO3-P2O5 glass has been performed to obtain amodel
of the glass structure. Pair distribution functions, coordination numbers, a Q-species distribution have been
calculated and compared with the available experimental data (Subcik, JNCS 2010) and some theoretical models.
adiscrepancy has been found mainly in the Q-species distribution. The dynamics of glass structure has been
studied within the harmonic approximation. Partial vibration spectra have been compared with the available
Raman data. amore detailed look has been provided by projecting of the normal modes of vibrations onto the
typical vibrational modes of the symmetrized structure units (PO4 tetrahedra, P-O-P bridges, etc.). This work
was supported by the Grant Agency of the Czech Republic through the Grant No. P108/10/1631.

ICG Prague 2013 103

599

The tellurium coordination and the role of oxygen

in pure amorphous TeO2 and tellurite glasses
Hannon A. C.1, Barney E. R.2, Holland D.3, Feller S. A.4,
Umesaki N.5, Tatsumisago M.6, Orman R. G.3
1

ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, OX11 0QX, UK

Novel Photonic Glasses Research Group, Electrical Systems & Optics Research Division,
Faculty of Engineering, University of Nottingham, Nottingham NG7 2RD, UK
3
Physics Department, University of Warwick, Coventry, CV4 7AL, UK
4
Physics Department, Coe College, 1220 1st Ave. NE, Cedar Rapids, IA 52402, USA
5
Division of Materials and Manufacturing Science,Osaka University,Suita, Osaka, 565-0871, Japan
6
Department of Applied Chemistry, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan
2

The structures of tellurite glasses are less well understood than is the case for other glass forming systems such as silicates, borates and germanates. Three factors which contribute to this lack of understanding are: 1) The basic structural unit in crystalline TeO2, the [TeO4] pseudo trigonal bipyramid, has two different Te-O bond lengths; 2) tellurite
glass shows acomplex, composition-dependent change in coordination from [TeO4] pseudo trigonal bipyramids to
[TeO3] trigonal pyramids; 3) Pure amorphous TeO2 cannot readily be prepared, with the consequence that it is little
studied, and usually it is assumed that its structure involves only [TeO4] units, as in crystalline -TeO2.
Neutron diff raction was performed on a sample of pure amorphous TeO2, prepared by a rapid quenching
twin-roller technique, yielding aTeO coordination number of 3.68(4), and acorresponding OTe coordination
number of 1.84(1). This shows that about 16% of the oxygens in pure amorphous TeO2 are terminal oxygens, and
the Raman spectrum of pure amorphous TeO2 is also consistent with the presence of terminal oxygens.
Neutron diff raction measurements on potassium tellurite and vanadium tellurite glasses yield aTeO coordination number which is constant (~3.7) for less than about 15mol.% K 2O, with adecline in the coordination number
for larger modifier contents. This decline is readily explained as occurring when the terminal oxygens are fully
coordinated by modifier cations.

104 Computer and Structural Modeling

Mechanical Properties

ICG Prague 2013 105

 106

094

Effect of salt bath composition on chemical

tempering of sodium-containing silicate glass
Sglavo V. M.
University of Trento, DIMTI, Trento, Italy

In the recent years, ion exchange process has re-acquired great interest due to the possibility of mechanically reinforcing glass articles of different shapes (even curved, wavy or hollow) and with limited thickness thus
improving the performances of several glass applications such as pharmaceutical packaging, transparent lightweight armour, transparencies for private vehicles, trains and aircrafts, 3D touch/flexible displays, photovoltaic
modules. In the present work, soda lime silicate float glass and sodium borosilicate glass from commercial source
were considered and subjected to ion exchange in different KNO3 salts thus promoting K-Na interdiff usion. The
treated samples were then characterized in terms of potassium penetration profi le, residual stress and mechanical
strength to point out the influence of the bath composition on final performances. It is shown that even small
amount of impurities are responsible for adifferent ion exchange process especially in terms of the real surface
activity of the exchanging ions, thus determining variable effects in terms of final mechanical resistance.

108

Elasticity and viscosity as probes of the structural

stability of glass-forming liquids at high temperature
Rouxel T., Clari F., Gueguen Y., Houizot P., Orain H.
LARMAUR, ERL-CNRS 6274, University of Rennes 1, France

Elastic moduli and viscosity coefficient are very sensitive to structural changes occurring in glass forming liquids.
For instance the glass transition range gives birth to asignificant change of the softening rate and crystallization
processes show up on both elasticity and viscosity curves. In this latter case, the kinetics of the increase in the
elastic moduli during an isothermal treatment allows for the detremination of the fraction of crystals versus
residual glass at any time in situ during crystallization. Structural relaxation has also adirect incidence on the
elasticity and viscosity curves. The temperature dependence of Poisson's ratio is another interesting feature to
evaluate the structural stability of glass-forming liquid through the glass transition range, i.e. in atemperature
interval where both shear and longitudinal wave velocities can be easily measured.

109

Photo and ultra-fast video imaging

of fracture of pristine silica glass fibers
Tokmakov K. V.1,2, Cumming A.1, Hough J.1, Jones R.1, Kumar R.1,
Reid S.4, Rowan S.1, Lockerbie N. A.2, Wanner A.3, Hammond G. D.1
1

SUPA, University of Glasgow, Glasgow, UK;

SUPA, University of Strathclyde, Glasgow, UK;
3
Max-Planck-Institut fur Gravitationsphysik, Hannover, Germany;
4
SUPA, University of the West of Scotland, Paisley, UK.
2

Modern detectors searching for gravitational waves radiated by astronomical sources operate by measuring the
relative positions of massive solids the mirrors of laser interferometers. These mirrors are suspended on thin
fibers as pendulums. acritical requirement for these pendulums is ultra-low mechanical loss factors (<10-8), and
thus low thermal displacement noise.For this reason the mirrors and their suspension fibers are produced from
pure silica glass. The mass of the mirrors (test masses) of the largest GW detector aLIGO is 40 kg, where each test
mass will be suspended on 4 fibers with diameter 400m. It is known from the literature that silica fibers can exhibit an ultimate breaking stress in excess of 5GPa. However many factors would significantly reduce the strength.
a preliminary study of the fabrication and breaking of flame and laser pulled fibers has been performed. For
abetter understanding of fracture mechanisms we conducted aseries of breaking experiments with high speed
photography and video imaging. We confirm that our preparation procedure (based on flame or laser polishing
of the silica stock) allows us to pull fibers with aflawless surface. However, thick fibers (diameter >230m) break

ICG Prague 2013 107

143

mainly at their ends at amuch lower stress. This reduction in strength is shown to correlate with heating of the
neck and stock area in order to aid in alignment prior to testing. Besides the initial fiber breaking (that occurred
usually near the thinnest point), an explosive fracture of silica glass is observed, mainly in the heated neck areas. This character of fracture is presumable caused by interaction of thermo-induced strength and shock elastic
waves propagating along fiber after breaking.

Ion exchange strengthening glasses

and glass-ceramics from Li2O-Al2O3-SiO2 (LAS) system
czka K.,Cholewa-Kowalska K.,czka M.
AGH University of Science and Technology, Faculty of Material Science and Ceramics, Departament
of Glass Technology and Amorphous Coatings, A. Mickiewicza Ave. 30, 30-059 Cracow;

218

Research were focused on strengthening the both glass and glass-ceramics of Li2O-Al2O3-SiO2 (LAS) system by
low-temperature ion exchange. In the glass-ceramic material from this system crystallization of both Li-di-silicate and Li-alumina-silicates occurs. P2O5 is used as anucleation agent for Li-di-silicate crystallization while the
ZrO2 acts as acrystallization nucleator of Li-alumina-silicates DTA method was used to determine nucleation
and crystallization conditions. Phase composition of obtained glass-ceramic materials was determine using XRD
method. The glasses and glass-ceramics were chemically strengthened by aion exchange Li+,Na+ K+ in asurface
layer of material. The samples were immersed for various time in abath containing amolten potassium salts. This
resulted in replacement smaller sodium and lithium ions in the glass surface by the larger potassium ions derived
from the salt bath. It involved the compressive stress in surface layer of materials making them more resistant
on bending. Glasses and glass-ceramics after ion-exchange process were characterized by over two times higher
flexural strength compared to the starting materials. Differences in behaviour of glasses and glass-ceramics of
this same composition during ion exchange were shown.

Approach to the mechanical properties

of inorganic glasses
Philipps K.1, Stoffel R.2, Conradt R.1, Dronskowski R.2
1
2

Institute of Mineral Engineering, RWTH Aachen University, Germany;

Institute of Inorganic Chemistry, RWTH Aachen University, Germany

264

For different applications (e.g glass fibres) glassy materials with very high elastic moduli are needed. It is the
purpose of the present contribution to help shift the development of such materials from amerely empirical to
asystematic approach. This novel approach to the mechanical properties of multicomponent glasses consists of
a combination of ab initio quantum-mechanical and thermodynamic calculations. The aim is to explore crystalline structures with outstanding mechanical properties, and to identify the structural changes invoked by
agradual increase of volume. This yields aset of properties of glassy entities isochemical to the single crystals explored. Then, the properties of glassy entities are superimposed to those of the multicomponent matrix by using
thermodynamic methods, and employing superimposition principles.

Evolution of mechanical properties with temperature

of ternary metallic glasses (Zr90-xCuxAl10)
Clari F.1, Idriss M.1, Yokoyama Y.2, Rouxel T.1
1
2

LARMAUR, University of Rennes1, France;

Institute for Materials Research, Tohoku University, Sendai 980-8577 Japan;

In this study, we measured the Youngs modulus (E) and the internal friction (Q-1) of bulk metallic glasses
Zr90-xCu x Al10 for x =30, 35, 40, 45 and 50. Using atechnique of resonant frequency and damping analysis, we

108 Mechanical Properties

recorded these parameters in real time from room temperature up to 800C. We performed two kinds of thermal treatment: i) bellow Tg during more than one day in order to analyze the annealing treatment; ii) above Tg
with constant temperature rate in order to characterize the crystallization process. The evolution of Q-1 and E
will be discussed and revealed interesting information concerning the changing of the structure during these
thermal treatments. In fact the internal friction evolution does not have the same behaviour for the heating and
cooling stages. We also investigate the effect of the annealing treatment on the hardness (Hv) and on the fracture
toughness (KIC). After the crystallisation treatment we performed phase characterization of the samples by X-Ray
diff raction technique. The crystalline phases and their influences on the evolution of Youngs modulus will be
discussed in respect with the Zr/Cu ratio.

268

Modern photoelastic technology

for residual stress measurement in glass
Aben H.1, Anton J.2, Errapart A.2, Paemurru, M.2
1
2

Institute of Cybernetics, Tallinn University of Technology, Estonia;

Glass Stress Ltd, Tallinn, Estonia

Photoelastic effect in glass was discovered by Estonian-German physicist Thomas Johann Seebeck in 1814. Since
then this effect has been used for the assessment of residual stress in glass products. For along time that was
made by visual observation of the photoelastic images in simple polariscopes. However, in parallel with the rapid
development of the photoelastic stress measurement technology in the second half of the last century, aqualitative change in the glass stress measurement methods has taken place. Modern computer controlled polariscopes
have been developed and are being manufactured by several companies. Residual stress measurement in glass has
obtained greater importance due to the fact that most of the glass products are nowadays manufactured using
tempering technology. To obtain optimum degree of temper, tempering stresses are to be measured with great
precision. Different measurement technologies are to be applied by measuring stress in glass. In flat glass, the
surface stress can be measured using the tunneling effect. More complete analysis of stress in architectural glass
panels and in automotive glazing can be obtained with the scattered light method. Stress measurement in both
thermally and chemically tempered flat glass with the scattered light method will be described. For stress measurement in glass articles of complicated shape like in hollow glassware, tubes, electric lamps etc, one has to use
transmission polariscopes, supplied with intelligent soft ware for the interpretation of the measurement results
using methods of photoelastic tomography. The paper is illustrated by numerous examples of stress measurement
in architectural glass panels, automotive glazing and hollow glass articles.

274

Process optimization for chemical

strengthening thin glasses
Patschger M., Rssel C.
Otto-Schott-Institute, Jena University, Jena, Germany

There are many requirements for glasses used as displays, touch screens, as well as in solar, transport and security
applications. In addition to transparency and scratch resistance, weight optimization is especially aspired. Achieving
constant mechanical properties while reducing the glass thickness, the strength of the glass must be increased.
While the theoretical glass strength is very high, the strength in applications is one to two orders of magnitude lower.
During the life span new contact damages in the order of several micrometers constantly arise and act as cracks in the
sense of the stability theory of Griffith. Therefore an active protection against unstable crack growth is required.
The method of chemical strengthening may be used to introduce compressive stresses near the surface of the
glass via ion exchange processes. The current state of the art provides the immersion of asodium-containing
glass in apotassium salt melt. Hence crack growth is only possible by overcoming these additional compressive
stresses. atechnological alternative to using asalt bath is presented. After spraying an aqueous salt solution on
the pre-heated glass surface, the ion exchange between the glass and the salt layer can be realized in conventional
annealing furnaces. The mechanical strength of the prepared ion exchanged glasses are compared with conventionally chemical strengthened glasses.

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456

Lattice dilation in an ion-exchanged glass

via direct strain measurements
King E. A., Zhao D., Allan D. C.
Science & Technology Division, Corning Incorporated, Corning, NY 14831, United States

528

Chemical strengthening of glass by ion exchange involves the mutual diff usion of alkali ions of differing size.
The atomic size mismatch of these exchanged alkali ions produces elastic strain, leading to dimensional changes
within the glass. The lattice dilation coefficient (B), defined as the strain per unit of molar concentration change
of the exchanged alkali ions, is fundamentally important to understanding strengthening mechanisms during
ion exchange. Previously, B has been investigated via measurement of the residual stresses introduced during ion
exchange. However, the value of B may have been underestimated due to the coexistence of structural and stress
relaxation during ion exchange processes. Here, for the first time, we access the B parameter via direct strain
measurements by tracking dimensional changes as afunction of ion exchange time and temperature in an alkali
aluminosilicate glass. The resulting dimensional changes are found to be linearly proportional to the weight gain
of the glass during ion exchange for relatively low ion exchange temperatures. Departure from this linear relationship is observed at higher ion exchange temperatures due to the presence of structural and stress relaxation.
aphysical model for the dimensional change of the glass during ion exchange is derived and the value of B found
is compared with that obtained from stress measurements. The respective role of stress and structural relaxation
in lattice dilation during ion exchange is also discussed.

Finite Element Analysis of container's geometry

DEste A., DallIgna R., Silvestri M.
Stazione Sperimentale del Vetro, Murano, Italy

FE Analyses of glass containers are usually carried out for three main purposes: verification, design or optimization of glass containers.
Verification aims to determine what is the stress field induced by external loads on agiven containers and to verify
whether it is allowable. Together with fracture analysis, verification analysis may also assess the load or stress at
which afailure occurred.
We talk about design analysis when anew container's geometry (i.e. thickness or shape) is sought in order to
achieve astress lowering or glass weight reduction. As the verification approach, also design is usually based on
limiting local stresses peaks.
A more advanced procedure to define both the geometry and weight of aglass container can be referred to as
optimization analysis, in which the bottle's shape ranking is not simply based on the reduction of the tensile
stress peaks. Indeed, the main target is to achieve minimum failure probability in service, which depends on the
extension and the location of the zones under tensile stress. This evaluation is carried out by means of the Weibull
statistic, using the parameters derived from breakage tests and fracture analyses on containers that have undergone the degradation resulting from normal manipulation.
This work elucidates the fracture probability assessment under amulti-axial stress state. How to estimate the Weibull parameters through burst testing and FEA of the tested bottles is also treated. Previous topics are combined
in order to evaluate the geometry of aglass container which is deemed capable of withstanding internal pressure.
Some practical case studies will be reported.

110 Mechanical Properties

537

Ionic exchange in glasses for new

mechanical and optical properties
Leboeuf V.1, Blondeau J.-P.1, De Sousa MenesesD. 2, Vaills Y.2
1
2

CEMHTI UPR3079 CNRS, Site Cyclotron, 3A rue de la Frolerie, 45071 Orlans Cedex 2, France
CEMHTI UPR3079 CNRS, Site haute temprature, 1D rue de la recherche scientifique,
45071 Orlans Cedex 2, France

Ion exchange in glass is a chemical tempering technic which gives rise to mechanical and optical properties
change. In the case of sodium for potassium ion exchange, glass will see improvement in his mechanical properties by higher incoming ion radius. Ion exchange is obtained by dipping the glass into abath of pure potassium
nitrate at atemperature above the eutectic. The experimental parameters are the temperature of the bath and the
exchange time. The different kinds of commercial silica soda lime glass are immersed at temperature below the
glass transition. In our case, the study is driven between 375 and 500C for an exchange time between 2 and 8
hours.. Ion exchange occurs between the incoming ion K+ and the out coming Na+ ion. As the potassium ion has
abigger ionic radius than that of the sodium or lithium, it leads to surface glass compression, while the central
part is in tension. For abetter understanding of the chemical tempering, different characterization techniques
have been employed for several glass compositions: Infrared spectroscopy is used to characterize changes in the
structure of the glass (Qn modes area evaluation around 1,000cm-1) and exchange mechanisms (NaO and KO
far infrared), scanning electron microscope allow to determine the concentration profiles of potassium and the
diff usion coefficient. This work is based on diff usion models according to the solution of the Fick equation. The
Brillouin diff usion can help us to determine the evolution of the mechanical properties of glass in function of the
exchange depth and the concentration profile of potassium for the different exchange times. This technic is based
on the transverse and longitudinal frequency use to determine the elasticity constant of the glass and subsequently the mechanical properties (Young modulus and Poisson ratio).

ICG Prague 2013 111

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Biomaterials

ICG Prague 2013 113

 114

111

Crystallization of chlorapatite
from chloride containing bioactive glasses
Chen X. J.1, Karpukhina N.1, Wilson R. M.2, Hill R. G.1
1
2

Dental Physical Sciences, Institute of Dentistry, Queen Mary University of London, London, United Kingdom;
School of Engineering and Materials Science, Queen Mary University of London, London, United Kingdom

Low sodium content fluoride containing bioactive glasses have been extensively studied for dental applications,
since they form Fluorapatite (FAP) which is more acid resistant compared with Hydroxyapatite (HAP) which
is acomponent of tooth enamel and bone material. However, excess fluoride leads to CaF2 formation and the
possibility of dental fluorosis. The fluorine containing glasses of low sodium content crystallize to FAP. Chlorine
and fluorine are both halogen elements. The chloride ion is larger in size, which could contribute to amore extended open glass network. The presence of chlorine in bioactive glass is considered to favour the crystallization
of Chlorapatite (ClAP). In addition, there is no restriction on chloride content of toothpaste. These advantages
make the chloride containing bioactive glass innovative and valuable in toothpaste applications, as abioactive
glass-ceramic bone substitute and radioactive waste vitrification.
The SiO2-P2O5-CaO-CaCl2 glasses with different CaCl2 contents and afixed network connectivity of 2 were designed
and synthesized by amelt and quench route. The glasses were characterized by differential scanning calorimetry
(DSC). The samples were heat treated and the crystallization was investigated using X-ray diffraction (XRD). The
microstructures of the crystallized glasses were evaluated by scanning electron microscopy (SEM). The 31P and 35/37Cl
nuclear magnetic resonance (NMR) was used to characterize the glass structure and crystalline phases formed. The
DSC results demonstrate adecrease in the glass transition temperature with an increase in CaCl2 content. The XRD,
SEM and NMR results confirmed the Chlorapatite crystallization in chloride containing glasses.

Kent N. W., Hill R., Karpukhina N.

Dental Physical Sciences, Queen Mary University of London, London, United Kingdom

Since the discovery bioactive glasses have been used for anumber of biomedical applications. akey application
has been as bone substitute materials where granules of bioactive glass are implanted into sites of bone defects.
However, granulated bioglass after implantation have no inherent strength and can erupt from the implantation
site. The presented research demonstrates the use of bioactive glasses as reactive precursors for the formation of
calcium phosphate cements. Glasses within the system of SiO2-CaO-Na2O-P2O5-(CaF2) were produced and the
effect of glass composition on cement properties was investigated. Bioactive glasses were mixed with Ca(H2PO4)2
to an overall calcium to phosphate ratio of 1.67, this mixture was then mixed with a2.5% solution of Na 2HPO4
to initiate the cement setting reaction. Each cement paste was then placed into cylindrical mold and allowed to
set for two hours, after which this was removed and immersed into Tris buffer solution. The results have shown
that changes in glass composition have an effect on the cement phase that forms. The cements with three different phases, brushite (CaHPO4.2H2O), octacalcium phosphate (Ca8(HPO4)2(PO4)4, OCP) and hydroxyapatite
(Ca10(PO4)6(OH)2, HAP), depending on glass composition have been produced. Increasing the phosphate content
of the glass had adramatic effect of the cement forming ability of the glass. The phosphorus-free glass had no
cement forming ability. Increase in P2O5 content from 2 to 6mol% led to formation of the water stable fast setting
cement. The results demonstrate the key role phosphate plays in the dissolution of bioactive glasses. When CaF2
was added to the glass composition the cement phase that formed was fluorapatite Ca10(PO4)6F2, FAP) rather than
HAP or OCP that both formed from the fluoride-free glasses.

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130

Bioactive glasses as reactive precursors

in the formation of novel calcium phosphate cements

135

In-vitro degradation of holmium

containing lithium silicate glasses
Zhang D., Li N., Hupa L.
Process Chemistry Centre, bo Akademi University, Turku, Finland

155

In the preset work the selection of suitable lithium silicate (LS) glass matrices for incorporation of holmium
oxide (1 and 2wt%) and the in-vitro properties of the Ho-LS glasses with potential of radiotherapy treatment for
cancer were studied. The dissolution behaviour of mixtures of the Ho-LS glasses and bioactive glass 45S5 was
also observed. Glass particles were immersed in SBF at 37C with aconcentration of 50mg/ml up to 4 weeks. At
selected time intervals, the pH and ion concentrations (ICP-MS) of SBF were determined. The change on the glass
was observed by SEM/EDXA. The results showed that by adjusting the composition of the LS glasses the in-vitro
degradation could be controlled. Four compositions showing different dissolution rates from slow to medium
and fast were selected as matrices for introducing holmium in the glass. Addition of holmium oxide did not evidently influence the high temperature properties of the glasses. The Ho-LS glasses dissolved slowly in SBF and
only minor contents of holmium were released into SBF within three weeks. During the radioactive period the
amount of holmium released from the target site would not be harmful to other tissues. In the mixtures of Ho-LS
and bioactive glass, dissolution of the Ho-LS glasses slightly increased, while the Bioglass 45S5 induced desired
calcium phosphate formation. The results suggest that Ho-LS glasses are good candidates as slowly resorbable
bone fi ller materials for local radiotherapy, and if used together with bioactive glass the mixture has potential to
simultaneously stimulate the regeneration of the tissue.

Degradation of zinc containing silicate glasses

Hill R. G., Chen X., Karpukhina N., McKay I. J.
Dental Physical Sciences, Institute of Dentistry, Queen Mary, University of London, London, United Kingdom.

168

The structural role of zinc oxide in silicate glasses is controversial. The charge to size ratio of the Zn2+ ion falls on
the boundary between being classified as anetwork modifying oxide and an intermediate oxide. This paper examines the dissolution and the zinc release particularly, using inductively coupled optical emission spectroscopy
as afunction of time from awide range of zinc containing glasses under both acidic and neutral pH. It is shown
that little or no zinc is released under neutral conditions but zinc is released in large amounts and very rapidly
under acidic conditions. The change in zinc release as afunction of pH is explained on the basis that zinc goes into
the silicate network as an intermediate oxide forming Zn-O-Si bonds that are acid hydrolysable in an analogous
fashion to the Al-O-Si bonds in aluminosilicate glasses. The applications of these glasses for the controlled release
of zinc for bactericidal coatings and toothpastes will be discussed.

Effect of mixed alkalis on ion release

from low-silica glasses
Fagerlund S.1, Brazda L.2, Helebrant A.2, Hupa M., Hupa L.1
1
2

bo Akademi University, Turku, Finland

Department of Glass and Ceramics, Institute of Chemical Technology, Prague, Czech Republic

The influence of replacing potassium oxide gradually for sodium oxide on chemical durability of glasses containing low-silica was studied. The composition of the glasses with around 52mol-% SiO2 corresponds to atypical bioactive glass, while the glass with around 60mol-% SiO2 are biocompatible but not bioactive. The goal was to study
how ion dissolution and development of asilica rich surface film depends on the silica content and the ratio of
Na/K in the glass. The ion dissolution was compared for the glasses treated in aqueous solutions using several different approaches in which the temperature, exposure time, surface area to volume ratio, and solvent were varied.
Static dissolution tests were performed using water (ISO 719) and the buffer solutions Tris and simulated body
fluid. The release of the ions from the glasses was measured using ICP-OES and the development of surface films
was estimated from SEM images of the glass samples. Finally, the ion release was studied in dynamic conditions

116 Biomaterials

using aflow through reactor coupled to ICP-OES. In all systems, the pH of the solution was also measured. The
results showed that the ion dissolution slightly decreased when replacing afew mol-% potassium oxide for sodium oxide. However, at higher replacement, the ion dissolution markedly increased. Although the ion dissolution
was clearly less for the glasses with higher silica content, the trend in the dissolution at the various Na/K ratios
were similar. The thickness of the silica rich surface film at the glasses was also affected by the Na/K ratio. These
results can be utilized when designing glasses for controlled release of ions and desired surface development giving either durable or bioactive compositions depending on the surface fi lm properties.

254

A time resolved 31P MAS-NMR study

of a novel bioactive glass
Mneimne M.1, Earl J.2, Brauer D.3, Gillam D.1, Karpukhina N.1, Hill R.1
1

Queen Mary University of London, Institute of Dentistry, Mile End Road, London, UK;
GlaxoSmithKline, Consumer Healthcare, Weybridge, Surrey, UK
3
Friedrich-Schiller-Universitt, Otto-Schott-Institut, Fraunhoferstr. 6, Jena, Germany

The aim of this study was to provide astructural and kinetic understanding of the formation of biomimetic
apatite from ahigh phosphate and fluoride containing bioactive glass. The principle application for this glass is
as aremineralising additive in toothpaste where the ability to form fluorapatite (FAp) in as short atime frame
as possible is highly desirable.
The dissolution and apatite formation in aphysiological buffer solution with pH 7.4 has been investigated for this
novel high phosphate containing glass (6mol%) and compared with alow phosphate containing glass (1mol%).
The degradation of the glass phase and crystallisation of apatite with time has been followed by 31P solid-state
magic angle spinning nuclear magnetic resonance spectroscopy (MAS-NMR) and X-ray diffraction (XRD). 19F
MAS-NMR was also used to distinguish the nature of the apatite formed.
31
P and 19F solid-state MAS-NMR results on the novel bioactive glass immersed in aphysiological buffer solution
showed the gradual atomic rearrangement around phosphorus and fluorine. Direct quantification of the time
resolved 31P MAS-NMR spectra gave clear information on rate of glass dissolution and apatite formation. Complimentary evidence from XRD and 31P MAS-NMR showed that the novel higher phosphate containing glass
formed apatite in asignificantly shorter time frame than the low phosphate glass used for comparison. 19F MASNMR showed that the presence of fluoride in the glass led to formation of FAp rather than hydroxyapatite (HAp).
In conclusion, fluoride and high phosphorus content in the bioactive glass promoted the rapid formation of FAp
which is more stable than conventional HAp and potentially more attractive for dental applications.
This project has been co-funded by GSK and the BBSRC.

261

Preparation of CaO-P2O5-Nb2O5-Na2O
glasses for biomedical applications
Maeda H.1, Miyajima T.1, Obata A.1, Ueda K.2, Narushima T.2, Kasuga T.1
1
2

Nagoya Institute of Technology, Nagoya, Japan;

Tohoku University, Sendai, Japan

To improve biocompatibilities of titanium and/or its alloys, which have been used as bone substitutes, it has been
proposed to be coated with bioactive materials. We have reported to prepare calcium pyrophosphate glasses in
the CaO-P2O5-TiO2-Na2O system, with excellent bioactive properties, to be coat with the glass on titanium by
using RF magnetron sputtering method. Recently, niobium ions have been suggested to promote osteogenic differentiation and calcification in the view of biology. In the present work, the calcium pyrophosphate glasses were
modified with niobium to add cell-activation effect for long periods.
60CaO-30P2O5-xNb2O5-(10-x)Na 2O (x=3-10) glasses were prepared by aconventional melting method. The
glasses were analyzed by TG-DTA and Raman spectroscopy. The ion releasing abilities of the glasses were
determined by ICP-AES.
To evaluate, the process window, which derived from glass transition temperature and crystallization temperature, was evaluated to the glass-forming property. Addition of Nb2O5 in the glasses enlarged the window. Raman

ICG Prague 2013 117

322

spectra showed that Nb species exist as NbO4 and NbO6 groups. It was also clarified that P-O-Nb bonds are
formed in the glasses. The NbO4 group contents increased with increasing the amount of Nb2O5 content. Niobium
ions were released gradually from the glasses, and their releasing abilities decreased with increasing the amount
of Nb2O5 content. It is proposed that newly formed P-O-Nb bond attributes to improvement of glass-forming
ability and chemical durability.

Osteoblast-like cell compatibility

of Nb-doped phosphate invert glasses
Obata A.1, Takahashi Y.1, Miyajima T.1, Maeda H.1, Ueda K.2, Narushima T.2, Kasuga T.1
1
2

Nagoya Institute of Technology, Nagoya, Japan;

Tohoku University, Sendai, Japan.

329

Phosphate invert glasses containing niobium in the 60CaO-30P2O5-(10-x)Na2O-xNb2O5 (mol%, x = 010) system were prepared by amelt-quenching method for the use in bioactive-coating materials for titanium alloys.
Wettability of the glass plate surface, ion release behaviours of the glass powders in cell culture medium, and pH
changes of the medium were evaluated. There were no significant differences in the wettability and pH values of
among the glasses including Nb2O5-free glass. The amount of sodium and niobium ions released from the glasses
increased with their contents in each glass system. The effects of niobium ions released from the glasses on murine osteoblast-like cells (MC3T3-E1 cell) were examined by cell culture tests with two systems; cell culture on
glass plates, or in culture media containing glass extracts (niobium ion concentration; 10-8 ~ 10-5 M). No obvious
differences were found in the cell morphologies cultured on the glass plates in the results of visual comparison
after 1 and 6 h-culturing. Alkaline phosphatase (ALP) activity in the cells cultured on the glass plates containing
3 and 5mol% of Nb2O5 was significantly higher than that on the Nb2O5-free glass, although proliferation was not
enhanced on all glasses containing Nb2O5. The activity in the cells cultured in the culture medium containing
10-7 M niobium ions was the highest in comparison with those in other media, regardless of the supplement of
osteogenic factors (ascorbic acid, -glycerophosphate, and dexamethasone) into the media. These results indicate
that the niobium ions released from the glasses enhance the differentiation rather than the initial adhesion or
proliferation, depending on the ion concentration.

Joining of glass and glass-ceramics to Ti-6Al-4V

Mallinson P. M., McCarthy F. H., Fernie J. A.
AWE, Reading, United Kingdom

Titanium and titanium alloys have an outstanding combination of strength-to-weight ratio and corrosion resistance. Thus, they are frequently the material of choice for the aerospace and biomedical industries. However,
applications such as electrical housing and feed-throughs are limited by the difficulty in producing suitable glassto-metal seals (in terms of strength, hermiticity and humidity resistance).
For example, conventional silicate sealing glasses are readily reduced by titanium (and its alloys) to form deleterious titanium silicides along the interface. These phases are incompatible with the production of arobust glassto-metal seal. Investigation into boroaluminate glasses have shown they are capable of overcoming these issues,
whilst forming the desired hermetic seal.
In this work arange of borate based glasses have been examined as candidate compositions for asealing system
comprising a Ti-6Al-4V alloy housing and a single pin of an appropriate alloy (Alloy 52, Alloy 48 or Kovar).
anumber of glass compositions were identified and characterised using dilatometry, DTA/DSC, XRD and electron microscopy. Optimised sealing procedures were then established and the bonds assessed as afunction of
hermiticity and microstructure.

118 Biomaterials

398

Influence of Na2O:K2O molar ratio

on bioactive glass properties
Brzda L.1, Fagerlund, S.2, Hupa L.2, Helebrant A.1
1
2

Faculty of Chemical Technology, Institute of Chemical Technology, Prague, Czech Republic;

Process Chemistry Centre, bo Akademi University, Turku, Finland

A weak point of typical bioactive glass is its tendency to devitrification. In order to improve bioactive glass properties
during high temperature processing potassium oxide was introduced into the glass composition. In this work several
glass properties were studied on three bioactive glasses in the system Na2O-K2O-CaO-P2O5-SiO2. Molar composition
of the glasses differed only in the Na2O:K2O ratio while the sum of alkali oxides was constant in all the glasses.
Glasses were prepared by traditional melting process and were used for experiments in different shapes blocks,
plates, particles or powders. Behaviour of the glasses at higher temperatures was studied using Hot Stage Microscopy. Degree of devitrification was observed with optical microscope and products of devitrification were determined by means of X-Ray Diffraction. For evaluation of chemical durability and bioactivity of tested glasses TRIS
buffered solution and Kokubos simulated body fluid (SBF) were used, respectively. Dissolution of the glasses as
well as back precipitation of calcium phosphates was calculated from solution analyses (AAS, UV-VIS). Changes
in the glass surface reaction layers were examined by means of Scanning Electron Microscopy. Antibacterial
properties of the glasses were proven on Escherichia coli colonies.
The results indicated that presence of K+ ions in the glass structure had significant influence on sintering properties and degree of devitrification of tested glasses. The presence of K+ ion had positive effect on HAp precipitation
in dynamic environment of the simulated body fluid and also caused slightly higher leaching of ions from the
glasses. All the glasses showed antibacterial properties; at some conditions glasses with higher potassium content
seemed to have stronger effect.

Massera J., Hupa L., Hupa M.

Process Chemistry Centre, bo Akademi University, Biskopsgatan 8, FI-20500, Turku, Finland.

Development of porous scaffolds or glass fibre containing implants for tissue engineering has been akey theme
within bioactive glass research during the past years. Bioactive glasses are low in silica and rich in lime which
makes them very sensitive to crystallization thus challenging manufacture of porous scaffolds via sintering or
drawing of continuous fibres. Accordingly, the two FDA approved bioactive glasses 45S5 and S53P3 are available
to certain clinical applications as particulates or tiny monoliths. Of these two compositions S53P4 (wt%: SiO2 53,
CaO 20, Na2O 23, P2O5 4) shows higher glass forming stability than 45S5. In this work we report the influence of
partly replacement of MgO and SrO for CaO on the thermal stability and in vitro properties of bioactive glass
S53P4. The thermal properties were measured using differential thermal analysis and hot stage microscopy. The
crystalline phases formed in thermal treatments were identified with X-ray diff raction, while the glass structure
was investing using FTIR-ATR. The formation of carbonated hydroxyapatite layer at the sample surfaces in simulated body fluid was assessed via SEM/EDXA and FTIR-ATR. The results indicated that the introduction of some
MgO or SrO in S53P4 increases the glass stability. The glass reactivity was found to depend on the alkaline earth.
As our final goal is to adjust the composition of bioactive glass S53P4 for amorphous products with ahigh surface
area to volume ratio, an increase in resistance to crystallization of the glass is adesired property. The results will
be used to further optimize the composition of bioactive glasses for novel product forms.

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418

Thermal properties and in vitro reactivity of MgO

and SrO substituted bioactive glass S53P4

432

Sintered wollastonite glass-ceramic

for biomedical applications
Daguano J. K. M. F.1,2, Soares V. O.1, Lombello C. B.2,
Bianchin O. S.1, Gonalves L. M. G.1, Zanotto E. D.1
1
2

Laboratrio de Materiais Vtreos Universidade Federal de So Carlos, So Carlos/SP, Brasil;

Centro de Engenharia, Modelagem e Cincias Sociais Aplicadas Universidade Federal do ABC,
Santo Andr/SP, Brasil.

Biomedical materials aiming bone restoration must be tough and strong to reduce prosthesis failure after implantation. Wollastonite ceramics have been studied as amaterial for artificial bone and dental restoration because
of their bioactivity, biocompatibility and good mechanical properties. This phase often presents acicular crystals, which could, in principle, increase toughness. In this work, novel sintered glass-ceramic (GC) compositions
based on the CaOMgOSiO2system were developed, varying the CaO content from 20 to 40 wt%. GC samples
having wollastonite as the main phase were produced by viscous sintering with concurrent crystallization at
different final sintering temperatures (7001,000C). Overall microstructural characterization, including the residual porosity, plus hardness, indentation toughness (Kc) and flexural strength were evaluated for each sample.
In addition, in vitro bioactivity and cytotoxicity tests were conducted for apreliminary biological evaluation of
these materials. The best glass-ceramic so far developed in our study still has some residual porosity, hardness
of 68GPa, indentation toughness of 1.82.2MPa.m1/2 and bending strength of 60100MPa. This value of Kc
represents an increase of about 150% when compared with the parent glass (~0.8MPa.m1/2). The effect of the
crystalline phases on the rates of hydroxycarbonate apatite (HCA) formation was followed by FTIR and showed
different bioactive levels. The glass-ceramic having 20wt.% CaO presented the most interesting result because the
onset for HCA formation is about 3-days. All samples were non cytotoxic. These results indicate that wollastonite
glass-ceramics could be promissing candidates to be used as bonegraft implants.

120 Biomaterials

TC16 Nanostructured
Sol-Gel Glasses

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 122

051

Synthesis and crystallization mechanism

of nano-crystalline lithium-mica glass-ceramic
prepared via aqueous Sol-Gel rout
Tohidifar M. R., Alizadeh P.
Department of Materials Science and Engineering, Tarbiat Modares University, Tehran, Iran

The nano-crystalline lithium-mica glass-ceramic with the crystallite size of about 15nm, taking the composition
LiMg3AlSi3(1+x)O10+6xF2 (x=0.5) and 8 mass% MgF2 was prepared using aqueous Sol-Gel technique. The structural
evolutions and microstructural characteristics of the prepared samples were investigated through X-ray diff raction, transmission electron microscopy and thermal analysis. It was found that the crystallite size of the mica
obtained from Sol-Gel method is smaller than the one synthesized via conventional melted method. The XRD
results also showed that the crystallization of mica occurred above 675C and it could originate from MgF2 particles. It was found that MgF2 nano-crystals perform as nuclei centres for the mica crystallization so that alarge
quantity of mica crystallites obtained following the nucleation treatment at 400C for 12 h. For both the un-nucleated and nucleated glass-ceramics, the crystallization activation energy was measured as 400.2 and 229.6kJ mol-1,
respectively. The calculated Avrami exponents demonstrated that the growth mechanism of mica crystallites,
while applying appropriate nucleation process, changes from needle-like to three-dimensional growth according
to the proposed Marotta model.

de Queiroz T. B.1, Botelho M. B. S.1,

Fernandez-Hernandez J. M.2, Eckert H., de Camargo A. S. S.1
1
2

Physics Institute of So Carlos, University of So Paulo, So Carlos-SP, Brazil;

Center of Nanotechnology, Westfaelisches Wilhelms Universitaet Muenster, Muenster, Germany.

Sol-Gel based mesoporous silicates are suitable hosts for highly efficient luminescent species such as lanthanide
and transition metal complexes with views to optical and electro-optical device applications. Particularly, Ir(III)
complexes exhibit impressive electroluminescent performance as aconsequence of fast singlet to triplet energy
conversion followed by very efficient triplet character emission. The ability to harvest both singlet and triplet
excitons, associated to the possibility of spectral tuning (blue to red), by choice of the apropriate ligands, place
these complexes among the favorite for organic light emiting diodes (OLEDs) and light emiting cells (LECs). So
far, mostly pure silica or organically modified silica and polymers (PEG) are used as hosts for such complexes,
involving relatively sophisticated or tedious chemistry. Thus, our contributions have been to propose simple and
innovative approaches to encapsulate neutral or charged Ir-complexes in silicate hosts using Sol-Gel methodology via two approaches: i) In situ assembly of the MCM-41 structure using CTAB micelles containing Ir-based
metallosurfactants as structure directing agents (in this case the complex is contained in the mesopores of the
host) and ii) Topotactic incorporation of acationic Ir(III)-complex in mesoporous sodium-alumino-silicate hosts
via ion exchange (in this case the complex is immobilized within the matrix by strong Coulombic interactions
with the negatively charged AlO4 sites). Besides detailed structural and photophysical characterization, we have
done asystematic study of the electronic structure of cationic Ir(III) complexes, as afunction of their chemical
environment through DFT and TDDFT calculations. Both synthetic approaches yielded materials with superior
photophysical properties (e.g. increased lifetimes and quantum yields) as compared to those of the complexes
in solution, and the theoretical approach helped to elucidate rigidochromic effects in the Ir complexes.

ICG Prague 2013 123

208

Optical materials based on Ir(III) complexes

incorporated in mesoporous silicate hosts:
In situ versus topotactic synthesis approaches
and electronic structure analysis

247

Silica mesoporous thin film containing semiconductor

or metal nanoparticles synthetized combining
Sol-Gel and impregnation techniques
Della Gaspera E.1, Buso D.2, Guglielmi M.3, Martucci A.3
1

University of California Los Angeles, USA;

CSIRO, Melbourne, Australia
3
Universit di Padova, Padova, Italy

269

Mesoporous Sol-Gel silica fi lms have been doped with PbS nanoparticles or with NiO and Ag nanoparticles by
atwo-step impregnation, using the mesopores as nanoreactors for the PbS or the Ag growth. Secondary ion mass
spectrometry and transmission electron microscopy characterizations demonstrated nanocrystals growth inside
the pores and throughout the fi lm thickness, pointing out the feasibility of an impregnation-based synthesis.
PbS nanoparticles have been formed by first impregnating the pores with the lead ions and secondly by the sulfur
ions, obtaining PbS nanocrystals with amean diameter of 5nm, which is compatible with the pore dimensions.
Optical absorption and Z-scan measurements indicated that PbS nanoparticles show aquantum confinement
effect, while the fi lms are characterized by high nonlinearities of the optical response.
SiO2 Sol-Gel mesoporous thin fi lms containing NiO nanoparticles have been synthesized and successively impregnated with Ag ions. asubsequent thermal treatment induces the precipitation of Ag nanoparticles and the
formation of Ag/NiO interfaces. NiO nanoparticles form upon annealing at 800C while the SiO2 matrix is still
highly porous due to the organic template removal. This porosity is useful for the impregnation process that is
composed by afirst pores functionalization with mercapto moieties and asecond impregnation with Ag precursor solution followed by the thermal reduction of Ag ions. Optical gas sensing tests for CO and H2 detection are
presented as one of the possible applications for these noble metalmetal oxides nanocomposites.

Multi-functional Sol-Gel layers on Ti substrate

Horkavcov D.1, Bloubkov T.1, Mizerov Z.1, Zmekal Z.1,
anda L.1, Clov Z.1, Helebrant A.1, astorlov M.2, Jablonsk E.2
1
2

Faculty of Chemical Technology, Institute of Chemical Technology Prague, Czech Republic;

Faculty of Food and Biochemical Technology, Institute of Chemical Technology Prague, Czech Republic;

The reason for the forming of multi-functional layers on titanium substrate was to utilize mechanical properties
of substrate and bioactive, adhesive and antibacterial properties of layers prepared by Sol-Gel method. By the
dip-coating technique we prepared three groups of layers: (I) silica-calcium-phosphate layers, (II) silica layers
with silver (AgNO3) and added brushite or monetite powders and (III) titania layers with silver added in different
form (Ag, AgNO3, Ag3PO4) on the mechanically and chemically pretreated titanium substrates. Coated Ti substrates were fired at different temperatures and adhesion, bioactivity and bactericidal properties were measured.
The adhesion of layers to substrates was measured by atape test (ASTM D 3359-2). All prepared layers showed
very good adhesion to the substrates. The bioactivity was measured by an in vitro test, where the coated substrates
were immersed into simulated body fluid. Precipitation of hydroxyapatite (HA) was the sign of bioactivity. anew
HA layer and HA islands were detected on the layers of (I) and (II) group. The antibacterial properties were measured by immersion of coated substrates into suspension of E.coli in physiological solution for 24 hrs. Subsequently,
the substrates were taken out and part of each suspension was spread onto LB agar Petri dish. The dishes were
incubated overnight at 37C, then photographed and the numbers of colonies of surviving E. coli were counted.
Under our experimental conditions, a complete inhibition of the growth of bacteria was observed for the silica-silver-monetite layers and titania-Ag3PO4 layers.

124 TC16 Nanostructured Sol-Gel Glasses

367

Weathering and Protection of Potash-Lime-Silica Glass

De Ferri L.1, Lorenzi A.2,3, Lottici P. P.3,4, Montenero A.2,3, Vezzalini G.1
1

Earth Science Department, Universit di Modena e Reggio Emilia, Modena, Italy

Chemistry Department, Universit degli Studi di Parma, Parma, Italy
3
CIPACK CENTER, Parma, Italy
4
Physics and Earth Science Department, Universit degli Studi di Parma, Parma, Italy
2

Potash-Lime-Silica (PLS) glass samples containing different amounts of K 2O as fluxing agent were produced
and aged in concentrated boiling H2SO4 and in high temperature-high pressure water to simulate two alteration
process separately (leaching and dissolution). Aged samples were studied by micro-Raman spectroscopy, XRD
and SEM-EDS technique, to identify the neo-formation of crystalline phases and the alteration layer thickness.
The leached samples (aged in sulphuric acid) displayed the co-existence of the three phases gypsum, bassanite
and anhydrite in the external part of the alteration layer. Glass samples subjected to the dissolution experiments
show a slight impoverishment in Si and the accumulation of Ca in the surface layer and the presence of abundant
crystalline silicate phases, with different morphologies. The complex Raman spectra revel the contribution of
different crystallized phyllosilicate and inosilicate phases (gyrolite, reyerite and charoite).
The sol-gel technology offers significant advantages in the preparation of protective fi lms for glasses as the
Si-alkoxides precursors are chemically similar to the substrate and the final product shows chemical resistance,
low viscosity and good adhesion to the glass.
We show here the results of water-repellent hybrid sol-gel coatings obtained by TEOS (Tetra-ethyl-ortho-silicate)
associated to different amounts of Si-alkoxides functionalized with alkyl groups, as OTES-CH3(CH2)7Si(OC2H5)3,
EDTMS-H3C(CH2)15Si(OCH3)3, MTMS-H2C=C(CH3)CO2(CH2)3Si(OCH3)3, TMES-(CH3)3Si(OC2H5) and MTESCH3Si(OC2H5)3. The treated surfaces were characterized by UV-VIS, FT-IR and Raman spectroscopy. Wettability
measurements (static and dynamic contact angle) were carried out to check the surfaces water repellency, while
colorimetric analysis indicate that no color changes were induced by the presence of the fi lm. Ageing experiments,
were performed exposing the coated samples under UV-light and to SO2-saturated atmosphere.
The studied silica-based protective materials do not lead to reaction by-products, are found to be water-repellent,
compatible with the glassy substrate and are colorless and transparent, hence suitable for the protection of weathering-exposed Potash-Lime-Silica glasses.

Tadanaga K., Mori K., Tatsumisago M.

Osaka Prefecture University, Osaka, Japan

Wettability of solid surfaces with liquids is governed not only by the chemical properties but also the microstructure
of the surfaces. We have reported that pseudo-boehmite nanocrystals of several tens nanometers size were precipitated on Sol-Gel derived Al2O3 thin films through immersion of the Al2O3 gel films in hot water [1]. We found
that the alumina thin films with asmall roughness show excellent antireflective properties in the wide visible light
wavelength region on soda-lime glass, non-alkali glass and quartz glass substrates [1]. We also found that asuperhydrophobic surface can be prepared by coating of partially hydrolyzed heptadecafluorodecyltrimethoxysilane, which
is one of fluoloalkylsilane (FAS), on the boehmite-precipitated alumina films. However, as awater repellent agent,
achemical without fluorine is preferred from viewpoint of the environment load. In addition, condensation of FAS
is known to be difficult, and thus only thin layers can be formed on the surface.
In the present study, silica-based thin fi lms were prepared from octyltriethoxysilane and teteraethoxysilane
(OcSiO3/2-SiO2) on the Sol-Gel derived Al2O3 fi lm with a small roughness. The Al2O3 fi lms coated with
OcSiO3/2-SiO2 showed higher transmittance than aglass plate, and the contact angle of water of the double layer
fi lm leached 154 with coating of small thickness of silica-based layer.

ICG Prague 2013 125

407

Preparation and characterization of silica-based thin

layer-coated Al2O3 films with a small roughness

452

Li+-ion conduction in Sol-Gel processed

chalcogenide glass
Choi Y. G.1, Cho Y. G.1, Chung W. J.2, Shin D. W.3
1

Korea Aerospace University, Goyang, Gyeonggi, Republic of Korea;

Kongju National University, Cheonan, Chungnam, Republic of Korea;
3
Hanyang University, Seoul, Republic of Korea

527

Amorphous chalcogenide electrolyte that features the agile electrical conduction by Li+ ions would be akey component in realization of high-capacity all-solid-state lithium-ion battery. Some Li+-containing chalcogenide glasses exhibit ionic conductivity greater than 10-4 S/cm at room temperature, which deserves practical applications
as asolid electrolyte. Here, it is worth mentioning that in order to prepare the Li-containing chalcogenide glasses
melt-quenching and/or mechanical alloying techniques have exclusively been used so far. We thus come up with
that a new and viable fabrication technique for Li-conducting chalcogenide glasses would be more cost-effective and/or energy-efficient. Based on these considerations, in this study, we have aimed at exploring new solution-based processing routes for Li-containing Ge-Ga-S glass. Starting materials of Li, Ge, Ga and S were all dissolved to become asolution. Every mixing step was carried out in anitrogen-filled glove box in order to prevent
unwanted contamination. After drying, the mixture was heat treated to minimize impurities. The resulting powders were then characterized by using scanning electron micrograph, X-ray diffraction pattern, EXAFS spectrum
and Raman spectrum. The ionic conductivity was determined based on impedance spectrum. Approximately
1,000-fold increase of ionic conductivity was observed just after the introduction of Ga to Li-Ge-S system. The
structure tended to become more amorphized upon the addition of Ga. As for aseries of samples processed under
the same conditions but containing varying amount of Ga, amaximum ionic conductivity of ~7104 Scm1 appeared at the nominal Ge/Ga ratio of 2. The Li+-ion conductivity appeared to be quite sensitive to the Ga content
as well as other processing parameters. In summary, the ionic conductivity of our solution-processed Li-Ge-Ga-S
electrolyte is quite comparable with that of melt-quenched or mechanically alloyed counterparts. Th is is the first
experimental demonstration, to authors knowledge, proving that the solution process is promising indeed in
fabricating the Li-conducting chalcogenide electrolytes.

Silk fibroin-siloxane hybrid material

as efficient hosts for emissive devices
Ribeiro S. J. L., Silva R. R., Santos M. V., Cavicchioli M.,
Nighogossian K., Peres M. F. S., Roncalho L., Moraes M., Pecoraro E.
Institute of Chemistry, So Paulo State University UNESP. CP 355, Araraquara-SP, 14801-970, Brazil

Biopolymer-siloxane hybrid hosts can be successfully used for fabrication of multifunctional photonic devices
due to good optical properties, biocompatibility, remarkable mechanical properties and the wealth of chemical
functionalization. Particularly, silk fibroin (SF) biopolymer presents awide range of suitable properties for photonic applications that were not fully exploited. The present work is divided in two parts. In the first part we show
the down-shift ing and up-conversion properties of SF-siloxane materials containing either Eu3+ or Yb3+-Ho3+
doped ytrium vanadate nanoparticles. Visible emission and infrared-to-visible upconversion have been explored.
In the second part distributed feedback (DFB) and Random laser operation are shown for SF-siloxane fi lms doped
with Rhodamine 6G dye. The hybrid grating structures were fabricated using standard blank digital versatile disc
(DVD) as template The addition of silica or silver nanoparticles to the SF fi lm led to enhanced emission due to the
multiple scattering of light by the nanoparticles and afurther reduction of linewidth due to the contribution of
the localized surface plasmons associated to the Ag nanoparticles.

126 TC16 Nanostructured Sol-Gel Glasses

TC6-TC7-TC8
Topological Principles
in Glass Science

ICG Prague 2013 127

 128

012

Topological approach to predicting

the properties of glasses
Smedskjaer M. M.1, Mauro J. C.2, Yue Y.1
1

Section of Chemistry, Aalborg University, DK-9000 Aalborg, Denmark

Science and Technology Division, Corning Incorporated, Corning, NY 14831, USA

Predicting the properties of new materials prior to manufacturing is atopic attracting great industrial and scientific
interest. Property prediction for ceramic materials is facilitated by the periodic short and long-range order of crystals.
However, for glassy systems the lack of long-range order and the long time scales for relaxation greatly complicate the
traditional modeling efforts. We show that the key for making progress has been to extract the key physics governing
the macroscopic properties by using topological constraint theory, which was originally developed by J. C. Phillips
and M. F. Thorpe around 1980. By further including the Gupta-Mauro temperature dependence of the constraints, the
composition dependence of properties such as hardness and viscosity can be quantitatively predicted for oxide network
glasses of industrial interest, such as borates and borosilicates. Moreover, the modeling approach enables adetailed understanding of the microscopic mechanisms governing macroscopic properties. Finally, we also present aphenomenological model offering an improved description of the composition and temperature dependence of the shear viscosity
of multicomponent liquids, for which the existing analytical models currently do not apply.

026

Polyamorphism of silica glass

Sonneville C., Deschamps T., de Ligny D., Martinet C.,
Mermet A., Margueritat J., Martinez V., Champagnon B.
Institut Lumire Matire, Domaine scientifique de la Doua, Universit de Lyon, Universit Lyon1, France

The polyamorphism is defined in glasses in analogy with the phenomenon of crystalline polymorphism by the
possibility that more than one distinct amorphous phase may be formed from the same substance. These distinct
phases, each with adifferent atomic structure, are distinguished by their density which is areliable order parameter for polyamorphism. Low Density Amorphous (LDA) and High Density Amorphous (HDA) phases are their
usual denominations. Polyamorphism of ice has been extensively studied. Due to asimilar tetrahedral coordination, silica glass was also early recognized as acandidate for polyamorphism. In this presentation polyamorphic
transitions in silica are studied under pressure up to 26.2GPa by Raman and Brillouin spectroscopy. The first
reversible transition is characterized by an abrupt decrease of the Si-O-Si inter-tetrahedral angle at 2.5GPa corresponding to the elastic anomaly of silica. This result is interpreted as areversible transition between two Low
Density Amorphous phases LDALDA similar to the - transition of cristobalite crystal under pressure. The
second polyamorphic transition is observed for silica glass samples compressed up at different maximum pressures
Pmax between 12GPa and 26.2GPa and recovered at ambient pressure. It corresponds to an irreversible and progressive transformation from the LDA phase to aHigh Density Amorphous (HDA) phase. This HDA phase is characterized by an increase of the statistic distribution of 4- and 3-membered rings of SiO4 tetrahedra with anarrowing of
inter-tetrahedral angles distribution. avanishing of the elastic anomaly in the HDA phase is observed.

Rouxel T.
LARMAUR, ERL-CNRS 6274, University of Rennes 1, France

The glass network cross-linking degree which can be estimated from the expected coordination numbers of the
constituents is an important parameter to understand the properties of glasses. However there are numerous cases
where the trend is different from what could be anticipated from the coordination change. This shows that other
structural features come into play, such as the network energy and the chemical affinity. As amatter of fact it is
generally difficult to predict the properties from an ab-initio topological analysis. Examples from chalcogenide, oxynitride, oxycarbide and boroaluminate chemical systems will be discussed in the light of their mechanical behavior
and known structural characteristics.

ICG Prague 2013 129

107

The way coordination and network energy

affect the mechanical properties of glasses

239

The topological approach to a description

of glass structure and glass formation
Hobbs L. W.
Massachusetts Institute of Technology, Room 13-4054, Cambridge, MA 02139, U.S.A.

316

The description of crystalline structure has, since the 19th century, been addressed in the language of symmetries
and periodic translation and, later, translatable unit cells and atom positions in the unit cell. It was clear, even in
the very first attempt to represent the atomic structure by Zachariasen, that the way atoms are connected together
is of paramount importance to both adescription of glass structure and the ability to construct non-crystalline
arrangements. afew subsequent treatments of glass structure, notably those of the late Doris Evans, continued to
explore the role of atom connections, though construction of glass models in subsequent years, both by hand and
by simulation, has still tended to be dominated by attention to bond angles and not connectivity at intermediate
range. Beginning in the mid-1980s, the present author and students have addressed both simple glass structures
and the glass-forming ability of elements and compounds from the singularly local point of view afforded by
connectivity topology, an approach summarized in arecent review [1]. What emerges is apowerful description of
intermediate-range connectivity that distinguishes one glass structure from another and its relationship to crystalline counterparts. All solids must exhibit closed circuits (rings) of connectivity in order to avoid adensity
catastrophy, and the most important of these are primitive rings that cannot be decomposed into sets of smaller
rings; the atoms belonging to the set of primitive rings passing through any atom comprise the local cluster for
that atom- an intermediate-range structural entity, much like aunit cell for acrystal, that describes structure of in
terms of connectivity topologies and not symmetries, translations or Euclidean atom coordinates. The power of
this approach is classically illustrated for the structures of silica polymorphs (both glassy and crystalline) and by
recent work on densification of GeO2 glass, alkali borosilicate nuclear waste glass structure, defects in aperiodic
SiC, and radiation-induced amorphizability of silicate and titanate ceramics.

Topological heterogeneity in borosilicate glasses

Reibstein S., Wondraczek L.
Otto-Schott Institute, Jena, Germany

370

Glasses, by definition, miss astrict symmetrical atomic arrangement on intermediate or higher lengthscale. The notion
of "topology" was introduced as atheoretical formalism to describe the basic geometrical arrangement of the structural
units and their atomic decoration. Experimentally, such "topology" is rather difficult to access. Tools for analyzing glass
structure (e.g. Raman spectroscopy, X-ray diffractions, infrared spectroscopy) usually address only the short or mid
range order, but are quite ineffective in resolving higher length-scale features. This study is focussing on the experimental topology of glasses by considering nanoscale heterogeneity. Topological heterogeneity is explored by small-angle
X-ray scattering, low frequency Raman scattering and Brillouin scattering. The results indicate the importance of topological heterogeneity for macroscopic properties such as crystallization and the glass transition.

Vibrational connectivity of oxide glasses from the

points of view of thermal conductivity and viscosity
Matsuoka J., Yoshida S., Sugawara T.
The University of Shiga Prefecture, Hikone, Shiga, Japan

Connectivity in the covalent bond network of oxide glasses is one of the key factors which determine many properties. In thermal and rheological properties which are related with the thermal activation process, the localization or delocalization of atomic vibration should also affects the properties.
In our previous studies, we show that aluminium in silicate glasses increases its thermal conductivity but boron
decreases it. This difference is due to the fact that vibration frequency of Al-O bond is similar to that of Si-O, but
B-O is not. Therefore, aluminium increases the phonon mean free path (PMFP) and boron decreases it. In other
words, aluminium connects the simultaneously vibrating region, but boron cut it. In our other study, we find that

130 TC6-TC7-TC8 Topological Principles in Glass Science

mixing of boron isotopes (10B and 11B) decreases the PMFP and thermal conductivity. This should be due to the
localization of atomic vibration due to the difference of the vibration frequency of 10B-O and 11B-O bonds. These
indicate that PMFP is ameasure of the vibrational or dynamic connectivity of glass network.
Viscosity of glass well above Tg is also found to be affected by the vibrational connectivity. In B2O3 and alkaline borate
glasses, mixing of boron isotopes decreases the viscosity. This would be due to the localization of vibration which will
increase the activation probability of bond breaking. Increase of the alkaline content decreases the magnitude of mixed
isotope effect (MIE). This may be due to the localization of vibration even in single isotope case, which is consistent with
ashort PMFP observed in thermal conductivity. In borosilicate glasses, the magnitude of MIE depends on the boron to
silicon ration and is consistent with the composition dependence of the glass transition temperature.
These results indicate the importance of the vibrational (or dynamic) connectivity of glass network.

390

Nanoscale heterogeneities in silicate

glasses: Implications for nucleation
Cormier L.1, Dargaud O.2,3, Radtke G.1,
Menguy N.1, Patriarche G., Jousseaume C.2, Calas G.1
1

Inst. de Minralogie et de Physique des Milieux Condenss, Univ. Pierre et Marie Curie CNRS, Paris, France;
Saint-Gobain Recherche, Aubervilliers, France;
3
Cit de la cramique, Svres, France
4
CNRS, Laboratoire de Photonique et de Nanostructures, Marcoussis, France
2

A precise description of intermediate range order remains achallenging and lively issue in glass science. Inhomogeneities on length scale 15nm can be evidenced by numerous techniques in oxide glasses but a detailed
description of their exact nature at the atomic and nanoscale is lacking. The development of advanced TEM
techniques modifies this view and compositional fluctuations or atomic-scale structural information become
accessible for oxide or non-oxide glasses [Dargaud et al., Appl. Phys. Lett. 99(2011)021904; Hirata et al. Nature
Materials 10(2011)28]. Because these inhomonogeneties play acrucial role in the crystallization processes, as they
are often the first step evoked in the nucleation process, it is critical to have adetailed description of the segregation, chemical and structural fluctuations occurring in glasses.
In this talk, we will present recent results obtain on silicate and aluminosilicate glasses studied by STEM-HAADF
(Scanning Transmission Electron Microscopy High Angle Annular Dark Field). With this technique, chemical/structural heterogeneities on the nanoscale range can be directly observed. adirect relationship is obtained
between these inhomogeneities and nucleation processes. This allows abetter understanding of the role of nucleating agent (Zr, Ti) and of phase separation in the nucleation mechanisms. The intrinsic inhomogeneous nature
of the glass structure is akey structural arrangement from which energetic barriers can be easily overcome to
promote crystal growth. We show that the self-organization of the parent glass structure drives directly the crystallization and explains the efficiency of crystal formation in glass ceramics.

391

Density-driven structural transformations

in network-forming glasses
Salmon P. S.
Department of Physics, University of Bath, Bath BA2 7AY, UK

The method of in situ high-pressure neutron diff raction provides complementary information to X-ray diffraction
on the density-driven structural transformations in network-forming glasses. In particular, recent advances have
made it possible to apply the method of neutron diff raction with isotope substitution to provide detailed information on the mechanisms of structural collapse in liquids and glasses at pressures up to 18GPa and temperatures up
to 200C. Results will be given for the case of GeO2, in which there is atransformation from atetrahedral to an
octahedral glass, and for other network glass-forming materials such as GeSe2 and As2Se3. The experimental results will be compared to molecular dynamics simulations in order to test their efficacy and to provide additional
information on the nature of density-driven topological changes.

ICG Prague 2013 131

422

Structural similarity / dissimilarity between glass

and isochemical crystal and the nucleation ability
Zanotto E. D.
Vitreous Materials Lab., Federal University of So Carlos, Brazil (lamav.weebly.com)

435

The nature of the nucleation process is afundamental problem in glass science and governs the stability of glass against
devitrification. It should be stressed that only ahandful of glasses show measurable internal homogeneous nucleation
rates in alaboratory time scale, e.g. Li2O-2B2O3, Li2O-2SiO2, CaO-SiO2, BaO-2SiO2, Na2O-2CaO-3SiO2, 2Na2O-CaO3SiO2 and afew others. The vast majority of glasses only crystallize heterogeneously from their external surfaces, hence
one is often forced to discover powerful nucleating agents to induce internal nucleation (if, for instance, one wants to
develop aglass-ceramic). It has been hypothesized that the nucleation mechanism (homogenous vs. heterogeneous)
of agiven glass forming composition is correlated with the extent of structural similarity at the short (modifier cation
coordination) and intermediate-range level between the glass and crystal phase to which it transforms. However, little
information is available to test this hypothesis because of the lack of long-range periodicity in glass and the absence
of effective analysis methods. In this work we critically review some attempts that have been made to shed light into
this issue with EXAFS, NMR and density techniques. While some observations indicate the existence of acorrelation
between structural similarity / dissimilarity at both short and intermediate length scale and the nucleation mechanism,
this issue has not been sufficiently generalized and further work is needed for adefinitive conclusion.

A bifurcation of the stretching exponent

in glass confirmed experimentally ( = 3/5 for stress
relaxation and = 3/7 for structural relaxation)
Potuzak M., Welch R. C., Mauro J. C.
Science and Technology Division, Corning Incorporated, Corning, NY 14831, USA

485

The physical origin of stretched exponential relaxation is considered by many as one of the oldest unsolved problems in science. The functional form for stretched exponential relaxation can be deduced from the axiomatic diffusion-trap model of Phillips. The model predicts atopological origin for the dimensionless stretching exponent, with
two magic values emerging: =3/5 arising from short-range molecular relaxation pathways and =3/7 for relaxation dominated by longer-range interactions. In this presentation, we report experimental confirmation of these
values using microscopically homogeneous silicate glass specimens. Our results reveal abifurcation of the stretching
exponent, with =3/5 for stress relaxation and =3/7 for structural relaxation, both on macroscopic length scales.
These results point to two fundamentally different mechanisms governing stress relaxation versus structural relaxation, corresponding to different effective dimensionalities in configuration space during the relaxation process.

Combining thermodynamics and topology

in describing the mechanical properties of oxide
glasses and their isochemical crystals
Conradt R.
RWTH Aachen University, conradt@ghi.rwth-aachen.de

Phenomenological properties of oxide glasses and their isochemical crystals are compared, comprising molar volumes,
and elastic constants. It is shown that for both glasses and crystals, these properties sensitively depend on the symmetry, connectivity, and packing density of individual structural entities. The presence or absence of angular constraints
among these entities plays amajor role. In the present paper, conclusions derived by means of thermodynamics via
the so-called chemical structure are contrasted by conclusions obtained via the counting of topological constraints.
acombination of both approaches although not measuring up with afully-fledged quantum mechanical assessment
of local structures turns out to be suitable tool helping to engineer of glasses with specific properties.

132 TC6-TC7-TC8 Topological Principles in Glass Science

502

Topology of ionic transport in glasses:

Watching moving calculations
Greaves N.
Materials Science & Metallurgy, University of Cambridge, Cambridge, CB2 3QZ, UK

Isosurfaces, used to define the microsegregation of modifying cations within the silicate network, reveal the
topology relevant to ionic transport, the free volume accessible for hopping, and its cooperative nature. Collective
motion is found to be promoted by THz vibrations mobile ions moving in anti phase. Moreover their ranking
fast to slow is thermally activated, matching the primitive activation energy of the incoherent scattering structural relaxation time. Furthermore, ionic channels in mixed alkali glasses are topologically similar to single alkali
glasses. The familiar non-linear transport effects follow reductions in accessible free volume, because alkalis of
different size pack more efficiently.

509

Rings in covalent glass and an evaluation

of configurational entropy associated with rings
Gedeon O.1, Lika M.2
1
2

Faculty of Chemical Technology, Institute of Chemical Technology, Prague, Czechia;

Vitrum Laugaricio, Trencin, Slovak Republic

Molecular dynamics was used to prepare structure of vitreous silica. Algorithms based on the remove of the
non-essential bonds (transient as are being inscribed into structure by ultrafast computational cooling) are
used to decrease the number of overbonded atoms. The algorithms were found to be very effective and led
to the experimentally comparable amount of the overcoordinated silicon atoms what made topological network of glass more realistic. Therefore it seems the use of the appropriate method for bond analysis can overcome the extended overcoordination commonly attributed to the fast cooling rate in molecular dynamics.
The decomposition of the established glass topological network into disjunctive set of rings and the residual
network units (topologically open and linear) is suggested. The decomposition into disjunctive structural
units enables to calculate configurational entropy on base of ideal mixing. The calculated ring-entropy
reflects topology of rings in glass and therefore is closely related to medium range order of glass. Temperature evolution of ring-entropy enables to calculate the specific heat drop at glass transition temperature.
Calculation of viscosity and fragility by means of Adams-Gibbs theory shows the better agreement with
experimental data than VFT equation.

Sierka M.
Institute of Materials Science and Technology, University of Jena, Jena, Germany

Silica remains one of the most important oxides in many modern technologies. In recent years, ultrathin crystalline and vitreous silica fi lms grown on different substrates, e.g. metal surfaces and graphene, have drawn increasing interest due to their potential applications in advanced technologies insulating layers in integrated circuits,
protective fi lms against corrosion, and supports for metal nanoparticles in sensors and catalysts. Such materials
are also excellent systems for studying structure-property relationships, since their electronic and chemical properties can be examined by avariety of surface-sensitive techniques, as well as modern computational methods.
The key prerequisite for understanding physical and chemical properties of ultrathin fi lms is adetailed knowledge of their atomic structure. However, such materials frequently present complex structures to solve. This is
because on one hand the structural information is difficult to access experimentally and on the other hand the
accuracy of theoretical tools that can be applied to extended systems is often limited. The results reviewed in my
lecture demonstrate that often the only way for an unambiguous atomic structure determination of ultrathin
fi lms is a combination of computational and experimental studies. Among different computational methods,

ICG Prague 2013 133

522

Crystalline and vitreous ultrathin silica films:

Synergy between theory and experiment

567

global structure optimization at an ab initio level of theory has proven very useful in an automatic structure resolution of ultrathin silica fi lms on various metal substrates. In particular, structure determination of avitreous
silica fi lm on Ru(0001) enabled for the first time to resolve the atomic structure of asilica glass in real space.

Bond constraint theory and the glass transition

temperature of metaphosphate glasses
Rodrigues B. P., Wondraczek L.
Otto-Schott-Institut fr Glaschemie, Friedrich-Schiller-Universitt, Jena, Germany

Recently the bond constraint theory has been successfully used to understand the compositional dependence of
the glass transition temperature of chalcogenide, alkali borate and alkali phosphate glasses, and also the surface
hardness of alkali borate glasses. An exact knowledge of the glass structure is needed in order to correctly count the
number of bond constraints. From arecently published topological analysis of alkali phosphate glasses the number
of constraints is mainly affected by the coordination number of the modifying cations. In order to test this assessment we took published glass transition temperature data for several metaphosphate glasses and compared with the
predicted glass transitions according to the coordination number of the modifiers. We found that smaller cations
have their glass transition underestimated, and larger cations have their glass transition temperature overestimated.

134 TC6-TC7-TC8 Topological Principles in Glass Science

TC20 Photonic Glasses

ICG Prague 2013 135

 136

037

Glass formation and crystallization

in magneto-optical terbium-gallium-germanate glasses
Winterstein A. 1,2, Wondraczek L.1
1
2

Otto-Schott-Institute, University of Jena, 07745 Jena, Germany

Max Planck Institute for the Science of Light, Gnther-Scharowsky-Str. 1, Building 24, Erlangen, Germany

The search for magneto-optically active glasses is still amatter of research interest. Thereby, the figure of merit is
ahigh Faraday rotation angle, expressed by the Verdet constant, at low optical loss. This can typically be achieved
in heavily rare-earth doped materials, as the f-shells of the employed rare-earth species are well-isolated what
results in arelative independence of their optical and magnetic properties of the host matrix. Glass systems which
can incorporate ahigh concentration of rare earth ions, particularly Tb3+ therefore become very interesting. Here,
we concentrate on the magneto-optical properties of terbium-gallium-germanate (TGG). We report on glass formation and crystallization in this system and discuss the suitability for optical fiber production.

061

Near-Infrared down-conversion
of Pr3+/Yb3+ co-doped SLABS glasses
and LaBO3 glass ceramic for photovoltaics
Gao G. J.1,2, Wondraczek L.1,2*
1
2

Otto-Schott-Institute, University of Jena, 07743 Jena, Germany

Chair of Glass and Ceramic, Department of Materials Science, University of Erlangen-Nuremberg,
91058 Erlangen, Germany

We report on the NIR down-conversion of one blue photon into two NIR photons (~10,000cm-1) from Pr3+/Yb3+
co-doped SLABS glasses and LaBO3 glass ceramic. The broad absorption bands of Pr3+ in the spectral range
of 415505nm are helpful to absorb light that can not be used by solar cells, then transferred to Yb3+ ions and
ultimately converted to NIR light that can be used efficiently by solar cells. The decrease of all Pr3+ PL bands in
intensity and lifetime of both Pr3+:3P0 and Pr3+:1D2 levels decreases with increasing Yb3+ doping concentration
along with the observation of typical Pr3+ PLE bands by monitoring PL at 976nm of Yb3+ indicates the energy
transfer occurs through both Pr3+:3P0 and Pr3+:1D2 levels to Yb3+. The energy transfer from Pr3+:3P0 level to Yb3+ is
adown-conversion of one visible photon into two NIR photons process (one photon to two photons), whereas that
from Pr3+:1D2 level to Yb3+ is adownshifting of one NIR photon into one NIR photon process. The energy transfer
efficiency from the Pr3+:3P0 level is more efficient than that from the Pr3+:1D2 level to Yb3+. The estimated highest
total theoretical quantum efficiency is as high as 183%, if only the down-conversion energy transfer process
from Pr3+:3P0 to Yb3+ is considered. The premium doping concentration of Yb3+ for down-conversion is ~0.5mol%.
Crystallization of the as-quenched SLABS glass sample leads to the appearance of amain crystal phase LaBO3 and
aminor crystal phase SrAl2B2O7. Both Pr3+ and Yb3+ ions occupy the La3+ ion cites in the LaBO3 crystal structure
after crystallization resulting in the improved PL properties.

Ferencz J. A. P. F., Belanon M. P., Barbosa L. C.

Institute of Physics Gleb Wataghin, University of Campinas,13083-089 Campinas, SP, Brazil

Tellurite glasses have been extensive studied because they have ahuge range of possible technological applications.
In general, this based glass presents low melting temperature (~800C), high linear refractive index, short band
gap, interesting transparence in infrared region, high dielectric constant and optical non-linearity. It is necessary
to construct supplementary bands amplifiers for telecommunication which justifies many studies of new glasses

ICG Prague 2013 137

065

CsCl concentration effect in thermal and optical

properties of (100-x)(2.2La2O3-4.9Na2O-19.6ZnO-73.3TeO2)
+ xCsCl (%mol) where x = 0; 1;5; 10, glass system

106

for photonics applications. We have studied the glass composition: (100-x)(2.2La 2O3-4.9Na2O-19.6ZnO-73.3TeO2)
+ xCsCl (%mol) where x=0; 1; 5; 10. Our analysis show that when CsCl concentration increase absorption coefficient decrease, band gap is shorted, linear refractive index is softly reduced, glass network is almost no modified
and thermal stability increase. Then, we can improve optical and thermal properties of this vitreous system which
expands enormously the range of application possibilities.

Method of fabrication of silica-based optical materials

for active optical fibers by sintering a mixture of oxides
Velmiskin V. V. 1, Egorova O. N. 1,
Iskhakova L. D. 1, Mishkin V. P. 2, Nischev K. N. 2, Semjonov S. L. 1
1
2

Fiber Optics Research Center RAS, Moscow, Russia

Ogarev State University, Saransk, Mordovian Republic, Russia

118

The report describes amethod of fabrication of active or special silica-glass optical fibers. It is based on sintering
of high-purity silica sand consisted of relatively large particles mixed with powders of different dopants. By this
method we fabricated anumber of the preforms and fibers doped by ions of aluminium, phosphorus, ytterbium,
and bismuth. Structural, optical and luminescent properties of obtained samples were investigated. Fabricated
optical fibers demonstrated good quality and comparatively low level of optical loss. For example, the minimum
level of optical background loss in the fiber containing 2wt% Al2O3 was 60 dB/km at awavelength of 1um.
Such quality of optical materials was achieved by using aspecially developed and optimized technique of reduction of optical and concentration fluctuations in obtained materials to submicron sizes. Detailed description of
the process of homogenization will be presented.

PbS quantum dots precipitation in glasses

containing Ag nanoparticles
So B. J., Xu K., Heo J.
Pohang University of Science and Technology (POSTECH), Pohang, Republic of Korea

Glasses doped with semiconductor quantum dots(QDs) have potential photonic applications due to the size-tunable optical properties of QDs. PbS QDs can have atunable absorption and photoluminescence wavelength in
near-infrared spectra showing the strong quantum confinement effect due to their narrow gap energy (Eg=0.41eV
at 298K) and large exciton Bohr radius(aB=18nm). Thermal treatment has been used to form QDs in glasses, but
it is difficult to precisely control nucleation and growth of the QDs. Ag nanoparticles (NPs) can act as nucleating
agents for controlled crystallization of glasses. Furthermore, because of surface plasmon resonace (SPR), Ag NPs
have local heating effect when excited by light with acertain wavelength. This local heating can lead to an increase
in temperature near Ag NPs and allows the formation of PbS QDs.
In this work, we investigated the influence of Ag NPs and their local heating effects on the formation of PbS quantum dots in glasses. The glasses were prepared using aconventional melt-quenching method. Ag NPs were incorporated into glasses through ion-exchange and subsequent thermal treatment at low temperature (~300C). First,
we investigated the influence of heat-treatment (T: > 400C) on the formation of PbS QDs in glasses containing Ag
NPs. PbS QDs thus formed in the Ag NPs-containing regions were larger than those in Ag NPs-free regions. Second,
532-nm laser was used to irradiate the Ag NPs-containing glasses to induce the local heating near the Ag NPs. PbS
QDs was found to form near the Ag NPs regions after laser irradiation. Transmission electron microscopy, absorption and photoluminescence spectra were used to investigate the local heating effects on the formation of PbS QDs.

138 TC20 Photonic Glasses

149

Excitation-emission properties of Bi-doped

silica-based fibers in UV, visible and IR regions
Bufetov I. A.1, Firstov S. V.1, Khopin V. F.2, Guryanov A. N.2, Dianov E. M.1
1
2

Fiber Optics Research Center, Russian Academy of Sciences, Moscow, Russia;

Institute of Chemistry of High-Purity Substances, Russian Academy of Sciences,
Nizhny Novgorod, Russia

Bi-doped optical fibers based on fused silica are broadband gain media. The optical gain spectral range is dependent on the composition of bismuth doped fiber core, which may consist of an alumosilicate, germanosilicate, phosphosilicate, or germanophosphosilicate glass. All these fibers taken together provide currently optical
gain and lasing in the range from 1.15 to 1.55m. But the physical nature of bismuth active centers (BACs) in
acore glass was not elucidated up to now. One way to clear up this problem is extensive investigation of BACs
optical properties. We have performed detailed measurements of the luminescence intensity of Bi-doped glasses depending on both emission and excitation wavelengths, which were varied in aspectral range from 250 to
1,700nm. Such measurements in the UV wavelength band (250450nm) were carried out for the first time. The
data measured allowed us to construct corresponding 3D luminescence spectra clearly demonstrating distinction
between BACs in fibers and glasses of different composition. Optical losses in Bi-doped specimens and lifetime
of luminescence in each wavelength band were also measured. The positions of the five low-lying energy levels of
the BACs in Bi-doped silica glass free of other dopants and BACs in germania glass have been determined. It was
shown that BACs in silica are more suitable for optical amplification and laser generation. And abismuth fiber
laser based on this kind of BACs with an output power of more than 20 W and arecord efficiency of ~50% has
been demonstrated near =1,460nm.
The results obtained are useful criteria for the validity of suggested numerous and varied physical models of BACs
in glasses.

Glebova L.1, Mingareev H.2, Glebov L. B.2

1
2

OptiGrate Corp. Oviedo, FL, USA

CREOL, University of Central Florida, Orlando, FL, USA

The photo-thermo-refractive (PTR) glass is an optical material widely used as amedium for volume holograms.
Its main use is low loss robust mirrors for external resonators in laser systems. As has been shown in our recent
work, doping the PTR glass with rare earth elements, such as Nd and Yb provides luminescence enabling the gain
and the lasing action. At the same time these glasses retain the photosensitivity allowing recording the cavity
mirrors directly into the gain medium. This feature opens anew way for constructing amonolithic laser system,
in which asingle optical element acts as both the gain medium and the resonant cavity. This work addresses the
optical properties of PTR glass doped with Nd and Yb, focusing on the photosensitivity of the doped material. It
was found that the rare earth ions added to PTR glass reduce photosensitivity of the material. Induced refractive
index, luminescence, absorption and crystallization properties of original, UV exposed and thermally developed
glass are studied. It was shown that doping with rare earth ions increases viscosity and crystallization temperature of glass. Conditions that provide both efficient luminescence and high photosensitivity are discussed.

ICG Prague 2013 139

170

Photosensitivity of photo-thermo-refractive
glass doped with Nd+3 or Yb+3
as new media for a monolithic laser

177

Phosphors in fluorescent glasses (PiFGs)

for warm-white light emitting diodes
Seungryeol Yi*1, Jong Heo1, Woon Jin Chung2
1

Department of Materials Science and Engineering and Division of Advanced Nuclear Engineering,
Pohang University of Science and Technology, Pohang, Republic of Korea;
2
Division of Advanced Materials Engineering, Kongju National University, Cheonan, Republic of Korea

213

Commercial dichromatic white LEDs are composed of blue LEDs and yellow phosphors. YAG:Ce3+ is used in
white LEDs as color converting material, which converts a part of blue LED light( = ~460nm) into yellow
light(=~550nm). Light emission from YAG:Ce3+ covers green and red region of visible light wavelength range,
but intensities of these two visible emissions are not equal. As aresult of relatively weak red emission, the white
LEDs using YAG:Ce3+ is usually shifted to bluish (cold) white light. This work reports the phosphor-in-glass
composites for white light generation from blue LEDs, replacing polymer resins with glass frits for phosphor
binders. New glass frits containing specific amount of red-emitting components were developed for a matrix
of YAG:Ce3+ phosphor to supplement the red portion of the white light. Absorption and emission properties of
phosphors-in-fluorescent glass (PiFG) composites containing transition metal ions and rare earth ions were investigated. Efficiencies of the light conversion and color coordinates of specimens were examined.

2000nm spanning supercontinuum

in suspended-core As2S3 microstructured optical fibers
Mouawad O.1*, Dsvdavy F. 1, Charles J. C. 1, Gadret G. 1,
Fatome J. 1, Kibler B. 1, Kawashima H.2, Gao W.2, Ohishi Y.2, Smektala F.1
1

Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Universit de Bourgogne,

21078 Dijon, France.
2
Reaserch Center for Advanced Photon Technology, Toyota Technological Institute,
Nagoya 468-8511, Japan

234

Chalcogenide are known as highly nonlinear glasses. Corresponding microstructured optical fibers (MOFs) are
of great interest for infrared nonlinear optics. Their remarkable geometry exhibit avariety of nonlinear effects. It
is efficient for supercontinuum generation which finds applications in different fields as diverse as optics, biology,
environmental sensing We report the fabrication of low loss As2S3 glass optical fibers, typically around 1dB/m
at 1.55m. Glass performs were prepared by mechanical drilling, while microstructured fibers were designed to
shift chromatic dispersion around 2m. By mean of an optical parametric oscillator Ti-Saphir, investigated
MOFs have been pumped near their zero-dispersion wavelength in the femtosecond regime. We present the latest
experimental observation of supercontinuum generation extended up to 3.2m, in As2S3 suspended core microstructured fibers. Group velocity dispersions of tested fiber were measured and compared to numerical analysis.
Using measured MOFs parameters, in conjunction with the split-step Fourier-based solving of the generalized
nonlinear Schrdinger equation, we were able to accurately model the experimental results. To our knowledge,
reported spectral enlargement is the highest ever reported for As2S3 MOFs.

Energy conversion devices based on nanoparticles

of copper, silver and gold in glassy matrices
Rademann K., Simo A
Humboldt-Universitt zu Berlin, Institut fr Chemie, Brook-Taylor-Strasse 2, 12489 Berlin, Germany

We report on the formation processes of noble metal nanoparticles (copper, silver and gold) in soda lime silicate
matrices. We describe the fundamental growth mechanisms, which significantly differ for these three metals.
The growth mechanisms depend not only on the nature of the metal, but also on the fact that the stabilities of
the respective oxides are remarkably different. As for copper, we find that copper is bound firmly to the glass
matrix, while silver oxides are only stable up to a sharp borderline temperature (410C). Finally, gold oxides

140 TC20 Photonic Glasses

inside the glass matrix are not stable and cannot be formed. It has been shown explicitly by SAXS and ASAXS
measurements under ex-situ and in-situ conditions that gold clusters are homogeneous. Indeed, the Guinier-plots
as afunction of X-Ray energies exhibit aconstant slope irrespective of the applied energies. This means that gold
nanoparticles are not inter-connected to the glassy network.
Understanding the fundamental formation mechanisms becomes straightforward as soon as the underlying individual processes (reduction, diffusion, nucleation, growth, Ostwald ripening and Delayed Ostwald ripening can be
separated and studied independently. This approach allows us to create and fabricate agreat variety of weakly or
heavily doped glasses with abroad range of novel applications. Several prototypic devices will be presented in detail:
(1) Planck-white light emitters in silver doped glasses
(2) Emission color tuning by anovel energy transfer mechanism
(3) Conducting metal/metal-oxide composites
(4) Seebeck glasses for applications in energy converting devices
(5) IR-Up conversion glasses
(6) UV-Down-conversion devices
(7) SERS substrates with buried silver nanoparticles for long term stability

240

The upconversion luminescence

of rare earth doped chalcogenide glasses
for solar cell efficiency enhancement
Zhang J. 1,2, Liu C.2, Tao H.2, Zhang G.1, Zhao X.2
1
2

State Key Laboratory of Silicate Materials for Architectures

School of Resources and Environmental Engineering, Wuhan University of Technology,
122 Luoshi Road, Hongshan, Wuhan, Hubei 430070, P. R. China

By converting the near-infrared (NIR) light to short wavelength region, upconversion luminescence of rare-earth
doped glasses have potentials to improve the silicon solar cell efficiency. To realize the efficient upconversion,
host materials are of great importance, especially their maximum phonon energy. In this study, the upconversion luminescence of different rare earth doped chalcogenide glasses and the effects on solar cell were evaluated. Pr3+/Yb3+, Er3+/Yb3+, and Ho3+/Yb3+ co-doped Ge-Ga-S(Se) and Ge-Ga-S(Se)-CsI glasses were prepared by
melt-quenching method. Under 1,550nm, 1,200nm infrared laser or concentrated solar irradiation excitation,
the NIR upconversion luminescence at ~980nm and visible luminescence were observed. The addition of CsI can
improve upconversion luminescence further due to the changes in the environment of rare earth ions. Doping
with Yb3+ ions not only increased the emission intensity at 980nm, but also enhanced the visible emission from
Er3+, Pr3+ or Ho3+ due to the mutual energy transfer processes. The upconversion mechanisms were analysed based
on the rate equation and dynamic parameters calculations. The effects of upconversion luminescence on the solar
cell efficiency under solar simulator excitation were investigated. The results show that the efficiency of silicon solar cell can be improved due to efficient upconversion luminescence from rare earth doped chalcogenide glasses.
This is anew application for chalcogenide glass.

256

Blue upconversion emission in germanate

glass co-doped with Yb3+/Tm3+
Dorosz D., Kochanowicz M., Zmojda J., Dorosz J.
Bialystok University of Technology, Department of Optoelectronics and Lighting Technology,
Bialystok, Poland

In the paper upconversion luminescence of GeO2 Ga2O3 BaO glass system co-doped with Yb3+/Tm3+ ions
was investigated. Strong blue emission at 477nm corresponding to the transition 1G4 3H6 in thulium ions was
measured under the excitation of a976nm diode laser. The dependence of the upconversion emission upon the
thulium ions concentration was studied in order to determine the optimal conditions of energy transfer between
energy levels of active dopants. The most effective energy transfer Yb3+ Tm3+ was obtained in glass co-doped

ICG Prague 2013 141

257

with molar ratio of dopant 0.7Yb2O3/0.07Tm2O3. The increase of thulium concentration over 0.07mol% results
in the effect of reverse energy transfer from Tm3+ Yb3+, which leads to rapid quenching of the luminescence
line at the 477nm wavelength. Other physical (refractive index) and thermal (thermal stability) properties were
optimised in order to fulfil optical fibre technique requirements. Co-doped Yb3+/Tm3+ glass was used as acore
in manufactured optical fibre whose luminescent parameters were evaluated. The presented results indicate that
elaborated germanate glass co-doped with 0.7mol%Yb2O3/0.07mol%Tm2O3 is apromising material which can be
used to produce superluminescent optical fibre sources generating radiation in the visible spectrum.

Preparation of Sn2+ containing oxide

glasses and the emission property
Masai H.1, Fujiwara T.2, Tokuda Y.1, Yoko T.1
1
2

Kyoto University, Uji, Japan;

Tohoku University, Sendai, Japan

285

Recently, strong, sharp emissions of rare earth (RE) cations have been used in the white light-emitting diodes
(LED) that will replace the conventional white fluorescent lamp. Although various kinds of RE-doped phosphors
have been actively developed worldwide, the host materials for these phosphors, such as silicone, still remain
limited with respect to high-power or short-wavelength excitation light sources, because of degradation. Thus,
anovel, inorganic, low-melting material will be needed as an alternative to organic sealing materials in the future.
If white light can be attained only by the combination of aUV LED and an inorganic cover material that possesses
white light emission properties, such inorganic materials would be desirable.
In the present paper, we demonstrate light emission in RE-free Sn 2+-containing oxide glasses that were prepared
using melt-quenching method. The RE-free transparent oxide glasses showed light emission with high quantum
efficiency (QE) values, comparable to conventional crystalline phosphors, by excitation with deep-UV light. The
broad emissions of the Sn2+ emission centre, whose emission is strongly affected by the coordination field, could
be continuously tuned by both the amount of activator and the composition of the glasses, without reduction of
the QE values. In the case of Sn2+- Mn2+-codoped samples, several glasses show white light emission consisting
of broad emission bands. We have found that Sn2+ emission property of phosphate glass is different from that of
borate glass. The important point of our results is that amorphous oxide glasses possessing random structures
demonstrate high QE values comparable to conventional crystalline phosphors. For future emitting devices, we
believe that the low-melting glasses will constitute one of the most industrially favourable inorganic materials
possessing transparency and emitting properties.

Novel photo-thermo-refractive glasses

for photonic applications: Optical, spectral,
luminescent and ion-exchangeable properties
Nikonorov N. V., Aseev V. A., Dubrovin V. D.,
Ignatiev A. I., Nuryev R. K., Sgibnev E. M., Sidorov A. I.
St. Petersburg National Research University of Information Technologies,
Mechanics and Optics, St. Petersburg, Russia

Today photo-thermo-refractive (PTR) glass is avery attractive material for recording volume phase holograms and
developing avariety of devices for photonics. This sodium-zinc-aluminum-silicate glass doped with cerium, silver,
antimony, fluorine and bromine exhibits agrowth of complicated crystalline phase of NaF-AgBr on silver nanoparticles and anegative refractive index modulation after exposure to UV radiation followed by athermal treatment. In
the present work three types of PTR glasses for photonic applications have been developed. The first laser PTR glass
was doped with erbium and ytterbium ions. This material combines itself some opportunities: fabrication of lasers
or amplifiers, recording of volume Bragg gratings, and fabrication of planar waveguides and fibers. The glass can
be classified as an optical polyfunctional material. The second PTR glass was doped with variable halides (fluorides,
bromides and chlorides) and their concentrations. The photo-thermo-induced crystallization results in agrowth of

142 TC20 Photonic Glasses

variety of nanocrystalline phases of NaF, NaBr, NaCl, AgBr, AgCl and their combinations. The growth of silver bromide and chloride phases result in apositive increase of refractive index modulation. The glass host of the third PTR
glass contains high refractive index oxides of metals that also allowed us to increase the refractive index modulation.
The structure of silver clusters and nanoparticles, and haloid nanocrystals, as well as optical, spectral, luminescent
and ion-exchangeable properties of three types PTR glasses has been demonstrated.

286

Rare-Earth doped transparent

lead-oxy-fluorine nano-glassceramics
Aseev V. A., Kolobkova E. V., Nekrasova Y. A., Nikonorov N. V.
The National Research University of Information Technologies,
Mechanics and Optics, St. Petersburg, Russia

Currently, transparent glassceramics are of great interest for the modern element base of photonics. Because they
have intermediate state between crystalline materials and glasses, these ceramics combine the best properties of
crystals (high mechanical and thermal strength) and glasses (pressing and molding possibilities, optical fibers pulling and carrying out ion exchange to fabricate waveguide structures). Lead-oxy-fluorine nano-glassceramics doped
with rare-earth ions (Tm, Ho, Pr, Er, Yb) have been developed and synthesized. In the present work nano-glassceramics 30SiO2-18PbF2-7.5Al2O3-5ZnF2-29CdF2-3YF3 doped with different RE ions of Tm, Ho, Pr, Er, and Yb have
been developed and synthesized. In this system, the crystalline phase is precipitated upon heat treatment. It was
shown that RE ions plays arole of nucleation centers for PbOY(1-x) Ln(1-x)F3 crystal phase growth. The dependence
of the low-level cell size and the volume of crystal fraction on heat-treatment conditions were determined. The size
of crystal phase achieves up to 40nm. Also, elementary cell size changing dependencies on the rare-earth ion radius
were researched, spectral and luminescence properties of nano-glassceramics were investigated. It is shown that
repeated heat treatment leads to absorption and luminescence spectra shape changes, emitting probabilities changes
and up-conversion process effectiveness changes. Stark structure become apparent in absorption and luminescence
spectra after heat treatment, witch is evidence of rare-earth ion entry to crystal phase. For example, the band width
of emission spectrum at 1.55m achieves 70nm for Er-doped nano-glassceramics. Prospects of using such materials
as laser media, white LED luminophors and solar battery up-converters were shown.

305

Rare earth doped alumosilicate glasses

as potential high-power laser materials
Herrmann A.1, Kuhn S.1, Tiegel M.1, Rssel C.1,
Krner J.2, Klpfel D.2, Hein J.2, Kaluza M. C.2, Paulus G. G.2
1
2

Otto-Schott-Institut, Jena University, Germany;

Institute of Optics and Quantum Electronics, Jena University, Germany

Rare earth doped alumosilicate glasses are promising materials for high-power lasers and optical amplifiers. They
are relatively easy to produce in high quantity and show broad band fluorescence excitation and emission spectra and relatively low phonon energies. Furthermore alumosilicate glasses have very favorable mechanical and
thermo-mechanical properties as low coefficients of thermal expansion and ahigh microhardness which should
make them most suitable for ultra high-power laser applications. Despite of these properties only few systematic
investigations of structure-property-relations in alumosilicate glasses have been published so far.
Glasses of the system SiO2 Al2O3 RO2/RO/R 2O3 (R: Li, Na, Mg, Ca, Zn, La) have been doped by Sm3+ and Yb3+
ions in order to measure fluorescence excitation & emission spectra, cross sections and fluorescence lifetimes.
Doping concentration of the rare earth ions has been varied to study fluorescence quenching. Typical phonon
energies and thermo-mechanical properties as the coefficient of thermal expansion have been measured in dependence on the network modifier ion and network modifier content. The results are compared to the properties
of other optical glasses as borosilicates, phosphates and fluoride-phosphates.

ICG Prague 2013 143

342

Thermally poled oxide and non-oxide glasses:

Polarization mechanisms vs. structural
rearrangements and second order optical properties
Dussauze M.1, Cremoux T.1, Yang G.1, 2,
Cardinal T.2, Fargin E. 2, Richardson K.3, Rodriguez V. 1
1

Univ. Bordeaux, ISM, CNRS UMR 5225, F-33400 Talence, France;

Univ. Bordeaux, ICMCB, CNRS UPR 9048, F-33600 Pessac, France;
3
School of Materials Science and Engineering, Clemson University, COMSET,
161 Sirrine Hall, Box 340971, Clemson, SC 29634, USA

351

Poled glasses are promising materials for alarge variety of applications such as for photonics or biomaterials. In
order to control their physical and chemical properties, one needs to determine and understand the different
mechanisms occurring during thermal polarization treatments. To progress in this direction, we have investigated the structural rearrangements induced by poling on alarge variety of both oxide and non-oxide glasses.
To determinate the space charge implemented, the Maker fringes technique and second harmonic generation
imaging have been employed. Structural changes were studied by micro-Raman and infrared vibrational spectroscopy, and have highlighted strong correlations between space charge and structural modifications. Careful
assignments of the vibrational spectra have permitted to describe the polarization processes. In addition, the
influence of poling conditions on the optical and chemical properties of the poled glasses has been characterized.
This large base of results is of agreat interest to progress towards future applications.

Glass and glass-ceramics elaborated

within the (Nd3+, Yb3+) doped TeO2-Nb2O5-WO3
system for microlaser applications
Dardar H 1,2, Bertrand A1, Labruyre A.2, Carreaud J.1, Duclre J.-R.1,
Delaizir G1., Dutreilh-Colas M.1, Masson O.1, Couderc V. 2, Thomas P. 1
1

Laboratoire de Sciences des Procds Cramiques et de Traitements de Surface, UMR7315 CNRS/Universit de Limoges, Centre Europen de la Cramique, 12 rue Atlantis, 87068 Limoges Cedex, France
2
XLIM, UMR 6172 Facult des Sciences et Techniques, 87060, Limoges Cedex, France

In this work, the elaboration of miniature laser sources aimed at being employed in the cellular diagnostic has
been investigated. At first, glass samples of molar composition 75TeO2-20NbO2.5-5WO3 doped with NdO1.5 or
YbO1.5 (1mol%) have been prepared and tested as microlasers. Laser emission has been successfully obtained in
the Nd3+-doped glass, with aslope efficiency of 4.6% and alaser threshold reached at 5mW. Interestingly, adependence of the laser emission spectrum (enlargement towards highest wavelength) with the pump power has
been observed and related to thermal effects. Nevertheless, in Yb-doped samples, the laser emission has required
higher pump power and was unstable: the emission intensity starts decreasing after ~20s to finally completely
vanish after ~100s. To improve the mechanical and lasing properties, new transparent glass-ceramics elaborated
within the same chemical system were targeted. Our efforts were concentrated towards the obtention of crystals
homogeneously distributed within the bulk, and not only at the surface, of the samples. Conventional (ventilated
furnace) and non-conventional (Spark Plasma Sintering (SPS), laser irradiation) methods were explored. In particular, for SPS experiments, parameters like, atmosphere, powder granulometry were tested. For laser irradiation
experiments, the pulse energy, laser wavelength and number of pulses were varied.

144 TC20 Photonic Glasses

361

Implantation of oxygen into glasses already

implanted with Cu+, Ag+ or Au+ ions
Vytykacova S.1, Svecova B.1,
Nekvindova P.1, Spirkova J.1, Mackova A.2,3, Malinsky P.2,3
1

Department of Inorganic Chemistry, Institute of Chemical Technology, Prague, Czech Republic;

Nuclear Physics Institute, Academy of Sciences of the Czech Republic, Rez, Czech Republic;
3
Department of Physics, Faculty of Science, University J. E. Purkyne, Usti nad Labem, Czech Republic

It has been shown that glasses containing metal nanoparticles are perspective photonics materials for fabrication
of all-optics switches. Resulting optical properties of the nanocomposite glasses depend on the composition and
structure of the glass, as well as on atype of the metal ion and involved experimental procedures. The main aim
of this contribution is to study the influence of oxygen co-implantation on the properties of glasses already implanted with gold, silver and copper ions and on formation of metal nanoparticles in such glasses.
Three various types of silicate glasses were implanted with Cu+, Ag+ or Au+ ions under the same conditions (energy 330keV and fluence 1.1016 ions/cm2). Subsequently, all glasses were implanted with O+ ions into the same depth
as metal ions. All samples were annealed around transformation temperature of the glass (600C) in air for various times ranging from 1 to 5 hours. The samples were then characterized from the point of view of: nucleation of
metal nanoparticles (linear optical absorption), migration of the Cu, Ag, Au ions through the glass matrix during
the implantation and post-implantation annealing (Rutherford Backscattering Spectroscopy), and the oxidation
state of the Cu, Ag, Au ions (photoluminescence).
The obtained results showed that sequential implantation of oxygen influenced the range of the implanted particles and caused the shift of Cu, Ag and Au deeper into the glass substrate. Moreover, it was found that the implantation of oxygen had positive effect on nucleation and growth of metal nanoparticles in the glass.
Acknowledgement: SPIRIT 227012, IGA UJEP 5322215000301 and CANAM.

384

Photodarkening in Yb-doped fibres for high

power lasers: Investigation of structural
changes within the EU project LIFT
Milanese D.1, Chiesa M.2, Pavese M.1, Taccheo S.3, Gebavi H.3,
Robin T.4, Lablonde L.4, Mattsson K.5, Mechin D.6, Monteville A.6, Virga A.1, Giorgis F.1
1

Politecnico di Torino, Torino, Italy;

Universit di Torino, Torino, Italy;
3
Swansea University, Swansea, UK;
4
iXFiber, Lannion, France;
5
NKT Photonics, Birkerd, Denmark;
6
Perfos, R&D Platform of Photonics Bretagne, Lannion, France;
2

Ytterbium doped silica based glasses, thanks to their outstanding thermo-mechanical properties and ease of integration with commercial components, are key materials for the fabrication of optical fibres suitable for high power
lasers. In recent years with laser output powers having reached the kW range, abroadband absorption in the visible
and near infrared (NIR) was observed in silica glass after prolonged operation, thus affecting the overall performance of the device. The issue, known as photodarkening (PD), has been to acertain extent solved with the addition
of co-dopants (i.e. P, Ce), but aclear understanding of its mechanism is still far from being reached.
Th is work reports on the investigation of the effects of PD on the materials after irradiation with photon sources of different energies: NIR, high intensity X-rays and gamma rays were used to irradiate optical fibres and
preforms doped with different amounts of Yb3+ ions and co-doped with Al, P and Ce. Electron Paramagnetic
Resonance spectroscopy was used to detect paramagnetic defects, while UV-VIS and Raman spectroscopy
provided information on the structural changes. The obtained results are reported together with the associated
interpretation of the generated colour centres. abenchmark of the prepared materials was carried out aiming
at selecting the best candidates for the optical fibre lasers.

ICG Prague 2013 145

477

Optical characterization of zinc antimonate

oxy-bromide glasses doped by RE3+
Zavadil J.1, Kostka P.2, Legouera M.3, Gladkov P.1, Kohoutkov M.2, Prochzkov O.1
1

Institute of Photonics and Electronics AS CR, Prague, Czech Republic

Institute of Rock Structure and Mechanics AS CR, Prague, Czech Republic
3
Dpartement de Gnie Mcanique, Universit de Skikda, Algrie, Algeria

489

It follows from our previous work that the Sb2O3-ZnBr2 binary system shows alarge glass-forming region in the
range of 2090mol% Sb2O3. Chemical analysis showed that bromine concentration decreases during synthesis
with the initial Sb2O3-ZnBr2 binary system transforming into the Sb2O3-ZnBr2-ZnO ternary system. The optical
transmission region can be found between absorption edges at 0.4 and 7m and the refractive index is about
2.02.1. Glass transition occurs at around 300C. In some compositions, specifically in those containing
5060mol% Sb2O3, no crystallization exotherm was identified by differential scanning calorimetry performed at
heating rate of 10K/s. In view of these findings the 60Sb2O3 40ZnBr2 composition was chosen for doping with
rare earths (RE) elements and for detailed optical characterization. anumber of RE were used for doping, including Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb. In addition to those RE the glasses were also doped by Lu. We report the
investigation of prepared glasses by using room temperature transmission and low-temperature photo-luminescence spectroscopy. The optical band gap of the base glass was deduced from the high-energy absorption edge.
In addition to relatively sharp 4f-4f emission bands of RE3+ ions we also observed, at low temperature, abroad
luminescence band of the base glass mediated by the deep electronic energy states in the gap. Due to their exceptional thermal stability, low phonon energies and good solubility of RE, the studied glasses are suitable materials
for infrared transmission applications and for manufacturing of active fibres.

Rare-earth-doped glasses for high

peak power fiber lasers
Jiang S.
AdValue Photonics Inc., Tucson, AZ 85714, USA

Fiber lasers are of great interest because of its outstanding reliability and maintenance-free operation. Industrial
applications of fiber lasers are positioned to exceed free-space solid-state lasers. However, the peak power and pulse
energy of fiber lasers are still limited due to the relatively small core diameter and long gain fiber length. along fiber
length and asmall core diameter results in alow threshold of optical nonlinearity. In many cases, the performance
of pulsed fiber lasers including both Q-switched nanoseconds laser and mode-locked picoseconds lasers are limited
by optical nonlinearity. Multi-component glasses having ahigh rare-earth doping concentrations could be asolution for this challenging. ahigh rare-earth doping can produce ahigh gain per unit length, resulting arelatively short
gain fiber length, which effectively suppress the optical nonlinearity. Optical nonlinearity including stimulated Brillouin scatting, four-wave mixing as well as stimulated Raman scatting in fiber lasers will be discussed. Performance
of Yb-doped, Er-doped and Tm-doped multi-component glass fibers for Q-switched fiber lasers and mode-locked
fiber lasers will be presented. The outlook of high peak power fiber lasers will be described.

146 TC20 Photonic Glasses

496

Rare earth-activated nano-composites

glass systems for photonics
Chiappini A.1, Lukowiak A.1,2, Armellini A.1,3, Davor R.1,
Chiasera A.1, Duverger Arfuso C.4, Boulard B.4, Pelli S.5, Righini G. C.5,6, Ferrari M.1
1

CNR-IFN, CSMFO Lab., Via alla Cascata 56/c, Povo, 38123 Trento, Italy.
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, ul. Okolna 2,
50-950 Wroclaw, Poland.
3
FBK, via Sommarive 18, Povo, 38123 Trento, Italy.
4
Institut des Molcules et Matriaux du Mans, UMR 6283, Equipe Fluorures, Universit du Maine,
Av. Olivier Messiaen, 72085 Le Mans cedex 09, France.
5
MDF Lab., IFAC CNR, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy.
6
Museo Storico della Fisica e Centro di Studi e Ricerche Enrico Fermi,
Piazza del Viminale 2, 00184 Roma, Italy.
2

The scientific and technological activity involving the development of materials at nano-micro scale and related
converging technologies allows progress in the conception, design, and realisation of systems and devices with
substantially improved performance and significant scientific results. The specific properties of the Sol-Gel technique make this approach very effective to succeed in the above mentioned topics, with special regard to the
development of advanced materials for photonic applications. Some examples will be discussed at the conference,
starting with the analysis of different colloidal systems. Silica and polystyrene spheres are presented, as well
as core-shell spheres activated by rare earth ions. Starting from the nano spheres, 3D photonic crystals can be
fabricated. Some examples of opals are given and it is demonstrated that it is possible to tune the position of the
stop band infiltrating the voids of the opal structures with suitable materials. Other examples are presented referring to the case of planar waveguides; here, relevant results have been obtained for rare-earth-activated amorphous and nanostructured SiO2-HfO2 and nanostructured SiO2-SnO2 systems. Of particular interest appears the
demonstration of the role of SnO2 nanocrystals as rare earth sensitizers and the possibility to develop suitable
fabrication protocols allowing the fabrication of rare earth activated glass ceramic waveguides.

521

Europium- and dysprosium-doped optic

active phosphate-based glasses
M. Kilo1, A. Deinhardt1, S. Dembsky1, S. Schweizer2, M. Dyrba2
1
2

Fraunhofer ISC, Neunerplatz 2, 97082 Wrzburg, Germany;

Fraunhofer CSP, Walter-Hlse-Str. 1, 06120 Halle, Germany

For applications like solar cells or for light emitting diodes (LEDs) it is desirable to tune the optical spectrum of
the transmitting light while keeping the total transmission as large as possible. There are two methods to tune the
transmitting spectrum, optical up-conversion and down-conversion, where either two photons are combined to
one high-energy photon, or one photon is split into two low-energy photons.
In this paper, the optical properties of some barium phosphate-based glasses doped with Europium and Dysprosium, respectively, were investigated. By using nanoparticles as carrier for the lanthanide dopant elements, it
was possible to get the lanthanide element on well-defined lattice places. The optical properties of the prepared
glasses were investigated using UV/vis-emission spectroscopy. Optical emission spectroscopy showed that both
lanthanide elements were found on two different lattice sites, Depending of the oxidation state of Europium, the
conversion can be in abroad energy band with high efficiencies.

ICG Prague 2013 147

536

Glass-ceramics for photonics:

Advances and perspectives
Chiappini A.1, de Pablos-Martin A.2, Lukowiak A.1,3, Ristic D.1,
Tran Ngoc K.4, Berneschi S.5,6, Duverger Arfuso C.7, Turrell S.8, Ivanda M.9,
Duran A.2, M. J. Pascual2, Boulard B.7, Pelli S.5, Righini G. C.5,6, and Ferrari M.1
1

CNR-IFN, CSMFO Lab., Via alla Cascata 56/c, Povo, 38123 Trento, Italy.
Instituto de Ceramica y Vidrio (CSIC), C/Kelsen 5, Campus de Cantoblanco, 28049 Madrid, Spain.
3
Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
ul. Okolna 2, 50-950 Wroclaw, Poland.
4
Lab. of Optoelectronic Materials, International Training Institute for Materials Science (ITIMS),
Hanoi University of Technology, No 1 Dai Co Viet Street Hanoi Vietnam.
5
MDF Lab., IFAC CNR, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy.
6
Museo Storico della Fisica e Centro di Studi e Ricerche Enrico Fermi,
Piazza del Viminale 2, 00184 Roma, Italy.
7
Institut des Molcules et Matriaux du Mans, UMR 6283, Equipe Fluorures, Universit du Maine,
Av. Olivier Messiaen, 72085 Le Mans cedex 09, France.
8
LASIR (CNRS, UMR 8516) and CERLA, Universit Lille 1, 59650 Villeneuve dAscq, France.
9
Ruer Bokovi Institute, P.O. Box 180, 10002 Zagreb, Croatia.
2

575

Glass-ceramics are nanocomposite materials which offer specific characteristics of capital importance in photonics.
This kind of two-phase materials is constituted by nanocrystals embedded in aglass matrix and the respective composition and volume fractions of crystalline and amorphous phase determine the properties of the glass-ceramic. Among
these properties transparency is crucial, in particular when confined structures, such as dielectric optical waveguides,
are considered, and several works have been devoted to this topic. Another important point is the role of the nanocrystals when activated by luminescent species, as rare earth ions, and their effect on the spectroscopic properties of
the glass-ceramic. The presence of the crystalline environment around the rare earth ion allows high absorption and
emission cross sections, reduction of the non-radiative relaxation thanks to the lower phonon cut-off energy, and tailoring of the ion-ion interaction by the control of the rare earth ion partition. Fabrication, assessment and application
of glass-ceramic photonic systems, especially waveguides, deserve an appropriate discussion which is the aim of this
lecture, focused on luminescent glass-ceramics. At the conference consolidated results and recent advances in this
important scientific and technological area will be presented, and some perspectives will be outlined.

Advanced chalcogenide glasses for next

generation photonic applications
Richardson K. A1., Musgraves J. D1., Wachtel P.1, Novak S.1,
Danto S.1, Agarwal A.2, Singh V.2, Lin P-T2, Kimerling L. C.2,
Hu J.3, Yi Z. 3, Lin H.3, Giammarco J.4, Soliani A. P4, Luzinov I.4, Hensley J.5
1

Townes Laser Institute, CREOL, College of Optics and Photonics, Univ. Central FL, Orlando FL
Microphotonics Center, Massachusetts Institute of Technology, Cambridge MA
3
Department of Materials Science and Engineering, University of Delaware, Newark, DE
4
School of Materials Science and Engineering, Clemson University, Clemson, SC
5
Physical Sciences Inc., Andover, MA
2

Planar optical structures based on functionalized chalcogenide glasses provide asuperb device platform for chemical and biological sensing applications. Chalcogenide glasses have demonstrated promise as materials for infrared sensing as they exhibit transparency over alarge range of infrared wavelengths and tunable optical properties
through doping and/or compositional tailoring. Waveguides, resonators and other components processed on-chip
(silicon, Si) can be realized such that the strong enhancement in the electromagnetic field confined within ahigh
index contrast resonator, leads to highly sensitive photon-matter interactions in asmall footprint. In this paper we
discuss the development of highly sensitive chalcogenide glass based microdisk resonator sensors that measure
resonant peak shifts caused by refractive index change upon exposure to achemical analyte. The specificity of the
microdisk resonator sensors is enhanced by applying specialized polymer films and nanofoams that respond in
apredictable fashion when exposed to achemical analyte of interest. Discussed are key material science challenges
needed to enable highly sensitive and specific sensors based on such complex multi-material assemblies and the
fabrication issues that ultimately define resulting optical performance.

148 TC20 Photonic Glasses

TC17 Archaeometry of Glass

ICG Prague 2013 149

 150

014

Trace elements in provenancing Roman glass-making

Brems D., Scott R. B, Degryse P.
KU Leuven, Leuven, Belgium

After decades of research, it still remains extremely difficult to determine the provenance of Roman natron glass.
This type of material was made by melting three components (i.e., quartz sand, natron and lime) at temperatures
of about 1,100C. During the production of natron glass, the raw materials are completely transformed and all
their visible characteristics are lost, leaving only bulk chemical data as apotential discriminating feature. Unfortunately, the compositional variation of sodalimesilica glass is limited due to the maximum attainable furnace
temperatures and the shape of the Na 2OSiO2CaO ternary phase diagram itself. As aresult, all Roman glass is
relatively uniform in its major elemental composition.
During the last few years, however, studies on the provenance determination of ancient glass have revived due to the
introduction of trace element and isotope analysis. The trace elemental composition of Roman natron glass will be
acombination of elements derived from the sand, the natron and the lime, and possibly from any (de)colourants that
were added to the glass batch. In this study, we investigate the variation in trace element signatures of 11 potential glassmaking sand raw materials to examine whether that kind of data can be used to distinguish between these possible
sources of natron glass and raw glass from the known primary production centres in the Levant and Egypt.
It is shown that the combined use of Nd isotopic and trace element analysis can indeed be efficient for provenancing Roman natron glass. Elements that proved to be the most diagnostic are Ti, Cr, Sr, Zr and Ba. Apart from Ba,
which is often associated with Mn decolourants, these elements are seldom influenced by the addition of colouring agents or recycling, and should provide direct information about the nature of the silica source used.

Scott R. B.1, Brems D.1, Degryse P.1, Shortland A.2

1

KU Leuven, Leuven, Belgium; 2 Cranfield University, Shrivenham, UK

Roman natron glass has been the focus of provenancing studies for anumber of years. This type of glass was made
from silica sand, mineral soda, and asource of lime either in the form of shell or limestone. The interpretation
of compositional data of Roman glass is complicated by the fact that the Romans were known to recycle glass.
The archaeological and literary evidence suggests that the practice of collecting and recycling glass occurred on
asystematic basis. It has been suggested that the incorporation of recycled glass in amelt can be seen in the levels
of certain trace elements in the final glass, in particular, transition metals which are often used to (de)colour glass.
Elevated levels of these elements, i.e. above the natural background level found in the sand raw material, but
below the amount classed as adeliberate addition, in other words, below the amount needed to have anoticeable
effect on the colour of the glass, are used to suggest that the glass sample in question resulted from the recycling
of cullet including small amounts of coloured glass.
A series of melting experiments were devised to examine what happens to the trace element signature when
different glasses are mixed together. The fi rst of the experiments mixed combinations of plant ash, natron
and modern soda-lime-silica glass, at temperatures achievable in Roman furnaces. The aims were two-fold, a)
can different glass technologies be successfully mixed, and b) what happens to the trace element signature? In
asecond experiment, varying amounts of blue glass were (re)melted together with colourless glass to see how
much coloured glass can be incorporated as recycled material in acolourless glass melt before it starts to significantly affect the colour of the fi nal glass.
The trace element concentrations of all the resultant glasses are determined, and compared to adatabase of glass melting sands to investigate which elements have elevated levels, and to determine the extent to which the recycling of
glasses affects this. An evaluation is also made of the effect of recycling glasses from different technologies i.e. plant
ash and natron glass. The implications of the research for archaeological glass provenancing studies are also discussed.

ICG Prague 2013 151

028

The effect of mixing and recycling on the trace element

composition of experimental Roman natron glasses

069

Heating optical microscope for indirect viscosity

evaluation of archaeological glass
Montanari F.1, Boschetti C.2, Henderson J.2, Leonelli C.1
1
2

Department of Engineering Enzo Ferrari, University of Modena and Reggio Emilia, Modena, Italy;
Department of Archaeology, University of Nottingham, Nottingham, UK

084

The heating microscope is awidely used instrument in many industrial applications, especially in the ceramic field,
to obtain information on the sintering behaviour and, indirectly, on the viscosity curves of glass. This analytical
technique is therefore important for the study of glass technology, especially when the information available about
the ancient technology is limited. Usually, heating microscopes work by taking images of the sample profile, during
apre-set thermal cycle, and collecting asintering curve. Both of these sets of information have been used to define
five characteristic temperatures corresponding to specific viscosity values necessary to plot the Log10() vs T curves.
In this research, we applied heating microscopy to aselection of Roman glasses (1st century AD), both transparent
and opacified and in so-doing, evaluated their working properties. The use of this technique, for the limited amount
of powdered glass required (about 5mg), has been shown to be an excellent tool to characterize ancient glasses.

Glass in Central Europe from late-medieval to end

of pre-industrial era: A materials science approach
Kunicki-Goldfinger J. J.
Institute of Nuclear Chemistry and Technology, Warsaw, Poland

236

The paper is an overview of the technological and compositional development of vessel glass in central Europe
from the late-medieval to the end of pre-industrial era. Concentrating on glass as amaterial, it outlines the basic
types of glass composition, their historical development and geographical distribution. This process is shown in
the wider context of European glass technology.
The paper is based on the results of quantitative chemical analyses of several hundred glass vessels from various
historical collections and archaeological deposits. Moreover, the results of over one thousand vessels analysed
non-destructively with the use of EDXRF are included. They concern mostly valuable museum objects, which
could not be sampled.
The paper focuses on the glass composition and its evolution throughout the centuries drawing attention to local
variations. Special emphasis is placed on the late and post-medieval glass including the seventeenth century
change, as it opened anew era in glass technology.
The nature of crystal glass adiscussion which has occupied art historians and glass researchers is demonstrated based upon written sources and analytical results. Three widely encountering vessels types: nuppenbehers,
vessels made in Venetian style and Baroque goblets are discussed in more details.
Two fundamental problems are addressed to summarize the paper. The first asks what glass was used in central
Europe and how did it evolve and impact upon the wider European glass technology? The second asks to what extent, an understanding of the chemical composition of glass can help the glass researcher in his historical studies.

Early glass engravings (c. 15851700)

with focus on works by Caspar Lehmann
and by the Schwanhardt workshop in Nuremberg.
Part I: Introduction and art historical view
Schommers A.
Bavarian National Museum, Munich, Germany

Hand in hand with technical innovation the transfer of engraving techniques for rock crystal to glass in the late
1500s led to the subtle refinement of artistic expression in the 17th century. Caspar Lehmann (Uelzen 1563/65,
Prague 1622) and his apprentice Georg Schwanhardt the Elder (1601, Nuremberg 1667) created a style of en-

152 TC17 Archaeometry of Glass

graving for plates and glasses which found favour at European princely courts and among nobles, patricians
and wealthy burghers. Differentiating between the works of the early protagonists and their successors, such as
Schwanhardts sons Heinrich and Georg (the Younger) or other competing engravers in Nuremberg, is stylistically difficult. An interdisciplinary survey (art historical, technological and analytical) over 80 objects from nine
collections in Germany, Austria and the Netherlands was made in order to obtain new criteria for the attribution
and dating of what are mostly unsigned glasses and rock crystals objects (seven items). Such an approach seems
of particular interest since the number of art historical publications (case studies and older surveys) outweighs
technological literature of more general kind and because exceedingly few analyses of glass have been published.
Partly contradictory, these art historical publications served as abasis for the selection of the studied objects.
Observations on the dating of the scenes, persons, heraldic motifs and inscriptions engraved, as well as marks on
silver mounts were therefore also entered into the data collection. This is the first time that an attempt has been
made to link stylistic considerations with observations found using the binocular microscope in order to better
identify the possible handwritings of different engravers (see also Part II).

237

Early glass engravings (c. 15851700)

with focus on works by Caspar Lehmann
and by the Schwanhardt workshop in Nuremberg.
Part II: Technology a macroscopic view
Richter R. W.
State Art Collections Dresden, Green Vault, Dresden, Germany

Technology is primarily to thank for the rapid evolution of techniques for engraving glass in the late Renaissance
and not least great mechanical improvements in turning devices and the use of predominantly copper wheels
in readily available sizes and shapes. Unlike hard stone, glass was less resistant and thus particularly suitable for
delicate engraving with rotating copper-discs in combination with grinding and polishing media in suspended
form (e.g., emery, red iron oxide, tin oxide). The matt intaglios with which glass was cut were further differentiated by employing various methods of polishing (from the 1620s onwards), diamond point engraving (already
applied for outlining in the 1580s) and acid-etching (presumably from the 1670s onwards). When grinding, the
blank had to be pressed against the rotating wheel by hand giving to expect, that one might be able to identify
the handwritings of different individuals. Therefore, with the aid of abinocular microscope (c. 620x), asearch
for characteristic features, such as precision in execution of straight and curved lines, the treatment of accidents,
the quality of artistic expression etc., was conducted. Comparison was also made of commonly depicted motifs
such as facial features, flowers, insects, lettering) in terms of applied techniques. These findings were documented
in written form. acomparative visual assessment was enabled by the taking of digital images (c. 0.42.8x) of selected spots on all of the objects examined with areflex camera (Canon D 50, Canon Macro 28105 mm in retro
position). Focus stacking was applied using the image processing soft ware Helicon Focus, to obtain acompletely
sharp image, even for curved motifs on glass vessels. An extract of the results of each macroscopic examination
was then added to the above mentioned art historical data collection.

Stege H.
Doerner Institut, Bayerische Staatsgemldesammlungen, Munich, Germany

A representative selection of c. 60 engraved glass objects from various collections in Munich, Nuremberg and
Vienna were analysed non-destructively using acompact hand-held XRF spectrometer (Niton XL 3t, Thermo
Fischer Scientific, with helium purging, calibration with glass standards). The XRF measurements have to be

ICG Prague 2013 153

238

Early glass engravings (c. 15851700)

with focus on works by Caspar Lehmann
and by the Schwanhardt workshop in Nuremberg.
Part III: Analysis of base types of glasses

333

regarded per se as semi-quantitative, especially for light elements, due to observable glass corrosion phenomena.
Although the element sodium could not be quantified, its presence in sodium-rich glasses could be concluded
indirectly with the detection of bromine (as marker for halophytic plant ash) and with the calculated potassium
and calcium values. Nevertheless, XRF offered aquick and portable method to classify the different chemical base
types of glass. Measurements were also achieved by some additional XRF examinations using other spectrometer
types (Rijksmuseum Amsterdam, Kunsthistorisches Museum Wien).
The early period of engraving was mastered on glass of different base types. Sodium-rich glasses form the majority,
with roughly half being of cristallo and vitrum blanchum quality. As late as the 1680s/90s many of the baluster
goblets regarded typical of Nuremberg were made of soda-rich glass. The new type of crystal glass developed in
Brandenburg and Bohemia using potash or saltpetre as flux and arsenic as decolourizer, could only be detected
among comparably late Nuremberg glasses (after c. 1690). In addition anumber of colourless wood ash glasses,
traditionally decolourized with manganese, were detected. Information about the base type of glass including
the notation of suggestive dating markers, as derived from the analysed elemental composition of the glass, completed our data collection. aplanned publication in the recent future will provide amuch broader overview on
the data and results of this interdisciplinary research project, including the results of quantitative PIXE/PIGE
measurements on 6 further engraved glasses (Helmholtz-Forschungszentrum Dresden-Rossendorf).

Chemical analytical evidence for 12th

century glass melting in Sweden
Jonson B.1, Ihr A.2
1
2

Linnaeus University, Vxj, Sweden;

University of Gothenburg, Gothenburg, Sweden

462

Recent excavations in the town of Ldse, close to Gothenburg in Sweden found remnants of abrick kiln. C14 analysis
dated the findings to the period of around 1260 AD. As building material in the kiln and in stratigraphic older layers
below it, acrystalline material was found together with aglassy material or possibly aslag. The glassy material was
found to be too low in its content of carbon to originate from the smelting of minerals to metal in ablast furnace.
Chemical analysis found the excavated glass to consist of approximately (in wt-%) 3% Na2O, 3% K 2O, 4% MgO,
18% CaO, 11% Al2O3, 4% Fe2O3 1% P2O5 and 55% SiO2. Window glasses with known archaeological context, the
priory church, were cross-analysed in order to investigate if the glass material recently excavated was amelting
made to produce these windows. The window glass composition were found vary, but ageneral composition was
(in wt-%) around 1% Na2O, 13% K 2O, 5% MgO, 24% CaO, 2% Al2O3, <1% Fe2O3 5% P2O5 and 46% SiO2. The fingerprints of trace elements in the glassy materials compared with the cross referenced material differ significantly
indicating different raw material sources and thus different melting sites of the respective glasses.
The site in Ldse is therefore the earliest evidence of glass production in Scandinavia, re-dating the geographic
areas knowledge of glass melting by 300 years.

Investigation of optical properties

of protective layer for glass medieval mosaic
of Last Judgement from St. Vitus cathedral in Prague
Valach J., KocourV., ern M.
Institute of Theoretical and Applied Mechanics of AS CR, Prague, Czech Republic

The Mosaic of Last Judgement from St. Vitus Cathedral in Prague is amedieval masterpiece created in late 14th
century by Venetian craftsmen. If very dramatic history and various problems encountered are taken into consideration, the current state of preservation is acceptable, perhaps mainly due to systematic effort to protect the
valuable item of cultural heritage. The research project, part of which is presented here, also aims on developing
effective means for preservation of the precious object. It concentrates on finding formula for creation of protective layer that eliminates influence of chemicals present in air and in water, while being stable itself. The main goal
of the investigation is to help in finding the best formula for protective layer that is most stable itself, i.e. which

154 TC17 Archaeometry of Glass

does not represent afuture obstacle in viewing the mosaic, e.g. because of losing its transparency. The stability is
considered from the optical properties point of view: it means surface roughness, reflectivity and transparency
have to be measured in order to evaluate visual properties of the layer. Therefore adedicated computer controlled
device has been constructed to determine reflectivity on full range of incidence and reflectance angles. Candidate protective layers are subjected to harsh exposition to elements, acids, light exposure and their degradation
as afunction of time is recorded using the device. The study presents results as time series of visual properties of
several candidate layers and estimates time it would provide effective protection for the mosaic.

ICG Prague 2013 155

 156

TC05 Waste Glass Chemistry

ICG Prague 2013 157

 158

017

The incorporation of sulphate and chloride

in strontium-barium borosilicate glasses
Tan S., Hand R. J., Hyatt N. C., Ojovan M. I.
ISL, Department of Materials Science & Engineering, University of Sheffield,
Sir Robert Hadfield Building, Mappin Street, Sheffield, S1 3JD, UK

Anionic species such as sulphate and chloride pose significant challenges for nuclear waste vitrification. Glasses containing significant amounts of alkaline earths have been shown to have good sulphate and chloride
retention. Hence aseries of borosilicate glasses containing 20mol% alkaline earth oxide MO (M=Ba, Sr, Ca
or combinations of these), have been designed to immobilise sulphate and chloride containing wastes waste.
It is shown that up to ~5mol% sulphate and ~15mol% chloride can be incorporated into the glasses. Barium is
more beneficial than strontium in terms of incorporating sulphate and chloride. Scanning electron microscope
(SEM) is used to identify the micro-inclusions that affect glass homogeneity. The incorporation of sulphate and
chloride leads to prominent changes in the Raman spectra while there is no visible change in X-ray diff raction
(XRD) patterns. Glass compositions are measured by Energy Dispersive X-ray Spectrometer (EDS) and Inductive Coupled Plasma Atomic Emission Spectrometer (ICP-AES). Density, thermal behaviour and chemical
durability of the prepared glasses have also been determined.

Boccaccini A. R.
Department of Materials Science and Engineering,
University of Erlangen-Nuremberg, 91058 Erlangen, Germany

Glass-ceramics, polycrystalline silicate materials of relatively fi ne and homogeneous microstructure produced

by the controlled crystallisation (devitrification) of aglass, can be developed from abroad number of silicate
wastes and combination of wastes. Both hazardous and non-hazardous wastes have been considered to develop
awide range of glass-ceramic materials in the last 50 years. Coal combustion ash, slag from steel production,
fly ash and fi lter dusts from waste incinerators, air pollution control residues from energy-from-waste facilities,
mud from metal hydrometallurgy, different types of sludge, glass cullet, glasses from TV set and electronic
equipment components and mixtures of them have all been considered for the production of glass-ceramics.
In this presentation the development of glass-ceramics from waste using different processing methods, mainly
based on melting or sintering, will be discussed comprehensively, covering R&D work carried out worldwide
in the field and focusing on the types of waste used and on the properties and applications of the different
glass-ceramics produced. Indeed considerable knowledge and expertise has been accumulated on the process
of transformation of silicate waste into useful glass-ceramic products. It is recognised that most studies were
aimed at developing and optimizing glass-ceramics for structural applications, e.g. building materials, and
only few studies were aimed at achieving glass-ceramics with functional properties. However controlling the
processing parameters and the chemical composition of the wastes used, magnetic, electrical, thermal, sound
and radiation insulation properties can be induced into waste derived glass-ceramics. Opportunities for further research focusing on the functional applications of glass-ceramics made from smart combinations of
silicate waste will be discussed highlighting potential areas of applications of these materials. Issues that remain to be resolved to increase the social acceptability and broader commercial exploitation of waste derived
glass-ceramics will be discussed which are related to the safe use and disposal of the products. In this context
the need for comprehensive cytotoxicity measurements of the products will be discussed which should lead
to a better understanding of the materials biocompatibility beyond the conventional leaching or chemical
durability investigations. Previous attempts to commercialise glass-ceramics from waste and to scale-up production for industrial exploitation will be also discussed and future opportunities in the context of sustainable
material developments based on vitrified waste derived glass-ceramics will be evaluated.

ICG Prague 2013 159

049

Glass-ceramics from hazardous and non-hazardous

waste: Past, present and for the future

207

Noble metals redox behaviour in nuclear glass melt

Pinet O.1, Laplace A.1, Mure S. 1, Goss S.2
1
2

CEA, DEN, DTCD/SECM/LDMC Marcoule, F-30207 Bagnols-sur-Cze, France

CEA, DEN, DEN/DANS/ DPC/SCCME/LM2T Saclay, F 91191 Saclay, France

224

High Level Waste glass contains dispersed non dissolved particles of noble metals which redox behaviour differs
from other multivalent species dissolved in the glass.
This study highlights the role of two platinum-group metals, ruthenium and palladium, in the redox equilibria
of nuclear waste containment glass considering also interaction with some minor elements as tellurium. Electrochemical measurements in simplified R7/T7 glass melts were used to develop athermodynamic model of ruthenium redox equilibrium. The oxygen fugacity at equilibrium, corresponding to the coexistence of ruthenium oxide
and ruthenium metal dispersed in the molten glass, was measured at different ratios at temperatures ranging
from 1,000C to 1,200C. Experiments were carried out on glass with and without Pd, revealing the combined
role of palladium and tellurium on redox equilibria in the glass. The formation of palladium-tellurium alloys in
nuclear glass was observed to result in oxidation of the elements dissolved in the melt. These experimental results
are in good accordance with theoretical predictions based on thermodynamic data. In more complex systems,
differences observed are explained by kinetics effect.

Understanding the effect of refractory spinel

phases on high level waste glass processing
Stevens J. R.1, Hyatt N. C.1, Hand R. J.1, Bingham P. A.2, Gandy A.1
1
2

University of Sheffield, Sheffield, England

Sheffield Hallam University, Sheffield, England

321

Refractory spinel phases are known to form during the vitrification of wastes arising from nuclear fuel reprocessing. These crystals may cause processing challenges that in turn may lead to expensive downtime or may adversely
affect the long term durability of the waste form. UK nuclear waste is vitrified using atwo-step process: calcination of High Activity Liquor followed by vitrification in association with apre-made frit. Here we present work
undertaken to understand the route of formation of the spinel crystals found in vitrified UK HLW. Characterisation of the spinel crystals formed has been undertaken using various techniques including optical microscopy
coupled with image processing, scanning electron microscopy, X-ray diffraction and Raman spectroscopy.
The spinel density has been measured at 4.51 0.05g/cm-3, and produces asimilar XRD pattern to donathite (Fe,
Mg)(Cr, Fe)2O4 [22349] but having an average stoichiometry of (Mg0.83, Ni0.17)(Al0.12, Cr0.66, Fe0.22)2O4 anormal
spinel, occupying aunit cell of side 8.30 0.03.
Findings associated with non-linear liquidus, density and crystal fraction data with waste loading show that there
are arange of stoichiometries that the spinel can take. The quantity and distribution with waste loading of the crystals has been investigated and are presented along with radiation stability results of the spinel and glass matrix.

Crystal-tolerant glass approach for mitigation

of crystal accumulation in continuous
melters processing radioactive waste
Maty J.1, Rodriguez C. P.1, Lang J. B. 1, Owen A. T. 1, Kruger A. A.2
1
2

Pacific Northwest National Laboratory, Richland, USA

U.S. Department of Energy Office of River Protection, Richland, USA

For more than two decades, the loading of high-level waste (HLW) in borosilicate glasses has been limited by the
minimum liquidus temperature (TL) or the maximum equilibrium fraction of crystallinity at agiven temperature. These constraints were imposed to prevent clogging of the Joule-heated ceramic melter with spinel crystals
[(Fe, Ni, Mn, Zn)(Fe, Cr)2O4] during idling. In the melter, the glass discharge riser is the most probable location

160 TC05 Waste Glass Chemistry

for crystal accumulation because of low glass temperatures, stagnant melts, and small diameter. To address this
problem, aseries of lab-scale crucible tests were performed with specially formulated glasses to simulate accumulation of spinel in the riser. Thicknesses of accumulated layers were incorporated into an empirical model of
spinel settling. In addition, the TL of glasses was measured to show this constraint is not reliable in preventing the
accumulation of crystals, and the impact of particle agglomeration on accumulation rate was evaluated. The empirical model predicted well the accumulation of single crystals and/or small-scale agglomerates, but, excessive
agglomeration observed in high-Ni-Fe glass resulted in an underprediction of accumulated layers, which gradually worsened over time as more agglomerates formed. The accumulation rate of ~53.8 3.7m/h determined for
this glass will result in a~26mm thick layer after 20 days of melter idling.

ICG Prague 2013 161

 162

TC05 Waste Glass Structure

and Characterization

ICG Prague 2013 163

 164

034

High-level nuclear waste conditioning:

An original approach combining experimental
studies with statistical analysis
Perret D., Schuller S., Giboire I., Bousquet N., Penelon B., Dussossoy J. L.
CEA Marcoule, Bagnols-sur-Cze, France

Glass formulation for the vitrification of high-level nuclear waste has been under investigation at CEA for many
years. Beside the complexity of nuclear glass formulation (more than 40 components in the final industrial nuclear glass plus many constraints between all these components), nuclear glass also needs to meet requirements
which are specific to the industrial vitrification process. Viscosity, density, electrical and thermal conductivities,
and of course, long term behaviour of the glass, are properties that have to be perfectly understood and controlled.
Therefore, developing new glass formulations is very challenging because it requires optimizing in the mean time
the microstructure of the glass and its physical and chemical properties.
The objective of this paper is to present an original approach using relevant statistical methods we have developed to
analyze our whole set of experimental data. Knowing the maximum incorporation rate of elements having limited
solubility into the glass melt is of major importance in order to assure the properties of the glass. We have developed
some statistical methods which enable the visualization and the analysis of large amounts of formulation data. In this
paper, we show how these methods can be used to quantify the limit of molybdenum incorporation, and how we can
determine when the mechanisms of molybdates and spinels crystallization occur.
Then, considering the complexity of the glass formulations in question, we necessarily have to use aDesign of
Experiments approach for building property-to-composition predictive models. In this paper we present an
original way of making Mixture Designs which are well suitable for modeling the physical properties in large
and complex domains of composition.
Finally, the statistical methods we present help understanding the physical and microstructural behaviour of the
glass, they are also useful to specify the boundaries of glass composition domains with abetter accuracy.

Lemesle T.1,2, Mear F. O.2, Campayo L.1, Pinet O.1, Montagne L.2
1
2

CEA, DEN, DTCD/SECM/LDMC Marcoule, F-30207 Bagnols-sur-Cze, France

University Lille Nord de France, UCCS-UMR-CNRS 8181, Villeneuve dAscq, France

Nuclear industry uses glass matrices for long-lived wastes conditioning. Borosilicate composition is the glass
reference for this type of waste. However, due to its high elaboration temperature, this glass is unsuitable for the
conditioning of radionuclides like iodine 129. Thus, this work aims at studying phosphate glass for this application. Actually, this glass can be elaborated at lower temperature (under 700C) which allows to minimize iodine
volatilization and to incorporate high contents of iodine. In the present study, the structure and thermal properties of AgI-Ag2O-P2O5-Al2O3 glass system have been investigated and their chemical durability (i.e., aqueous
resistance) determined. The effects of the incorporation of Al2O3, up to 5mol.%, and silver iodide, up to 30mol.%,
were assessed for several Ag2O/P2O5 molar ratios (from 1 to 3). Electronic microprobe analysis and 31P, 27Al and
109
Ag MAS NMR showed the influence of the Ag2O/P2O5 ratio and of the Al2O3 and AgI incorporations on the micro and local structure, respectively. In terms of structural properties, the absence of AgI clusters within the glass
was clearly demonstrated. ashortening of phosphate chains was also evidenced along with AgI incorporation.
However, for aAg2O/P2O5 ratio of 1, the formation of aluminophosphate-based crystallizations was observed. It is
explained by acompetition between Al2O3 and AgI insertion in the glassy network. DSC analysis further revealed
the correlation between glass structure modifications and thermal properties. In this way, it has been observed
that Tg decreased with the incorporation of AgI whereas it was found to increase with Al2O3 content. At 50C, for
astatic leaching test in pure water (MCC1-like test), it has been showed the formation of athin layer containing
-AgI and the initial dissolution rate was estimated to be 0.11g.m-2.d-1.

ICG Prague 2013 165

073

Incorporation of iodine in phosphate-based glasses

162

Defects induced luminescence in gamma irradiated Dy3+

and Eu3+ doped oxyfluoride glass and glass ceramics
Sharma G.1, Nancy1, Kothiyal G. P.2, Bagga R.1, Falconieri M.3
1

Department of Physics, Kanya Maha Vidyalaya, Jalandhar-144004, India;

Glass and Advanced Ceramics Division, Bhabha Atomic Research Centre,
Trombay, Mumbai-400085, India;
3
ENEA, C. R. Casaccia, via Anguillarese 301, 00123 Rome, Italy.

165

The irradiation behaviour of inorganic glasses is governed by their structure and by defects. Most of the studies on
irradiation effects are focused on oxide glasses, whereas oxyfluoride glasses and glass ceramics have been less explored in this direction. Oxyfluoride glasses are of interest for the development of unique materials for many optical
applications like laser materials, phosphors and scintillators. The glass ceramic combines the advantages of both the
fluoride and oxide glasses and in addition if GCs are doped with RE ions, they partition into the nanocrystals, which
strongly influences the optical properties of the material. Radiation hardness represents an outstanding requirement
for the photonic devices and RE ions introduced into glass help to study the nature of radiation induced trapping
centers produced due to gamma irradiation. It is reported that fluorine ions are important dopant in improving the
radiation hardness of SiO2 glasses due to the formation of stronger Si-F bonds. In addition, fluorine doping breaks
up the glass network thereby decreasing the concentrations of strained Si-O-Si bonds.
The main aim of the present study is to carry out the measurement of photoluminescence (PL) and UV-VIS
spectra before and after successive gamma irradiation on glasses and glass ceramics with composition 47SiO2
23Al2O3-19Na2O-(9-x)YF3-2B2O3-x(Eu, Dy)F3 where x=0.8-1.6mol%. The gamma irradiation dose was varied
from 100Gy to 300kGy. The changes induced in PL spectra were attributed to the formation of various defects induced due to gamma irradiation. The integrated peak intensities have been calculated to estimate the behavior of
the PL originating from the defect centers. The decrease in intensity ratios in comparison to the pristine glass signifies that in comparison to adisordered surrounding in the glass the heat treated samples might have developed
ordered environment at some positions. After irradiation absorption is strong in the visible range, confirming
the formation of positively charged defects, such as hole centers and also induces the formation of non-bridging
oxygen hole centers (NBOHC) around Si-O-Al site and absorbing at 500700nm. Radiation damage effects on
optical transmission are dependent on the nature of rare earth as well as the host matrix composition.

Structural characterization of peraluminous

glassy network using NMR approach
and Nd3+ optical absorption
Gasnier E.1,2,3, Giboire I.1, Montouillout V.2,3,
Pellerin N.2,3, Allix M.2,3, Caurant D.4, Massoni N.1, Poissonnet S.5, Massiot D.2,3
1

CEA/DEN/DTCD/SECM/LDMC Marcoule, F-30207 Bagnols sur Cze, France

CEMHTI, CNRS UPR 3079, 1D Avenue de la Recherche Scientifique, 45071 Orlans Cedex 2, France
3
Universit d'Orlans, rue de Chartres, 45071 Orlans, France
4
ENSCP (Paris Tech), LCMCP UMR CNRS 7574 75231 Paris, France
5
CEA/DEN/DANS/DMN/SRMP Saclay, F-91191 Gif-sur-Yvette, France
2

Part of the Research and Development program concerning waste containment glasses aims to assess new glass
formulations. In this context, peraluminous glasses containing high rare earth content are under study. This
work aims at analysing the rare earth elements incorporation in the network, since considered as good minor
actinide surrogates, and focuses on investigating structural organization of peraluminous network, as still unknown in such systems. Glasses have been investigated in the SiO2-B2O3-Al2O3-Na2O-CaO-RE2O3 system (RE:
rare-earth=La or Nd) with increasing rare earth elements content from 2.3 to 10mol%. The structural role of aluminium, silicium, boron and sodium ions have been investigated using 29Si, 27Al, 11B, 23Na MAS and/or MQ MAS
NMR experiments. Local environment of rare earth element has been probed by Nd3+ optical absorption. 27Al
and 11B MAS and MQ-MAS results have shown that rare earth elements stabilizes fivefold and sixfold aluminium species and increases [BO4] content. Moreover 29Si NMR study seems to indicate adepolymerisation of the
network with the presence of high content of rare earth elements. To complete these observations and envisage

166 TC05 Waste Glass Structure and Characterization

afull description of the glassy network, 11B/27Al and 11B/23Na vicinity have been probed by heteronuclear double
correlation NMR experiments using REDOR sequence. Then 29Si enriched-samples have been analysed using
INEPT, D-HMQC and HMQC sequences to determine 29Si/27Al, 29Si/11B and 11B/11B connectivities.

387

Impact of B2O3 on the environment

and solubility of rare-earths in oxide glasses
Tregouet H.1, Caurant D.1, Majrus O.1,
Cormier L.2, Charpentier T.3, Vezin H.4, Pytalev D.5
1

Laboratoire de Chimie de la Matire Condense de Paris, Chimie-ParisTech, Paris, France;

Institut de Minralogie et Physique des Milieux Condenss, UPMC, Paris, France; CEA,
3
IRAMIS, Laboratoire de Structure et Dynamique par Rsonance Magntique, Gif-sur-Yvette, France ;
4
Laboratoire de Spectrochimie Infrarouge et Raman, UST Lille, Villeneuve dAscq, France
5
Institute of Spectroscopy, Russian Academy of Sciences, 14190 Troitsk, Moscow, Russia
2

Rare-earths (RE) are used for their optical properties in glasses. RE are also abundant fission products formed
in the nuclear fuel of power reactors and are then immobilized by dissolution in complex borosilicate glasses
after spent fuel reprocessing. The solubility of RE in glasses and their tendency to crystallize in rare-earth-rich
phases during melt cooling or glass heat treatment depends on glass composition. As SiO2 and B2O3 represent the
main oxides forming the glassy network of borosilicate nuclear glasses, it is very important to improve the knowledge on how the composition and structure of glasses may affect the environment and the solubility of the RE.
In this paper, we investigated the structure and the crystallization tendency of RE-rich glasses derived from the
SiO2-B2O3-Na2O-RE2O3 system with RE=La, Nd, Eu, Yb. For instance, the RE-rich metaborate composition 3B2O3.
RE2O3 was studied. As B2O3 is known to dissolve in the structure of SiO2, we also studied the incorporation of RE
in the SiO2-B2O3 system and in the SiO2-B2O3-Na2O system (the introduction of Na2O leading to the formation of
non-bridging oxygen atoms on the SiO4 units and of BO4 units that could facilitate RE incorporation in glass structure). For all the samples (amorphous or partially crystallized), the environment of optically active RE was followed
by optical spectroscopy and pulsed EPR whereas glasses structure was studied by WAXS, MAS-NMR and Raman
spectroscopies. The microstructure of partially crystallized glasses was studied by XRD and SEM.

Caurant D.1, Loiseau P.1, Majrus O.1, Charpentier T.2

1
2

Laboratoire de Chimie de la Matire Condense de Paris, Chimie-ParisTech, Paris, France;

IRAMIS, Laboratoire de Structure et Dynamique par Rsonance Magntique, Gif-sur-Yvette, France ;

Because of their high field strength (HFS), cations such as Ti4+, Zr4+ and Hf4+ may exhibit low solubility in supercooled silicate melts and may thus lead to the crystallization of Ti-, Zr- and Hf-rich phases when heating glasses
above their transformation temperature. In this paper, we studied the impact of composition changes on the solubility of HFS cations in acalcium aluminosilicate glass containing Ln3+ (Ln=La or Nd), Ti4+ and Zr4+ or Hf4+
cations. We showed that composition changes may strongly affect the solubility of these cations. For instance, increasing Al2O3 content may strongly increases the crystallization tendency in the bulk of (Zr, Hf)-rich phases such as
Ca(Zr,Hf)Ti2O7 (zirconolite) which could be helpful to prepare highly durable glass-ceramics for nuclear waste immobilization because actinides simulated in this work by lanthanides can substitute Ca and Zr in the zirconolite
crystals. On the contrary, the addition of increasing amounts of Ln2O3 to the glass composition lead to avery important increase of Zr solubility (decrease of CaZrTi2O7 crystallization tendency). This result suggests that too high
actinide concentrations would probably lead to asuppression of zirconolite crystallization in the bulk. Glass crystallization was followed by XRD and DTA with glass powders of different particle sizes. In order to try to understand
these evolutions of solubility with composition changes, the structure of the glassy network was investigated by
MAS-NMR and Raman spectroscopies whereas the local structure in the surrounding of Ln3+ cations was studied
by optical absorption spectroscopy and that of Zr4+ and Ti4+ cations was followed by X-ray absorption spectroscopy.

ICG Prague 2013 167

388

Controlling Zr4+, Hf4+ and Ti4+ cations solubility

in calcium aluminosilicate glasses

487

Effect of alpha radiations on the SON68 French

nuclear waste glass durability and properties
Karakurt G.1, Abdelouas A.1, Guin J. P.2, Sauvage T.3
1

SUBATECH laboratory (UMR 6457), Nantes France;

LARMAUR, University Rennes 1, FRANCE;
3
CEMHTI CNRS, Orlans, FRANCE

In this work we study the effect of alpha radiation damages on chemical and mechanical properties of the inactive
SON68 French nuclear waste glass in order to gain adeeper insight on radiation damages that could occur within
the glass during the storage. Although studies on the French nuclear waste glass properties after irradiation have
already been studied at amacroscopic scale. Our study is focussed at amuch lower scale. Using instrumented
indentation, atomic force microscopy, Raman spectroscopy, as well as specially designed corrosion experiments
the effect of alpha radiation on chemical and mechanical properties at asubmicrometer scale is studied. Using
those tools adirect link between surface damage (nanoindentations, alpha irradiation), their associated structural modifications and local variations of the dissolution rate is established and used for probing structural
modifications (bond angles variations, connectivity loss). For instance the effect of alpha radiation on the durability of pristine glass or on pre-damaged glass surface (i.e densified and shear flowed through nanoindentation
test) will be presented. In this study 4 different glass compositions were studied: an inactive SON68 waste glass,
ahigh-purity silica glass (Spectrosil 2000), awindow glass (Planilux) and a6-oxides borosilicate glass named
CJ4. To understand the cumulative effect of alpha doses, indented glasses were irradiated with 1 MeV He+ ions
using aVan de Graaff accelerator (CEMHTI, France). Alpha dose effect is studied by varying fluencies in order to
reach arange of alpha decay doses up to 1x1018g-1. Furthermore, radiation effects on the glass alteration rate were
performed by monitoring the release of glass alteration tracer elements like B, Na, Li, and Mo.

168 TC05 Waste Glass Structure and Characterization

TC05 Waste Form Processing

ICG Prague 2013 169

 170

018

Microwave processing of glass composites

for irradiated graphite waste immobilisation
Hilmi M. M. Z.1,2, Stennett M. C.1, Hand R. J.1
1

Immobilisation Science Laboratory, Department of Materials Science and Engineering,

The University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield S1 3JD, UK;
2
Faculty of Science, Technology and Human Development, Universiti Tun Hussein Onn Malaysia,
86400 Parit Raja, Batu Pahat, Johor, Malaysia

Currently there is no disposal strategy for irradiated graphite from nuclear reactors such as the UK Magnox
and Russian RBMK reactors. Due to the vulnerability of the irradiated graphite to oxidation, the possibility
of using microwave processing to incorporate graphite into vitreous wasteforms has been investigated. Iron
phosphate glass and iron phosphate composites have been prepared from mixtures of NH4H2PO4, Fe3O4 and/or
simulated irradiated graphite waste. The samples were subjected to microwave sintering for various exposure
times ranging from 1 to 20 minutes and conventionally sintered at temperatures suggested by differential thermal analysis (DTA) measurements. Analysis methods employed include assessing mass loss during processing,
X-ray diff raction (XRD), scanning electron microscopy (SEM), density measurement and chemical durability
test (C 1220-98). Based on the data, it is suggested that the graphite does not react with the iron and phosphate
in the microwave processing. As aresult, there is no loss of graphite in the produced iron phosphate composite
by using microwave processing. Work is ongoing to understand more fully the effect of process variables and
to improve the mechanical integrity of the simulated wasteforms.

Girold C.1, Pinet O. 1, Piroux J. C.2, Naline S.3

1

CEA, DEN, MAR, DTCD, LCV, SECM Marcoule, F-30207 Bagnols sur Cze, France
AREVA, LCV Marcoule, F-30207 Bagnols sur Cze, France
3
AREVA, DIRP, RDP, La dfense, Paris, France

The vitrification of High Level Waste produced by the reprocessing of spent fuel is amore than forty years industrial experience in France. This unique know-how has been made possible thanks to aconstant improvement
served by acontinuous growth of the knowledge on the glass material. The very strong link between academic
research on material and process development has been carefully sustained through these decades. The understanding of the relations between glass composition, in the liquid and solid state sometimes down to the intimate
atomic structure, and its physical properties is essential to face development issues, to improve glass quality, to
reach higher waste loading, to increase production capacity or robustness of vitrification shops. More, it is essential to accommodate new types of waste or to develop complex modelling of the vitrification process using
physical properties to composition predictive models.
We will develop the large range of physical properties that have to be understood with focus on latest progress
in their knowledge, for example: glass redox with multivalent cations, chemical reactivity between additives,
nucleation and growth kinetics of crystals, phase separation mechanism, thermal conductivity, influence of
noble metals on melt viscosity or electrical conductivity. We will also link the inputs of these basic researches
to the resolution of difficulties through various examples such as development of new glass formulation for
various waste composition or new vitrification technology. We will illustrate for example how knowledge about
redox or thermal conductivity in the molten glass has been decisive when developing anew vitrification technology such as the cold crucible induction melter.

ICG Prague 2013 171

081

Academic research on glass and process development

combined for nuclear waste vitrification progress

104

Vitrification of post operational

clean out waste at Sellafield
Steele C. J.1, Maxwell L. J.1, Dunnett B. D.2, Gribble N. R.2
1
2

Sellafield Limited, Sellafield, United Kingdom;

The National Nuclear Laboratory, Sellafield, United Kingdom

139

The post operational clean out (POCO) of the highly active storage tanks will require the removal of residual solids
from the heel of the storage tank. These solids have accumulated as aresult of precipitation over anumber of years
during effluent transfer operations. The heel content is expected to contain higher levels of fission products such as
Molybdenum and Zirconium which have settled in the tank during operations. The quantity of these solids has been
estimated and it is known that there is asolubility limit of molybdenum in the mixed alkali borosilicate glass matrix
which is used to immobilise the radioactive fission products and inactive oxides. From initial laboratory studies using
non-radioactive simulants it has been possible to enhance the existing glass formulation to increase the molybdenum
concentration in the glass matrix. afull scale experimental trial using non-radioactive simulants has demonstrated the
feasibility to process adifferent waste composition using the vitrification process. The key challenges to address are to
optimise throughput and performance, to avoid the risk of additional solid blockages and produce an immobilised
waste form with consistent product quality that is suitable for long term storage and final disposal in the UK.

The use of hot isostatic pressing in the vitrification

of clinoptilolite ion exchange material
Hand R. J, Heath P. G, Hyatt N. C.
University of Sheffield, Sheffield, United Kingdom

225

The zeolite clinoptilolite is used in the U.K. as an ion exchange material for the removal of aqueous radioactive caesium and strontium. alarge inventory of this material, in terms of both activity and volume, exists from the operation
of the site ion exchange plant on the Sellafield site. This material is classified as intermediate level radioactive waste.
No accepted processing or final disposal pathway for this radioactive waste stream currently exists. This work has
studied the potential application of Hot Isostatic Pressing (HIPing) in transforming spent clinoptilolite into avitreous waste form. This method of processing has several potential advantages, including lowering the melting point
of the mineral, eliminating volatile losses, decreasing residual porosity whilst providing aself contained final waste
form. The processing parameters and addition of various additives has been studied in relation to product quality.
Caesium retention during processing has been quantified. MCC-1 and PCT glass leaching tests have been use to
measure waste form dissolution and caesium loss whilst in contact with aqueous solution.

Material and process modeling

for nuclear waste vitrification
Chouard N.1, Ribet I.2, Cartalade A.3
1

AREVA, DIRP, RDP, Paris La dfense, France

CEA, DEN, MAR, DTCD, LCV, SECM Marcoule, Bagnols-sur-Cze, France
3
CEA, DEN, DANS, DM2S, STMF, LATF Saclay, France

In La Hague plant in France, fission products and actinides arising from spent uranium oxide fuel reprocessing
are confi ned in aborosilicate glassy matrix with acalcination/vitrification process. Understand and be able to
describe the physico-chemical phenomena that occur during this two step glass elaboration process are the key
points to reinforce our technical expertise, to improve economical and safety performance, to innovate and to
master R&D cost and time for material optimization and development. As aresult, new tools and approaches
such as material and process modeling are developed in order to help guide experiments or lead to better understanding of material and process behavior.
Th is talk will present an overview of material and process modeling which is currently developed by Areva and
CEA concerning the nuclear waste vitrification, and will include some examples of how these techniques are
used to develop new products and processes.

172 TC05 Waste Form Processing

280

Bottom and fly ashes from MWI

as secondary raw materials in the industrial
production of stonewool and glass frits
Falcone R.1, Hreglich S.1, Bertuzzi P.2, Ercole P.2, Ramon L.2
1
2

Stazione Sperimentale del Vetro, Venezia Murano, Italy

SASIL S.p.A, Brusnengo (BL), Italy

Alternative and advanced technological solutions for the reuse of bottom and fly ashes produced by MWI as secondary raw materials (SRMs) were developed in the framework of the research project VALIRE (VALorisation of
Incineration Residues) financed in part by the European Union LIFE+ 2010 program),
The chemical and physical properties of several tens of samples of these hazardous wastes, collected from different Italian incineration plants, have been detected by XRF, XRD, DTA, and wet chemistry. The results indicated that bottom and fly ashes, together with other waste materials, can be suitable SRMs for the production of
stonewool and glass frit. Nevertheless several melting tests performed in asmall industrial furnace evidenced
that the presence of significant amounts of chlorine in the fly ash samples represent aserious drawback. Due
to the low solubility of chlorine in the glass, emission of high levels of chlorinate compounds, such as PCDDs
and PAHs, occurred during the melting process.
The use of low-chlorine washed fly ash, provided by the SOLVAY company, was therefore taken in consideration.
The chemical and physical characterization of several washed fly ash samples was performed. Moreover the hazardous organic compounds emission temperature range was determined by means of thermal treatment tests.
Based on the results, the construction of acontinuous pilot plant for the production of stonewool and glass frit using
bottom and washed fly ashes as SRM and with controlled emissions of hazardous organic compounds was planned.

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TC06 Indentation
and Nanoindentation

ICG Prague 2013 175

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007

The mechanical properties of the surfaces

of soda lime silica float glass as a function
of hydration time and temperature
Gonzalez Rodriguez J., Hand R. J.
University of Sheffield, Sheffield, United Kingdom

Damage to glass surface can occur through high temperature contact during processing and chemical and mechanical interactions after manufacture. The response of the air and tin sides of float glass to such interactions
occurring during manufacture and in service is expected to be different and they are investigated in this work.
The response of this type of glass to mechanical contact from room temperature to 600C is investigated through
instrumented micro-indentation using Vickers and tungsten carbide spherical indenters. As expected, hardness
and elastic modulus are observed to decrease with temperature and afactorial experiment is on-going to study
the effects and interactions of loading rate, dwell time and surface chemistry.
Nanoindentation, SEM/EDX and 4-point load bending have been used to study the nanohardness, reduced modulus
and fracture strength of specimens exposed to accelerated weathering conditions of 40C and 95% R.H. for 3, 7, 15,
19 and 49 days. asignificantly more rapid deterioration of the air side as compared to the tin side was observed.
The significance of these results for the performance of float glass in service will be discussed.

068

Plastic deformation and residual stresses

in amorphous silica pillars under uniaxial loading
Lacroix R.1, Kermouche G.1, Teisseire J.2, Barthel E.2
1
2

Universit de Lyon, ENISE, LTDS, UMR 5513, 42023 Saint-Etienne Cedex 2, France;
Surface du Verre et Interfaces, CNRS/Saint-Gobain, UMR 125, 93303 Aubervilliers Cedex, France

Micropillar experiments have been used extensively to characterize size effects in the plastic deformation of metals and ceramics. In terms of mechanisms for plastic deformation, silicate glasses bear alot of similarities to Bulk
Metallic Glasses, but they are singular in the substantial free volume they enjoy, which allows for permanent
volumetric deformation (densification). Pillar compression of amorphous silica was carried out because it is one
the very few possible micromechanical configurations which minimizes hydrostatic compression and enhances
shear [1]: it makes it possible to interrogate the yield surface under an appealing type of loading, with limited
densification. Etching of the pillars was carried out by Reactive Ion Etching and the design was analysed by Finite
Element Modeling (FEM), taking into account contact conditions, misalignment and substrate compliance. We
have measured load-displacement curves and observed the morphology of the pillars after unloading, providing
strong evidence for large plastic deformations [2]. Minor cracking is also observed, with awell-defined pattern.
We find that the van Mises stress in compression is comparable to the intrinsic tensile strength of silica. Precise
analysis of the deformation of the pillars has been carried out by Finite Element Modeling using the constitutive
equation determined previously [3], which quantitatively takes into account densification, shear flow and strain
hardening. The residual stress distribution we predict by FEM matches the observed crack pattern well.

097

Indentation behaviour of glass and G/K

Wilantewicz T. W.
Corning Inc., Corning, USA

The behaviour of avariety of compositionally diverse commercial inorganic glasses subjected to indentation with
aVickers diamond was studied and shown to correlate with the ratio of shear modulus to bulk modulus (G/K),
and relative plastic zone size beneath the indentations. Glasses with G/K > 0.75 (Poissons ratio < 0.2), in-elastically deformed mostly by densification, had high resistance to median-radial crack formation, and small relative
plastic zone size. Those glasses with G/K < 0.6 (Poissons ratio > 0.25) in-elastically deformed mostly by shearflow, as evidenced by numerous and well defined shear faults below the indentations, had lower resistance to
median-radial cracking, and large relative plastic zone size. The results are interpreted in terms of differences in
the structures of the glasses, including such characteristics as density and network dimensionality.

ICG Prague 2013 177

127

Crystal morphology and micro

and nano-scale deformations in transparent
glass-ceramics with nanocrystals
Shinozaki K., Honma T., Komatsu T.
Nagaoka University of Technology, Nagaoka, Japan

159

Transparent glass-ceramics with optical functional nanocrystals are attractive materials for various devices. Usually, such glass-ceramics are fabricated through well-controlled heat treatments in an electric furnace and desired
nanocrystals are formed in the interior of glasses. For instance, oxyfluoride glass-ceramics with CaF2 nanocrystals shows excellent luminescence and desired material in the application of laser materials. It is required to clarify
mechanical and elastic properties and fracture mechanics in application. In this study, we focused our attention
on the deformation and crack initiation from the viewpoint of the crystal morphology, glass structure and stress.
Crack initiation and deformation were examined using nanoindentation technique and Vickers test. The crystal
morphology are observed using TEM. In glass-ceramics with the composition of 25CaF2-5CaO-20Al2O3-50SiO2,
nanocrystals with the size of ~30nm were observed in the inside region. However, nanocrystals were not formed
in the surface region (~150nm). Compositions were estimated using STEM-EDS. The F / O ratio was decreased
with close to surface. Elastic moduli and hardness of asurface and inside region were evaluated by nanoindentation. The surface glass region was hardened due to the desorption of fluoride ions.

Nanomechanical properties
of multi-layer coatings on glass
Wondraczek L.
Otto-Schott-Institute, University of Jena, 07743 Jena, Germany

169

The mechanical properties of PVD-derived multi-layer stacks, single layers and stacks-on-glass have been explored in amulti-method approach to discern the individual contribution of each layer and the substrate itself
on the nanoscale. From this knowledge, the effect of thermal annealing on exemplary low-emissivity coatings
was explored. In this talk, the employed analytical tools nanoindentation, nano-scratching, lateral-force testing,
nanoscale residual stress analyses and nano-abrasion testing will be presented and discussed with respect to
their applicability for specific glass problems. The development of resistant low-e coatings will be presented as an
example where nanomechanical analyses can provide valuable information.

Direct observation of indentation deformation

and cracking of silicate glasses
Yoshida S., Kato M., Matsuoka J., Soga N.
Center for Glass Science and Technology, The University of Shiga Prefecture, Shiga, Japan

It has been well known that various types of cracks are observed on glass surface after indentation using adiamond indenter, such as Vickers indenter. Although such indentation cracks are sometimes used to model macroscopic fracture of glass, remarkable compositional variation of crack morphology prevents one from comparing
brittleness or strength among various glasses. In order to understand such wide variety of indentation cracks
on glass, it is essential to evaluate asequence of cracking events of glass and to know what happens during the
loading and unloading indentation cycle. However, there are very few reports on in-situ observation of indentation cracking on glass. An important paper is the one by Cook and Pharr (J. Amer. Ceram. Soc. 73 (1991)787.).
Although they clearly showed cracking sequences of glasses and ceramics under Vickers indenter, low magnification of their experimental set-up made it difficult to see fine cracks or shear faults and to determine the contact
region under the indenter during the indentation cycle.
In this study, aself-made indentation device is constructed in order to observe deformation and cracking of silicate
glasses during loading and unloading. Using the device with aVickers indenter, the sequence of micrographs at

178 TC06 Indentation and Nanoindentation

high magnification is successfully obtained during the indentation cycle. From direct observations, an experimental
evidence of sinking-in, or pin-cushioning, during aloading half-cycle can be acquired for some silicate glasses and
obvious shrinkage of the contact area is observed during an unloading half-cycle. Edge cracks, which are parallel to
the edges of indentation imprint, are found to generate not only during loading, but also during unloading. It is also
found that median/radial cracks generate during unloading, which is in good agreement with the previous reports.

501

Densification and incipient cracking

under nano indentations in oxides glasses
Guin J-P., Han K.
LARMAUR ERL-CNRS 6274, Universit de Rennes 1, Rennes, France

If the fracture of the screen of your smartphone is unpleasant it often results from micro-cracks created by acontact with particles either through an impact or ascratch. In order to apprehend the genesis of such damage it is
necessary to study them at apertinent scale, usually at the sub micrometer level. Oxide glasses present apermanent deformation phenomenon under sharp contact conditions. Shear flow and densification are usually assumed
to be responsible for such abehavior. Although densification of oxide glasses has been extensively studied the size,
the shape and the nature of the densified volume under nano indentations are still unknown. Such adensification
phenomenon involves structural changes in the glassy network (number of SiO4 units per ring, Si-O-Si intertetrahedral angle, connectivity loss). In this work, adirect link between such densification induced structural
modifications and ameasured enhanced dissolution rate at nano indentation sites is established. When coupled
with precise AFM measurements, it is further used for probing the densified volume under nano indentations
(200N to 50mN range) made on various glass compositions. The 3D shape of the densified zone reconstructed,
with ahome-developed algorithm, from AFM images taken at different dissolution times will be presented. Furthermore the effect of indentation load on the densified zone size will be discussed. Finally this technique is also
suitable for the observation of incipient cracking underneath nano indentations as well as the reconstruction of
the nano-crack network and its progressive organization with increasing indentation load.

524

Low melting high strength phosphate

glasses with high transparency
Calahoo C.1, Werner-Zwanziger U.1,
Zwanziger J. W 1, Zhou G2, Lebullenger R.2, Calvez L.2, Rocherull J.2
1
2

Chemistry Department, Dalhousie University, Canada

Institute of Chemical Sciences, Glass and Ceramic group, University of Rennes, France

Glasses have been prepared from formulations using sodium and calcium phosphates as main reagents. To substantially improve the durability, additions of zinc oxide and various transition metals (titanium, niobium)
have been made. The environmental impact (CO2 balance, energy cost) has been minimized by the search for
compositions with low melting temperatures (Tm 1,000C).
The glasses have been initially characterized from athermal standpoint by Differential Thermal Analysis (DTA) and
Thermo-Mechanical Analysis (TMA). The optical transmission in the UV-Visible range has been studied using the
diffuse reflectance spectroscopy. The chemical durability (in renewed water at 95C) and the mechanical properties
(micro-hardness, elasticity) have also been evaluated. The use of small amounts of oxidizers, during the melting
step, has allowed to considerably reduce the coloration of the glasses and to give ahigh transparency. Finally, abulk
sample with ahigh transparency has been prepared and characterized. Its characteristics have been compared to
those of window glass. It exhibits lower values of the melting temperature and of the glass transition temperature.
The Vickers micro-hardness and the elastic moduli are enhanced and the chemical durability is comparable.

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TC26 Student Project Outcomes

(ICG Summer School)

ICG Prague 2013 181

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544

ICG Summer School

Each year aone week Summer School is organized by ICGs TC23 at Montpellier in the South of France. During
the event the students listen to lectures from around 10 eminent glass scientists. Their understanding is tested by
agroup exercise that has proved popular with the students but which also generates for the lecturers interesting
insights through the eyes of the next generation of Glass Practitioners. The organizers of the Summer School
would like to give awider audience the opportunity to be stimulated and surprised by what the students, working
in groups of 5 or 6, having managed to achieve over just afew hours. Four topics will be covered. The titles and
presenters are listed below. And the students themselves of course would love to hear the reactions of awider audience to their proposals. The talks will therefore be followed by ashort discussion session on the content of the
talks and also on the principles of this approach to teaching.
1) Ines Ponsot on An article for Wikipedia justifying the immobilisation of nuclear waste in aglassy matrix
2) Laura Munoz Senovilla and Vincent Vercamer on An application for amobile phone that will be of value to
aglass technologist.
3) Katharina Phillips on A call for research applications that utilise glass in energy production/savings, listing 5
areas to receive funding and indicating the division of funds.
4) Cerinne Claireaux and Prashant Rajbhandari on An analysis of an archaeological artefact that purports to be
alachrymarium.

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TC11TC13TC14
TC15TC18TC21
Glass Trend

ICG Prague 2013 185

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TC11TC14TC18
Glass Trend
Refractory Materials

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002

Refinement of refractory for the glass industry

Weigand R., Hessenkemper H., Rssel A.-K., Tritschel D., Khne R.
University of Mining and Technology Freiberg, Germany

The production of glass is an energy intensive process. Due to the political pressure and climate change problems
it is necessary to lower the energy consumption for glass production. anew way is the refinement technology of
TU Bergakademie Freiberg which minimise the interaction of refractory and glass melt and generates asaving
potential around 500.000 Euro. The refinement technology is asurface refinement of porous refractory bricks
which lowers on the one hand the corrosion of the brick and on the other the blistering and the crystallisation
behaviour in the interface glass melt and refractory. This is important for often changed components like orifice
ring, plunger and tube. Tests in laboratory shows adecrease of the corrosion in static finger test about 80%. Also
80% less blistering and a minimisation of the crystallisation behaviour were measured. This fact creates the
potential for abatch adjustment, which is attended by alowering of the fining temperature about 20K. Tests in
industrial scale approve this tendency and the effect of the technology.

036

The development of non-destructive inspection method

of AZS and the results of actual glass melting furnace
Yamamura S.1, Ushimaru Y.2, Kokumai H.1, Ishino T.2
1
2

AGC Ceramics Co.,Ltd Development Center, Hyogo, Japan;

AGC Ceramics Co.,Ltd Head Office, Tokyo, Japan

The quality of fused cast refractory has implication for the life of glass tank furnace. Fused cast refractory is manufactured by electro-fused and casting process, and its well-known that it has alow porosity characteristic and
high corrosion resistance. In the casting process, molten material is poured into the mould, and the shrinkage of
material has been occurred by cooling and solidification of the melt. So shrinkage cavity (so called void) appears
inside the block, and the location of it is controlled by casting techniques. Generally, void free or semi void free
product, which is manufactured by removing the upper portion of casting block, is used for the glass contact of
the furnace. It is no exaggeration to say that its important to check the internal quality of the block accurately
because unusual void may leave at the unexpected location of the block due to the unbalance of solidification
speed. It causes local heavy corrosion in the furnace, and it may reduce the life of it. The non-destructive method
has been developed by using electromagnetic radar in 1991, and it has begun to check for all AZS blocks that is
used for glass contact, such as side wall, throat, dam wall, and so on. It has been continued for over twenty years,
and prevented from shipping the block which contains unusual void. Now, many furnaces, installed the inspected
AZS blocks, have finished their lives without any troubles and the effect of its internal quality check has been confirmed. It is reported in this paper that this technique is useful to the reduction of unusual local heavy corrosion
which causes the leakage trouble of molten glass, and help us to improve the casting techniques.

Dunkl M.1, Meynckens J.-P.2, Zborowski J.3,

1

Dr. M. Dunkl Consulting, Germany

AGC, Belgium
3
AGH, Poland
jeanpierre.meynckens@eu.agc.com
2

To date, the glass furnaces cold repairs and green field are driven by an uncertain long term economy requiring
ahigh level of flexibility, combined with the target to obtain asustainable environment and alower specific
consumption. Knowing the impact of the fused cast refractories on the capital expenditure and on the glass

ICG Prague 2013 189

204

Selection criteria for the fused cast refractories

in the glass furnaces; industrial applications
and expectations for new developments

205

quality, the glass industry is searching for stable refractories grades compatible with their budgets, their furnace output and the required glass quality.
The glassmaker expects from their refractories suppliers aperfect knowledge of their process (e.g. raw material molds
melting annealing) and atrustable quality insurance prior the final inspection by the customer and the delivery.
Besides the supplier control, several selection criteria applied by the glass makers are described in this paper
amongst the corrosion and the exudation results combined with the chemical analyses correlations (bulk,
glassy phase, residual carbon).
Finally, some industrial results are disclosed to underline the glass industry expectations in the field of the fused
cast refractories. The accent will be put on the superstructure qualities regarding their glassy phase, the requirement of stable and insulating refractories for the crowns in oxy fired furnaces and the revised choices of the fused
cast grades for the glass contact after the evaluation of the stagnant zones and the critical zones.

Characterisation of fused cast refractories

regarding their glass defect formation behaviour
Dunkl M.1, Meynckens J.-P.2 , Zborowski J.3
1

Dr. M. Dunkl Consulting, Dsseldorf, Germany;

AGC Glass Europe, Jemeppe-sur-Sambre, Belgium,
3
AGH, University of Science and Technology Cracow, Poland
2

206

Performance of refractories significantly influence the life time of glass tank and the quality of glass thus determining the economical feasibility of glass making process in technical devices. Therefore it is necessary to prove
several characteristics essential for the behaviour of refractory material in glass tank prior to its application. The
choice of refractory to be finally used based on the result of such tests is going to be right in the only case when
appropriate test methods have been applied for its characterisation and funded understanding of interrelations
between properties of refractories and their performance is provided. Some tests methods enabling the relative
assessment of glass defects formation potential of refractories, as corrosion, blistering and knots formation test,
are briefly described and evaluated regarding the meaning of their results. Taking exudation behaviour as an
example some considerations concerning the choice of testing methods and their limitations are presented in
comparison to the methods standardised and recommended by TC 11 of ICG. aguide for refractory users in glass
melting regarding the appropriate interpretations of characteristics, as usually given in data sheets, their meaning
and assessment is provided. The interpretation restrictions originating from the need to differentiate between
behaviour observed under lab test conditions and that in areal tank are also formulated in concluding remarks.

The benefits of using fused magnesia

in rebonded magnesia brick production
for glass furnace regenerator application
zdemir B.1, zmirliolu B.2
1
2

Kumas Manyezit Sanayi A.S., Kutahya, Turkey

Trkiye ie ve Cam Fab. A.. Analytical Services

Regenerators checkers and wall bricks are exposed to severe conditions such as high temperature, thermal shock effects, carry over, redox effects and alkali vapours condensation. Rebonded magnesia bricks play essential role under
these conditions with their superior properties. Raw materials used in the production of magnesia bricks are determine the performance of the bricks at the application area. In this study, the bricks characteristics were examined
which was developed by using fused magnesia and advantages were submitted against the bricks have been revealed.

190

TC11TC13TC14TC15TC18TC21 Glass Trend Refractory Materials

423

Post mortem study of standard silica, silica

without lime and fused cast materials
for oxy fuel glass melting furnace
Bei R.1, Santowski K.2, Majcenovic Ch.2
1
2

RHI Glas GmbH, Wiesbaden, Germany.

RHI AG, Technology Center, Leoben, Austria.

Because of energy saving and environment protection, oxy fuel furnaces become popular for glass melting. The
higher corrosion of the melter crown, caused by ahigher content of NaOH in the atmosphere, is one of the problem for oxy fuel glass melting furnaces. In this paper the post mortem study of standard silica, silica without lime
and fused cast materials used for oxy fuel furnace crown will be reported.
424

New refractory mortar solution for the glass industry

Gaubil M., Consales T.,Cabodi I.
1

Saint-Gobain CREE R&D Center, Cavaillon France, France;

Refractory Mortar Solution are for awhile complementary solution to Fused Cast material. These mortars are mainly
constituted by fused cast grains and present good glass contact properties and good compatibility with the fused cast
blocks. Nevertheless, because of the more severe operating conditions in some application like extra white glasses
which requires safer bottom solutions and also because of more flexible setting conditions required by the glass industry, SEFPRO designed two new refractory mortar solutions. We will present the properties of these new products
in terms of thermal expansion, corrosion resistance and glass compatibility. We will also show the complete different
possible setting conditions achievable with these self leveling mortars. The new formulations have been determined
with the support of physical principle used in the civil work industry and industrial application will be also presented.

Bouvry B.1, del Campo L.1,

De Sousa Meneses D.1, Gaubil M.2, Lechevalier L.3, Echegut P.1
1

CNRS, UPR3079 CEMHTI, 1D avenue de la Recherche Scientifique, 45071 Orlans cedex2, France
Saint-Gobain CREE, 550, Avenue Alphonse Jauffret BP 224 84306 Cavaillon, France
3
Saint-Gobain High Performance Materials NWRDC, 9 Goddard Road, Northboro, MA 01532, USA

The development of oxy fuel combustion glass furnace requires the use of high performance refractory materials
for superstructure and crown application. Because of their corrosion resistance towards alkali wet vapors and
creep resistance at very high temperature, low glassy phase AZS and alpha-beta alumina fused cast material are
recommended material especially for crown application. High creep resistance of sintered Mullite is also amaterial of choice for oxy fuel furnaces for specialty glasses.
In order to take in account the radiative properties of these products in glass furnace heat balance simulation,
anew device has been developed at CEMHTI laboratory to measure the normal spectral emittance of materials in
awide range of temperature, i.e. from 400 to 2,500K. Heating is done with aCO2 laser on both sides of the sample
to ensure homogenous temperature distribution. The apparatus includes two Fourier transform spectrometers
that allow performing measurements from far-infrared to visible range. Diff use reflectance and transmittance
measurements are also possible by using an integrating sphere and MIR and NIR infrared light sources.
In this work, Mullite, Jargal M and AZS product, currently used as superstructure refractory materials, have been
characterized. Diff use reflectance and transmittance spectra at room temperature measured on different sample
thicknesses allowed to evaluate the mean transport length of photons inside the media. Emittance measurements
showed that these materials are good far and mid-infrared emitters, but poor in near-infrared and visible spectral ranges. Comprehension of radiative behavior implies having agood knowledge of the microstructure of the
samples such as grain size, porosity and grain boundaries, where impurities and new phases can be found. All
these aspects will be discussed at the light of the microscopic mechanisms of absorption occurring in the thermal
radiation range, and their impact on the radiative behavior of refractory materials will be shown.

ICG Prague 2013 191

500

Optical characterization of refractory materials

used in glass furnace superstructures

551

Chromium oxide refractory

with enhanced resistance to sublimation
Fourcade J., Citti O.
Saint-Gobain Northboro R&D Center, Northborough, USA;

552

Chromium oxide refractories are widely used in the glass industry for their superior resistance to corrosion by
glass melts. In case of soda-lime-silica glasses, they are typically used in high wear areas such as throat and corner
blocks; in E glass furnaces, however, they are used for all the glass contact in the melter as well as in the forehearth. Although chromium oxide refractories have limited corrosion by the melt, they tend to oxidize rapidly
when directly exposed to the atmosphere to form very volatile species such as Na2CrO4, K 2CrO4, CrO3, CrO2(OH).
Oxidation and sublimation occur at different temperature levels, based on what species is formed: Na2CrO4 starts
to form at 800C while CrO3 will only form at temperature above 1,200C. Consequences of oxidation and sublimation of chromium oxide refractories are several: (1) rapid deterioration of exposed surfaces that can limit
the lifetime of the material, (2) condensation of chromium compounds on superstructures potentially leading
to glass defects later on, (3) significant chromium emission in the exhaust fumes and (4) potential exposure of
workers to hazardous hexavalent chromium.
C12LS is anew dense chrome refractory material developed by SEFPRO to have superior resistance to oxidation
and sublimation. Based on experimental techniques developed in our R&D facilities, C12LS presented 10 to 40%
lower sublimation than standard chromium oxide materials, depending upon testing temperature and pO2 of the
atmosphere. C12LS also showed superior resistance to corrosion in dynamic corrosion testing in E glass melts for
both below and above glass line.
Actual performances of C12LS are currently being assessed in several furnaces producing reinforcement fibreglass.

Experimental studies
on regenerator refractory corrosion
Faber AJ.1, Lessmann S.1, van Limpt H.1, Bei R.2
1
2

CelSian Glass and Solar, Eindhoven, The Netherlands,

RHI Glas GmbH, Wiesbaden, Germany
anne-jans.faber@celsian.nl

Clogging of the regenerator checkers and corrosion of the regenerator refractories are common problems in the
glass industry. This paper is focused on simulating the refractory corrosion of regenerator checkers of container
glass furnaces by cooling sodium vapors combined with sulfur dioxide.
In this paper, results obtained by the application of dedicated laboratory equipment for testing (candidate) regenerator checker refractory materials will be presented.
The set-up of the experiment is acombustion chamber connected (downstream) to alaboratory scale tube furnace.
The gases used for the flame inside the combustion space are adjustable (natural gas with air or oxygen) and are
generally set to normal oxidizing conditions. But also near stoichiometric or slightly reduced conditions can be
set. Inside the tube furnace atemperature gradient is formed by the heat of the incoming combustion gases. The
refractory samples, to be investigated, are placed inside the tube furnace with the flue gas cooling from about
1,000650C (corresponding to the condensation zone inside the regenerator). asodium hydroxide solution is
injected inside the flame, resulting in sodium vapors inside the system. Sulfur dioxide is injected near the connection point of the combustion space and the tube furnace. These two components create an atmosphere inside the
tube furnace rich in SO2 and sodium vapors (high temperature) and sodium sulfate condensates (formed at low
temperature from sodium vapors and SO2). The applied concentrations are much higher than in an industrial regenerator. Thus test conditions are more severe in order to approach long time duration behavior of the refractory
exposed to these vapors and condensation products. After exposure to the corrosive components the samples are
tested on weight gain and are analyzed with SEM/EDX.
Results of testing different refractory materials will be shown.

192 TC11TC13TC14TC15TC18TC21 Glass Trend Refractory Materials

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Melting Process Modelling

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113

Gas-liquid two-phase flow simulation

of bubble in glass melt
Enomoto T.1, Urata S.1, Ose Y.2,3, Kunugi T.2
1

Asahi Glass Co., Ltd., Kanagawa, Japan

Kyoto University, Kyoto, Japan
3
Yamato System Engineer Co., Ltd., Ibaraki, Japan

Understanding of bubble behaviour in glass melt is very important to improve glass productivity since bubbles
are applied to control melt convection and gas concentration in melter. Numerical simulation is an effective tool
to elucidate bubble behaviour in the glass melt. However, it is still difficult to simulate bubble deformation and
gas diff usion from bubbles in glass melt using gas-liquid two-phase flow simulation because of high density and
viscosity of glass melt. In this study, we have thus developed amodel for bubble expansion and contraction associating with gas diff usion with applying the MARS (Multi-interfaces Advection and Reconstruction Solver). At
first, several mass transfer jump conditions, such as aconstant gas concentration (Dirichlet condition), aconstant
gas flux condition (Neumann condition) and aRobins condition, at the gas-liquid interface subjected to the gas
transfer were examined. Next, abubble constriction model caused by the gas transfer through the bubble interface has been developed, and then the numerical simulations based on the MARS with the developed bubble constriction model have been conducted for abubble rising problem in very high viscous fluid. To validate the model,
we conducted the water diff usion experiment from arising vapor bubble in glass melt by using amicroscope FTIR. As aresult, it is found that the numerical simulation result using constant gas flux condition at the gas-liquid
interface is in fairy good agreement with the waster concentration distribution observed by amicroscope FT-IR.

185

How online automatic batch identification

can improve glass furnace control
Muller J., Bodi R., Viktorin P.
Glass Service Inc., Vsetin, Czech Republic

The conditions for float glass production have been developed in last few decades. The times with stable pull
rate, similar produced thicknesses, the same or very similar color or batch composition, etc. are gone now. The
customers push the glass producers for higher flexibility, for various thicknesses including the extreme values,
different glass colors. Moreover, all the glass products have to be prepared just in time.
This situation looks like abig challenge for glass producers. Thus very experienced workers are required either for
furnace operations as well as for melting process control. Continuous changes of aproduction result into different setups like gas distribution profi le, temperature profi les, etc. Standard operators approach moving manually
the total fuel with aview to stabilize the hot spot or refiner temperature is not safe and efficient as there can be
some disproportion among temperature and fuel profi les, batch length, etc. At the end the glass quality can be
disturbed as well and this is unwanted situation, definitively.
Glass Service, Inc. has been working in advanced process control area since 1996 and approximately 90 successful
installations in glass industry confirm the leading role on this field. Nowadays the process control is not about
the temperatures control only like it was even few years ago. The customers need acomplex tool for day-to-day
control all over the year, including the frequent job changes. Thus the combination of flexible advanced control
system Expert System ESIIITM with batch monitoring system ESIIITM Camera seems to be agood solution.

Eisenga, M.1, Muller J.2, Bodi R.2

1
2

Glass Service B.V., Maastricht, The Netherlands

Glass Service Inc., Vsetin, Czech Republic

The glass melting process is characterized by slow process changes with extremely long reaction times. Typically,
glass resides 24 hours or longer in the furnace and any change in the furnace heat input can easily take 4 till 8
hours before the impact on the glass temperature is observed. This makes it difficult for operators to run the fur-

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186

Advanced model based predictive control improves

glass furnace fuel efficiency and lowers NOx emissions

187

nace stable in their limited 8 hour shifts, and also conventional automatic controllers are not suitable to handle
such long term process changes either.
The Model-based Predictive Controller (MPC) is the main controller engine inside ES IIITM . Unique process models inform the controller about the actual response of the furnace, including dead times between heat input and
change in glass temperature. ES IIITM continuously monitors the actual situation in the furnace and forehearth
and predicts future trends based on the process models and recent control actions. If anew temperature set-point
is required, the ES IIITM system predicts the necessary changes in firing to achieve the new temperature in afast
and optimal way, just like acar navigation system optimizes the directions to anew destination. Despite agood
process model, the glass melting process is unfortunately not 100% predictable so (just like the weather forecast)
acontinuous adjustment of the long term prediction is inevitably necessary. For glass melting and conditioning,
the prediction update of the process every couple of minutes is sufficient and the operator is informed by clear
trend lines in the ES IIITM graphical user interface

Modeling of the glass melting process. How validated

simulation tools can help to improve the glass
melting efficiency. An ICG TC21 contribution
Muijsenberg H. P. H., Krobot T.
Glass Service Inc., Vsetin, Czech Republic

379

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. astep 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 afairly 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.

Film drainage of viscous liquid on top of bare bubble:

Influence of the Bond number
Korkov H.1, Rouyer F.2, Pigeonneau F.1
1
2

Surface du Verre et Interfaces (UMR 125 CNRS/Saint-Gobain), Aubervilliers, France;

Universit Paris-Est, Laboratoire Navier (UMR CNRS 8205, Ecole des Ponts Paris Tech, IFSTTAR),
Marne la Valle, France

In glass melting process, ahuge quantity of bubbles is created. The purpose of the fining process is to remove bubbles by aphase separation at the free surface using the buoyancy force. The bubble lifetime at the free surface of
the glass bath can lead to acreation of foam layer. The thermal insulation property of foam reduces dramatically
the energetic efficiency. Since few years, we have developed aresearch to understand the physics of glass foam
stability through experimental and numerical works.
We first present experimental results of film drainage on top of gas bubbles pushed by gravity toward the free
surface of highly viscous Newtonian liquids with auniform surface tension (two molten glasses and two oils at
room temperature). The temporal evolution of the thickness of the fi lm between asingle bubble and the air/liquid
interface is investigated via interference method under various physical conditions, range of viscosities and surface tension of the liquid, and bubble sizes.

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The bubble rising and film drainage are addressed numerically using an integral formulation of Stokes equations
valid for ahigh viscous fluid. aboundary element method has been developed in two-dimensional axisymmetric
configuration. acollocation method is used to solve the integral equation with adaptive time step and mesh refinement to describe accurately the film lubrication.
Both experimentally and numerically, results evidence the influence of the deformation of the thin fi lm on the
thinning rate and confirm the slowdown of fi lm drainage with Bond number (ratio of buoyancy to surface tension
forces). asimple model that considered the liquid flow in the cap squeezed by buoyancy forces of the bubble is in
good agreement with experimental and numerical data. Qualitatively, smaller is the area of the thin film compare
to the surface of the bubble, faster is the drainage.

488

Numerical simulation of electromagnetically

controlled flow in glass melting tanks
Soubeih S.1, Luedtke L.1, Halbedel B.2
1

Ilmenau University of Technology, Faculty of Electrical Engineering and Information Technology,

Department of Electrothermal Energy Conversion, Ilmenau, Germany
2
Ilmenau University of Technology, Faculty of Mechanical Engineering,
Department of Inorganic-Nonmetallic Materials, Ilmenau, Germany

Glass production is atime and temperature dependent process where the residence time distribution and flow
conditions of the glass melt within the melting tank play an important role in defining glass quality and production efficiency.
Aiming to control the flow conditions and optimize the residence time distribution in glass melting tanks heated
directly using electrodes, we investigate the possibilities of utilizing an externally generated Lorentz force in the
glass melt to achieve our objective.
Applying Lorentz forces in the glass melt is anew and innovative approach which offers acontrollable electromagnetic regulation of the flow pattern in the glass melt.
Lorentz forces in the glass melt are generated when an electrical current imposed by means of bottom electrodes
interacts with amagnetic field generated by external coils placed in the insulating material underneath the melting tank. Placing the coils and electrodes at strategic spots called boosting zone results in acontrollable material-free wall in the glass melt, thus increasing electromagnetic boosting.
For such investigations numerical simulations are highly important for estimating the feasibility and paving the
way for practical applications. We simulated and studied the flow conditions in the glass melting tank without
and with the externally generated Lorentz forces using the commercial soft ware Fluent which was developed to
calculate flow and temperature fields. Additionally, we included the magnetic field calculation in Fluent using
the diff usion equations and the so-called user defined scalars. This is how we were able to achieve the three dimensional coupled simulation, since the electrical conductivity and other material properties of glass melts are
strongly temperature dependent.

542

Simulation of essential process steps

in industrial glass melting
Beerkens R.
CelSian Glass and Solar, De Rondom 1, 5612 AP Eindhoven, the Netherlands, ruud.beerkens@celsian.nl

In industrial glass melting processes, the conversion of raw material mixtures into ahomogeneous molten glass
without inclusions, involves several process steps, preferably taking place after each other. The performance of
each step depends on the heating rate or heat transfer, achieved temperature level, the local chemistry in the batch
or obtained melt, the flow or convection conditions and residence times. Different process steps require different
circumstances. Heat transfer rates to and into the raw material batch determine the initial stages of batch melting-in and the contact between different raw material grains strongly influence the rate of reactive melting. The
next stage, in soda-lime-silica glasses mainly starting at about 950-1,000C, is the dissolution of sand grains in
the alkali alkali-earth-silicate melt. Essentially, the sand grains should be completely dissolved before the onset

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of fining, starting with the steady release of fining gases from the melt. After primary fining, usually taking place
in the hot spot area of the melting tank, the molten glass should be cooled down, with rather slow temperature
decrease in the secondary fining range.
After chemical homogenization of the melt and removal of inclusions, the glass melt has to be conditioned to
auniform viscosity (temperature) to control the forming processes.
In this presentation the different process steps and their optimum conditions will be described and some experimental methods will be demonstrated to study these process steps on laboratory scale. Understanding of the
mechanisms of each individual process step and conditions for optimum performance will support the development of new glass melting technologies with lower average residence times and improved energy efficiency.

Impact of glass melter stability on glass

defects in container glass manufacturing
van Santen P.1, Koenraads A.1, Stelwagen S.2
1
2

CelSian Glass & Solar BV, Eindhoven, The Netherlands

Ardagh Glass, Dongen, The Netherlands

548

Computational Fluid Dynamics (CFD) models are nowadays broadly accepted to calculate the temperatures, mass
flows and glass properties in aglass melt for the purpose of furnace design, optimization and trouble shooting
The CFD package GTM-X from CelSian Glass & Solar is capable of detailed, fast and accurate simulation the time
dependent behavior of the process and able to cope with complex geometrical structures at the same time. In
asingle effort these models can be used twice: for design and optimization of the melter or forehearth and for the
configuration of model based supervisory process control systems for these glass processes. This type of control
systems are indicated with rigorous Model Predictive Control (rMPC).
An rMPC can be configured to optimize between several control objectives: minimize energy costs, maximize
throughput of the furnace or improve furnace stability.
In along term observation of an rMPC application on afurnace for colored container glass running high percentages
recycled glass with varying quality, the relationship between furnace stability on glass defects is investigated.
The paper will present backgrounds of the applied technology and results of these investigations with respect to
optimization between energy sources, energy consumption and the effects on glass quality.

Intelligent simplicity instead

of multicolored complexity
Meuleman R. R.
Global Glass Industry Technical Leader, Invensys Operation Management-Eurotherm

How compliant are our process control systems to the future demands of the glass industry? That is of course,an
ongoing discussion we have at InvensysEurotherm and we have to admit that it is adifficult question to answer
because demands change over time and are not necessarily synchronized with the glass manufacturing sites
campaign dynamics.
After 10 or perhaps even 15 years of furnace operation, the time eventually comes to make ahuge step change
in process control during afurnace repair; but what if there are multiple furnaces at one location or if there are
multiple sites belonging to one company? Introducing new control methods and human machine interfaces on
arefurbished furnace becomes difficult when part of the system needs to stay untouched because it is still operational for the other furnaces. How can we keep the whole system consistent and still move forward?
Since IBM introduced the first DCS system in 1964 many things have changed. From the second generation
DCS onwards the capabilities of these systems have increased dramatically but it seems that their functionality
stayed behind. Our operators are still gazing for eight hours at colorful pictures showing multiple PID controller
faceplates on overloaded LCD screens, sometimes even displaying all that information in 3D form which, while
aesthetically pleasing, adds zero value. Why are batch house, hot-end, manufacturing control and maintenance
systems mainly managed by different systems on different platforms and in separated databases? Do we ever
question if that still makes sense?

198 TC11TC13TC14TC15TC18TC21 Glass Trend Melting Process Modelling

This paper will present an alternative approach for corporate process visualization and data management which is capable of serving all users with adequate manufacturing, process control and bench marking information. Intelligent, versatile, lean, grey and dull could become the new keywords for manufacturing processs visualization and management.

549

Furnace design optimization by CFD

simulations and industrial measurements
a new modern container glass furnace
Habraken A. F. J. A., Lankhorst A. M., Thielen L.
CelSian Glass & Solar B.V., Eindhoven, The Netherlands

At alarge container glass manufacturer, anew modern container glass furnace is designed. CelSian Glass & Solar
BV, formerly known as the TNO Glass Group, is supporting the design procedure by industrial measurements,
analysis of historical data on energy consumption and emissions, and performing detailed CFD simulations.
Based on the original design of the glass melting tank of the end-port fired furnace, the general design of the
combustion space, port necks, gas nozzle lay-out and superstructure is modified and optimized with respect to:
1. Energy efficiency
2. CO2 emission
3. NOx emission
4. Volatilization
5. Carry-over
6. CO level in regenerators
7. Refractory hotspots
8. Furnace lifetime
The optimized design has to lead to aglass quality that at least is equal to or better than the current glass quality.
Moreover, combustion space design changes have to be compatible with the constraints with respect to the currently available space within the existing steelwork.
The paper first focuses on the validation of the CFD model results by detailed measurements carried out for the
current furnace, which is used as areference situation for actual energy consumption, emissions and glass quality.
Subsequently, the impact of various combustion space design steps on the parameters as indicated above will
be discussed. The relative improvements as compared to the original design will be shown. For the simulations,
GTM-X is used, which is an industrially validated body-fitted multi-physics CFD code, developed and owned by
CelSian Glass & Solar BV and used for and by the glass industry worldwide.
Using the results obtained by the modeling in combination with the industrial measurements, an optimal new
design is found. This design has been applied for the new furnace. After this furnace became operational, it was
closely monitored to validate the design process, and to further optimize energy use within the constraint of
product quality, emissions, and furnace lifetime.

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Glass Trend
Melting Studies

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070

Development of eutectic compositions

in the quaternary system CaOMgOAl2O3SiO2
for continuous single-filaments
Hellmann K., Conradt R.
RWTH Aachen University, Institute of Mineral Engineering, Department of Glass and Ceramic Composites

The motivation for the development of new glass compositions for continuous fibres goes back to the increasing
demand of high modulus fibres for reinforcement applications such as in wind turbine blades. This study constitutes afundament for the future design of glass compositions in consideration of the ability to fiberize the glass,
and of the resulting mechanical properties respectively.
In this work compositions from the quaternary system CaOMgOAl2O3SiO2 are generated theoretically with
the help of the commercial soft ware FactSageTM, followed by experimental fibre drawing tests (single fi laments)
performed at the laboratory.
The basis of this study is apublication of Koch et al. which includes adepiction of eutectic points within the quaternary system CaOMgOAl2O3SiO2. When developing suitable oxide compositions, it is helpful to take into account the crystalline reference state of aglass. With this information and with the related co-existing phases one
can employ three different approaches to obtain suitable oxide compositions. By using thermodynamic calculations the solidus temperature of each preliminary composition can be determined, and furthermore the eutectic
composition belonging to the determined solidus temperature can be read out. Based on this, abatch calculation
is carried out to melt the respective glass.
Before investigating the ability for continuous fibre drawing in form of single fi laments, the liquidus temperature
of glasses is verified with agradient furnace and the fibre drawing forming temperature T(3.0) denoting the viscosity level of 103.0 dPas was determined.

Boehm P., Mller-Simon H.

Httentechnische Vereinigung der Deutschen Glasindustrie e. V. (HVG), Offenbach, Germany

During the float process fining sulfur diff uses from the glass ribbon into the tin bath and reacts to SnS. SnS is
very volatile and enriches in the protective gas above the glass ribbon. If the temperature decreases for instance
at the surfaces of cooling devices or cold areas at the roof, SnS reacts with hydrogen and forms liquid tin. This
tin accumulates and may drop onto the surface of the glass ribbon causing imprints which disturb the further
processing, especially coatings. In order to develop counter measures against such glass failures, it is important
to monitor the sulfur concentration in the tin bath as well as in the protective gas.
This is now possible with anew sulfur-sensitive sensor.
The new sulfur sensor is an electrochemical concentration chain which is based on a(SrF ) (LaF ) solid electro2 x
3 y
lyte provided by the Institute of Electronic and Sensor Materials, Freiberg, Germany. The sensor has been tested
under laboratory and under industrial conditions. It shows reasonable reactions in case of intended sulfur concentration variations in the protective gas and the liquid tin in alaboratory scale tin bath model.
Sensors were in use for several months under industrial conditions in the atmosphere of float chambers. During
this time studies on the behavior of the sensor as well as on the correlations between production data and measured sulfur concentrations have been carried out.
The signals have been interpreted by the assistance of asimple sulfur balance model. The main influence on the
sulfur distribution seems to be given by the flow of protective gas while the influence of the glass is negligible.

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087

A sulfur-sensitive sensor for application in the tin bath

and the protective atmosphere of float chambers

150

Temperature measurements on feeder systems

Bergmann G., Mller-Simon H.
Httentechnische Vereinigung der Deutschen Glasindustrie e. V. (HVG), Offenbach, Germany

440

The glass distribution of aglass container is primarily caused by the flow behavior of the glass melt during forming. Due to the strong dependence of viscosity on temperature, the temperature distribution is the key to an
optimum glass distribution.
Extended temperature measurements have been carried out on different sections of the feeder head as well as on the
produced gobs. For that purpose pyrometric techniques have been applied as well as thermo-couples. Results from
different feeder types and with different glass colors will be presented. The measurements will be critically discussed
especially with respect to parameters such as emissivity of refractory material and optical density of the glass melt.

Evaluation of the glass melt homogenization

in a feeder channel with the novel
electromagnetic mixer technique
Torres J. O., Halbedel B.
Ilmenau University of Technology Institute of Materials Engineering Department
of Inorganic-Nonmetallic Materials, Gustav-Kirchhoff-Strae 6, D-98693 Ilmenau/Germany

553

The production of some glasses, like the optical glass, requires higher degree of homogenization which is achieved
with amechanical stirrer. Disadvantages of this technique are the formation of undesirable particles due to the
mechanical wear, produced mainly in the moving parts, and an expensive sophisticated design.
We offer an alternative technique with the advantage of static parts and amore precise flow control. It is made
with aspecial electrode arrangement and activation generating time as well as space-dependent distribution of
the electric current density in the glass melt. Such generated current densities together with an external magnetic
field create aLorentz force density distribution. This force distribution is used to control the flow.
This presentation illustrates with numerical simulations that it is possible to control the laminar melt flow, hence
folding and stretching it to mix the glass melt. The simulation of the coupled hydrodynamic, thermodynamic and
electromagnetic problem was done with the temperature-dependant physical properties of astandard soda-lime
glass as well as with realistic mass flow inlet and wall temperature of the feeder.
The mixing grade produced by the electromagnetic mixer was quantified with the spatial distribution in the
outlet channel of agroup of particles injected at the inlet of the feeder. This was compared with that of ahighly
optimized mechanical stirrer to show the possibilities of this new mixing technique.

Laboratory tests and other tools to simulate

essential process steps of industrial glass melting
Beerkens R., Rongen M.
CelSian Glass and Solar, Eindhoven, the Netherlands

Industrial glass melting processes involve many steps required for conversion of araw material batch into ahomogeneous molten glass without inclusions. Melting-in of batch, dissolution of sand, removal of gas bubbles and
partly removal of dissolved gases are essential process steps taking place in glass melting tanks for almost all
types of glass products. CelSian Glass and Solar developed several experimental set-ups and procedures to simulate these process steps on laboratory scale, but applying industry-like conditions. Furnace atmospheres, batch
compositions and applied heating rates resemble industrial practice.
Evolved Gas Analysis systems are developed in combination with observation of the melting-in and fining process to study the gas evolution and melting characteristics during heating of industrial composition batches.
Furthermore, foaming studies are carried out and equipment has been developed to investigate evaporation and
carry-over processes. The effect of glass composition, furnace atmosphere composition, gas flow and temperature

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on evaporation of alkali, boron, chloride, fluoride or heavy metal components from molten glass is measured.
CelSian also developed an experimental method to evaluate the behaviour of regenerator refractory materials
exposed to cooling flue gases from glass furnaces. Many studies have been performed for commercially available
checker refractory. The flue gases contain alkali compounds and other species evaporating from the glass melt.
Results of these experimental studies, such as fining behaviour, fining onset temperature, gas, evaporation kinetics and thermodynamic data are used in CFD modelling studies, predicting the behaviour of glass melt in
industrial glass furnaces.

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New Melting Concepts

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086

Application of the in-flight melting technology

using RF plasma to alkaline free silicate glass
Ohkawa S., Tanaka C., Miyazaki S., Shinohara N., Sakamoto O.
Production Technology Center, Asahi Glass Co., LTD.

In-flight melting (IFM) facilitates rapid and homogeneous melting by feeding granulated raw materials into high
temperature flames so it is expected to save much energy in glass melting furnaces. We have developed IFM technology for an alkaline free aluminoborosilicate glass to realize that radio-frequency (RF) plasma is more effective
in melting granules to ahigh vitrification degree than oxygen-fuel burner. Here we applied the technology to
amagnesium aluminosilicate glass (10MgO-25Al2O3-65SiO2 (wt%))which is thought more hard to melt. Granules
of the above composition were fed into the flame of 100kW RF plasma at some feed rates, and the vitrification degrees of particles after IFM were determined by X-ray diffraction analysis of crystalline silica and alumina. They
found to be vitrified during the flight entirely at the feed rates below 80g/min and to 92% at the feed rate110g/
min. Melted particles were collected to abulk glass in acrucible installed below the in-flight melting chamber,
where the granules were fed to the crucible (a) passing through the flame or (b)directly without passing through
the flame. In the case (a), bulk glass was found to contain no unmelted matters even at the feed rate of 110g/min.
In the case (b), unmelted matters were found on upper part of the melt at the feed rate of 80g/min. These studies
show that bulk glass containing no unmelted matters is available instantly by IFM. It is understood that plasma
IFM is very effective in rapid melting of the hard-to-melt glasses. This study is financially supported by NEDO
(New Energy and Industrial Technology Development Organization, Japan).

336

Bubble elimination behaviour in in-flight

melted soda-lime-silica glass melts
Yano T.1, Miyake Y.1, Ogata J.1, Yutaka Koshizawa,
Nakada Y.1, Sato K.2, Iwamoto M.2, Ebihara Y.2, Inoue S.3
1

Tokyo Institute of Technology, Tokyo, Japan

Toyo Glass Co., Ltd., Tokyo, Japan
3
National Institute for Materials Science, Tsukuba, Japan

Bubbles formation and elimination behaviours are quite important to consider the quality of glass products. In
innovation energy-saving glass-melting technology, In-Flight Melting can reduce time to complete vitrification
of raw materials in several milliseconds orders, because the glass raw materials are heated in flight inside very
high-temperature zone produced by oxy-fuel combustion burner, plasma and/or their combination. This new
vitrification process is expected to bring alarge reduction of energy for melting of materials, reduction of melter
size and some subsidiary merits.
Melting using In-Flight Melting method forms glass melts underneath the heating zone. Such glass melts include alot
of bubbles inside. In order to know the capability of the In-Flight Melting technology to fabricate the glass products
with high quality, the elimination of these bubbles (fining and refining) has to be focused necessarily.
In-Flight-Melted soda-lime-silica glass samples collected from the melter under the oxy-fuel combustion burner flame
are re-melted in the transparent crucible in the electric resistance furnace, and the changes of bubbles contained in the
sample melt at the temperature from 1,300C to 900C are observed for 24h. Size of the residual bubbles changed with
time and temperature, and their number decreased largely before the time less than 10 h passed.
This study was financially supported by the Energy Innovation Program of NEDO (New Energy and Industrial
Technology Development Organization).

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591

Fundamental aspects of glass melting

Nmec L., Jebav M., Dyrkov P.
Laboratory of Inorganic Materials, joint Workplace of the Institute of Chemical Technology and the Institute of Rock Structure and Mechanics, v.v.i., Prague, CR.

Four aspects of the industrial glass melting should be considered, namely the kinetics of partial melting phenomena,
melting phenomena ordering, the utilisation of the melting space for phenomena and utilisation of supplied energy.
When inserting the aspects into the definition of the specific melting performance and specific energy consumption
of the glass melting process, the potentials of the effective melting may be revealed. The literature references give
some answers to the increase of melting kinetics and energetic eficiency of glass melting, as well as to their application in the industrial scale. However, the space utilisation with ordering aspect have not been adequately applied
in practice till this time. The quantity space utilisation expresses the glass flow character with respect to the given
process and its high value is demanded, leading to lower energy consumption and higher melting performance. The
uniform or helical characters of flow are the representants of the effective flow which facts were ascertained by modelling achannel with glass melt. The setting and maintaining the demanded flow character under industrial conditions are nevertheless constrained by the strong effect of batch blanket on the melt flow. The effective heating of the
batch and arising glass melt in the batch region becomes the prerequisite for the effective melting under conditions
of the controlled melt flow. The relevant increase of the batch conversion rate fits then the enhanced homogenization
capacity of the melt, achieved by the faster phenomena kinetics or higher space utilisation.

210 TC11TC13TC14TC15TC18TC21 Glass Trend New Melting Concepts

TC14TC15TC18TC21
Glass Trend
Redox Equilibria

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009

The effect of cobalt on the coloration

of industrial soda lime glasses
Akerman M.1, Toffoli S. M.2
1
2

Glass School Brazilian Technical Glass Association(ABIVIDRO), So Paulo, Brazil;

Polytechnic School University of So Paulo, So Paulo, Brazil
Department of Metallurgical and Materials Engineering

Color is an important attribute of products manufactured with glass. It is obtained by the incorporation of colorant substances in the glass composition, which interact with the light transmitted through the glass and generate
color. Cobalt is one of the oldest and most traditional colorants employed by glassmakers. The objective of this
work was to establish acorrelation between the amount of cobalt present in the glass and the effect onto the color
generated in the glass, through the analysis of industrially manufactured products. Different base glass chemical
compositions have been evaluated and also different types of furnaces. The effect of cobalt in the glass color was
also evaluated for two different coloration processes: i) in the glass bath; and ii) in the feeder channel conducting
glass already elaborated from the furnace to the conformation machine. The results show that the color generated
by cobalt is independent of glass composition, melting processes and coloration system.

062

Influence of some multivalent ions

on Fe Redox in soda lime silicate glass melts
Kim K. D., Kim M. S.
Department of Materials Science & Engineering, Kunsan National University, Chunbuk, Korea

Influence of some multivalent ions on Fe redox in soda lime silicate melts and glasses was studied by square
wave voltammetry and spectrophotometer, respectively. Voltammograms of melts doped with Fe exhibited apronounced peak due to Fe3+/Fe2+-reduction. The temperature dependence of the Fe3+/Fe2+-peak potential recorded in
voltammograms showed anormal behavior, in other words the corresponding peak potential (Ep) moves toward
the negative direction with adecrease of temperature, indicating that the equilibrium state of Fe redox reaction
shifts towards to the oxidation state. However, when S or Sn or Ce was doped to those melts the Fe3+/Fe2+ peak
potential was shifted to negative or positive direction depending on the second multivalent ion. For the glasses
the depth change in absorption band of Fe2+ or Fe3+ in UV-Vis-NIR spectra showed also negative or positive direction under presence of second multivalent ion. Comparison of the results in both voltammograms and spectra
indicated asimilar tendency in melts and glasses from the view point of Fe redox: Fe2+ was favored by presence
of S and Sn. But Fe3+ is afavorite state under doping of Ce. Based on those results the corresponding interaction
between two different multivalent ions was described by redox reaction.

080

Oxygen behavior in the tin bath

for float glass production
Maehara T.1, Laimbck P.2
1
2

Production Technology Center, Asahi Glass Co., Ltd., Yokohama, Japan;

ReadOx & Consultancy B.V., Valkenswaard, The Netherlands

The pO2 of the tin melt and atmosphere in industrial tin baths for the production of float glass is continuously
measured using oxygen sensors from the hot end to cold end. Under normal production conditions, the pO2 of the
atmosphere is determined by the water dissociation equilibrium. The measured partial oxygen pressures of the
tin melt are higher than those of the atmosphere in aparticular bay, indicating that that the oxygen from the glass
ribbon is entrapped in the tin melt underneath it. The oxygen level in tin decreases on moving from the hot end to
the cold end. arelation is derived to quantify the oxidizing or reducing effect of the atmosphere on the tin melt. It
shows that the driving force for tin deoxidation is smallest in the hot end. Therefore, the water vapor content low
in the hot end atmosphere should be kept low. This can be achieved by intense venting, good side wall sealing in
the hot end section. Back flow of relative water rich atmosphere from cold end to hot end should be prevented and
areduced tin temperature in the hot end also helps to keep the oxygen level of tin melt low.

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356

Thermal electromotive force in various molten glasses

Tojo S.1, Kawaguchi M.1, Futagami T.1, Nakamura A.2,
Kato M.2, Yoshida S.2, Sugawara T.2, Miura Y.2, Matsuoka J.2
1
2

Nippon Electric Glass Co., Ltd., Otsu, Shiga, Japan;

The University of Shiga Prefecture, Hikone, Shiga, Japan

426

In glass manufacturing processes, molten glass is cooled gradually from melter to forming area. athermal electromotive force (TEMF) is an electromotive force arising from adifference in temperature at two points along
acircuit. For high quality glass production, Platinum (Pt) alloys are used for production equipment. If the TEMF
exceeds the decomposition voltage of the glass melts, bubbles are formed from agalvanic cell phenomena with
the Pt alloys and the glass melt as electrolysis. Therefore, to evaluate the compositional variation of the TEMFs of
glass melts is important, but few experimental data are available up to now.
In this study, TEMFs of industrial glasses, such as asoda-lime silicate glass (SLS), aborosilicate glass (BS), an
E-glass (EG), alithium aluminosilicate glass (LAS), and an alkali free alumino-borosilicate glass (ABS) are measured and the results are compared with athermal diff usion model proposed by Oldekop. TEMF measurements
are carried out by three-electrode method in atemperature-gradient electric furnace.
The value of TEMF depends on the kind of main mobile ion in glass. TEMFs of Lithium containing glass(LAS)
is the highest and that of alkali-free glasses are lower than other glasses. Oldekop model works well only for the
sodium containing glasses (SLS, BS). These results mean that thermal diff usion is considered one of the most
important factors for TEMF.

Control of the redox equilibrium

in the production of borosilicate glass
Kokov V.1, Zajc J.1, Smrek J.2
1
2

Kavalierglass a.s., Szava;

Electroheat s.v.p.d. Praha

554

In the manufacture of glass Simax should be monitored transmission of light throughout broad spectrum. It is
particularly important in the manufacture of tubes for solar technology. Therefore is monitored daily transmittance through spectrophotometric measurements both in the infrared, visible and ultraviolet spectra. In this way
can be determine the redox state of glass ratio of the absorption peaks at 1,049nm and 378nm, i.e, determining
the ratio of Fe2+ / Fe3+. Comparison with X-ray determination of the total iron was determined the extinction coefficients of the individual spectral bands. It is used to obtain highly sensitive monitoring of the iron content and
redox ratio in the concentration about 0.02% Fe2O3. It can be used not only for finish product evaluation, but also
to determine heat transfer through molten glass during all-electric melting. As highly sensitive position is shown
in the UV absorption edge, thus throughput 318 and 328nm. Scattering of spectrophotometric measurement is
discussed and its use for the evaluation of homogeneity of glass.

Parameters affecting the color mechanism

of manganese containing colored glasses
yiel A., ktem D., Akmaz F.
Research and Technology Directorate, Research and Technological Development Presidency
iecam, Istanbul, Turkey, aiyiel@sisecam.com

Although glass container does enjoy ahigh level of consumer acceptance in the packaging market, the container producers have to continue their effort in order to serve their customers from beverages, alcoholic drinks,
food, cosmetics to pharmaceutical industry sectors, against alternative packaging materials. Color is an important tool for glass industry in this battle, to let the product gain additional aesthetic and functional properties forced by the market demands.

214 TC11TC13TC14TC15TC18TC21 Glass Trend Redox Equilibria

Since most of the colors are affected by the furnace conditions such as temperature, redox level etcetera, it becomes very important to understand the color forming mechanism better, in order to obtain the target color in
the product and to improve the yield during the production.
A detailed experimental study for container production was carried out in order to investigate the relationship between the color formation mechanism in manganese containing glass and the redox conditions. All experiments
were done at different levels of iron and manganese oxides. Color parameters (dominant wavelength, %brightness, % purity and Lab) were examined for large intervals of batch redox states.
In this presentation, the results of above mentioned experimental studies are discussed together.

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Batch Melting Kinetics

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298

Reaction between carbonates during heating of glass

batch: Pathways to more efficient glass-making?
Papin S.1, McDonald N.2, Chopinet M.-H. 3, Gouillart E.3, Toplis M. J.4, Veron E.5
1

Saint-Gobain Recherche, Aubervilliers, France

Verallia SA, Courbevoie, France
3
UMR125 CNRS, Saint-Gobain, Aubervilliers, France
4
IRAP-OMP, UMR5277 Universit de Toulouse, France
5
CEMHTI, UPR3079 CNRS, Orlans, France
2

Many of the recent improvements in specific energy consumption for the glass industry have focused on furnace
design. In parallel, acontinuing desire to reduce the environmental footprint of glass production is currently motivating research into optimizing raw materials. As early as the 1950s the impact of raw material particle size on
melting kinetics (as well as final glass quality and chemistry) was investigated via crucible melting experiments. It
was demonstrated that adecrease in the grain-size of limestone considerably reduces chemical heterogeneity of the
melt, i.e. the presence of an upper layer enriched in silica, and alower layer enriched in lime. In this study, differential thermal and gravimetric analyses have been carried out to understand how limestone grain size influences
reaction pathways during melting, with afocus on the possible interactions between carbonates. Experiments have
been performed with binary mixtures of sodium carbonate and fine or coarse limestone. For experiments using
coarse limestone, the calcination process seems to be the same as limestone on its own. When fine limestone is
used, an alternative pathway interrupts CO2 loss from limestone, that is interpreted to be the reaction between the
two carbonates. These results confirm findings reported in the literature concerning the impact of limestone grain
size on calcination. However, DTA-TGA experiments performed under different gaseous atmospheres demonstrate
that the reaction between sodium and calcium carbonates is also sensitive to CO2 partial pressure. In detail, in-situ
XRD and DTA results may be used to identify crystalline double carbonate (Na2Ca(CO3)2), but only when samples
are heated under aCO2 atmosphere. These DTA-TGA results provide new insight into the reactions responsible for
the reduction in residual defects when finer limestone is introduced in crucible melting experiments, opening the
possibility to identify ways to reduce energy consumption during glass production.

377

Glass batch reactions followed

by ultrafast in-situ tomography
Boller E.1, Chopinet M. H.2, Gouillart E.2, Grynberg J.2, Toplis M. J.3, Woelffel W.2
1

ID19, European Synchrotron Radiation Facility, BP 220, F-38043 Grenoble cedex, France
Surface du Verre et Interfaces, Joint Unit CNRS/Saint-Gobain, Aubervilliers, France
3
IRAP (UMR 5277, CNRS/University of Toulouse III), Observatoire Midi Pyrnes, 14, Ave. E. Belin,
31400, Toulouse, France.

Industrial synthesis of good-quality soda-lime glass is generally carried out at 1,500C, despite the fact that typical compositions are completely molten at 1,000C. Industrial-glass raw materials are coarse granular powders,
and their reaction kinetics at high temperature are strongly determined by the initial granular geometry, and
the interspecies contacts. Therefore, the granular geometry leads to heterogeneous compositions of melts, and to
unmolten sand grains, requiring high temperatures to get rid of these defects.
In order to visualize the different reactions occurring in parallel at high temperature, we have performed in-situ
microtomography experiments of glass batch melting on the ID15A and ID19 beamlines at the European Synchotron Radiation Facility (ESRF). In X-ray tomography, one reconstructs three-dimensional volumes of the X-ray
absorption of the imaged sample. Thanks to recent developments, the acquisition time can now be as short as one
second, which is fast enough to follow glass melting from the inside and in 3-D. We have studied the melting of
small binary and ternary mixtures of sand and carbonates, using different thermal treatments. Such experiments
have revealed new mechanisms undocumented so far because of the lack of direct 3-D observation, such as the
production of crystalline sodium silicates on quartz surfaces not in direct contact with sodium carbonate. Our
tomography results, coupled to thermogravimetric analyses, reveal that several reaction mechanisms between sodium carbonate and quartz operate simultaneously when in solid state. In general, short-range packing arrangements are found to have a profound influence on local reaction pathways, with drastically different reactions
depending on the presence of contacts with sodium carbonate. We also measure the trapping of gas bubbles as
liquid interfaces collapse when eutectic melts are produced.

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430

Assessing container glass melt quality

using batch melting kinetics
Janiaud E.1, Baret B.1, Meulemans J.1, Saget A.2
1
2

Saint-Gobain Recherche, Aubervilliers, France;

Saint-Gobain Conceptions Verrires, Aubervilliers, France

486

Numerical simulations provide detailed information on heat transfer and fluid flows within industrial furnaces
but are yet unable to accurately quantify final glass quality. areliable criterion is needed in order to compare and
interpret numerical simulations and relate them to melt quality.
Based on crucible melting tests, aphenomenological approach was developed in order to derive apractical fining
criterion that can be integrated into numerical simulations. This criterion is based on an extended batch-free time
protocol (i.e. the time necessary to eliminate batch stone at agiven temperature) that enables the precise characterization of glass melting reaction rate as afunction of time and temperature. For agiven batch composition
and temperature, different melting time samples are prepared. The quality is assessed by the defect ratio present
on athin glass sheet by image processing analysis. These steps are repeated for samples at different temperatures
in order to derive acomplete time and temperature function that describes the reaction rate, in the spirit of R. E.
Bastick (symposium sur laffinage du verre, 1955).
In this presentation, we will explain the details of the experimental methodology and present some results on flint
container glass compositions as well as the effect of the sulphate and cullet contents on batch fusibility. Finally,
we will conclude on the potentials and limitations of such afining criterion in terms of industrial applications.

Identical glass formulae by different batches

impact of raw material variation
on furnace performance and glass quality
Conradt R.
RWTH Aachen University, conradt@ghi.rwth-aachen.de

556

It goes without saying that agiven glass composition can be produced from avirtually infinite number of differently
designed raw material batches. Thus, for aconstant glass composition, the choice of raw materials may influence the
course of the melting process, and hence, the furnace performance and the glass quality in asignificant way. From
the point of view of thermodynamics, the initial and final stages of batch melting, i.e., the mixture of raw materials,
and the workable melt, respectively, are well-defined states characterized by an enthalpy difference H. Different
batches may have different H. This leads, in turn, to adifferent amount of power drawn from the melting furnace.
But batches with identical H may still differ with respect to the reaction path taken. This is due to grain size distribution, batch homogeneity, batch compaction, or pre-design of granules or pellets. Batches taking different reaction
paths influence the furnace performance via the dwell time required to reach the envisaged glass quality. Dwell time,
in turn, determines the power demand of afurnace per mass unit of melted glass. The present paper deals the above
non-trivial interdependence by evaluating results obtained at the lab scale as well as during industrial campaigns.

Advantages of pelletized raw materials

Rongen M., van Limpt H.
CelSian Glass and Solar, Eindhoven, The Netherlands

The energy contents of flue gases from glass furnaces, typically contributes for 3035% of the energy input in the
glass melting process. The recovery of the energy content of the waste gases from glass furnaces shows amajor
potential for energy efficiency improvement in industrial glass melting. Raw material batches for glass production
are prone to segregation and the contact between the different raw materials in abatch may be poor, thus lowering
the overall reaction kinetics of fusion of the batch. Pelletized raw materials might deliver amaterial with intense
contact between the batch grains and without the risk of de-mixing during transport and batch charging.

220

TC11TC13TC14TC15TC18TC21 Glass Trend Batch Melting Kinetics

However, pelletizing and/or briquetting needs some modifications in the types of batch components, the adaptation of the granulometry of the batch materials, and sometimes asks for abinder or extra water for obtaining
stable pellets or briquettes. The evaporation of this water in the downstream pellet or briquette drying process
requires extra energy. Generally, this energy is available in the flue gases delivered by regenerators or recuperators
or directly released from oxygen-fired glass furnaces. The use of flue gas heat to dry and pre-heat pelletized batch
will offer an efficient way for heat recovery. Application of preheated pellets or briquettes will not only improve
the homogeneity of the batch and resulting glass melt, but can save typically around 20 % energy for glass furnaces. Furthermore carry-over of fine raw material particle during batch charging will be very low in case of pellets or
briquettes. Another advantage of pelletized batch is the faster melting rate and thus alower batch melting onset
temperature in aglass furnace resulting in ashorter batch blanket and improved heat transfer.
This paper shows results of laboratory studies on the possibilities and advantages for batch pelletizing/briquetting
and the impact on glass furnace energy consumption. Melting tests performed show the melting performance
difference between normal batch and pelletized batch materials.

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Glass Trend
Waste Glass Treatment

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003

CompGlass fiber-reinforced composites

Hbner L., H. Hessenkemper H., Weigand R.
University of Mining and Technology Freiberg, Germany

Due to climate change and increasing costs for raw materials it is necessary to use alternative construction materials than concrete. There are many aspects to prefer aerated concrete. So through the much lower heat conductivity
porous concrete can be applied for insulation material. This material conserves dramatically resources. 1m raw
materials arise to circa 5m building material, which is an increasing in volume by factor five. The emission of CO2
compared to production of conventional concrete is much lower due to the low energy process of autoclaving.
The only disadvantage poses the marginal strength. Through areinforcement of aerated concrete this problem is solved.
The use of conventional fiberglass as reinforcement is not possible, because it will be corroded while autoclaving. So the
work of CompGlass is to modify glass surfaces in such away, that chemical resistance is high enough to resist corrosive
conditions during autoclaving. The modification will be optimized for an online procedure while manufacturing glass
fibers. The focus is on the modification of sodium-silicate-glass to lower the costs for the final product.

063

Recycling of TFT-LCD cullet as a raw material

for soda lime silicate glasses
Kim K. D.
Department of Materials Science & Engineering, Kunsan National University, 573-701 Chunbuk, Korea

The two outstanding characteristics of alkali free alumino-borosilicate LCD glasses, low impurities and high homogeneity can offer arecycling possibility of their cullet as araw material for some commercial soda lime silicate
glasses from the viewpoint of raw material cost and saving of energy. In the present work several soda lime silicate
industrial glass batches with LCD cullet for flint bottle glass and flat glass with low iron content were prepared depending on iron content of LCD glass and melted in the laboratory. Some properties of melt and glass related with
viscosity, devitrification, refractory corrosion, transmittance and water durability were determined for these glasses.
In the case of flint glass, there was no serious change in melt properties up to 10wt% replacement of original glass by
LCD cullet and the use of alkali feldspar as supplier of Al2O3 among the raw materials could be excluded. Flat glass
containing LCD cullet up to 10wt% of total glass showed no serious change in UV-Vis-NIR transmittance. Especially, the water durability of the resulting glasses showed astrong improvement by introduction of LCD cullet. Now
LCD cullet is being applied to some industrial plants for flint bottle glass in Korea. LCD cullet with low iron content
could be also apotential raw material to produce pattern flat glass as photovoltaic cover.

138

Glass-ceramics from low-temperature

sintering of glass and industrial wastes
Ponsot I., Marangoni M., Bernardo E.
Padova University, Padova, Italy

Successful investments in research have opened new hopes for the valorisation of many industrial waste materials. The
amount of projects on characterization of industrials waste, for their reuse into glass compositions, has considerably
increased for last 50 years. Particularly, foamed glass-ceramics have been elaborated with vitrified industrial wastes.
In the present study, mixtures are selected using recycled glass from dismantled CRT (cathode ray tubes) and
various materials of industrial or natural origin: MSWI (municipal solid waste incinerator) ashes, coal fly ashes,
iron-rich slag, AFS (fume abatement systems) residues, and clay. Thermal process is between 800C and 1,100C.
Low apparent density (below 2 g/cm-3) as well as low water absorption (below 2%) is achieved, making the resulting materials suitable for use as lightweight insulating panels. In particular, the specific strength values (strength
to density ratios) are close or even exceed those of traditional ceramics (e.g. porcelain stoneware).
Chemical inertia of all investigated materials was assessed by TCLP testing (European Standard EN 1457-2), with
promising results.

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192

Microwave preparation of calcium-borosilicate

glass for nuclear waste immobilisation
Mandal A. K.*, Mandal S., Sen S., Sen R.
CSIR-Central Glass and Ceramic Research Institute, Kolkata, India

380

In microwave heating, electromagnetic waves cause the molecules to oscillate resulting in heat generation. Microwave heating of materials is often considered beneficial due to significant reduction of energy consumption,
shorter processing time, improved microstructures and properties, and synthesis of new materials. In the present
work, 60g glass having composition of wt% (54.50) SiO2, (10.80) B2O3, (14.20) Na2O, (1.20) K 2O (6.00) CaO, (4.00)
Fe2O3 and (9.30) TiO2 was experimentally melted in 3KW multimode microwave furnace at 1,350C. In parallel to
this melting, 60g glass having same batch composition was also melted in aconventional resistance heating furnace of similar cavity size at the same temperature. Molten glass was cast into apreheated steel mould followed by
annealing at 560C for 2 hours to eliminate thermal stress. Both the glasses prepared in microwave heating and
in electric heating were characterised by adopting standard methods to compare the properties. XRD analysis
of the samples prepared in both methods has confirmed the amorphous nature of the samples. Glass transition
temperatures for glasses prepared in conventional and microwave heating route were 576.3C and 569.5C respectively. Density was also found less in glass prepared using microwave radiation. Improved hardness was obtained
in microwave prepared sample. The maximum microwave input power was recorded as ~1kW and total electrical
power requirement for the glass melting in conventional method was found 3 to 4 times more than that of microwave melting route. Further, the time required in microwave glass melting was one third of that in conventional
glass melting method. Hence, this new process of glass melting using microwave radiation which has been successfully utilized to prepare calcium borosilicate glass for nuclear waste immobilisation, may bring positive result
from the viewpoint of clean process, energy saving and optimisation of economy.

High insulation foam glass material from

waste cathode ray tube panel glass
Knig J.1,2, Petersen R. R.1, Yue Y. Z.1
1
2

Section of Chemistry, Aalborg University, DK-9000 Aalborg, Denmark

Advanced Materials Department, Joef Stefan Institute, Ljubljana, Slovenia

Recycling of materials from obsolete equipment has become an important part of global waste management.
With responsible collecting, dismantling and materials separation, majority of materials can be recycled. Cathode ray tube (CRT) glass represents as much as two-thirds of the weight of aTV. In general CRT consists of two
types of glasses: barium/strontium containing glass (panel glass) and lead containing glass (funnel and panel
glass). In this work we present the possibility to produce high performance insulation material from the recycled
lead-free glass. We studied the influence of foaming parameters on the characteristics of foamed glass.
CRT panel glass was crushed, milled and sieved below 63m. Activated carbon used as a foaming agent and
MnO2 as an oxidizing agent were mixed with glass powders by means of aplanetary ball mill. Foaming effect was
observed in the temperature range between 750 and 850C. We investigated the influence of milling time, particle
size, foaming and oxidizing agent concentrations, temperature and time on the foaming process, foam density,
foam porosity and homogeneity. Only moderate foaming was observed in carbon containing samples, while the
addition of the oxidizing agent greatly improved the foaming quality. The results showed that the amount of
oxygen available from the glass is not sufficient to combust all of the added carbon, therefore, additional oxygen
was supplied via manganese reduction. In general, aminimum in the foam glass density was observed when the
foaming parameters were changed. Finally we were able to reduce the density of the obtained foam glass down to
130kg/m3 and hence the thermal conductivity down to 0.042 W/mK.

226

TC11TC13TC14TC15TC18TC21 Glass Trend Waste Glass Treatment

446

Oxynitride foam glasses from industrial

wastes: Synthesis and properties
Lebullenger R.1, Sangleboeuf J. C.2, Rocherull J.1, Tessier F1.
1
2

UMR 6226-ISCR-Verres et Cramiques, Rennes, France

LARMAUR ERL 6274, Rennes, France

Glass foams were produced using soda-lime silicate glass from automotive industrial wastes and aluminium nitride used as foaming agent. Steel-making wastes and other oxides (TiO2, CeO2) were added to prepare expanded glassy materials. Process parameters such as temperature, time and initial batch compositions were studied in
awide range. Redox behaviours of the different batches are discussed.
Structural characterisation by X-ray diffraction reveals amorphous or crystalline nature depending on process
parameters. Apparent density varies from 0.2 to 1.2 and pycnometric density from 1 to 2.2. The pore size distribution and nature (close or open) are correlated to the experimental parameters. Open and closed porosities varied
between 5 to 80%. Chemical analysis showed than nitrogen is present in the oxynitride glassy material.
Filtration tests were performed. Mechanical characteristics such as compression, torsion and tenacity were
achieved. Mechanical strength is discussed in function of porosity and pore size values.

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Combustion Process

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112

Alternative fuels for glass melting

DAgostini M. D., Goruney T., Poussou S., Wang J., Watson M. J.
Air Products and Chemicals, Inc., Allentown, United States

While the global demand for natural gas continues to rise, an increasing share of supply is forecasted to come
from unconventional sources such as those produced from shale formations. This abrupt change in supply chain
has already triggered large variations in fuel prices across different geographies, which in turn has impacted many
industries including glass manufacturing that heavily relies on natural gas and fuel oil for glass melting, particularly in parts of the world that lack indigenous supply of natural gas. As aresult, astrong demand has emerged
to utilize less expensive alternative fuels while meeting increasingly stringent environmental regulation targets
without compromising glass quality and productivity. This has introduced several major challenges for the use of
alternative fuels in traditional air-fuel combustion, such as decreased productivity induced by low heating value
fuels, flame stability issues associated with difficult-to-ignite fuels, lower glass quality driven by particulate matter emissions, as well as challenges arising in the attempt to blend multiple fuel sources to achieve an optimized
balance of combustion stability and efficiency, glass furnace productivity and cost. In order to address these issues, Air Products has developed oxy-fuel combustion technology that can utilize awide range of alternative fuels
including but not limited to coal oven gas (COG), pulverized coal, pet-coke, and combinations thereof for glass
manufacturers looking for anew solution to substitute the traditional air-fuel combustion of natural gas and fuel
oil in the glass melting process. In this paper, anumber of examples on various uses of alternative fuels in glass
melting applications will be demonstrated via both laboratory test results and CFD simulations, and commercial
installations. Emphasis is on how the aforementioned challenges associated with the use of alternative fuels are
overcome via oxy-fuel combustion technology.

Vojtech P.1, Muijsenberg H. P. H.2

1
2

FlammaTec Ltd., Vsetin, Czech Republic;

Glass Service Inc., Vsetin, Czech Republic

This paper will present the practical results of an application of aflexible duel gas injector by FlammaTec, Ltd.
(FlammaTec), at some tableware plant with detailed real data and also some other furnaces.
In todays world market there are many issues facing the glass manufacturing industry, including both economic and
environmental challenges. The price of energy is high. Also, there are many environmental regulations in terms of
emissions levels, and the related potential penalties associated thereto, if these limits are not achieved. Glass Industry
often seeks to replace their existing burners and achieve an improved furnace operation and energy savings.
Existing or current burner technology has utilized aduel gas injector since the 1960s. Gaz de France published
its first version of this twin gas burner in 1968(1). Subsequently, other burner manufactures introduced their own
versions of the dual gas nozzle burners, but their identifying feature was that there was one (1) gas inlet to the
burner with the independent gas streams only later separated within the burner itself.
Advantages of anew burner concept were developed for the FlammaTec Flex Burner in the years 2006 and 2007.
The Flex Burner utilizes two (2) fully separate gas inlets and gas flows into the burner which would be controlled
and measured independently. The burner tip was optimized utilizing computational fluid dynamic modeling to
minimize turbulence at the burner tip. The burner nozzle was also designed to be fully adjustable. Hence, the new
burner design offeres some technological advantages.

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184

Successful furnace combustion system conversion

by installing new low turbulence flexible gas injectors
with target to lower emissions and save fuel

191

Investigation into the applicability

of fermentation gas for melting glass
Fleischmann B.1, Giese A.2, Maertin M. 2, Wuthnow H.3
1

Huettentechnische Vereinigung der Deutschen Glasindustrie e.V. (HVG), Offenbach am Main, Germany;
Gas und Waerme-Institut Essen e.V. (GWI), Essen, Germany
3
Forschungsgemeinschaft Feuerfest e.V. (FGF), Hoehr-Grenzhausen, Germany

545

In order to reduce the CO2 footprint of glass production and to minimize the impact for CO2 trading on the glass industry, alternative, sustainable fuel sources become more and more interesting. In this context, acooperation of three
research associations in Germany deals with the suitability of fermentation gas for glass melting applications. This fuel
gas is typically characterized by amethane content of more than 50 vol.-%, the rest being more or less CO2.
In the scope of the research project, various aspects are investigated. The components of different fermentation
gases are determined as well as their variation due to circumstances of production. The influence of the fermentation gas on specific glass properties (colour, oxidation state, etc.) is investigated as well as the interaction of
the flue gases with typical refractory materials is studied. In addition, the impact of the fermentation gas on the
combustion process and technique is given acloser look.
Some results of 5 week test run using a purpose built test rig to combust untreated fermentation gas will be
presented. The influence of fermentation gas on the combustion process itself as well as on glass and refractory
samples will be discussed.

In-situ CO sensor for combustion control

in industrial glass furnaces
Faber A. J.1, van Kersbergen M.1, Sanders T.1, Dang D. D.1
1
2

Celsian Glass and Solar, The Netherlands

NEO, Norway

Currently, many glass companies use ZrO2 /Pt oxygen sensors for continuous monitoring of the combustion process of high temperature furnaces. In order to avoid post-combustion in the exhaust of the furnaces, there should
be sufficient oxidant, air or oxygen, to assure complete combustion. However, large air or oxygen excesses lead
to reduction in the thermal efficiency of the furnaces and promote NOx formation. The residual oxygen concentration in the exhaust gases partly indicate the completeness of the combustion process. However, especially at
near stoichiometric combustion conditions, oxygen measurement in the flue gasses downstream is less suitable
for accurate burner control. In-situ detection of CO in the hot flue gases is abetter and more sensitive method for
optimization of the combustion process.
In this paper anewly developed measuring system for CO detection, based on laser absorption, is described. The results
of industrial tests with aprototype system at both aregenerative glass furnace and at an oxy-gas fired furnace are presented. The results show that by reducing the air excess within certain limits (CO levels in burner port up to 4,000ppm)
the NOx emission levels of the regenerative end-port fired furnace could be reduced by around 50%. The estimated
energy savings in atypical 200 ton/day regenerative container glass furnace range between 1 and 3 %, corresponding
to about 6 TJ energy savings per year. By reducing the oxygen excess (e.g. O2/gas ratio from 1.86 to 1.81) the potential
oxygen savings are estimated on about 700.000m3 oxygen/yr for an oxy-fired container glass furnace of 300 ton/day,
corresponding to about 2.5 TJ savings on primary energy per year, for generating the oxygen.

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546

Oxygen Enhanced NOx Reduction (OENR)

in glass furnaces: A combustion optimization
method to achieve below 500mg NOx/Nm3
Kobayashi H.1, Pedel J.1, Torkamani S., de Diego Rincn J.2
1
2

Praxair, Inc., 39 Old Ridgebury Road, Danbury, CT 06810, USA

Praxair Euroholding S.L., Orense 11 9a, Madrid 28020, Spain

:Container and flat glass manufactures in EU are required to comply with new NOx emissions limits in the range
of 500 to 800mg/Nm3 at 8% O2 dry. With modifications of the primary air combustion system such as the optimization of natural gas injection method relative to the preheated air flow from the regenerator port, most furnaces
have been able to reduce NOx emissions below 1,000mg/Nm3. However further reduction to the 500 to 800mg/
Nm3 range was shown to be difficult for many furnaces by the modifications of the fuel injectors alone. Combustion staging to reduce the stoichiometric ratio of the primary air flame by secondary oxidant injection at astrategic location of the furnace has shown further significant reduction in NOx emissions in many furnaces. Praxair
has applied Oxygen Enhanced NOx Reduction (OENR) Technology to an oil fired seven-port float glass furnace
to minimize NOx emissions. asmall amount of oxygen was injection near exhaust ports within the furnace to
burn out CO after the primary air flame was optimized for NOx emission. NOx emissions as low as 380mg/Nm3
at 8% O2 dry flue gas conditions were achieved by the OENR Technology while maintaining good glass quality,
high heat transfer and energy efficiency. This paper presents several examples of OENR technology applications
to optimize combustion conditions for NOx reduction.

zel Uar S., Eltutar Z., nsel L.

Melting Technologies and Engineering Directorate, Research and Technological Development Presidency
iecam, stanbul, Turkey, sozel@sisecam.com

Air staging decreases the flame temperature and NOx emissions by burning asmall portion of the fuel at afurther
point in the glass furnace. In an end-fired furnace the amount of air in the port is reduced and corresponding
amount is fed into the furnace from the side walls. The position and geometry of the air staging nozzles, the temperature and amount of air in the nozzles determine the efficiency of the application.
The parameters of air staging are also related to furnace design. For both increasing energy efficiency and reducing NOx emissions, it is important to find the correct position and level of staging with respect to furnace
dimensions. Thus, these are investigated by iecam Mathematical Model for end-fired furnaces and the results
are discussed in the paper.

ICG Prague 2013 233

550

Mathematical modeling analysis of air staging

for end-fired regenerative furnaces

 234

TC13-TC18TC21
Glass Trend
Furnace Design
and Waste Heat Recovery

ICG Prague 2013

235

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110

19622012, 50 years that have deeply

changed the world flat glass industry
Savate B. J.
BJS.Diffrences, Courbevoie, France

This presentation will be in three parts. The first section will review the four industrial revolutions that have influenced the flat glass industry manufacturing (Leblanc chemical soda ash, Siemens continuous furnace, Fourcault
sheet glass, Pilkington float glass), the key processes that have impacted the flat glass fabrication (flat glass tempering, large area coating technology, reliable production of insulating glass units) and the glass as astructural
material influencing its usage. I will present the key highlights and the main innovations in flat glass manufacturing and products spanning over the last two millennia, two centuries & fift y years.
Section two will focus on the key changes along last 50 years in the world of flat glass: the move from sheet
glass to float glass and the associated consolidation of the Western flat glass industry and arrival of new comers
(some with new business models), the relocation of manufacturing, starting in early 1980s, from Western Europe,
Northern America to China and other rapidly growing Asian countries, the change in flat glass prices versus other materials; the evolution of products (with aspecial focus on coated glass for energy management, utilization of
glass as astructural material for construction, and extra thin glass for display and communication applications),
along with the evolution of the key companies participating in the business.
The fi nal section will address the current status of the industry with data describing its structure, the global
footprint of flat glass production lines, major producers, and key products and profitability of those fi rms and
the industry as awhole.
In conclusion I will present key challenges the flat glass industry is facing and my expectations for the years to come.

217

Thermodynamic and kinetic study

of boron containing flue gases
Thiele S., Conradt R.
RWTH Aachen University, Institute of Mineral Engineering, Department of Glass and Ceramic Composites

Due to evaporation from glass melts, the flue gases of glass melting tank furnaces can generate environmentally
hazardous emissions. Environmental protection, and therefore the reduction of the level of emissions, has become aquest worldwide. Primary control measures are usually not sufficient to reach the limits set by national
authorities. Flue gas fi lters are an effective tool to reduce the level of emissions. However, their operation is often
based on experience and empirical data. abetter understanding and reliable data for the condensates forming in
the flue gas fi lters are necessary to assure solid afilter operation.
While many problems during fi lter operation can be avoided by acontrol of water vapour and oxygen partial pressures of the flue gas, an effective control of gaseous boron species is still in the explorative stage. The main problem during the production of boron containing glasses is the slip-through of high levels of the gaseous species
(HBO2)n and H3BO3. Another problem is the back-reaction of already precipitated filter dust to gaseous species.
The paper presents athermodynamic and kinetic study of conditions in the system Na-O-H-B under which these
undesired effects may occur. An experimental set-up is presented by which the mass transfer conditions in aflue
gas channel can be simulated in such away that the results may be transferred to the industrial scale.

van Limpt H.1, de Wit E.2

1

CelSian Glass & Solar, P.O. Box 6235, 5600 HE Eindhoven, The Netherlands
HyGear B.V., P.O. Box 5280, 6802 EG Arnhem, The Netherlands

Large parts of the energy supplied to fossil-fuel fired glass furnaces are lost through the chimney. Even todays
most efficient regenerative or oxygen-fired furnaces typically show waste gas heat losses of 2530% of the total

ICG Prague 2013 237

555

Application of Thermo-Chemical Recuperator

in the glass industry; overview of the latest developments

557

glass furnace energy input. In arunning research project CelSian Glass & Solar and HyGear investigate the application of aThermo-Chemical Recuperator (TCR) to convert natural gas, water and waste heat into ahigh calorific
reformer gas mixture. In aTCR system, natural gas is converted into hot synthesis gas (mainly CO and hydrogen)
with higher energy contents than this natural gas. For this highly endothermic reaction, waste gas heat is used.
This technology is interesting for oxy-fuel fi red as well as recuperative glass melting furnaces and other fuel fi red
furnaces or kilns. Energy savings can be 25 % or higher, depending on the temperature of the reformer and the
obtained reformer gas composition, and depending on the type of furnace. Highest energy and costs savings are
expected for recuperative and oxy-fuel furnaces.
Glass furnace flue gas first flowing through areformer unit is then used to generate steam. This steam and de-sulfurized natural gas are mixed and further heated, and finally the natural gas (mainly CH4) and steam (H2O) mixture is exposed at atemperature level of 600900C to acatalyst in the reformer unit, heated by the flue gases from
the furnace. The hydrocarbon molecules and water react and form hydrogen and CO, so-called syngas (reformer
gas). The hot syngas can directly be used as fuel for the glass melting process. The syngas composition depends
on the molar ratio of water (steam) to hydrocarbon molecules, the temperature of the reformer and the catalyst
activity. This TCR-system requires: asteam boiler (heated by flue gas), super heater, anatural gas de-sulfurization
process, arecuperator (in case of an air-fired furnace), areformer system (using acatalyst) and adapted burners
in the furnace and modified combustion gas skid system.

Sorg-efficient Oxy-fuel fired furnace solution in practice

Lindig M.
Nikolaus Sorg GmbH, Lohr am Main, Germany

Based on special efficientair-gas furnace design solutions, Sorg has invented anew Oxy fuel furnace design and
investigated the solution with mathematical modeling. With additional design features in the superstructure,
the flue gas exit temperature should be reduced by about 200C, which corresponds with areduction in energy
consumption by at least 8%. With calculations this efficiency improvement could be confi rmed. In November
2012 the special furnace solution was realized in agreen field project in Poland. The furnace has amelting area
of 65m 2 and athroughput of 130t/d special container glass with high quality demands. The furnace went in
November 2012 into operation. The expected energy efficient improvements could be confirmed. About 8.5%
energy reduction were achieved. Furthermore, flue gas heat recovery solutions behind that special Oxy fuel
furnace are possible.

238

TC21-TC25
Glass Trend
Glass Forming

ICG Prague 2013 239

 240

008

Friction measurements at the glass/mould

interface during hot forming cycles
Moreau P. 1,2, Lochegnies D.1,2, Montoya D.1,2, Vivier H.3
1

PRES Universit Lille Nord de France, Lille, France;

UVHC, TEMPO, Valenciennes, France;
3
Sogelub Special Lubricants, Marquain, Belgium

A better understanding of the frictional behaviour between glass and moulds at elevated temperatures is essential in the luxury perfume bottle industry. The objective is to prevent the sticking at the glass/mould interface to
make it easier to release the mould and avoid the defects on the glass surface. Lubrication is one factor to make
the forming process successful and to respect the desired high quality level on the final product.
The present study concerns the analysis of the impact of lubrication on the mechanical behaviour at the glass/mould
interface. Successive forming cycles are performed on the experimental Glass/Tool Interaction (GTI) platform in the
TEMPO Laboratory (Valenciennes, France). Each forming cycles combines apressing phase, when the hot glass is
pressed by the punch, and arotation phase between the glass and the punch to estimate the friction force.
For different punch lubrication conditions (bare punch, swabbed punch, coated punch and coated/swabbed
punch) flint glass forming cycles were realized on GTI for the friction analysis at the glass/punch interface. The
friction analysis is based on the evolution of the friction coefficient during forming cycles on the GTI platform.
By using the swabbed punch, the influence of the initial temperature of the glass on the friction coefficient for the
glass forming is also presented.

126

Numerical and experimental investigation

of fiber drawing process
Chouffart Q.1, Simon P.2, Terrapon V. E.1
1
2

University of Lige, Lige, Belgium;

3B The fibreglass company, Battice, Belgium

The manufacturing process of glass fibers used for the reinforcement of composite material consists in drawing
liquid glass at high temperature into fibers. This process is very complex and sensitive to numerous disturbances
that can cause the breaking of the forming fibers. Breaks have astrong negative impact on the process efficiency.
It is thus very important to understand the mechanisms of fiber breaking in order to optimize the manufacturing
process. As afirst step towards elucidating the causes of these failures, we investigate here the underlying physics
of the forming of asingle fiber through numerical simulations. In particular, we focus on the region from the
hole tips at the bushing plate to the glass transition point. The influence of key parameters (e.g., glass flow rate,
drawing velocity, external environment, glass properties) on the fiber radius attenuation and the internal stresses
is investigated through asensitivity analysis. Finally, these numerical studies are compared with experimental
data measurements obtained from adedicated fiberization unit for asingle fiber. These experimental results also
serve as additional insight into the forming process and as validation of the physical models, such as glass rheology or heat transfers. Comparisons between numerical and experimental results show agood agreement and
demonstrate that simulations can provide auseful tool to gain insight into the underlying physics and to devise
new strategies for adjusting the process operating window.

158

Modeling the temperature distribution

in feeders and gobs
Bergmann G., Lber N.-H., Mller-Simon H.
Httentechnische Vereinigung der Deutschen Glasindustrie e. V. (HVG), Offenbach, Germany

The glass distribution of aglass container is primarily caused by the flow behavior of the glass melt during forming. Due to the strong dependence of viscosity on temperature, the temperature distribution is the key to an
optimum glass distribution.

ICG Prague 2013 241

271

Extended temperature measurements have been carried out on different sections of the feeder head as well as
on the produced gobs at several production sites. In order to predict the temperature distribution in the gob by
means of common production data, the temperature data have been analyzed by finite element modeling. To
achieve reasonable results with acceptable effort the measured data have been combined with asimple model to
amodel based interpolation. This allows areasonable assessment of the quantities in demand. Furthermore, an
easy approximation of limited known material data such as heat conductivity at high temperatures is possible.
This method gives also insight in the interdependencies of the feeder parts.

Effects of asymmetric gob temperature

on container glass forming
Moeller A.
Nogrid GmbH, Bodenheim, Germany

291

In order to achieve the increasing product quality by simultaneously reducing the costs it is fundamental to understand all mechanisms in glass forming processes. Some mechanisms are hidden and coupled with each other and
therefore it is very difficult to distinguish between them by experiments. Fortunately in computer simulations we are
able to separate the conditions and as aresult we are able to investigate the dependencies step by step.
The most important and most sensible material property for the forming process is the viscosity of the glass, which depends on temperature. For this reason, it is essential to set the temperature for the initial gob accurately. Unfortunately,
the temperature of the initial gob is usually entirely unknown and can be measured only with considerable effort. For
that reason one important question very often is: What is the influence of the gob temperature on the container wall
thickness distribution and what happens if the temperature distribution within the gob is not homogeneous?
In this paper we will give answers on that questions. We investigated the influence of asymmetric gob temperature distributions on the glass forming process and on the container wall thickness distribution as well. As in
reality, the simulation starts with gob loading and ends at take out. All process steps are integrated into one computer model and all walls are switched on and off at the corresponding time step given by the IS machine time
data. The shape of the bottle can be each possible 3-D shape. Thus, there are no limits regarding bottle design
and we can test and evaluate acontainer design without restrictions. The asymmetric distributions are applied to
typical glass containers and the process type used is the blow and blow process.
All computations presented in this paper were performed by using the Nogrid computational fluid dynamics
(CFD) soft ware The soft ware is based on the Finite Pointset Method (FPM) and it is agrid-free method which,
in contrast to classical numerical methods, such as Finite Elements or Finite Volumes, does not require agrid or
mesh. An unstructured point cloud is the sufficient geometrical basis for this method, i.e. the construction of expensive meshes/grids, as known from the classical CFD solvers, is not at all an issue for FPM. FPM can excellently
be applied in the case of all those problems, where grid-based methods reach their limits and especially glass
forming processes can be handled easy and fast.

Numerical simulation of radiative and conductive heat

transfers throughout glass thermoforming process
Bau L.1, Collin A.2, Jeandel G.2, Le Corre B.2,3, Meshaka Y.3
1

cole Europenne dIngnieurs en Gnie des Matriaux, Nancy, France;

Laboratoire dnergtique et de Mcanique Thorique et Applique, Vanduvre-ls-Nancy, France;
3
Institut Jean Lamour, Nancy, France

In glass industry, thermoforming is commonly used for processing, e.g., windshields, optical lenses for scientific
settings or artworks. In this study, we focus on moulding aglass sheet by gravity sagging. The sheet is heated up
in afurnace. As temperature rises, viscosity decreases and glass can fit the shape of amould placed below.
From apractical point of view, it is avery difficult task to get the required final sample geometry. To better understand the process, we propose to numerically model it. Forming depends on viscosity which is strongly influenced
by temperature. Consequently, the determination of temperature field into the glass sample must be very precise.
Special care is required for radiative transfers because IR resistances are commonly used for heating up glass into

242 TC11TC13TC14TC15TC18TC21 Glass Trend Glass Forming

the furnace and glass is known as an absorbing, emissive and non-scattering medium. Thermal properties, especially optical indexes, can change according to wavelength and temperature so these variations should be considered. As the model is complex, we use areciprocal Monte Carlo method to calculate the radiative source term
for any considered volume element of glass. Conductive transfers are supported by the commercial finite-element
method soft ware (Abaqus). By implementing glass mechanical behaviour, we can thus observe glass deformation
during the process and compare the results of our simulations with data we get from an experimental set-up.

428

Analysis of viscous-elastic response

of glass melt during pressing
Matousek I.
Technical University of Liberec, Liberec, Czech Republic

Virtual modelling of technological processes has been already regarded as apowerful tool for research and development. Its application in the pre-manufacture stage allows reducing physical testing, the rate of rejects and
material waste as well as accelerating cost-effective product development. afundamental problem of virtual modelling of glass forming processes is the accuracy of the numerical outputs. Critical factors include not only
definition of boundary conditions, but also aspecification of material properties of glass melt to be formed. The
number of methods was suggested for the identification of viscous-elastic behaviour of glass melt. One of the frequently used methods for assessing rheological behaviour of silica glass melts is isothermal compression method.
The principle of this method is simple andits application is relatively easy. However, the key issue for the efficient
use of this method is the evaluation of experimental measurements, especially in the course of second stage,
when the deformation of the analyzed sample is controlled by viscous flow. There are two ways for identification
of the rheological behaviour of analyzed glass melt sample either to use some of the previously derived equations
or numerical methods integrated in modern computer programs (CAE). Practical applicability of above mentioned equations is limited only to small sample compressions and strictly isothermal conditions. CAE programs
provide relatively accurate outputs, however their application is time consuming and less efficient in this case.
Based on the analysis of real compression process of glass melt sample, the limitations on the use of the equations
mentionedabove, as well as computer model are determined. In the conclusion new model for identification of
rheological behaviour of glass melt subjected to compression loads is suggested.

ICG Prague 2013 243

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TC13TC15
Glass Trend
Analytical Techniques

ICG Prague 2013 245

 246

161

Environmental Barriers of the Glass Industry Growth

Sluncik P.
University of Economics, Prague, Czech Republic

The paper aims at the systemic approach to the environmental competitiveness within the sector of glass industry. The
impact of implementation of different environmental legislation on competitiveness of companies in glass production
is understood as an obstacle. There may also be competitiveness impacts relative to non-EU competitors. Globalization
is achallenge for various industries, the environmental issues alike. Systemic approach to analyse the complex of business environment brought progress to solve problems connected with articulation of integrated levels. Quality of political environment and mutual collaboration among all the actors is crucial for next development of successful sustainable growth both: the glass industry sector, national economy and the other actors (stakeholders). (Industrial) policy
and competitiveness do not have commonly accepted definitions; concepts on definitions differ across nations, regions,
stage of development and over time; in short or long time. Systemic as the interaction between the factors of competitiveness is just as important as the analysis of the policy elements. Policies to improve firm growth: if policymakers
want to increase firm growth, how does action to reduce trade costs compare interms of effectiveness to reductions in
innovation costs or lower taxes? The backbone of the paper is the orientation to work with the equlibrum within the
environmental legislation and the systemic approach due to meta-, mesa-, macro and microlevel participation. The
main policy indication that emerges from this paper is the focus on research, technology and innovation policies and
the ability of negotiations and lobby on the sectoral, national and international levels how to achieve the eqiulibrium.
Environmental policy in the context of sector strategy requires the use of ideas from fields as diverse as economics
strategic management, law, politics and environmental studies. It also classifies major environmental regulations and
incorporates adiscussion of public policy. Firms engaged in international business not only need to be aware of environmental issues but, must also have in place astrategy to deal with environmental regulations.

344

Image analyses for 3D modelling of glass products

Hota V.
Technical University of Liberec, Department of Glass Producing Machines and Robotics,
Studentsk 2, 460 17 Liberec 6, Czech Republic

Vision systems for monitoring and control in aglass industry are applied for quality monitoring of container
glass ware, window glass and automotive glass, domestic glass, glass fibres, technical, optical and laboratory glass.
Todays trend in aglass production is ause of virtual modelling. The 3D model can be obtained by avision system
and the model in computer then represents areal captured product. The model in agood accuracy and resolution
can be used for quality inspection. Speed and acontactless way of the inspection are the main advantages.
The contribution discusses and presents possibilities of the modelling that are based on the theory of Shape from X and
3D scanners (time-of-flight, triangulation). The limitation of the theory and scanners use is primarily transparency.
Hence, only some standard approaches for non-transparent objects can be used for glass transparent products.
The contribution also presents possibilities of glass shapes detection using their reflection. The approach is presented on gravity formed flat glass, like automotive one.

Cook S.1, Donthu S.2, Lever D.1

1
2

Rio Tinto Minerals, London, United Kingdom;

Rio Tinto Minerals, Singapore

Analysing the composition of glass is of great importance in industry and academia. Common reasons for measuring the composition of glass are (i) to compare it to astandard or specification; and (ii) to compare one glass
composition with another. The accuracy and precision of the analytical technique determines how effectively
these objectives can be achieved.

ICG Prague 2013 247

417

A comparison of the precision of two analytical

methods for determining boron in glass

510

Boron, because of its small atomic number, is one of the most challenging elements to analyse in glass. The current
method employed is to digest the glass sample into acidic solution, introduce this solution into ahigh temperature
induction coupled plasma (ICP), and then analyse the resultant optical emissions spectrum (OES) to determine
the amount of boron.
In the present study we have investigated the suitability of another analytical technique, Electron Probe Microscopy (EPM), as an alternative for measuring the amount of boron in glass. We have used astatistical method,
Measurement Systems Analysis, on both techniques to identify sources of variation in each measurement method,
and compare their precision.
From this study we have been able to determine which analytical method is able to measure boron in glass with
the highest precision. We have also been able to statistically quantify the confidence interval of an individual
measurement with each system, and hence determine the ability of each method to distinguish between two
different glass compositions.

A modified approach to glass containers colour control

Bertolin M.
Vetri Speciali SpA, Ormelle, Italy

559

Glass colour control remains one of the critical and qualifying parameters for glass containers. The ability to develop
and maintain consistent colour over the time represents achallenge when high recycling rates become mandatory and
cost reduction pressure suggest cheaper and less stable raw materials. Smaller companies may find new opportunities
in shorter runs and high frequency colour changes: predictable results are mandatory to keep the balance sheet in order.
Early in the 90s cheap spectrophotometers become available and photodiodes allowed asimpler and faster spectrophotometric control but the frequency was still limited to once or twice per shift, typically. The paper will describe anew
method for glass colour control based on continuous image analysis of glass containers. Objective advantages have
been found either on steady colour control as well as in colour changes. Flint glass may be controlled with amodified
setup and algorithms have been developed to maintain meaningful results in clear colours as well as with dark colours
and heavy bottles. An extensive set of samples was used to validate the results and define relationships with colouring
elements concentrations. The method is not limited by glass colour inhomogeneity, acritical factor for spectrophotometric measurements in the early steps of colour changes. The possible batch adjustments there may avoid more
dramatic corrections at alater time and improve colour chance predictability and robustness. amodified model for
over-doping has been developed using the practical results from different industrial furnaces.

How to make bushing control green?

Meuleman R. R.1, Rutkowski S.2, Moeginger M.3
1

Global Glass Industry Technical Leader, Invensys Operation Management-Eurotherm,

Senior Applications Engineer; BSEE, RoMan Manufacturing Inc.
3
Technical Application Engineer; UAS Germany

Objective is: Improving the efficiency and profitability of bushing positions by smart design of the entire system
from the incoming power to the precious metal.
Continuous fibre glass became commercially viable after electrical controlled fibre glass bushings became available.
Over the years, those bushings became bigger and bigger, requiring higher amounts of power as well as more precise
temperature control. Today, modern glass fibre bushings require up to 70kW of power. Due to their relatively low
resistance they need to operate at around 8 Volts at currents up to 10,000 Amps. Those high currents can only be
supplied by specially designed transformers and intermediary high current busbar systems. Since Ohms and Maxwells laws become very dominant in high current environments, bushing, transformer, busbar and power controllers need to be well designed and matched to each other in order to obtain best possible loop impedance (Resistance
and Reactance). The electrical efficiency differences between anormal designed bushing position and an optimized
position can reach up to 30%. The paper will explain how bushing loop impedance can be improved, how special
designed bushing transformers will lower resistive losses and how sophisticated load tap changing power control
lower reactive power (cos ) and improve overall efficiency. Finally the paper will show how acarefully designed
overall bushing system will improve fibre quality, reduce fibre breakage and extends bushing lifetime.

248 TC11TC13TC14TC15TC18TC21 Glass Trend Analytical Techniques

Modern bushing control also means using a modern generation of controllers which provide high-performance control with cost-effective redundancy options in aversatile modular system. Special control strategies
and asophisticated HMI-System improve the handling and helps increase production quality. Using Touch
Panels for local control in combination with modern SCADA applications and integrated database provides
amaximum availability for the operator.

560

Development of Radiation Burner

for glass conditioning improvement
Jatzwauk Ch., Moaveni M., Griebenow P.
HORN Glass Industries AG, Bergstrasse 2, D-95703 Plssberg, Germany, jatzwauk@hornglas.de

Heat transfer through radiation is the most significant heat transfer mechanism at high temperature processes,
like in glass production. In addition, molten glass as asemi-transparent media allows the radiation to be the most
effective heat transfer mechanism in the glass bulk. Based on these facts, HORN has developed the ``Radiation
Burner`` to be installed in forehearth and distributor channels.
Through combination of theoretical thermodynamics and material science considerations and practical tests in
apilot forehearth, the special design of aburner and suitable material has been specified by HORN. Besides the
development of the new burner, the forehearth superstructure shape has been modified accordingly, in order to
succeed highest efficiency of firing system as well as fast and safe burner installation during construction. The radiation burner, utilizing high quality refractory material, emits radiant heat precisely to the molten glass without
flame impingement. Fast and controlled heating in forehearth/distributor as well as improvement of glass thermal conditioning are the result of this new firing concept. Through the focused radiation to desired surface areas,
effective independent control of left/right forehearth temperature even in achannel with asymmetric geometry is
possible. The higher heating efficiency of this burner leads to significant energy savings. Multi-functional features
allow the burner to be used for awide range of applications in container glass, tube glass and fiber glass production. The new burner has been installed and proved in two real forehearths. The mentioned improvements have
been verified through evaluation of experimental data from running forehearths.

ICG Prague 2013 249

 250

Poster Contributions

ICG Prague 2013 251

 252

001

Surface refinement of glass

LubriGlass and MagicLiquid
Weigand R., Hessenkemper H., Hbner L., Htzel M.
University of Mining and Technology Freiberg, Germany

For cheap producing of high qualitative glasses it is necessary to increase the surface quality of the product, because the important properties of glass like strength and hydrological resistance are determinate by the surface.
LubriGlass is anew lubrication for container and rolled glass production which based on aluminum and interacts
with the hot glass during the forming process. In different industrial tests the effect were shown by an increasing
of the bursting pressure container. Also the corrosion of the moulds decreases dramatically and the lubrication
interval extended. Another possibility of online surface refinement of glass is using MagicLiquid. It increases the
chemical, mechanical and optical properties of glasses and can easily installed as an online-process after forming.
Online tests on flat glass line and also in container glass production were done. Using MagicLiquid for an inner
surface refinement of the bottles leads to an increase of the hydrological resistance and notch test strength.

004

Batch briquetting
Weigand R., Hessenkemper H., AlHamdan K., Hbner L.
University of Mining and Technology, Germany

Glass production as ahigh energy consumption industry has to search for new ways to reduce energy. The known
processes of batch compaction were investigated and further developed. In laboratory and half industrial tests
the new techniques proved astrong improvement concerning kinetic of batch reactions, SiO2 dissolution and
refining. In addition less evaporation for instance for boron and an improved homogeneity of the glass was proven which should influence in apositive way the mechanical strength. From this apull rate increase or decreased
melting temperatures are possible. Intensive studies concerning the additional costs and resulting economic advantages has been made demonstrating that in most cases the situation is in favor for the briquetting technique.

Atiar Rahaman Molla*, Anal Tarafder, Upender Gangadharini, Basudeb Karmakar

Glass Science and Technology Section, Glass Division, CSIR-Central Glass and Ceramic Research Institute,
196 Raja S. C. Mullick Road, Kolkata 700 032, India

Barium bismuth titanate, (BaBi4Ti4O15) (BBTi) precursor glasses are prepared by the melt-quench technique in
the SiO2-K 2O-BaO-Bi2O3-TiO2 (SKBBT) glass system without and with Eu2O3 doping. Glass-ceramic (GC) nanocomposites of BBTi have been derived by controlled heat-treatment of glass. Thermal properties of the precursor
glasses as well as glass-ceramics are determined and activation energy for crystallization has been estimated
using different models. The structural properties of the heat-treated GC are investigated using X-ray diff raction
(XRD), electron microscopy (FESEM, TEM) and FTIR reflectance spectroscopy. FESEM images demonstrate the
formation of randomly oriented polycrystalline hexagonal rod shaped crystals of 200400nm and TEM images
reveal, 1020nm crystallites after heat-treatment. asignificant increase of r values from 25 to 47 were observed
for the BBTi50Eu samples with increase in heat-treatment time span from 1 to 100 h at 610C. However, the undoped precursor BBTi glasses exhibit increase in r values from 13.0 to 21.8 with increase in BBTi content from
20 to 60mol%, whereas, their heat-treated glass-ceramic counterparts show increase in r values from 14.2 to
43.7. The excitation spectra have been recorded by monitoring emission at 613nm corresponding to the 5D07F2
transition and observed an intense 466nm excitation band corresponding to the 7F05D2. Emission spectra were
recorded by exciting the glass samples at 466nm and observed that with increase in heat-treatment time the intensity of red emission at 612nm increases by 15-fold which transpired due to the occupancy of Eu3+ ions in the low

ICG Prague 2013 253

015

Fabrication and properties of Eu+3

doped ferroelectric barium bismuth titanate
containing glass-ceramic nanocomposites

019

phonon energy crystal sites of BBTi. The hardness (3.85.1GPa) and fracture toughness (K1c) (1.83.5MPam0.5)
values measured in the glass-ceramics are significantly high and suitable for structural applications with reasonably good mechanical reliability.

Crystallization characteristics and chemical

durability of some lithium borosilicate
glass-ceramics containing GeO2 and Fe2O3
Salman S. M., Salama S. N., Mahdy A. Ebrahim
Glass Research Department; National Research Centre; Cairo; Egypt

027

The crystallization characteristics of the glasses based on Li2O-B2O3-SiO2 system had been investigated. The base
glass composition was modified by partial replacement of GeO2 for SiO2 and Fe2O3 for B2O3. The effect of the compositional variation on the crystallization products of the glasses and the type of the phases formed as well as the
resulting microstructure was traced by using DTA, XRD and SEM. The chemical durability of the resulting glass-ceramics was also determined. adecrease in the endothermic and exothermic temperatures was detected by the all
replacement processes. The main crystalline phases formed after controlled heat-treatments were lithium disilicate,
lithium diborate, lithium metasilicate as well as lithium iron silicate phase of pyroxene family. The crystallization of
meta and disilicate, and their ratios, depends on the temperature and duration of the process. The chemical durability of the crystallized glasses was improved with the replacement processes. The durability data obtained depend
on the nature, concentration of crystalline phases formed, the nature of glassy matrix and the microstructure.
The role played by the glass oxide constituents in determining the crystallization behaviour, microstructure and
the chemical durability of the prepared thermally treated glasses was discussed.

Some aspects concerning the glassmaking

technology of medieval bracelets from 11th c. A.D.
Velinova R.1, Detcheva A.1, Dimitriev Y.2
1
2

Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria
University of Chemical Technology and Metallurgy, Sofia, Bulgaria

Archaeological excavations in medieval villages and necropolises have proved that glass was widely used on Bulgarian territories. Most of the glass artefacts are investigated by Bulgarian archaeologists and stored in museums.
Among them are the medieval glass bracelets from South-East Bulgaria. All glasses are homogeneous, without gas
bubbles and crystalline inclusions and questions arise concerning the technological level of glassmaking in this
period. It is well known that local craftsmen used different raw materials and recipes for glass production. According to their chemical composition all investigated fragments are soda-lime-silica glasses. In the present study
model glasses were prepared and investigated. Their chemical composition is identical with the average composition of the medieval bracelets fond in Haskovo region. Two experiments were carried out. In the first experiment
technical raw materials and metallurgical slag were used. It is demonstrated that metallurgical slag was most
probably used for colouration of archaeological glasses. In the second experiment batches containing one part
sand and two parts forest ash were prepared. Heat treatment of model batches was performed by different temperatures for different time. All products were analyzed by means of X-ray diff raction and SEM-EDS. We proved
that it is possible to obtain homogeneous glasses applying relatively low melting temperature maintained for
sufficiently long time. Thus the technological parameters of medieval glass melting procedure were established.
Acknowledgements: The authors kindly acknowledge the financial support of the projects BG051PO001-3.3.06-0050,
2012 and DTK-02/05; 2010).

254

Poster Contributions

038

Magneto-optical quenching in transparent

manganese-phosphate glasses
Winterstein A. 1, 2, Mncke D. 1, Wondrazcek L. 1
1
2

Otto-Schott-Institute, University of Jena, 07745 Jena, Germany

Max Planck Institute for the Science of Light, Gnther-Scharowsky-Str. 1, Building 24, Erlangen, Germany

Transition metal ions (TM) such as Mn2+, Fe2+ and Co2+ offer an interesting alternative for rare-earth species in
magneto-optical materials. Especially Mn2+ exhibits low extinction coefficients in the visible spectral range and
ahigh effective magnetic moment compared to other transition metal ions. Here, we discuss the system Mnx
Sr1-x (PO3)2 (with x=0; 0.01...1.0). We show that strong clustering of Mn2+ species results in virtually complete
quenching of the Faraday effect. Despite the high theoretical magnetic moments this can be attributed to the
non-magnetic ground state (Ag term) and spin forbidden transitions.

048

Nanostructured glass-ceramics
as active media for eye-safe lasers
Yordanova A. S., Kosseva I. I., Nikolov V. S., Iordanova R. S., Milanova M. K.
Institute of General and Inorganic Chemistry, Sofia, Bulgaria

The subject of our investigation was the synthesis and characterization of glass-ceramic, where the active media is Cr4+
doped nanostructured olivine phases. This product could successfully substitute olivine single crystals. The synthesis of
the last creates many problems due to its high melting temperature, phase transition of phases and crystal defects.
It was shown that the main parameters of the synthesis, as initial composition of the glasses, condition for glass
preparation, annealing and time of glass treatment determinate the chemical composition of the crystalized
phase, as well as the concentration, distribution into the volume and particles size distribution. This main characteristic of glass-ceramics influences on the main optical parameters for laser applications as absorption spectra,
emission spectra and time decay. The obtained data were discussed from apoint view of potential application.

Taki Y., Honma T., Komatsu T.

Department of Materials Science and Technology Nagaoka University of Technology, Niigata, Japan

Rare-earth tungsten borate glasses with the compositions of 25RE2O3-xWO3-(75-x)B2O3 (RE=Gd,La) (x=25-50)
were prepared using a conventional melt quenching method, and phase separation and crystallization behavior were examined. The melt quenched glass itself with 40mol% of WO3 showed two endothermic peaks prior
to crystallization in the differential thermal analysis curve, and the presence of phase separation with the nano-scaled sea-island structure was confirmed from transmission electron microscope observations. The phase
separation was enhanced due to heat treatments at around the glass transition temperature. The crystalline phase
of Gd2(WO4)3 was formed in the tungsten rich phase. In the case of La2O3, the crystallization of La4B2WO12 and
LaBWO6 were confirmed. The present study proposes that the degree of phase separation in RE2O3-WO3-B2O3
glasses depends largely on the amount of WO3 and the kind of rare-earth oxides.

ICG Prague 2013 255

053

Phase separation and crystallization behaviour

RE2O3-WO3-B2O3 (RE = Gd, La) glasses

054

Ion mobility and structure of glasses

in the BiF3MFZrF4 systems (M = Li, Na, K, Cs)
Kavun V. Ya.1, Telin I. A.1, Alexeiko L. N.2, Voit E. I.1, Yaroshenko P. M.1, Goncharuk V. K1.
1
2

Institute of Chemistry FEB RAS, Vladivostok, Russia,

Far Eastern Federal University, Vladivostok, Russia

056

A search for new glasses with optical, electrophysical, and other properties suitable for practical purposes is
amain problem of current studies. In this report, we discuss the results of studies of the ionic mobility and structure of novel bismuth fluorozirconate glasses in BiF3MFxZrF4 (M=Li, Na, K, Cs; 0 x 45mol.%) systems to
find glasses with particular functional properties. Ion mobility in bismuthfluoride glasses in the BiF3LiF and
BiF3LiFxZrF4 systems (x 10mol.%) was studied by NMR method. Analysis of 7Li and 19F NMR spectra made it
possible to reveal the character of ion motion in the fluoride and lithium sublattices of the glasses under temperature variation, and to determine the types and temperature ranges in which they took place. It was found that the
main types of ion motion in the glasses were the diff usion of lithium ions and the reorientation of fluorine-containing groups. The diff usion of fluorine ions was observed only in crystallized glasses.
The results of research of ionic mobility and structure by (7Li, 19F, 23Na) NMR, IR and Raman spectroscopy of aseries of 45ZrF435BiF320MF (M=Li, Na, K, Cs) fluoride glasses were summarized. Major types of ion mobility
in these glasses at temperature of 400440K are alocal motion of fluorine-containing groups and adiff usion of
lithium ions. The temperature range, in which the diff usion of F ions is adominant type of motion in glasses, is
determined by concentration and nature of the cation M. The conditions determined base models of glass structure in BiF3MFxZrF4 systems were considered. The bismuth polyhedrons can take part in forming of the glass
net under such conditions. According to the results of IR and Raman spectroscopy, the network of this glass with
x=45mol.% consists of ZrF8 polyhedra linked into chains. At concentration ZrF4 less than 10mol% and BiF3 more
than 35mol% BiFm polyhedrons are present in the glasses in systems BiF3MFZrF4.

The study of crystallization of oxifluoroniobate

glasses by means of Raman spectroscopy
Ignatieva L. N.1, Savchenko N. N.1, Surovtsev N. V.2,
Adichtchev S. V.2, Polyshchuk S. A.1, Marchenko Yu. V.1, Bouznik V. M.3
1

Institute of Chemistry FEB RAS, Vladivostok,

Institute of Automation and Electrometry SB RAS, Novosibirsk,
3
A. A. Baykov Institute of Metallurgy and Material Science RAS, Moscow

The crystallization of glasses in the MnNbOF5-BaF2-BiF3 system was studied by means of Raman spectroscopy. The
glass compositions with various content of components such as glass-forming and modifiers are obtained. The structure of glasses in the systems of MnNbOF5-BaF2, MnNbOF5-BaF2-BiF3 and MnNbOF5-BaF2-BiF3-LnF3 were studied
earlier. The revealed features of the structure of glasses allowed assume the presence of amulti-stage crystallization
of glasses. The data of calorimetric studies have confirmed this assumption. The compositions of crystalline phases
were identified. The Raman spectra of the original samples of MnNbOF5-BaF2-BiF3 system and the samples heated
until high temperatures in acontinuous mode and mode of exposure were measured. The changes in high and
low-frequency region of the spectra observed in the process of changing the temperature of the samples were analyzed. The sharp crystalline peaks appear in the spectrum in the region of stretching vibrations and the boson peak during the heating of the sample. This study showed that the processes of the crystallization of oxifluoroniobate glasses
strongly depend on the composition of the glass. For some compositions, for example 20MnNbOF5-40BaF2-40BiF3,
20MnNbOF5-30BaF2-50BiF3, crystallization occurs with visible phase separation of processes, while, by Raman data,
crystallization occurs without noticeable liquation effects for glass of 30MnNbOF5-30BaF2-40BiF3. The dependence
of crystalline phase compositions on Nb/Ba, Nb/Bi, and Ba/Bi ratio is identified.

256

Poster Contributions

059

The development of laser phosphate

glass production at JSC LZOS
Avakyanz L. I., Babina T. O., Ignatov A. N., Krekhova E. Y., Pozdnyakov A. E., Surkova V. F.
Open Joint Stock Company Lytkarino Optical Glass Factory (JSC LZOS), Lytkarino, Moscow Region, Russia.

The first production of laser glass on JSC LZOS dates back to 1960s, and since that time, JSC LZOS has achieved
significant successes in production of silicate-based laser glasses. JSC LZOS started developing atechnology of
commercial production of phosphate laser glass. In early 2000s, these developments resulted in production of
LFS5 glass with all the necessary characteristics. Nowadays, JSC LZOS continues its work on improvement of the
laser glass composition. One of the latest researches resulted in the series of composition branded KNFS, which
is used in production of disk elements. Production of laser phosphate glass is nowadays carried out using an
original method in aplatinum crucible. The desired operating characteristics of laser phosphate glass can only be
achieved when specific values of lifetime of ions on metastable level (), coefficient of inactive absorption at the
generation wave length =1,053nm (cm-1) and damage threshold, are present. In order to achieve the first two
characteristics, in addition to glass composition, purity of raw materials, application of technological practices
for melting and preparation of melting, work zones air humidity is kept on 20% level (which is possible only in
winter) and measures are taken to minimize the amount of impurities. Regarding these facts JSC LZOS is working now at creating anew workshop for production of large-sized disc active elements (DAE) of laser phosphate
glass. The needed parameters of humidity and air-purity will be maintained throughout ayear with the help of
newly developed original scheme of climatic equipment. At the same time, the new glass melting technology
will be based on two-stage melting in atwo-level glass-melting unit. Therefore, commissioning of several units
of such construction will allow all-year round production of high-quality laser phosphate glass blanks up to
40420790 mm in size of glass compositions with various Nd2O3 concentrations.

060

Involvement of characteristic molecular

entities in structural relaxation description
Svoboda R., Mlek J.
Department of Physical Chemistry, University of Pardubice, Pardubice, Czech Republic

Although the glass transition phenomenon is known for centuries, its exact fundaments are still undisclosed. In
fact, the understanding of physical processes that occur during and after glass forming is one of the major scientific challenges in condensed matter physics. Number of equations and models have been developed over time
in order to obtain areliable and meaningful approximation of the structural relaxation behaviour. Nowadays, it
is the phenomenological models that provide most accurate and flexible description of the relaxation features.
However, the question stands, whether the precise description of experimental data outweighs the missing physical meaning of model parameters. For this reason, there has always been an effort to somehow interpret these
parameters and link them to the particular relaxation features or concrete relaxing molecular structures. In our
work, we would like to introduce such interconnection for the current top phenomenological relaxation model
the Tool-Narayanaswamy-Moynihan model.
An thorough study of relaxation behaviour was performed for number of compositions from the Se-Te, Ge-Se
and As-Se glassy systems. Enthalpy relaxation was measured by means of differential scanning calorimetry;
curve-fitting as well as various non-fitting methods were applied to reliably determine and confirm the values of
TNM parameters corresponding to each composition. The compositional dependencies of TNM parameters were
then explained in terms of anovel introduced conception. This conceptual description then appears to represent
aunique connection between the various molecular structures and parameters of the phenomenological TNM
model an interpretation that has been intensively sought over past decades.
This work has been supported by the Czech Science Foundation under project No.P106/11/1152.

ICG Prague 2013 257

074

Determination of trace metals in soda lime

silicate glass by Isotope Dilution Inductively
Coupled Plasma Mass Spectrometry
Saijo Y., Suzuki Y., Akiyama R.
Corporate Research Center, Asahi Glass Co., Ltd., Yokohama, Japan

083

Determination methods of trace copper, nickel and silver in soda lime silicate glass by Isotope Dilution (ID)-ICPMS has been investigated. Since glass contains trace titanium and zirconium as impurities, it is difficult to determine nickel and copper due to mass interference of titanium oxide ion and to determine silver due to zirconium
oxide ion by ICP-MS. The contamination from environment should also be reduced during pretreatment.
In order to separate the elements from titanium or zirconium, asolid phase extraction (SPE) method is utilized for copper and nickel, and an anion exchange method for silver. ID method is also combined with each pretreatment because
the elements cannot be recovered completely. In order to reduce the contamination from environment, glass is decomposed with asealed PFA vessel in aclean room. The trace elements can be successfully determined by aquadrupole type
ICP-MS without interference. The determination limit is 0.05 g/g for copper and nickel, 0.01 g/g for silver.

Morphology of multilayer thin films of SiO2/Fe3O4

nanoparticles prepared by Sol-Gel dip-coating method
Gabrene A., Juhnevica I., Setina J., Mezinskis G.
Institute of Silicate Materials, Riga, Latvia

090

This study present two methods of production multilayer fi lms of SiO2/Fe3O4 nanoparticles: adding of prepared
magnetite direct to SiO2 sol and encapsulation magnetite between two SiO2 layers. Better quality was for sandwich type fi lms obtained by encapsulation magnetite.
Magnetic nanoparticles Fe3O4 were prepared using coprecipitation method. An argon flux was used to deoxygenate water to prevent Fe2+ oxidations. acoprecipitation in alkaline media starting amixed FeSO47H2O/FeCl36H2O
solution with amolar ratio of Fe2+/Fe3+=0.5. Black precipitate was producted immediately by adding ammonium
hydroxide (NH4OH). To prepared Fe3O4 particles, the samples were washed with ethanol and dried at 45 C.
The multilayer fi lms consist three layers on aglass substrate. The first and third layers are aSiO2 layer prepared
by dip-coating from tetraethylortosilicate solutions and subsequent calcination at 400C temperature in air. The
second layer was prepared by dip-coating from the aqueous colloidal dispersion of previously synthesized magnetite. All the glass substrates were initially modified to obtain aclean and rough or smooth surface. The phase
structures, morphologies and particle sizes of magnetite nanoparticles and glassy nanocomposite fi lms have been
characterized by X-ray diffraction, Fouries transform infrared spectroscopy, scanning electron microscopy and
atomic force microscopy. The average size of synthesized magnetite nanoparticles was estimated to be c.a. 15nm.
The calcined fi lms reported here exhibit crack-free morphology, consisting of aggregated silica/magnetic nanoparticles, with afinal average size of c.a. 100nm. Future controlled advancement of this method could provide
alow cost solution for mechanically stable composite thin fi lms with various, technologically useful, properties.

Glass and Ceramic Composites for high

technology applications (GlaCERCo) Marie
Curie Initial Training Network (ITN)
Bernardo E.1, GlaCERCo Team
1

Dipartimento di Ingegneria Industriale, University of Padova, Italy

The project GlaCERCo-ITN is intended to provide high-quality research training to young researchers, by the
collaboration of many European partners, from both academic and industrial worlds (Politecnico di Torino and
Universit degli Studi di Padova, University of Erlangen-Nuremberg, CNRS-Rennes and Institute of Physics of

258 Poster Contributions

Materials, Materials Engineering Research Laboratory Ltd, Colorobbia Italia S.p.A, Nuova Ompi s.r.l., Nanoforce
Technology Limited and nLIGHT Corporation), having top class expertise in glass science and technology, modelling, design, characterization and commercialization of glass based products.
The present paper is dedicated to the mid-term key results of the project, involving experiments in several strategic fields such as medicine (bioactive glasses as bone replacement and drug delivery systems), telecommunications
(glass devices for broad-band applications), photonics (glass based photonic sensors), clean energy (Solid Oxide Fuel
Cells glass sealants), waste management (re-use of waste by vitrification and/or development of glass-based products), oil and gas exploration and carbon capture (glass reinforced plastic pipes). In all fields, case studies of innovative, cost-competitive and environmentally acceptable materials and processing technologies, will be illustrated.

092

Crystallization behaviour of nonlinear

optical KNbO3 and NaNbO3 in glasses
Kioka K., Honma T., Komatsu T.
Department of materials science and technology, Nagaoka University of Technology, Japan

Perovskite-type alkali niobium oxides of KNbO3 and NaNbO3 show excellent optical nonlinearity. Therefore,
these crystals are expected as alternative materials for lead containing Pb(Zr,Ti)O3. This study focuses on crystallization of these materials by glass-ceramics method. Crystallizations of KNbO3 and NaNbO3 were examined
in aluminoborate (40K 2O-25Nb2O5-25B2O3-10Al2O3 (x=0-5)(mol%))and alminosilicate (30Na2O-25Nb2O5-(45-x)
SiO2-xAlO1.5 (mol%))glasses, respectively. In the case of KNbO3, ametastable phase was formed from the surface
at ~550C. And the metastable phase transformed to aperovskite-type stable KNbO3 phase from the surface at
~700C. It was found by two-step heat-treatment that the presence of the metastable phase strongly affects for the
formation of perovskite-type KNbO3. KNbO3 precipitated glass-ceramics showed clear second harmonic generations by Nd:YAG laser irradiation. On the other hand, in the case of NaNbO3, any metastable phase was not
formed and perovskite-type NaNbO3 was crystallized directly in the heat-treatment of glass samples. The glass
samples showed bulk crystallization behaviour. The degree of the optical transparency for the glass-ceramics was
significantly related with SiO2-Al2O3 ratio. The crystal size of NaNbO3 decreased with the substitution of Al2O3 to
SiO2. The crystallization mechanism of KNbO3 and NaNbO3 in glasses was proposed.

095

Photoluminescence and laser patterning

of RE2(WxMo1-xO4)3 crystals in glasses
Wang Y., Honma T., Komatsu T.
Department of Materials Science and Technology, Nagaoka University of Technology, Nagaoka, Japan

Molybdenum oxide (MoO3) or tungsten oxide (WO3)-based crystals containing rare-earth ions (RE3+) are extremely attractive as optical materials. We succeeded in pattering of ferroelastic -RE2(MoO4)3 crystal lines on the
surface of RE2O3-MoO3-B2O3 glasses (RE: Sm, Gd, Tb, Dy) by laser (Yb:YVO4 fiber laser: wavelength =1,080nm)
irradiation and found that the periodic degree of refractive index changes observed in -RE2(MoO4)3 crystal
lines depends on the kind of RE3+ ions. In this study, RE2O3-WO3-B2O3 glasses (RE: Gd, Eu) were prepared by
aconventional melt quenching method, and -Gd2(WO4)3 and -Eu2(WO4)3 crystals were synthesized through
their crystallization. The crystallized samples containing -Eu2(WO4)3 exhibit strong red emissions under the
excitation at 396 and 467nm, although the base glass has no photoluminescence emission. -Gd2(WO4)3 and
-Eu2(WO4)3 crystals were patterned on the glass surface by laser irradiations. We also investigated that the effect
of the substitution of WO3 for MoO3 on the formation of RE2(MoO4)3 crystals. The glasses with the compositions
of 22.5Gd2O3-xWO3-(47.5-x)MoO3-30B2O3 (x=10, 20, 30, 40) were also prepared. It was found that the substitution of WO3 for MoO3 has astrong effect on the crystalline phase forming during heat treatment. In the case of
the glass with x=10, the formation of both -Gd2(WxMo1-xO4)3 and -Gd2(WxMo1-xO4)3 crystalline phases was
confirmed, and it was suggested that the substitution of WO3 enhances the transformation of -Gd2(WxMo1-xO4)3
crystals to -Gd2(WxMo1-xO4)3 at high temperatures. The -Gd2(WxMo1-xO4)3 crystal lines were patterned by laser
irradiations on the surface of the glass with x=10. The periodic structural changes observed in -Gd2(WxMo1O ) crystal lines are clearly induced along the laser scanning direction.
x 4 3

ICG Prague 2013 259

100

Glass solder sealing of solid oxide

fuel cells via laser heating
Willberg M., Menzler N. H., Vaen R., Buchkremer H. P.
Forschungszentrum Jlich GmbH,
Institute of Energy and Climate Research, IEK-1, 52425 Jlich, Germany

102

A new approach for Solid Oxide Fuel Cell (SOFC) sealing using laser induced heating is examined. The state
of-the-art to seal SOFCs is to heat up a stack of cells mounted in a metallic frame and separated by metallic
interconnectors within afurnace. The steel parts are connected via glass solder. Glass is chosen for the joint for
several reasons. It is chemically inert towards the fuel gases as well as electrically isolating to prevent ashort circuit. Its coefficient of thermal expansion is adapted to the one of the used steel. The glass is molten in afurnace
at temperatures of around 900C for ca. 10 hours. The molten glass solder then crystallizes to aglass ceramic at
slightly lower temperatures over aduration of ca. 100 hours. In order to reduce the length of the production time
and therefore the production costs the glass joints could be treated with alaser instead of putting the whole stack
into afurnace. The laser induced soldering theoretically takes just afew minutes, while the preparation is similar
as for the furnace joining. Furthermore new glasses could be used, whose transformation temperature is higher,
since the thermal load on the metallic SOFC components will be negligible. This allows for glasses with ahigher
SiO2 amount. Such glasses are more chemically inert than typical glasses used for SOFC joining. The research is
done within the scope of an EU project, which deals with the prospect on mass manufacturing of SOFCs. The
energy coupling into glass solder has been examined and evaluated. In contrast to the glass solder treated within
the furnace, the laser treated glass solder stays amorphous. This has no impact on the stability of the glass itself,
though astable connection between glass and steel is still acritical point.

Crystallization behaviour
of europium-doped aluminophosphate glasses
Monteiro R. C. C.1, Soares R. S.1, Lopes A. A. S.1, Lima M. M.1, Elisa M.2, Sava B. A.2
1
2

Faculty of Sciences and Technology, Universidade Nova de Lisboa, Caparica, Portugal;

National Institute of R & D for Optoelectronics INOE 2000, Magurele, Romania

105

The crystallization behaviour of aluminophosphate glasses belonging to the Li2OBaOAl2O3La2O3P2O5 system and containing Eu3+ ions has been studied using differential scanning calorimetry (DSC), X-ray diff raction
(XRD) and scanning electron microscopy (SEM). The crystallization kinetics under non-isothermal conditions
was investigated from the results obtained by DSC at different heating rates, and the activation energy of crystallization and the Avrami parameter (n) were determined. The activation energy value was 225kJ/mol, and n
was approximately 1 suggesting surface crystallization. The crystalline phases produced by heat treatment of the
glasses were identified by XRD. Aluminium phosphate (AlPO4) and aluminium metaphosphate (AlP3O9) were
present after treatment at 600C, and two additional minor phases, barium phosphate (Ba 2P2O7) and lithium
phosphate (Li3PO4) were present at 680C. The microstructure of the crystalline phases was observed by SEM and
the development of various features under different heat treatment conditions was analysed.

Eu3+ doped 1La2O3:2WO3:1B2O3 glass

and glass-ceramic for optical application
Aleksandrov L. I.1, Iordanova R.1, Dimitriev Y.2, Komatsu T.3
1

Institute of general and inorganic chemistry, Bulgarian academy of sciences, Sofia, Bulgaria;
Department of silicate materials, University of chemical technology and metallurgy, Sofia, Bulgaria
3
Department of materials science and technology, Nagaoka University of technology, Nagaoka, Japan

This work is acontinuation of our previous investigation [1]. The glass with nominal composition 1L2O3:2WO3:1B2O3
doped with 0.01mol.% Eu2O3 was synthesized by melt quenching method. The amorphous phases were characterized
by X-ray diffraction (XRD), differential thermal analysis (DTA), UV-VIS, infrared spectroscopy (IR) and photolumi-

260

Poster Contributions

nescence spectroscopy (PL). According to the DTA date the glass transition temperature is around 570C and crystallization temperature is 674C. Structural model for the glass network was suggested on the base of IR spectral investigations. The bands from 680 to 800cm-1, can be assigned to WO4 and WO6 structural units and the bands in the range
(1,1901,380cm-1) can be associated with the presence of BO3 and BO4 polyhedral. The glass is transparent in the visible
region with typical absorption band of Eu3+ ions. Glass-ceramic consists of Eu3+ doped LaBWO6 crystals is synthesized,
and enhanced photoluminescence emissions due to the 4f transitions 5D07Fj (j=0-4) of Eu3+ ions is observed.

114

Improving the efficiency of conventional

pot furnace by batch modification
Tapasa K., Meechoowas, E., Naknikam U., Jitwatcharakomol T.
Thailand Center of Excellence for Glass, Department of Science Service, Bangkok, Thailand

The majority of glass factories in Thailand is small and medium size enterprises (SMEs), which are using the
conventional pot furnaces. According to the policy of floating price of NGV and LPG, the margin cost of glass
production is rising up to 20 %. Therefore, the manufacturers need to find the ways in order to keep the business
running. Batch modification is the effective approach to reduce the melting energy without investing in expensive
equipment. In this project, batch modification for the glass manufacturer who produces tableware is studied. For
example, wollastonite (CaSiO3) is used instead of calcium carbonate (CaCO3) in the glass batch. From the thermodynamic calculations, the glass batch with CaSiO3 exploited ahigher heat for batch-to-melt conversion than
the batch with CaCO3. The properties of the glass for new batch formula, i.e. chemical compositions, coefficient
of thermal expansion, viscosity, light transmittance and color, are shown as well as the comparison of the furnace
performance in terms of energy consumption before and after the batch modification.

119

Study of dehydration behaviour

of soda lime silica glass in float process
Miyasaka S., Hayashi Y.
Production Technology Center, Asahi Glass Co., Ltd., Yokohama, Japan

The water content profiles on top surface of commercial float glass were investigated by using SIMS and FT-IR combined methods. The water content gradually decreases with the decreasing distance from surface. The decrement of
water content may indicate that the water in glass is emitted into atmosphere during the float process because water
vapour partial pressure in atmosphere is kept very low in float bath chamber. The water content decreases within
adistance of approximately 150m from surface in case glass thickness is 3mm and 60m in case of 0.7mm.
Effect of temperature, holding time and atmosphere on dehydration behaviour of top surface was examined by
laboratory test. In laboratory test, the glass samples were prepared with uniform distribution of water content.
Samples were heated by using electric furnace with varying temperature from 600C to 1,200C and holding time
up to 72 hours in N2 or 10% H2-N2 atmosphere. For heated samples, diff usion coefficient of water in glass and
mass transfer coefficient at top surface were determined by comparing the water content profi le with diff usion
equation. The calculated water content profi le considered with temperature dependency of these coefficients and
temperature and thickness history at float process was in good agreement with measurement profile of float glass.

Tamura K., Nakamura R., Hashimoto A.

1

College of Engineering, Nihon University, Koriyama, Japan

The standard compact tension specimen, namely the CT specimen with anatural precrack, is used to measure
the fracture toughness values of industrial materials. It is easy to introduce precracks into CT specimens made of

ICG Prague 2013 261

120

Controlled precracking of glass CT specimens

and fracture toughness values

121

metal materials using fatigue tests. However, it is thought that introducing precracks into the CT specimens made
of brittle materials such as glass, ceramics, and rocks is very difficult. By the recently developed SEPB method,
namely single edge precracked beam method, the bending test using the single edge beam is being standardized.
On the other hand, we have succeeded in developing amethod that the length of the precrack can be controlled
into CT specimen made of glass, acrylic and granite. The method is as follows. First, in order to stop the progress
of the precrack, the frictional force of the compression is produced at the surface of the CT specimen. Then in
order to generate the precrack into the CT specimen, atensile load is produced by the test machine. The characteristics of this method are that the precrack is almost straight, the precrack is perpendicular to the face of the CT
specimen, and the length is controllable.
This paper presents the experimental results not only concerning precracks introduced into glass CT specimens
by using the developed method, but also concerning fracture toughness values measured by using glass CT specimens with the precracks. The experiments were carried out using Soda-lime glass having various thicknesses. The
experimental results were compared with the precracks indicated in the previous paper. Then, it was concluded
that the precracks introduced into glass CT specimens showed good reproducibility and that the fracture toughness values were within the range of expected values for the glass.

Glasses of PbO(ZnO) Sb2O3 P2O5 systems

Holubov J.1, ernoek Z.1, Rsslerov I.1, ernokov E.2
1

Department of General and Inorganic Chemistry, Faculty of Chemical Technology,

University of Pardubice, Czech Republic.
2
Joint Laboratory of Solid State Chemistry of Institute of Macromolecular Chemistry
of Czech Academy of Sciences, v.v.i., and University Pardubice, Czech Republic.

124

The glasses of compositional series (50-x) PbO (ZnO)-xSb2O3-50P2O5 (x=0, 5, 10, 15, 20, 25 and 30) were prepared
and their thermoanalytical properties and structure were studied by differential scanning calorimetry, thermodilatometry, Raman and UV/VIS spectroscopy.
Using DSC and dilatometry it was found that glass transition temperature of these two glass-forming systems depends on the content of Sb2O3. Supercooled melt of the lead-phosphate system crystallized during heating, the
crystalline phases were identified by XRD and Raman spectroscopy as Pb(PO3)2 and SbPO4. Supercooled melt
of zinc phosphate glasses are thermally stable, only the melt with the highest content of antimony crystallizes
partially forming SbPO4. Raman spectrum showed that the addition of antimony trioxide induces the initial depolymerization polymetaphosphate network in both systems. Measurement of UV-VIS spectra allowed
estimation of the optical gap width and its compositional dependence for both glass-forming systems. Th is
can be explained on base of supposition that localised states at the top of valence band are formed by Sb(III)
non-bondig electron pair. In summary it has been found that the studied properties of the two systems are
fundamentally influenced by antimony.

Fused silica containing powders for low sintering

(1650C) mullite-zirconia composites
Sojref R.1, Schreiber R2., Makrlik A.2, Schadrack R.1, Mueller R.1
1
2

BAM Federal Institute for Materials Research and Testing, Berlin, Germany;
TKC-Technische Keramik GmbH, Meissen, Germany

Mullite and mullite-based composite ceramics are used in applications demanding materials with improved thermal shock behaviour compared to widely used alumina or zirconia ceramics. Factors influencing synthesis and
sintering of mullite are widely discussed in scientific literature. Nevertheless, manufacturing of dense, high-purity, low-sintering mullite ceramics from readily available raw materials is still an issue.
In this work, fused silica, corundum and zirconia submicrometer-sized powders were mixed with stoechiometric
composition of mullite. Small quantities of commercially available mullite were added as crystallization seeds.
Powders suitable for reaction sintering to dense ceramics could be attained by mean of stepwise dispersant-aided
desagglomeration of the components followed by careful mixing and drying. Critical factors for manufacturing
dense mullite ceramics from oxidic components were identified, as the choice of submicrometer-sized raw mate-

262 Poster Contributions

rials, appropriate dispersion of powders and stabilization against re-agglomeration, addition of mullite crystallization seeds and prevention of demixing during drying.
It could been shown that reliable processing of oxide powder mixtures is akey factor in manufacturing of dense,
low-sintering mullite-based ceramics with high mechanical strength.

125

Structure and properties of lead borophosphate

glasses modified by tellurium dioxide
Rsslerov I.1, Koudelka L.1, Moner P.1, ernoek Z.1, Montagne L.2, Revel B.2
1
2

University of Pardubice, Faculty of Chemical Technology, 532 10 Pardubice, Czech Republic

University of Lille, 59655 Villeneuve d`Ascq, France

Phosphate glasses doped with TeO2 are characterized by many interesting properties as low melting temperature,
good infrared transmissions and high dielectric constant. These glasses with TeO2 offer awide range of perspective applications such as optical materials used in laser technology and glass fibers for infrared optics. The effect
of TeO2 additions on the properties, thermal behavior and structure of lead borophosphate glasses was studied
in the compositional series (1-x)[50PbO-10B2O3-40P2O5]-xTeO2 in abroad concentration range of x=070mol%
TeO2. Glasses were prepared from reagent grade PbO, H3PO4 H3BO3 and TeO2. Glass density of the prepared
glasses increases slightly with increasing TeO2 content from 5.0g.cm-3 (x=0) up to 5.5g.cm-3 (x=70), whereas
molar volume Vm decreases within the range 35.130.0cm3.mol-1. Thermal properties of the prepared glasses were
studied by differential thermal analysis and dilatometry. From the thermoanalytical curves the glass transition
temperature Tg, dilatometric softening temperature Td and coefficient of thermal expansion were determined.
The structure was studied by Raman spectroscopy. According to the Raman spectra TeO2 is incorporated in the
structural network of these glasses in the form of TeO3, TeO3+1 and TeO4 structural units. At low TeO2 content
(x=1040mol% TeO2) trigonal pyramidal units TeO3 prevail in the glass structure as dominant units, while at
x=4070mol% TeO2 their transformation to TeO4 trigonal bipyramidal units takes place. The incorporation of
tellurite structural units is accompanied by the depolymerization of phosphate chain structure.

Matsuyama T., Sakuda A., Hayashi A., Tatsumisago M.

Osaka Prefecture University, Osaka, Japan

Amorphous titanium trisulfide (TiS3) as an electrode active material was prepared by amechanical milling technique from aequimolar mixture of TiS2 and S. The amorphous TiS3 was applied for bulk-type all-solid-state lithium secondary batteries using sulfide solid electrolytes. The diff raction peaks attributable to crystalline TiS2 and S
gradually decreased with an increase in the milling time and halo pattern was almost dominant after milling. Raman bands attributable to TiS3 were observed in the milled sample, suggesting that the amorphous TiS3 was prepared by milling. Charge-discharge measurements of the cells Li-In / 80Li2S20P2S5 glass-ceramic / amorphous
TiS3 were carried out at the current density of 0.064mA/cm-2 at 25C. The initial discharge capacity of the cell
using the amorphous TiS3 was approximately 400mAh/g-1. The all-solid-state cell using the amorphous TiS3 retained ahigh capacity of over 320mAh/g-1 after 10 cycles. The structure change of the amorphous TiS3 before and
after charge-discharge tests was evaluated by XRD and Raman spectroscopy. The XRD pattern of the electrode
after the initial charge-discharge measurement was similar to the pattern before the measurement; the crystalline
peaks due to titanium sulfides active materials were not observed. The Raman spectrum of the electrode after the
measurement was similar to that before the measurement. These results suggest that the structure of amorphous
TiS3 electrode did not largely change during the initial charge-discharge process. The all-solid-state cells with the
amorphous TiS3 as an electrode showed good cyclability, because the amorphous TiS3 active material retained its
structure during the initial charge-discharge measurement.

ICG Prague 2013 263

128

Structural analyses of amorphous titanium trisulfide

electrodes in all-solid-state lithium secondary batteries

129

Preparation of Li2S-GeS2-P2S5 glass electrolyte

thin films using pulsed laser deposition
Ito Y.1, Sakuda A.1, Ohtomo T.1,2, Hayashi A.1, Tatsumisago M.1
1
2

Osaka Prefecture University, Osaka, Japan;

Toyota Motor Corporation, Shizuoka, Japan

131

All-solid-state lithium secondary batteries using inorganic solid electrolytes have been widely studied as next
generation batteries. Solid electrolyte thin films are useful for bulk-type batteries with an ideal electrode-electrolyte interface. We reported the preparation of amorphous 80Li2S20P2S5 (mol%) solid electrolyte thin films for
surface-coating on LiCoO2 particles by pulsed laser deposition (PLD). In order to improve the battery performance, solid electrolyte thin films with higher lithium-ion conductivity are indispensable. We focus on so-called
mixed anion effect to increase ionic conductivity of glass electrolytes. In this study, xLi4GeS4(100-x)Li3PS4
(x=25~75mol%) solid electrolyte thin fi lms were prepared using PLD. Morphology, chemical compositions and
ionic conductivities of the thin films were investigated.
Amorphous Li4GeS4-Li3PS4 solid electrolyte thin films prepared by PLD were dense and attached firmly to aSi
substrate. The 33Li4GeS467Li3PS4 (mol%) thin fi lm showed glass transition phenomenon at 160C, suggesting
that the obtained amorphous fi lm was in aglassy state. Raman spectra showed that the thin fi lm was mainly
composed of Li+, GeS44 and PS43 units. The thin fi lm exhibited higher ionic conductivity than the Li4GeS4 and
Li3PS4 thin fi lms. Furthermore, crystallization of the thin film increased ambient temperature conductivity from
1.110-4 S cm-1 to 1.810-3 S cm-1.

Preparation of glass surface

for Sol-Gel derived thin films
Setina J., Mezinskis G., Gabrene A., Pludons A., Juhnevica I.
Institute of Silicate Materials of Riga Technical University, Riga, Latvia

Obtaining thin films on the glass using Sol-Gel technology, needs special preparation of surface. There were
different chemical methods for surface preparation of glass microscope slides adopted such as cleaning by ultrasonic treatment in organic solvents, or etching in NaOH, H2SO4, HF. Etching methods enlarge surface area
and generate anew surface by removing material from original glass. Products of interaction with surface and
etching media have been removed by washing slides in different regime with C2H5OH or mix of C2H5OH/HCl.
The glass surface was examined by AFM, SEM, XRD. The obtained results illustrated that surface property and
morphology of glass are changed by all methods of etching. Hydrothermal treatment with NaOH caused hydroxyl ion attack to silica network, converting bridging oxygen into anon-bridging one, thus disrupting the network.
Gel-like layer formed during etching by NaOH solution typically provided smoothening effect of surface. Topography and measurements of surface roughness obtained by AFM showed channel like structure, etched layer was
24nm in depth with an average roughness 1.71.8nm. Structured glass surface with holes and cavities could
be obtained by combinations of etching media (H2SO4 or HF) and treatment regimes. The atomic percentage of
sodium on surface decreases by treatment with H2SO4. Amount and size of cavities has been handled by etching
time and depth of cavities increased up to 78nm. Treatment with HF decreased amount of Si on surface and
created cavities or holes. The depth of holes and surface roughness depend on concentration of acid, AFM showed
average roughness 2.16.8nm.
The deposition and immobilization of magnetite nanoparticles on etched glass surface was performed by Sol-Gel
dip-coating method.

264

Poster Contributions

134

Characterization of sintered glass-ceramic

tile glazes containing wastes
Wasylak J., Reben M., Lisiecki M., Kuciski G.
AGH University of Science and Technology, Faculty of Materials Science and Ceramics,
al. Mickiewicza 30, 30-059 Cracow, Poland

The present paper discusses sintered glassceramics with attractive appearance, which are formed with use of
industrial wastes such as: Cathode Ray Tube (CRT) glass cullet mixed with calsiglass and fluidized bed combustion slag (FBCS). The crystallisation behaviour of the material was evaluated by DTA and XRD, while the
microstructure was observed by SEM microscope. The studied glass-ceramic system exhibits ahigh resistance to
abrasion and surface scratches thanks to the diopside and wollastonite crystals formed during firing. The final
products (tiles) were characterized in terms of microstructural changes and phase formation and hardness. Due
to high content of barium oxide in the CRT glass cullet the chemical durability of tiles was characterized by toxic
characteristics leaching procedure (TCLP). The test indicate that the amount of barium leached from aglazed
tiles containing 2.08% of barium oxide is very low. Traditionally, ceramic products have been created using raw
materials that require high firing temperatures and intensive processing steps. Sintered ceramic tiles produced
from wastes offer the same quality as traditionally manufactured tiles, but require substantially less energy to
produce. Our studies have demonstrated that products created using the new processing method are less sensitive to contaminants in the glass cullet and can be made from CRT waste glass, which are difficult to recycle. The
sintered materials were found to be good candidates for building applications (tiles, bricks, etc.), i.e. they showed
large compressive strength for practical use.

Taylor T.1, Harrison M. T.1, Steele C. J.2

1
2

National Nuclear Laboratory, Sellafield, United Kingdom;

Sellafield Ltd, Sellafield, United Kingdom

The Waste Vitrification Plant (WVP), operated by Sellafield Ltd, converts Highly Active Liquor (HAL) from the
reprocessing of spent nuclear fuel in the UK into avitrified product suitable for safe interim storage with aview
to its ultimate disposal in ageological repository. One of the important aspects to understand in relation to the
disposal of HLW glass is its behaviour over long timescales in aqueous conditions and, to this end, aprogramme
of non-active laboratory-based leach tests is currently being undertaken. The aim of these tests is to determine
the envelope of behaviour of the expected range of WVP glass compositions using astandard test protocol, i.e.
the ASTM Product Consistency Test (PCT). From the results obtained to date for test durations up to six months,
the long-term durability of standard UK vitrified HLW depends on anumber of key species, namely: aluminium,
lithium and magnesium, as the concentration of these can vary significantly from one WVP campaign to the next
depending on the HAL feed. For example, all UK vitrified HLW produced to date contains magnesium from the
reprocessing of Magnox reactor spent fuel, with aconcentration ranging from ~1 to 8 oxide weight%. This could
yield awide range of dissolution behaviour due to the complex role of magnesium in determining the aqueous
durability of borosilicate glasses. Hence, this paper reviews the PCT response for awide range of simulated WVP
vitrified product as afunction of their magnesium content with aview to improving the understanding of the
potential impact of this element on the disposability of UK HLW glass.

ICG Prague 2013 265

137

Investigation of the role of magnesium

in the durability of UK vitrified high level waste

144

Cords at the tableware glass melting

composition and potential sources
imurka P.1, Kraxner J.1, Vrbel P.2, Pauo T.2
1
2

Institute of Inorganic Chemistry of Slovak Academy of Science, Bratislava, workplace Trenn, Slovakia;
Rona a.s., Lednick Rovne, Slovakia

145

Homogeneity of glass is an essential parameter in glass manufacturing in order to provide required mechanical and
optical properties of the product. Apresence of inhomogenities at final products during industrially glass melting
results to the lower efficiency of production. Aknowledge of their origin can help make glass production effective.
One of the main sources of defects in glass melts is the corrosion of materials used, especially of refractories.
The impact of refractory corrosion on the quality of glass and evolution of defects is the subject of this work. An
occurrence of inhomogeneities in different stages of tableware glass production is evaluated. Samples of the final
products containing different types of inhomogeneities are collected during regular production in aperiod of 24
months and analyzed by SEM and EDX analysis.
Main types from the point of chemical composition are determined and the origin and source of these inhomogeneities is identified in connection with refractories used in aglass furnace.

The structure of Na2OAl2O3B2O3 glasses

at the sub-nanometric level
Dumitrescu O, Radu D.
University "POLITEHNICA" of Bucharest, Faculty of Applied Chemistry and Materials Science, Oxide Materials Science & Engineering and Nanomaterials Department., P.O.Box 12-134, Bucharest, ROMANIA

146

The glasses within Na 2O Al 2O3 B2O3 system show both practical and theoretical interest. The theoretical
one is motivated by the possible change of the coordination number for boron and aluminium as afunction
of actual chemical composition. Therefore it is to be expected that compositional and structural changes will
modify the glass properties.
While in the aluminosilicate glasses Al4 formation happens prior to all other net formation processes, in the
aluminoborate glasses Al and B compete almost equally as modifying oxide. The final ratio between the two conversion processes (B3 B4 and Al6 Al4) depends on the cation nature too. Na favour Al conversion resulting
in ahigher Al6 percentage in the structure.
Six glasses from the Na2O Al2O3 B2O3 ternary system were synthesized, with the molar formula: (35-x)Na2O.
xAl2O3.65B2O3 (x=0; 5; 10; 12.5; 15; 17.5 % mol.). In order to characterize the sub-nanometric structure of the
prepared glasses, several properties were determined: Tg, Tsoftening, linear thermal expansion coefficient, refractive
index, and density.
In this paper the coordination number of B and Al were determined using experimental measurements of glass
basicity (evaluated with the basicity percentage, pB)

Gel formation in the TeO2-TiO2-SeO2 system

Iordanova R. S. 1, Gegova R. D.1, Bachvarova-Nedelcheva A. D. 1, Dimitriev Y. D.2
1
2

Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria;
University of Chemical Technology and Metallurgy, Sofia, Bulgaria

The Sol-Gel processing offers an attractive route for the fabrication of TeO2-based materials but most of the authors
applied it mainly for obtaining of thin films. It was found that the addition of second component improve the thermal stability of TeO2 thin films. Up to now, the investigations concerning bulk and powder materials are scarce.
The purpose of this study was to verify the gel formation tendency in the TeO2-TiO2-SeO2 system applying aqueous Sol-Gel method. In order to overcome the problem with hydrolysis of tellurium alkoxides, the telluric (VI)
acid (H6TeO6) along with selenium oxide (SeO2) and titanium butoxide were used as anew combination of precursors during the synthesis. The structure and optical properties of several representative compositions with dif-

266

Poster Contributions

ferent TeO2:TiO2:SeO2 ratios were studied. The crystallization tendency of the powders in the temperature range
300900C was investigated. By XRD analysis was established that the crystallization process started at heat
treatment above 300C and mixtures containing TiO2 (anatase), -TeO2 and TiTe3O8 were obtained depending on
composition and heating temperature. IR spectroscopy showed that the organic constituents existed below 400C
and characteristic bands for -TeO2 and TiTe3O8 appeared at 500 and 600C. Samples with lower TeO2 content
exhibited better absorbance in the UV spectral region than those rich in TeO2.

147

Crucial influence of impurity content

on quality of chalcogenide glasses
Churbanov M. F.1, Shiryaev V. S.1, Plotnichenko V. G.2
1

G. G. Devyatykh Institute of Chemistry of High-Purity Substances of the Russian Academy of Sciences,

49 Tropinin Str., 603950 Nizhny Novgorod, Russia
2
Fiber Optics Research Center of the Russian Academy of Sciences, Moscow, 119333, Russia

Chalcogenide glasses are promising optical materials for transmission of radiation of the mid-infrared. There are
alot of chalcogenide glasses based on sulfides, selenides and tellurides of arsenic, germanium, and other elements
used or developed for various functional applications. anumber of properties of chalcogenide glasses exhibit high
impurity sensitivity. Dissolved impurities reduce the transparency range and transmission; change the physical,
chemical and electrical properties. Heterophase impurity inclusions cause scattering of radiation, heterogeneous
crystallization of glasses, reducing of laser damage resistance and mechanical strength. The factors determining
the purity and micro-homogeneity of glasses are: elemental composition, content and the molecular form of impurities, the synthesis temperature of glass-forming melt, the conditions of the cooling, the entrance of impurities
from the reactor wall to the melt, micro-inhomogeneities in the form of nanoscale heterophase inclusions and
striaes, the tendency of glasses to micro-phase separation and crystallization, the presence of homo-bands and
macro-components with high volatility. The influence of impurities on the optical properties is most noticeable
in the optical fibers. The minimum content of impurities in our prepared high-purity glasses based on arsenic
chalcogenides for optical fibers is following: transition metals <0.01ppm, oxygen and hydrogen <0.5ppm, carbon 0.5ppm, silicon 0.2ppm wt, heterophase inclusions <104cm-1. From these glasses the optical fibers are
produced with optical losses of 12100dB/km. The report gives the current status and ways to improve the purity
of chalcogenide glasses.

163

Multi-glasses optical fiber

for electro-optical applications
Rioux M.1-2, Ledemi Y.1, Viens J.1, Gravel J.-F.1, Lessard F.1, Messaddeq Y.1
1
2

Research Center on Optics, Photonics and Lasers (COPL), Quebec, Canada;

Chemistry department of Laval University, Quebec, Canada;

The conception of acomposite fiber that can be used to transmit both light and electricity represents one of many
challenges in the field of multifunctional fibers and electro-optical applications. Indeed, since the material selected to ensure the electrical properties will have to be shaped into afiber, it must necessarily be amorphous and not
crystalline. This property therefore is essential in the realization of electro-optical fibers. Today there are several
ions conducting amorphous materials, but the most conductive ones at room temperature are based of silver or
lithium (eg AgI-Ag2MoO4, AgI-AgPO3-MOx, AgI-Ag4P2O7, LiCl-Li2O-B2O3, LiI-Li2S-P2S5). As part of this project,
we focus mainly on silver iodide based glasses because they are the ones with the highest ionic conductivities at
room temperature and also because the lithium-based glasses are generally more hydrophilic, which affects the
durability of glass. For the transmission of light, transparent glasses made of NaPO3 and Nb2O5 are developed for
the core/cladding part of the fiber. In addition, another goal of the project is to develop amethod to obtain avery
good chemical durability for these glasses. Finally, the technique that will be used to manufacture the preform,
composed of three different glasses, consist of acylindrical mold with adjustable piston.

ICG Prague 2013 267

178

New opportunities of improvement

of chalcogenide glasses
Priven A. I.
Institute of Theoretical Chemistry, Newton, USA

183

Chalcogenide glasses have some specifics comparing to other types of inorganic glasses. One of their specific
features is a typically very sharp form of concentration dependences of physical properties, with multiple extremes, breaks etc. Simulation of such dependences is difficult; as aresult, it is difficult to predict the properties of
new glasses with prospective combinations of properties. The approach based on asimplified model of chemical
interaction between the components of chalcogenide glasses allows quantitative simulation and prediction of
various properties (density, glass transition temperature, coefficient of thermal expansion, refractive index etc.)
of chalcogenide glasses containing up to 16 chemical elements. The suggested model allows the transition from
trial-and-error method to directed search for new glasses with improved properties. Some statistical data about
the accuracy of property calculations are given basing on the published property data for about 10,000 glass compositions presented in the SciGlass Information System.

AFM study of surface properties of TiO2 films on glass

Pagov J.1, Plko A.2, Michalkov K.2, Tomagov M.2, Bielikov B.2
1
2

Faculty of Industrial Technologies, University of Alexander Dubcek in Trencin, Puchov, Slovakia;

University of Alexander Dubcek in Trencin, Trencin, Slovakia;

190

The functionalization of glass surface using the films prepared Sol-Gel method is useful to modify of various properties of glass. The composition sol as well as time from its preparation influences markedly the stability of sol and
consequently the properties of film. In this work the TiO2 sols were prepared by the Sol-Gel method and dip-coating
technique was used for preparation of films. The TiO2 films were made of sols with different aging time (013 days)
and they contained the addition of stabilizing reagent (acetylacetone or acetic acid). The influence of composition
and aging of TiO2 sols on properties of glass surface coated with films (morphology, topography, adhesive forces) was
studied using atomic force microscopy. The observed differences of surface properties of films could be explained by
help of growth of particles in sols as well as by processes during thermal treatment of xerogels.
Acknowledgement: This work was supported by the Grant Agency of the Slovak Republic Grant No. 1/0559/11,
by the project APVV-0487-11 and by the project CEKSiM, ITMS code 26220120056, of the Operational Program
Research and Development funded by European Fund of Regional Development.

Influence of sol composition and aging process

on the properties of TiO2 layers on glass surface
ulcov J.1, Pagov J.1, Bielikov B.2, Michlkov K.2, Tomagov M.2, Plko A.2
1
2

Faculty of Industrial Technologies, Alexander Dubek University of Trenn, Pchov, Slovakia

Alexander Dubek University of Trenn, Trenn, Slovakia

Modification of glasses by deposition of layers on their surfaces is still very important and commonly
used tool for adjusting the glass surface properties for particular practical application. Oxide layers on
glasses are prepared preferably by the Sol-Gel method. During deposition of oxide layers on the glasses
surface it is possible to control their resultant properties by thermal treatment, but mainly by the composition of the sol as well as by the time, that lapses from the sol preparation to its usage (aging of the sol).
We have investigated the inf luence of sol composition and its aging on the surface forces of TiO2 layers on
glass. For preparation of TiO2 layers there were used sols from titanium isopropoxide, isopropanol, nitric
acid, water and additives. Additives were used for modification of the sol aging process and inf luence
simultaneously the size of TiO2 particles. Layers were prepared from three sols: without additives, with
acetylacetone, and with acetic acid, respectively. From these sols, the layers were prepared in different
times from sols preparation. The contact angle of water and diiodomethane was measured to identify the

268 Poster Contributions

polar and disperse components of surface tension. The relation between disperse components of surface
tension and nanoroughness determined by AFM is discussed.
Acknowledgement: This work was supported by the Grant Agency of the Slovak Republic Grant No. 1/0559/11
and project APVV-0487-11.

194

Optical phosphate glasses doped with rare-earth

ions. Obtaining, structure and properties
Sava B. A.1, Boroica L.1, Elisa M.2, Beldiceanu A.3, Iordanescu R.2, Feraru I.2, Medianu R.1
1

National Institute for Laser, Plasma and Radiation Physics, Magurele, Bucharest, Romania;
National Institute of Research & Development for Optoelectronics INOE 2000, Magurele, Romania
3
Pro Optica S.A., Bucharest, Romania

The paper presents astudy on the preparation and characterization of optical phosphate glasses from the oxide
system Li2O-BaO-Al2O3-La2O3-P2O5, doped with 3mol.% rare earth ions, Dy and Tb, respectively. Mechanical
stirring of the melt was applied in order to obtain an optical quality glass. The optimum duration and rate of
the stirring were established. Annealing program was designed aiming at preserving the optical properties of
the obtained glasses. The program intends to avoid cracks on one side and to eliminate the possibility of glass
crystallization on the other. The optical homogeneity and the birefringence were evaluated by the polariscope
method based on interference in polarized white light which put in evidence the presence of stresses in the glass
bulk. The bubbles and other inclusions were detected by the microscope based on diffraction in polarized light.
Refractive index and dispersion for six different values of the wavelength have been determined by means of Abbe
and Pulfrich refractometers. Other defects in glasses were investigated by scanning electron microscopy (SEM)
and energy-dispersive X-ray spectroscopy microanalysis (EDX). The optical transmission in the visible range
was also measured. Structural investigations on the optical phosphate glasses were made by Infrared and Raman
spectroscopy and meta-phosphate chains were identified as network major structural units. The improvement of
the optical properties of the glasses obtained by this melting-stirring method was put in evidence comparatively
to the not-stirred glasses available. The rare-earth-doped phosphate glasses of optical quality can be used as optical displacement sensors and Faraday rotators due to their magneto-optical properties.

Netusilova M.1, Rohanova D.1, Novak P. 1, Klimov M. 2, Helebrant A.1

1
2

Faculty of Chemical Technology, Institute of Chemical Technology, Prague, Czech Republic;

University of Central Florida, Orlando, USA (Florida)

The GD-OES (Radio Frequency Glow Discharge Optical Emission Spectroscopy) was used except the standard
methods (SEM/EDS, OM, XRF) for the evaluation of the corrosion processes on the glass. The glass Float (AGC
Flat Glass Czech a.s.) has been exposed into demineralised water for the period from 1 to 12 weeks at 37C.
The S/V ratio was 60m-1 (S: sample surface area to V: volume of corrosion solution). The tests were performed
under static conditions (in the biological thermostat) or in a laboratory shaking machine (150rp.min-1). Both
SEM-EDX and XRF method didnt detect any considerable changes in the chemical composition on the surface and even depth-profi les measured by SIMS didnt changed distinctively. The GD-OES method analysing
the elements concentration (by optical emission spectrometry) was only able to detect slight changes in the
glass sample surface. Moreover, compared with similar methods (SIMS, ESCA) the analysing rate was higher
and allowed the measurement into the great depth of the sample surface (of the order 10m). The disadvantage of GD-OES method is the specific demands on the sample (perfect flatness and sufficient dimensions
of the sample surface) and moreover each measurement is destructive for the glass sample. The depth-profi le
of moveable Na (at the Float glass surface) changed remarkably depending on the corrosion time.
The depth-profi le of Si as well as Ca also changed reproducible but not so significantly. The formation
of the solution layer with highly corrosion effect near the glass surface under static conditions was also confirmed.
The methods of the solution analysis (AAS, ICP, pH measurement) together with the surface analysis by GD-OES
give important information for the description of the changes caused by the action of corrosion medium.

ICG Prague 2013 269

201

Corrosion of float glass analysed by GD-OES method

211

Structure and properties of silver

borophosphate glasses modified by TeO2
Vorokhta M., Moner P., Koudelka L., ernoek Z.
Faculty of Chemical Technology, University of Pardubice, Czech Republic

212

The work deals with the study of the effect of TeO2 on the structure and properties of silver borophosphate glasses
prepared in compositional series (100-x)[0.5Ag2O-0.1B2O3-0.4P2O5]-xTeO2 in aconcentration range of x=080mol%
of TeO2. Glasses were characterized by the measurements of density, molar volume and chemical durability. Thermal
properties were investigated by DTA, TD and HMTA methods. Their structure was studied by Raman spectroscopy. The obtained Raman spectra showed that the structure of 50Ag2O-10B2O3-40P2O5 glass is formed especially by
metaphosphate structural units (Q2) and diphosphate structural (Q1) units connected through P-O-P bridges. The
replacement of PO4 structural units by tellurate units is accompanied by the gradual depolymerization of phosphate
chains. At ahigh TeO2 content isolated PO4 tetrahedra are predominantly formed in the structure of glasses. Tellurium
oxide is incorporated in the structural network in the form of TeO3 trigonal pyramids and TeO4 trigonal bipyramids.
The ratio of TeO4/TeO3 structural units increases with increasing TeO2 content. The incorporation of TeOx structural
units into the starting 50Ag2O-10B2O3-40P2O5 borophosphate glass results in agradual decrease of their molar volume
within the range of 39.2-30.8cm3 mol-1 while their density increases. All glasses exhibit good chemical durability against
water corrosion. Thermoanalytical measurements showed that most of prepared glasses crystallize under heating in
the temperature range of 410520C and the surface nucleation mechanism prevails over the internal one. The highest
thermal stability and the lowest tendency towards crystallization were observed for the glasses with nominal TeO2
contents between 40 and 60mol% TeO2. Glass transition temperature and dilatometric softening temperature increase
with increasing TeO2 content, whereas thermal expansion coefficient decreases.

Formation and structure of sulfophosphate glasses

Mncke D.1, Kamitsos E. I.2, Wondraczek L.1
1
2

Otto-Schott-Institute, Friedrich-Schiller-University Jena, Germany

Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, Athens, Greece

215

Ionic sulfophosphate (SP) glasses of the system Na2SO4-Na2O-ZnO-P2O5 are interesting for applications as low
temperature sealing glasses, as well as for their high optical basicity, high polarizability and their capacity to
incorporate high concentrations of transition metal ions. SP glasses show also high photosensitivity upon irradiation and are currently studied for use as photochromic glasses.
The understanding of glass structure and of structure-property correlation in SP glasses is therefore central for an optimal utilization of this glass system for different applications. Preliminary crystallization experiments have shown that
Na+ ions charge-balance the sulfate anions, while Zn2+ ions were found in the vicinity of phosphate groups.
Infrared reflectance and Raman spectroscopy were used in this study to examine the glass structure, which
was found consists of pseudo spherical interstitial SO42 anions and phosphate groups which include, depending on glass composition, metaphosphate (Q2), pyrophosphate (Q1) and orthophosphate (Q0) entities (Qn indicates aphosphate tetrahedral unit with n bridging oxygen atoms). The weak IR activity of the totally symmetric
stretching mode (1) and the splitting of the asymmetric stretching mode (3) of the sulfate entities allows to asses
the deviation from tetrahedral symmetry. Shifts in the band position of the 1 mode may also be used to monitor
changes in the fictive temperature during glass preparation.

Assessment of batch melting behaviour a poster

how to close the gap between lab and industrial scale
Peters-Niessen V., Conradt R.
RWTH Aachen University, Institute of Mineral Engineering, Department of Glass and Ceramic Composites

Much effort has been invested by our research team, as well by other research groups, to establish ahighly effective arsenal of approaches to the melting behavior of industrial batches. Therefore the laboratory experiments will
be scaled up from milligram to the kilogram scale.

270 Poster Contributions

On the micro scale the batch will be analysed by using DTA-TG and Hot-Stage Microscopy, which involve small
sample sizes (<1g) for investigation of physical reactions of unary, binary and ternary batch systems. On the meso
scale with Conductometry and modified Batch-Free Time the local progress of batch reactions will be identified.
The methods yield fingerprints of the local melting process allowing to quantitatively compare the local reaction
rate in terms of water release, primary melt formation, rough melt formation and amount of residual solid and
bubbles. With the 10kg Test on the macro scale abatch blanket 5cm high is exposed to radiative heating from
above and to heating via batch-to-melt contact from below. The industrial scale comprised afurnace performance
analysis. agiven batch does not perform in the same way in all glass furnaces. Rather, the power vs. pull rate
characteristics of agiven furnace determine, which aspect of local kinetics, heat transfer or chemical turnover, is
rate controlling in areal furnace.

219

Photochromic fluorine-containing alkali borate glasses

Matevosyan A. B., Harutyunyan N. M., Knyazyan N. B.
Institute of General and Inorganic Chemistry, Yerevan, Armenia

The phase diagram and glass forming range of the LiF-Al2O3-B2O3 system have been investigated. The behavior of
transparent and liquating glasses by heat treatment, crystallization products, as abase for photochromic glasses
preparation, correlation between structure and photochromatic properties of glasses were studied as well. The
glass synthesis were conducted in electric furnace with carborundum heaters at the temperature 1,1001,250C
in platinum crucible during 4550min. The cooling rate of melt was ~102Cs-1. The derivatograph Q-1,500 with
platinum crucible used for DTA investigation of glasses at heating rate 15C/min. Formation of microseparative
ranges, phase boundaries and growth of crystalline phase up to nanosize particles caused promotes to obtain
nanosize (10100nm) uniformly spreaded crystals, without any other additional crystallization catalysts in the
glass matrix. This is the main importance in the polycristalline transparent glass structure. It is found that metastable liquation in the glass structure caused by incompatibility of Li(O,F)4, l(O,F)4, B(O,F)3 groups. Decreasing
of photochromic glass absorption intensity with inceasing of fluorine-containing oxyaluminate groups is due to
high solubility of colloidal mass (absorbtion photosensitive phase) in high alumin-containing fluorborate glass.
As result the base oxyfluoride glass was developed as abase for preparation crystal and transparent glasses with
temperature coefficient of thermal expansion from 15 to 28.10-7-1, and high transparency in visible regions of UV
spectrum. This glasses have low temperature of melting and two stage crystallization (450475 and 580600C).
Synthesized glass-ceramics are prosperous as thermostable substrates and covers for electric setups. Photochromic glasses have wide application as materials for recording information in storage devices.

220

Glass formation and properties

of glasses in lanthanum borate system
Kocharyan G. A.
Institute of General and Inorganic Chemistry, Yerevan, Armenia

The development of optical engineering needs new glasses with improved optical and physico-chemical properties. It is known that PbB2O4-La 2O3-LiF system glasses serves as base for preparation fl int glasses with reduce
relative dispersion in the blue part of spectrum. In this work the range of glass formation and melting diagram
in the PbB2O4-La 2O3-LiF system were investigated. The physico-chemical properties of glasses were studied depends on composition and temperature. Glass synthesis were carried out in corundum and platinum crucibles,
in the temperature range 1,0501,300. The losses during melting processes were calculated and corrected by
chemical analysis. The phase formation process at heat treatment of initial components and glass transition of
melts were studied by DTA and XRD methods. The wide range of glass formation have been revealed at combined insertion of La 2O3 and LiF, which conditioned by increasing of the possibility of formation of different
oxygen and oxyfluoride structural groups. With different binding energy favour the glass formation of melt.
The range of jamming glasses at high concentration of LiF associated with formation of LiF4, which is structurally not compatible with borate groups. The new ternary congruently melting compound LiPb2La 2B 4O11F was
revealed. The crystallization field of this compound located in the middle of the glass formation range. The

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glasses comparative resistant to crystallization formed near the ranges of binary and ternary eutectic of system.
Pb2+ and Li+ combined presence in the composition as ions-modificators leeds to change of B and La ions coordination. The influence of fluoride on thermophysical properties of glasses explained as areduction of amount
of tetrahedrons B(O,F)4, formation of B(O,F)3 and B(O,F)4 groups with non bridging anions characterized with
low strength of the bonds. The possibility of Pb2+ Li+ ions to surround them by energetically favorable way,
making unequal structural fragments Pb-O-BIII-O(F)-, Pb-O-BIV-O(F)-, Li-O-BIII-O( F) Li-O-BIV-O(F) increase in the glass structure. The peculiarities of arrangement and spatial connectivity of mentioned coordination polyhedrons determine properties of glasses.

Effective light scattering glass material modified

by ion exchange process for lighting applications
Sidelnikova O. N.1, Pozdnyakov G. A.2, Salanov A. N.3
1

Institute of Solid State Chemistry and Mechanochemistry, Novosibirsk, Russia

Khristianovich Institute of Theoretical and Applied Mechanics, Novosibirsk, Russia
3
Boreskov Institute of Catalysis, Novosibirsk, Russia

233

The presented research data are related to soda lime silica glass modified by the surface ion exchange process. The
special features of the optical properties of the modified glass material with and without the thin surface Au layer
are described and compared with that data related to chemically etched soda lime silica glass. The glass material
modified by surface ion exchange is characterized by more effective simultaneous light transmission and light
scattering and by more strongly pronounced spectral and angular dependences of the scattered light. anoticeably greater light intensity (up to 16 times!) was found at light propagating in the full internal reflection regime.
Such optical data may be useful in technical and decorative illuminating engineering. The presented scattering
glass material can be used for manufacture in the glass production of luminaries, light screens, indicator panels,
displays, decorative or technical images on glass and elements of architectural design, glass sculptures and others.

Novel X-ray fluorescence method

for investigation of glasses: The doping effect
on chemical bonding in selenium glass
Chechetkina E. A., Kupriyanova T. A.
Institute of General and Inorganic Chemistry, Moscow, Russia

The serial X-ray fluorescent spectrometers, such as our VRA-33 Carl Zeiss Jena, have aresolution too low for adirect probing of fine bonding effects such as chemical shift. Nevertheless, there was elaborated aspecial method,
which permits to extract this information based on the measured XRF spectra. The two lines that need are the
last emission line (LEL) and the neighboring normalized line (NL); LEL corresponds to the emission from the
valence band. The integral intensities of the lines are estimated, and the resultant value R=ILEL/INL is determined.
Considering R as ameasure of the valence electron density, one can investigate afactor that probably influence on
chemical bonding in the substance under consideration.
The method in illustrated using Se-X glasses (X=S,Te,As,Ge,Cl) as an example, the X content being relatively low
(from 0.3 at% for Cl to 10% for Te). In this case LEL corresponds to the 4p1s transition, and the NL corresponds
to the 3p1s transition, the both are for Se. astrong non-linearity on the R(N) dependence, where N is the second component concentration, is observed; the extremum type and location being depending on the X nature.
For example, there is the R(N) minimum at 1%Te, but the R(N) maximum at about 0.02%Cl. The reality of the
effects is confirmed by the same location of extrema, which are observed for the same Se-X series but for the other
properties. These properties are: the ultrasound velocity and the Se vibration bands intensity in fresh samples, as
well as the crystallization features both after the room-temperature ageing and after the high-temperature (at
5077C, i.e. some above the glass transition temperature) treatment in cavitation ultrasonic field. Combining
the data one can made definite conclusion about the nature of the changes in the chemical-bonding system of

272 Poster Contributions

glassy selenium due to doping. Unusual character of the effects needs new ideas, so we used the notions about
hypervalent bonding after Dembovsky and the bond wave model after Chechetkina for interrelated interpretation
of our data from the chemical bonding point of view.

244

GeO2 doped lithium borophosphate glasses

Moner P.1, Vorokhta M.1, Koudelka L.1, Mogu-Milankovi A.2, Montagne L.3, Revel B.3
1

Faculty of Chemical Technology, University of Pardubice, Pardubice, Czech Republic

Ruer Bokovi Institute, Zagreb, Croatia
3
Unit de Catalyse et de Chimie du Solide, Univ Lille Nord, Lille, France

GeO2 containing lithium borophosphate glasses were studied in compositional series (100-x)[0.5Li2O-0.1B2O3
-0.4P2O5]-xGeO2 with x=025mol% GeO2. Glasses were prepared by slow cooling of the melt in agraphite mould
from the temperature region of 1,0001,150C and characterized by the measurements of density, molar volume
and chemical durability. Thermal properties of glasses were investigated by DTA and TD methods; their structure was studied by Raman spectroscopy, 31P and 11B MAS NMR spectroscopy. The 31P MAS NMR spectra of the
glasses show that with the replacement of the starting 50Li2O-10B2O3-40P2O5 composition by GeO2, the ratio of
Q2 and Q1 units present in the structure slightly changes. The incorporation of germanate structural units was reflected in the middle-frequency part of the Raman spectra between 450 and 750cm-1 by the presence of vibrational
modes associated with P-O-Ge and Ge-O-Ge bonds. 11B MAS NMR spectrum of the starting 50Li2O-10B2O3
-40P2O5 glass showed one narrow symmetrical signal, characteristic of BO4 units coordinated by four phosphorus
atoms as B(OP)4. Germanium forms various mixed tetrahedral units with B-O-Ge bonds, where B(OP)4 structural units are gradually replaced by B(OP)4-n(OGe)n units. Increasing GeO2 content leads also to the partial
transformation of BO4 into BO3 units in the glass structure. The incorporation of germanate structural units into
the parent borophosphate glass results in adecrease of their molar volume and chemical durability while their
density, glass transition temperature, dilatometric softening temperature and thermal stability increase. Thermal
expansion coefficient obtained by TD measurements decreases slightly from 10.7 to 6.6ppmC-1 with increasing
GeO2 content. Major compounds formed by crystallization of glasses were LiPO3, Li4P2O7, BPO4 and LiGe2(PO4)3.

246

Tungstate-tellurite glass
and fibers for Mid-IR applications
Dorofeev V. V.1, Moiseev A. N.1, Kraev I. A.1, Motorin S. E.1, Churbanov M. F.1,
Kosolapov A. F.2, Philippovskiy D. V.2, Plotnichenko V. G.2, Dianov E. M.2
1
2

Institute of Chemistry of High-Purity Substances of RAS, Nizhny Novgorod, Russia

Fiber Optics Research Center RAS, Moscow, Russia

Wide transparency range of 0.45.5m, chemical stability, high nonlinearity and high solubility of rare-earth
elements make tungstate-tellurite glass the promising material for mid-infrared fiber applications. Special interest is located at wavelengths near 3m for medical, military and research use. The main problem of all actively
investigated mid-IR materials including tellurite glasses is high hydroxyl groups absorption loss beyond wavelength of 2m. Previously we have demonstrated the effect of OH-groups removal on optical loss in binary and
multicomponent bulk tellurite glass, the aim of the present work is investigation of correlation between purity of
initial glass and optic loss in resulted fiber mainly beyond 2m.
The glasses TeO2-WO3-La2O3-(Bi2O3) of cladding and core compositions were produced inside hermetic silica
chamber in the atmosphere of purified oxygen by melting the initial superpure oxides in gold or platinum crucibles. The monolithic preforms were fabricated after melting at 800C for several hours by the simultaneous melt
extrusion technique. Hydroxyl groups absorption of n10 -3cm-1 was attained near 3m. High-quality multimode
and singlemode step-index optical fibers with low optical losses at wavelength range of 1.23m were produced.

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249

Structural transformation in float glasses

after ion exchange with copper ions
Dimitrova M.1, Ivanova Y.1, Dimitriev Y.1, Salvado I.2, Fernandes H.2
1
2

University of Chemical Technology and Metallurgy, Sofia, Bulgaria;

University of Aveiro CICECO, Aveiro, Portugal

250

Ion-exchange processes between molten salt and glass surface were performed highly intensively in the 70s of the
last century modifying of some properties: mechanical, chemical resistance and coloring. Recently ion-exchange
glasses have been increasingly investigated for new technolgical applications such as optoelectronic components,
display devices, nonlinear optical materials and planar waveguides. In our previous researches we have developed
amethod for transformation of green colored glasses obtained by ion-exchange (Cu2+ +) into red colored by
UV and X-ray irradiation at appropriate thermal treatment. ared ruby layer was formed directly without reducing agents on the float glass by treating with vapor or melts of copper chloride containing salt due to the presence
of tin. In this study we are trying to clarify the structural changes and to determine the size of the obtained
nanoparticles. By spectral methods and microscopic analysis was established the influence of temperature, time
and method of treatment (vapor or melts) on the optical properties. On UV-VIS spectra of treated samples an
absorption peak was observed at 560nm, proving the formation of copper colloidal particles, causing red coloring
of the glass. The particle size and the roughness on the background of the structure are determined by AFM.
By Photoluminescence technique are obtained emission and excitation spectra. The bands around 520nm and
270310nm are typical for Cu+ ions located in distorted octahedral sites. The structural changes in the glass matrix
were studied with Raman and IR spectroscopy. After ion exchange ashift of the main (Q3) Si-O streching band at
1,093cm 1 (1,065cm1) and Si-O bending band at 565cm-1 (476cm1) was observed due to structural transformation.
We developed amodel for the simulation of the diff usion processes and penetration of copper inside of the glass
volume depending of the time and the temperature.

Chemical composition of Bohemian potassium glass

and the corrosion manifestation on excavated glass
Rohanov D.1, Randkov S.1, Bezdika P.2, Helebrant A.1, Tomanov O.1
1
2

Institute of Chemical Technology Prague, Czech Republic

Czech Academy of Science, Czech Republic

The potassium glass was melted on the area of Bohemia and Moravia from the beginning of the glass production,
i.e. the 2nd part of thirteenth century till 18th century. No significant changes of the Bohemian glass composition
through ages are mentioned in ascientific literature. Detailed analysis of glasses from asurvey of the middle age
town waste dumps in Chrudim, Brno, Hradec Krlov and Opava and the comparison with the published data of
excavated glass showed, that the glass production technology apparently came through the three different periods, which could be approximately connected with the architectural styles (gothic, renaissance and baroque). The
glass melted at each period was different not only by shape, but also by chemical composition and the raw materials used for the batch preparation. The chemical composition is tightly bonded with the chemical durability of the
glass. Potassium glass has lower chemical durability than sodium glass, mainly because of lower ratio SiO2/R 2O
(R=Na or K). Different corrosion phenomena were observed on archaeological potassium glasses excavated from
the waste dumps. The corrosion products were studied using OM, SEM/EDS, XRF and XRD microdiff raction.
Gothic glasses were often totally corroded or affected by pitting corrosion. Dulling and iridescence are typical for
glasses from renaissance period. Precipitated layer of hydroxyapatite or carbonates were found on both of gothic
and renaissance glass. The chalk glass produced in the baroque period (without ash addition) has higher chemical durability and the corrosion in the form of light iridiscence or dulling was observed.

274 Poster Contributions

255

Al-codoping effects on optical properties

of Pr-doped silica glass
Yamzaki H., Sekiya E. H., Saito K.
Research Center for Advanced Photon Technology, Toyota Technological Institute, Nagoya, Japan;

Pr3+ is expected to be an active ion for high efficiency wideband fiber laser, because its fluorescence spectrum
doesnt overlap with absorption spectrum. Its laser oscillation has been reported already in fluoride glass, but it
has not been reported yet in the silica fiber. In silica glass matrix nonradiative transition from 3P0 to 1D2 occurs
due to multiphonon relaxation because the phonon energy of silica is high. In order to solve this problem, we
investigated the effect of Al co-doping effects on optical properties of Pr-doped silica glass, because Al co-doping
was reported to be able to suppress the multi phonon relaxation in Tm-doped silica glass. Samples were fabricated
by the MCVD process. Determination of the dopants concentration was carried out by EPMA. It was found that
Al-codoping suppresses the multi-phonon relaxtion and increases the visible emission intensity. Furthermore,
amplification performance was investigated in the Pr-Al-doped silica fiber, where excitation source was Ar-ion
laser. Signal gain of 533nm and 633nm laser could be obtained. However, the efficiency is low and saturates with
increasing the excitation laser power. The fact that wide UV-upconnversion was observed suggests that the reason
of low efficiency is ESA from 3P0 to 4f5d.

263

Modeling of forming parameters influencing optical

instability of tableware blow blow process
Kovik I., Bujnoch M., Bren M., Kremr N., Vrbel P.
RONA, Lednick Rovne, Slovakia

Optical instability of stemware is adefect causing undesirable refraction of light during horizontal rotation of the
product. Refraction is aresult of unequal wall thickness distribution around the cup. This defect is created in the
process of forming. The essence of the optical instability is the temperature inhomogeneity of the gob. Temperature
inhomogeneity causes adifferent flow rate of the glass during first blow without mould. This inhomogeneity can
come directly from the outlet of the gob feeding mechanism. Alternatively, it can be restrained or highlighted by
changing process parameters. All tools coming into contact with adrop or various settings of the blow machine are
considered here. The aim of this work is the mathematical calculation of the optimal production parameters without
primary testing in production. Mathematical model based on finite element method (FEM) was applied. Calculation of pre-pressing and blow-blow process was created for in the code MSC MARC. The model was verified with
real manufacturing conditions. The effect of different parameters on the wall thickness distribution was simulated
(such as first and second blow intensity, gob homogeneity etc). The result of this work is aquantified sensitivity to
changes in the above described process parameters on optical instability. With this tool it is possible to reduce run-in
time of the new assortments with achievement of the better optical stability of the products.

267

Surface tension of phosphate glass melts

Lissov M.1, Koudelka L.2, Lika M.1, Moner P.2, Chromkov M.1, Plko A.1
1

Vitrum Laugaricio Joint Glass Center of Institute of Inorganic Chemistry SAS, Alexander Dubcek
University of Trencin and Rona Lednicke Rovne, Studentska 2, Trencin SK-911 50, Slovak Republic
2
Department of General and Inorganic Chemistry, Faculty of Chemical Technology,
University of Pardubice, 532 10 Pardubice, Czech Republic

Surface tension was studied for the glass melts of the ternary system PbO-WO3-P2O5. Three compositional series
of glass melts were chosen: a (100-x)[(0.5PbO0.5P2O5)]xWO3 (x=0, 10, 20, 30, 40, 50, 60); B 50PbO(50-x)
P2O5xWO3 (x=0, 10, 20, 30); C (100-x) PbO50P2O5xWO3 (x=0, 10, 20, 30, 40). Surface tension of studied glass
forming melts was obtained by least squares method by comparison of measured sessile and pendant drop profi les with theoretical ones obtained by numerical integration of Laplaces equation.
Density of the melt was calculated using temperature-independent values of thermal expansion coefficients of
glass and metastable melt, glass transition temperature Tg, and the density of the glass at room temperature.

ICG Prague 2013 275

275

The detailed statistical analysis of the obtained results unambiguously demonstrated the higher reliability and
accuracy of the surface tension values estimated from pendant drops profi les. The compositional dependence of
obtained surface tension values is discussed in connection with the structure of studied glass forming melts.
Acknowledgement
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project Centre of excellence for ceramics, glass, and silicate materials ITMS code 26220120056, based on
the Operational Program Research and Development funded from the European Fund of Regional Development.

Influence of the solvent structure in TiO2 synthesis

Gonzlez J. C.1, Ramrez M. A. 1, Carrillo E. G.1, Castaon Ma. C.2, Zayas Ma. E.3, Daz G. C. 1
1

Fac. de Ciencias Qumicas e Ingeniera, Universidad Autnoma de Baja California, Mxico

Centro de Ingeniera y Tecnologa, Universidad Autnoma de Baja California, Mxico
3
Centro de Investigaciones en Fsica, Universidad de Sonora, Mxico

276

The synthesis of TiO2 have been of great interest in recent years because this material to reduce its particle size
has better properties and extends its application as catalyst component of solar cells, gas sensors and humidity,
optical lenses and biological systems, to name apredominant applications. The paper presents early studies of
TiO2 synthesis by Sol-Gel method, using as precursor Ti[OCH(CH3)]4 in amolar ratio 1.5/2 with solvent. Four
different alcohol were used as solvent; aliphatic, alicyclic and aromatic structure. The thermal treatment was
500C/8h. The series of materials obtained were characterized by Infrared Spectroscopy (IR), X-ray Diffraction
(XRD), Scanning Electron Microscopy (SEM), Transmission (TEM) and Atomic Force (AFM). We obtained aseries of materials by synthesis reaction at the same experimental conditions, the variety in activity was the solvent,
mineralogically, presents the anatase phase to use all solvents and the mixture; anatase and rutile when an aromatic structure was used, likewise that the best solvent tested for synthesizing TiO2 nanoparticles, was an aliphatic alcohol because; form asingle phase crystalline, particles uniforms and asize range between 2.27 and 5.14nm.

Crystallization tendency of a new bioactive glass

Souza M. T.1,2, Peitl O. 1, Zanotto E. D. 1
1

Federal University of So Carlos (UFSCar) LaMaV Vitreous Materials Laboratory,

Department of Material Engineering,
2
PPGCEM Postgraduate Program in Materials Science and Engineering;

Bioactive glasses are known to have the ability to form ahydroxycarbonate apatite (HCA) layer at their surface
during in vivo tests. Th is and other relevant properties make these biomaterials osteoconductive and osteoinductive, allowing both bone and soft-tissue bonding. However, for clinical purposes, the use of bioactive glasses has been limited to particulates, since the great majority of compositions do not support repeated heat-treatments, as this procedure results in uncontrolled crystallization, which normally degrades their mechanical
properties and sometimes diminishes their bioactivity. The development of new bioactive glass compositions
that aim to increase the workability of this biomaterial could facilitate sintering processes and allow the manufacture of versatile products, such as 3D scaffolds, fibers, meshes, porous implants and glass microspheres.
Th is study focuses on the characterization of the glass stability (against crystallization) of anew bioactive glass
composition of the SiO2-Na 2O-K 2O-MgO-CaO-P2O5system that possesses alarge working range, avery low
devitrifying rate and high bioactivity.To analyze these characteristics, we use DSC techniques and aHeating
Microscope analysis for monolithic and powdered samples. The high bioactivity of the new composition was
confi rmed byin vitrotests with SBF-K9 solution from 4 hours to seven days, which was complemented by FTIR
and SEM. Our results indicate that the new glass preserved its amorphous nature and bioactivity even after
asintering process and other high temperature treatments.

276 Poster Contributions

277

Hard MgO-Al2O3-SiO2 glass-ceramics

Gallo L. S. 1,2, de Meo C. E.3, Rodrigues A. C. M. 1, Zanotto E. D. 1
1

Vitreous Materials Laboratory DEMa/UFSCar So Carlos, SP, Brazil;

Postgraduate Program in Materials Science and Engineering PPG-CEM/UFSCar, So Carlos, SP, Brazil;
3
Undergraduate student of the Federal University of So Carlos So Carlos, SP, Brazil
2

Three glasses, L2R4, 75-25 and 80-20, of the MgO-Al2O3-SiO2 system, containing additional components were
studied. Hardness and indentation fracture toughness (IFT) were measured using a Vickers indenter. a single-stage heat treatment applied to the L2R4 composition increased its hardness from 6.60.1 (parent glass) to
amaximum of 9.90.2GPa, and its IFT by about 90%. Transparent glass-ceramics (GCs) of this composition were
obtained after double-stage heat treatments, which presented ahardness of up to 9.50.2GPa and an increase of
about 72% in IFT compared to the parent glass. When subjected to single-stage heat treatments, the hardness of
the 7525 composition rose from 6.80.1 (parent glass) to 8.50.1GPa, accompanied by an increase of about 66%
in IFT. Transparent GCs were obtained after specific double-stage heat treatments, presenting ahardness of up to
9.90.1GPa and an increase of about 52% in IFT compared to the parent glass. After asingle-stage heat treatment,
the hardness of the 80-20 composition increased from 7.00.1 (parent glass) to amaximum of 9.10.1GPa, while
its IFT increased by about 65%. Some of the samples presented ahardness of up to 10.70.1GPa and an increase
of about 65% in IFT after double-stage heat treatments.

278

Interpretation of tableware glass melting

CFD models in the production process
Pauo T.1, Vrbel P.1, Jursek I. 1, imurka P.2, Kraxner J.2
1
2

RONA a.s., Lednick Rovne, Slovakia;

Institute of Inorganic Chemistry of Slovak Academy of Science, Bratislava, workplace Trenn, Slovakia

The method of using amathematical model of melting is presented here as apowerful tool for better understanding and management of the production process. Black box-type methods are somewhat limiting and conclusions
from them are ambiguous.
In reaching different goals such as improving the quality of melting glass, increase pullrate and lifetime of furnaces can be greatly helped using CFD models. The melting process becomes more transparent using amathematical
model, respectively simulator, especially in terms of simulated changes in input parameters and their importance
in the process. The object of the calculation is the double roof end port fired recuperative furnace with pullrate
average 30 t/day, corresponding to melting power of 1.4t/day/m2. Calculation is offering the characteristics and
flow profi le, temperature distribution in materials, combustion characteristics, melting glass residence time (fining, homogenization) and its critical path (cords). Also the comparison of the calculations in terms of energy
consumption is of interest. There are presented the results of the simulated impact of different parameters on the
melting process, such as change of melting temperature, yield, setting the ratio of gas and power of electric boosting. Simulation of corrosion rate of the throat verifies change of critical trajectory, depending on the pullrate for
different feeder channels. Interpretation of modeling results and their proper understanding helps in decisions
that may save energy, reduce emissions and optimize the operation of furnace during its lifetime. Obtained results help to solve everyday problems that occur in melting. Mathematical models can help in solving the modernization of existing and the construction of future melting furnaces.

Konidakis I., Palles D., Kamitsos E. I.

Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, Athens, Greece

Glasses in the system 0.40AgI0.60AgPO3 were synthesized by melt-quenching according to different protocols,
which involve the use of Pt and alumina crucibles as well as the intentional addition of Al2O3 to melts in Pt

ICG Prague 2013 277

282

Contamination of phosphate glasses prepared

from melts in alumina crucibles

287

crucibles. By comparing infrared and Raman spectra of glasses prepared with different protocols, it was found
that silver-metaphosphate-based fast ion conducting glasses prepared in alumina crucibles suffer from Al2O3
contamination due to leaching from the crucible. In particular, it was shown that Al2O3-contaminated or Al2O3doped metaphosphate glasses are characterized by an enhanced population of pyrophosphate species. The presence of pyrophosphate species in Al2O3-contaminated 0.40AgI0.60AgPO3 glasses is much stronger than that in
Al2O3-contaminated AgPO3 glasses. Possible mechanisms leading to contamination are discussed.

Kinetic regularities of the precipitation of PbSe(S)

quantum dots in fluorine phosphate glasses
Kolobkova E. V., Aseev V. A., Lebedev R. V., Nikonorov N. V.
Saint-Petersburg National Research University of Information Technology, Mechanics and Optics

288

It was known that glasses with lead chalcogenide nanocrystals quantum dots (QD) are promising materials for
saturable absorbers. Process phase separation and crystallization usually is used for preparing this transparent
glass ceramics. In this respect we perform a detailed investigation into the kinetic of precipitation of PbSe(S)
quantum dots in new Fluorine Phosphate glasses.
Kinetic of the formation of the nanostructured glass-ceramic materials based on Fluorine Phosphate glasses in
system N 2-25-G 23-1F3-Zn with lead selenide (selenide) PbSe is investigated using differential scanning calorimetry, X-ray prouder diff raction, electronic microscope, absorption and luminescent spectroscopy
The primary attention was concentrated on the elucidation of the mechanism of formation of the nanostructured
materials with ause of two-stage heat treatment in order to prepare high quality samples: a).with narrow size
distribution of the QD and b)controlled sizes with first exciton energy in the range 1,0002,500nm. The influence
of the two-stage heat treatment on the properties of material is studied. Independence of the size of the QD of
concentration of the semiconductor component dissolved in a glass is determined. Absorption spectra of the
glass with PbSe QD after heat treatment demonstrated formation of different sizes of the PbSe quantum dots with
D=2.011nm, The revealed kinetic regularities of the precipitation of the PbSe QD differ radically from those
usually observed for phase decomposition in the silicate glasses doped with semiconductor compounds. The
growth rate of QD depends substantially on treatment conditions and increases drastically with T2 increasing.
Narrow size distribution of the QD is defined by T1 at the beginning of the Tg region. The observed dependencies
of QD sizes on heat treatment time exhibit nonmonotonic behaviour for all tempaturesT2.

New fluorine phosphate glass-ceramics containing

fluorine nanocrystals with rare earth ions
Kolobkova E. V., Aseev V. A., Nikonorov N. V.
Saint-Petersburg National Research University of Information Technology, Mechanics and Optics

Transparent glass-crystalline materials containing rare earth (REI) metal ions included in fluorine nanocrystalline phases have attracted attention due to anumber of important spectroscopic properties. Such materials
combine all the positive features of the fluoride nanocrystals (control the optical properties of the rare earth ions)
and glass (simple technology of production, excellent microscopy features, chemical and mechanical strength
and the high optical quality). There are many investigation devoted oxyfluoride silicate glasses, but information
about similar materials, based on the phosphate matrix, is absent. Nanostructured materials based on the fluorine phosphate glasses are absent because the methods of the initiation of the bulk nucleation without surface
crystallization in this type of glass are not unknown.
In this research, glass samples based on fluorine phosphate glasses matrix in system 0.05(3)2 (0.85--)
(MgCaBaSrAl2F14) PbF2 LnF3 ( Ln=Er, Tb, Ho,Yb,,Dy, Nd, Pr, Ce) x=0, 0.1, y=0.05, 0.1, 0.15) are nvestigated. In study, oxyfluoride phosphate glass, were prepared by conventional glass melting in glass carbon crucible
and their crystallization behavior was analyzed using non-isothermal kinetics based upon scan results of differential scanning calorimetry (DSC), X-ray diffraction and optical spectroscopy investigations.
All observed crystalline phases formed in glasses containing more 10mol.% REI are the cubic. However, in X-ray
database PCPDWIN there are no crystal phases with the structure parameters which were obtained in the work.

278 Poster Contributions

Analysis of existing compounds suggests that crystalline phase can form compounds of SrLnF5, structurally
isomorphic for the known compounds of BaGdF5. These conclusions are confirmed by spectral-luminescence
studies, which give information about changing of the REI environment.

289

Development of novel mesoporous silica-based

bioactive glasses with enhanced mechanical
properties for Bone Tissue Engineering
Philippart A., Boccaccini A. R.
Institute of Biomaterials, University of Erlangen-Nuremberg, 91058 Erlangen, Germany

Bioactive glasses are widely used in bone tissue engineering approaches. These glasses can develop strong bonds
with bone through the formation of hydroxyapatite layers when they react with physiological fluids. This bonding
occurs with the simultaneous release of specific metallic ions, including Si, Ca and P ions, which finally stimulates
the formation of bone tissue. Mesoporous bioactive glasses (MBG) are an attractive group of bioactive glasses due
to their large surface area and their capacity of being functionalized with alarge variety of moieties. The Sol-Gel
process offers the possibility of fabricating glasses with high surface area and porosity, exhibiting higher bone bonding rates together with excellent degradation and resorption properties. The aim of this study was to develop anew
family of MBG of silicate compositions that can be used for the fabrication of 3D macroporous scaffolds for tissue
engineering and drug delivery applications. The incorporation of sodium oxide (Na2O) in the network was considered, since Na2O could contribute to enhancing the mechanical properties maintaining satisfactory biodegradability behavior of MBG. All compositions were synthesized by the Sol-Gel method. After the hydrolysis and condensation reactions, polyurethane foams were immersed in the solution in order to produce 3D scaffolds using the
foam replica technique. All compositions developed ahydroxyapatite (HA) layer in Simulated Body Fluid (SBF), as
revealed by Fourier Transform Infrared Spectroscopy (FTIR), confirming their bioactive character. The mesoporous
nature of the glasses was evaluated by Transmission Electron Microscopy (TEM), N2 adsorption porosimetry and
Brunauer-Emmett-Teller (BET) Surface Area Analysis, while scaffolds presented the required pore size (~500m)
and interconnectivity, shown by Scanning Electron Microscopy (SEM). Compressive strength tests were carried
out on 3D scaffolds. Summarizing, the synthesis of novel silica-based MBG was achieved, and fabricated scaffolds
presented suitable mechanical and bioactive properties for bone tissue engineering applications.

Elkhoshkhany,N.
Institute of Graduate Studies and Research, Alexandria University, Egypt

The tellurium-based glasses (100-x) TeO2 (x)WO3, (49)TeO2 (29.4) WO3 (19.6)PbO doped with different rare-earth oxides of the type La2O3, Sm2O3, Er2O3, and Y2O3 have been prepared by melt quenching technique. Optical
absorption studies are carried out on the glass system. The compositional dependence of different physical parameters such as density, molar volume, oxygen packing density, Molar refraction (R M), refractive index (n), metallization
criterion (M) and electronic polarizability of the oxide ion O2-(Eopt), and optical basicity (Eopt) have been determined from optical absorption data and their variations have been discussed in terms of the glass structure.

ICG Prague 2013 279

290

Optical properties of rear earth tellurite glasses

301

Relaxation and crystallization of CoP

metallic glass under radiation exposure
Pustovalov E. V.1, Modin E. B.1, Voitenko O. V.1,
Grabchikov S. S. 2, Plotnikov V. S.1, Grudin B. N.1
1
2

Far Eastern Federal University, Vladivostok, Russia

GNPO Scientific-Practical Materials Research Centre, NAS of Belarus, Minsk, Belarus

302

Amorphous structure and chemical composition of metallic glasses are determining the ultimate properties of such materials. Amorphous magnetic alloys used as part of various devices, for example as magnetic sensors or shields. Structure
relaxation and crystallization processes lead to changes in their magnetic properties. Despite of many investigation question of multiscale structure relaxation influence on magnetic properties in metallic glasses still open.
Thin fi lms of CoP amorphous alloy were deposited by electrochemistry process on conducting substrate. Films
have composition with 1822at/% of P. Structure and composition of the specimens were investigated by means
of scanning/transmission electron microscopy (S/TEM), energy dispersive X-ray microanalysis (EDS) and secondary ion mass spectrometry (SIMS). Amorphous alloys were exposed by Ga+ ions (5keV and 30keV), electrons
(3.5MeV, 300keV, 200keV, 80keV) and X-ray radiation (1.3MeV) with doses in range of 10121019cm-2. Atomic
and multiscale structure modelling of the metallic glasses and S/TEM image modelling and processing were
performed by own soft ware accelerated by GPGPU Nvidia Tesla 1070.
As-prepared structure of CoP fi lms were disordered with defects in range of 1100nm presence. EDS and SIMS
data show uniform chemistry composition of the fi lms. Samples have quasi-network structure with light contrast
of cell nuclei and more electronic dense border according to electron microscopy investigation. S/TEM investigation, image processing and atomic structure modelling shows us porous structure of multiscale network defects
in the fi lms structure. Ga+ ion exposures with doses 10121015cm-2 have effect in increasing network structure
contrast. Electron beam irradiation with doses 10151019cm-2 leads to crystallization process starting on the free
surface of the voids. Nanocrystals have distorted structure with unidentified phase of CoxP1-x. X-ray radiation
with doses 10151019cm-2 have almost no effect on the initial structure of the fi lms.

CoNiP metallic glass structure dynamics

under the thermal impact
Modin E. B.1, Pustovalov E. V.1, Kirillov A. V.1,
Grabchikov S. S.2, Plotnikov V. S.1, Grudin B. N.1
1
2

Far Eastern Federal University, Vladivostok, Russia

GNPO Scientific-Practical Materials Research Centre, NAS of Belarus, Minsk, Belarus

CoNiP metallic glass formed by electrolytic deposition method are perspective material with soft magnetic properties, low coercivity, high permeability and demonstrate giant magneto-impedance effect. So, these materials
can be widely used as magnetic field sensors, transformer cores and other devices. Besides their applied importance they are of great scientific interest allowing to investigate the amorphous state, processes of structure relaxation and crystallization. Structure of metallic glasses of CoNiP composition with 1822 % of phosphorous and
40% nickel were investigated by transmission electron microscopy and electron diff raction methods. The specimens were obtained via electrolytic deposition from sulfuric acids. The microstructure was studied using fi lms
with thicknesses of 400800 placed on standard copper grids for transmission electron microscopy. Annealing
of the samples was held with gradual increasing temperature with 1C step till 200C and isothermal annealing
at 200C for 7 hours. The structure dynamics in the process of heating was observed in the diff raction and TEM
modes. As aresult of experiment there were obtained TEM image series and electron diffraction image series. We
have developed number of computer programs based on graphic processors for experiment automation and data
processing. Also Gatan Digital micrograph with Diff-tools, PASAD-tools, RDF-tools plugins was used. Different
algorithms such as Hough transform, the center of gravity, downhill-simplex and cross-correlation with iterative
refinement algorithm were used for the diffraction image analysis and intensity profi le analysis. Observing the
evolution of the intensity profi le during isothermal annealing it is seen that the position of the first and second
diff usion peak remains stable 4.82nm-1 and 8.19nm-1. Polycrystalline rings appear gradually after three hours
of annealing. During the whole annealing in the amorphous matrix centers of ordering are formed, where subsequently began the growth of crystalline phases.

280 Poster Contributions

306

Study of the oldest Czech stained

window glasses from ebnice
Clov Z.1, Knov M.1, Drbkov K.1, Frda F.2, Kuerov I.1, Helebrant A.1
1
2

Faculty of Chemical Technology, Institute of Chemical Technology, Prague, Czech Rep.;

Museum of West Bohemia in Plze, Plze, Czech Rep.

Stained window glasses dated to the first half of the fourteenth century (originated from church of St. Jacob the
Bigger, in ebnice, Czech Republic) were placed in the Museum of West Bohemia in 1911. The stained glasses
were conserved at 2011 and the analytical research was carried out. This study describes the results of the research
and characterizes previous conservation intervention (i.e. previously used adhesives by FTIR). The chemical composition and degradation of the glass and grisaille were also described. Glass and lead strips surfaces were studied
by optical and scanning electron microscopy coupled with SDD detector. Chemical composition of glass was
studied by XRF. It was determined that the studied glass is the medieval wood ash glass with low silica content
(46.65wt%) and comparable amounts of potassium oxide (23.60wt%) and calcium oxide (20.78wt%). This type of
glass was typical for Central Europe glassmaking in aperiod 10001400 AC. Chemical durability of this glass
type is poor and glass fragments showed evidence of corrosion darkening, micro-pitting and presence of deposits (calcite and calcium oxalate were confirmed by FTIR).

312

Thin layers on glass surface

with superhydrophobic properties
Zontek-Wilkowska J., Wasylak J., Reben M.
AGH University of Science and Technolology, Faculty of Materials Science and Ceramics, Department
of Glass and Amorphous Coating Technology, Cracow, Poland

Nature has developed all kind of materials and processes that function form the macro scale to the nanoscale. All
coatings were obtained by Sol-Gel process, using dip-caoting method with the same speed of withdrawing. The
synthesis had been conducting at the room temperature (25C) air atmosphere, with use of tetraethylorthosilicate
(TEOS) as aprecursor and polidimethylosilane (PDMS), tetraethylotitanian (TEOT) as surface modifying agents.
The silica sol was prepared by keeping the molar ratio of TEOS:PDMS:TEOT at 1:1:1, in acidic conditions with
ethanol and iso-propanol, and 0.1 M HNO3. All hybrid systems were enriched with titanium(IV) isopropoxide
as the cross-linking agent. The higher value of static water contact angle (1193) was obtained for the silica fi lm
prepared with TEOS+TEOT+PDMS.
Under optimal synthesis condition, the hydrophobic coatings, exhibiting alow reflection in the visible range were obtained.

313

Hybrid silica layers obtained

by silkscreen printing technique
Lisiecki M., Zontek-Wilkowska J., Wasylak J., Reben M.
AGH University of Science and Technolology, Faculty of Materials Science and Ceramics, Department
of Glass and Amorphous Coating Technology, Cracow, Poland

Silica nanoparticles in different forms are widely used for various applications e.g. mechanical reinforcement,
biological membranes layers. Preparation of hydrophobic SiO2 thin film by Sol-Gel method, silkscreen printing
technology has been reported. Polidimetylosiloxane PDMS, tetraethylorthosilicate (TEOS) and colloidal silica
(CS) have been used as liquid precursors. UV-VIS spectroscopy, SEM, and contact angle (CA) studies were performed to measure the physical properties of the thin fi lms. The increase of contact angle CA was observed. In
case of samples where SiO2 particles had been partly replaced by CH3 groups, contact angle (CA) increased to 120
compared to the contact angle 40 of unmodified layer surface. The silkscreen printing technique was applied for
coating glass samples; it seems to be the cheaper and more efficient technique to achieve silica nano-domain.

ICG Prague 2013 281

314

Crystallization in basalt glasses

and fibers on their base
Gutnikov S. I., Manylov M. S., Kartashov A. A., Lazoryak B. I.
Lomonosov Moscow State University, Moscow, Russia

318

Basalt glasses belong to the iron-rich alumino-slicate systems. Due to their high thermal stability, chemical and
mechanical resistance and low cost there are many types of materials that are manufactured on their base: rock
(mineral or stone) wool, glass-ceramics and continuous fibers (BCF).
The object of the study were basalt glass and fibers with follows composition: in wt% 55.6% SiO2, 1.1% TiO2, 15.8% Al2O3,
10.5% FeO + Fe2O3, 3.7% MgO, 9.2% CaO, 2.2% Na2O, 1.8% K2O (Siltsevskoe deposit, Carpathians, Ukraine).
Using methodology based on DSC data analysis it was shown that in contrast to the bulk glass the crystallization
in continuous fibers begins on the surface. It was determined that activation energy of crystal growth (Ec) and
Avrami parameter (n) of BCF were 33.60.2 and 1.00.1 respectively
A phase transformations order was determined by quantitative phase analysis of basalt glass and fibers samples
that was annealed at 700, 800, 900 and 1,000C during 6, 12 and 24 hours. Using SEM and Mossbauer spectroscopy methods it was suggested the mechanism of crystallization of basalt glasses and fibers on their base. Crystallization in basalt glasses and fibers begins with liquid immiscibility. One of the liquid phases (iron-rich phase)
promotes formation of afirst crystal phase with spinel structure (spinelide). With afollowing thermal treatment,
amonoclinic pyroxene solid solution precipitates onto the spinel crystals, which act as nuclei for crystallization.
The work was carried out with asupport of Russian Foundation for Basic Research (#12-03-31072-mol_a).

Crystallization of CaO-Li2O-SiO2 glasses

Santos G. G.1,2, Zanotto E. D.1, Fokin V. M.3
1

LaMaV Vitreous Materials Laboratory, Federal University of Sao Carlos, Sao Carlos, Brazil
Postgraduate Program in Materials Science and Engineering, PPG-CEM, Sao Carlos, Brazil
3
S. I. Vavilov State Optical Institute, St. Petersburg, Russia

323

In this work we evaluate the crystallization behavior and resulting microstructures of glasses of the eutectic
CaO-Li2O-SiO2 system and also some mechanical properties of the resulting glass-ceramics. Glass compositions
in the range of 3250% mol CaSiO3 (the other part being Li2SiO3) were prepared and studied. Heat treatments
were conducted at temperatures between 400700C (simple and double). We focus on the internal crystallization
of wollastonite, which is apparently catalyzed by the initial precipitation of lithium metasilicate crystals; i.e. the
wollastonite phase crystallizes around the Li2SiO3 crystals. Evaluation of hardness and toughness were made by
Vickers indentation with the main focus on the effect of microstructure (number of phases, shape and size of the
crystals as well as crystallized fraction) on the mechanical behavior of the material. The best results so far were
obtained with acomposition of 44% mol CaSiO3, 67% crystallized fraction and mean CaSiO3 crystal size of about
5m, as follows: hardness of 6.7GPa and toughness of 1.9 MPa.m1/2. Despite the fact that the hardness values
did not show asignificant change compared to parent glass, the toughness increased by about 110%. X-ray tests
confirmed that the wollastonite phase was responsible for such an increase. This research work is still on going
because these glass-ceramics show promising mechanical properties.

Photobleaching in Yb-doped silica glass

Minami D., Saito K., Sekiya E. H.
1

Toyota Technological Institute, Nagoya, Japan;

Photodarkening is aserious problem in high power fiber lasers. Major origin of the photodarkening is pair generation of OHC (Oxygen Hole Center) and Yb2+ via charge transfer transition. P-doping is effective to suppress
the photodarkening, but perfect suppression is impossible. On the other hand, photobleaching is well known to
occur by irradiation of UV/V lasers with appropriate wavelength. However, the mechanism of photodarkening
has not yet been cleared. In this poster presentation, we will report our investigation of the following questions:
1) whether photobeaching is areverse process of photodarkening (i.e., pair annihilation of OHC and Yb2+), or not.

282 Poster Contributions

2) which wavelength is the most effective for photobleaching.

3) whether photobleaching depends on glass component and/or dopant concentration, or not.
4) what is the mechanism of photobleaching.
5) whether photobleaching is aeffective method to suppress the photodarkening, or not.

325

Fabrication of optical fibers

with F(B2O3)-Yb2O3-Al2O3-P2O5-SiO2 core by MCVD method
Lipatov D. S.1, Guryanov A. N.1, Bubnov M. M.2, Likhachev M. E.2
1

G. G. Devyatykh Institute of Chemistry of High-Purity Substances of the Russian Academy

of Sciences, 49 Tropinin Street, Nizhny Novgorod, 603950, Russia;
2
Fiber Optics Research Center of Russian Academy of Sciences, 38 Vavilov Street, Moscow, 119333, Russia

For fabrication of powerful fiber lasers the optical fibers are required with high content (more than 2mass%) of
rare-earth elements (REE) and with small difference between the refractive indices of core and cladding dn (not
more than 0.002). Phosphoralumosilicate (PAS) glass is the most suitable material for the core of these optical
fibers since it has actually the same refractive index and coefficient of thermal expansion (CTE) with quartz
glass but ahigh concentration limit for entrance of REE oxides (more than 1mass%). However, introduction of
more than 2mass% of REE into glass increases dn by more than 0.002. Increase in concentration of REE in PAS
glass with the same dn difference can be achieved by additional doping with fluorine or boron oxide. The work
is devoted to investigation of completely gas-phase doping process of quartz glass with 2O5, Al2O3, Yb2O3, B2O3,
F in MCVD method during fabrication of preforms for optical fibers. Refractive index, optical losses, CTE and
amplifying properties of B2O3(F)-Yb2O3-Al2O3-P2O5-SiO2 glasses and optical fibers on their basis in dependence
upon composition were investigated. The range of optimum composition of the core glass of optical fibers was
determined which is the most suitable for fabrication of powerful fiber lasers.

326

Preparation and optical properties

of yttrium-aluminum garnet photonic
crystals with inverse opal structure
Migt M.1,2, Sedlek J.2, Bodiov K.3, Galuskov D.2, Galusek D.2
1

Faculty of Chemical and Food Technology, Slovak University of Technology, Bratislava, Slovak Republic
Vitrum Laugaricio Join Glass Centre of the IIC SAS, TnUAD,
FChFT STU Bratislava and RONA jsc. Trenn, Slovak Republic
3
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Bratislava, Slovak Republic

Monodisperse amorphous SiO2 spheres 174650nm in diameter were prepared by Stbers Sol-Gel synthesis,
through hydrolysis and polycondensation of tetraethoxysilane (TEOS) as the source of SiO2 in aqueous ethanol
solution, with ammonia as acatalyst. Size and monodispersity of SiO2 spheres was influenced by concentrations
of the reactants. In order to create three-dimensional face centered cubic SiO2 opaline structure the microspheres
were deposited on asilicon substrate by dip coating, with subsequent drying and annealing, which ensured sufficient fi xation of microspheres at the surface of the substrate.
Sol-gel method has been then applied in order to obtain Y3Al5O12 (YAG) sol, which was prepared by Pechini
method with the use of the respective metal nitrates as the source of alumina and yttria, and citric acid as the
complexing agent. The YAG sol was then infiltrated into the SiO2 matrix, converted to YAG by high temperature
annealing, and the silica spheres were removed by etching in hydrofluoric acid. The inverse opal structure consisting of regularly spaced spherical pores of various sizes in YAG matrix was obtained.
The morphology of SiO2 photonic crystals and YAG inverse opals was examined by scanning electron microscopy
(SEM). The structure and optical properties of YAG inverse opals were characterized by X-ray powder diffraction
(XRD) and UV VIS NIR spectroscopy, respectively.

ICG Prague 2013 283

327

Glass forming region and properties of glasses

in the system Al2O3-Y2O3-SiO2 with 520mol.% of SiO2
Domanick A.1,2, Prnov A. 2, Klement R. 2, Migt M. 1,2, Bodiov K. 3, Galusek D. 2
1

Faculty of Chemical and Food technology, Slovak University of Technology, Bratislava, Slovak Republic;
Vitrum Laugaricio Join Glass Centre of the IIC SAS, TnUAD, FChFT STU Bratislava and RONA jsc.;
3
Institute of inorganic chemistry, Slovak Academy of Science, Bratislava, Slovak Republic

330

Glasses in the system Al2O3-Y2O3-SiO2 (AYS) with 5, 10, 15 and 20mol.% of silica were prepared by flame synthesis
from precursor powders, which were synthesized by precipitation and by the Pechini method. The composition
of basic undoped glasses was derived from eutectic composition in Al2O3-Y2O3 system with the lowest melting
temperature and tendency to crystallization. Typical glass forming oxide SiO2 was added to some compositions
in order to increase the glass forming ability, while Al2O3/Y2O3 molar ratio was kept constant and identical to the
eutectic composition. Yttrium aluminium garnet (YAG) and yttrium aluminium perovskite (YAP) compositions
with addition of SiO2 were also prepared in order to verify the extent of glass forming region at the low silica end
of the phase diagram. The glasses were prepared in the form of transparent microspheres with diameters from
afew to several tens of micrometers. According to X-ray powder diffraction studies the microspheres were mostly
amorphous, some with traces (up to 5 wt.%) of crystalline phases. Amorphous systems were doped with 15mol.%
of erbium and neodymium, without significant increase of their crystallinity. The UV-VIS-NIR reflectance spectra showed characteristic absorptions, due to the presence of optically active Nd3+ and Er3+ ions in the host glass.
DTA/DSC curves were recorded in order to study the kinetics of crystallization of prepared glasses. Improved
thermal stability of yttrium aluminate glasses with increasing content of silica was observed.

Vitrification of hospital waste incineration

ashes in borosilicate glass
Ciecinska M., Stoch P.
1

AGH University of Science and Technology, Krakow, Poland

The low level nuclear waste (LLW) resulting from the use of radioactive isotopes in medicine, industry, laboratories
and other purposes can be immobilized by vitrification, using methods applied in the nuclear power industry. Borosilicate glass is providing the very suitable medium for the majority of the species present in these wastes. Management of LLW waste begins with combustion reducing their amount. The obtained ash is suitable for vitrification by
incorporating it into the composition of borosilicate glass, similar to those used in nuclear power industry.
Model studies of immobilization of the hospital waste contaminated with radioactive 137Cs are subject of the
investigations. Influence of the main ash components on the structure of model glasses was investigated by FTIR
method. Glass crystallization was searched by differential scanning calorimetry (DSC). Phase composition of
samples were investigated by X-ray diff ractometry (XRD). Leachability studies according to PCT test were conducted and normalized elemental release rates were obtained.
The results confirmed that in the presence of even arelatively small amount of Cs2O the degree of polymerization
of the network and its durability increase which results simultaneously the increase of the chemical durability of
the glass. Cesium increases also the tendency for crystallization of the basic glass. Similar changes are induced
by the introduction CaO as the additional waste component. The proposed glass is suitable to vitrify the hospital
and laboratory ashes, contaminated with radioactive 137Cs.

284 Poster Contributions

337

Dissolved gas analysis of in-flight melting glasses

using oxy-fuel combustion burner flame
Yano T.1, Miyake Y.1, Ogata J.1, Nakada Y.1, Sato K.2, Iwamoto M.2, Ebihara Y.2, Inoue S.3
1

Tokyo Institute of Technology, Tokyo, Japan

Toyo Glass Co., Ltd., Tokyo, Japan
3
National Institute for Materials Science, Tsukuba, Japan

Reduction of energy of glass melting has been one of the most important issues in glass industry to save energy and reduce the emission of gases of global warming. anew innovative glass-melting technology, In-Flight Melting method,
has been developed in Japan, in which quite efficient energy transfer and rapid vitrification processes of raw materials
are accomplished by flying granular raw materials in high-temperature zone formed by oxy-fuel combustion burner,
plasma and/or their combination. For soda-lime silica glass melting, large energy reduction would be possibly attained
by oxy-fuel combustion burner heating. In flight, the granular raw materials receive energy from the burner flame via
direct contact, and high energy states of gaseous species in flame are considered to affect much the properties of the
resultant glass melts, especially their subsequent fining and/or refining behaviours.
In-Flight Melted soda-lime-silica glasses using various specific energy consumptions (SEC) are examined to evaluate the dissolved gas species inside. The glass sample was heated in aPt crucible in vacuum at 1,400C and the
released gases are trapped and analysed by Infrared absorption method.
The analysis results showed the detection of H2O, CO2, CO, SO2, COS and NO. High water content more 600ppm was
found to be released from the melts, and agreed with the value estimated by Infrared absorption method for bulk glass
sample. Dependences of these dissolved gas species contents on the In-Flight Melting condition (SEC etc) are discussed.
This study was financially supported by the Energy Innovation Program of NEDO (New Energy and Industrial
Technology Development Organization).

346

Preparation, characterization, and thermal

properties of glasses in the system Y2O3Al2O3ZrO2
Hruka B.1, Klement R.1, Bodiov K.2, Prnov A.1,Galusek D.1
1

Vitrum Laugaricio Joint Glass Center of the IIC SAS, TnU AD, FCHTP STU and Rona, a.s.,
tudentsk 2, SK-911 50 Trenn, Slovak Republic
2
Institute of Inorganic Chemistry, Slovak Academy of Sciences,
Dbravsk cesta 9, 845 36 Bratislava, Slovak Republic

The glasses in the ternary system Y2O3Al2O3ZrO2, derived from binary eutectic composition of the Y2O3Al2O3
system (76.8mol.% Al2O3) with ZrO2 content of 5, 10, 15 and 20mol.% were prepared from precursor powders by
flame-spraying technique in the form of transparent microspheres. The precursor powders were synthesized via
modified Pechini Sol-Gel route. The glass microspheres were characterised by optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The DSC
was used to determine the crystallization kinetics parameters describing nucleation and crystal growth in glasses
during the heat treatment. The phase evolution during crystallization process in the prepared glasses was studied
in-situ by the high temperature XRD (in the temperature range 7001,200C, with the step 5C), and obtained
results were compared with DSC measurements.

349

Phosphate-based glasses
for magneto-optical applications
Volceanov A.1, Dima V.1, Eftimie M.1, Stoleriu S.1, Elisa M.2, Sava B. A.2, Boroica L.2
1
2

University Politehnica of Bucharest, Bucharest, Romania;

National Institute for Research and Development in Optoelectronics

Many efforts have been devoted to the characterization of the nanosized layered systems as thin fi lms and exchange coupled multilayers, presenting interesting magnetic phenomena like as exchange spring and exchange

ICG Prague 2013 285

363

bias with direct applications in nanoelectronics. Doped silicate and borate glasses were widely studied and used
as glassy matrix materials for magnetic applications.
The primary trend of our wider study is to develop glass compositions having alarge specific Faraday rotation and
low absorption in the visible and near infrared regions.
Our purpose is to investigate and produce mainly phosphate glass as base vitreous matrix that will be doped with
rare-earth ions, transition and post-transition ions. Phosphate glasses are attractive materials for awide range
of photonic applications such as lasers, amplifiers, photosensitivity sensors, optical storage and Faraday rotators.
They demonstrate high UV transmission, low linear and nonlinear refractive index, low viscosity, low melting
temperatures and non-thermal behavior. In addition, they are excellent host materials for active rare earth (RE)
ions due to advantageous local structure effect and high RE ion solubility.
As afirst step, the main basic properties of the obtained doped phosphate glasses, such as thermal expansion,
characteristic temperatures og glasses, density, viscosity, hydrolytic stability using conductometric method were
measured. In order to examine potential thin layer properties, scanning electron microscopy (SEM) coupled
with energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction methods were employed for evaluation of
compositional and crystallization behaviour. The results are discussed in connection with compositions, thermal
history, doping elements used in phosphate vitreous matrix.

Structural relaxation in AgPO3 glasses observed

through electrical conductivity measurements
Bragatto C. B. 1,2, Szemkus S.3, Cassar D. R.1,2, Rodrigues A. C. M.1
1

Laboratrio de Materiais Vtreos (LaMaV), Universidade Federal de So Carlos, So Carlos (UFSCar), Brazil;
Programa de Ps-graduao em Cincia e Engenharia de Mateirais (PPG-CEM),
Universidade Federal de So Carlos, So Carlos (UFSCar), Brazil;
3
Friedrich-Schiller-Universitt Jena, Jena, Germany.
2

365

Structural relaxation in glass can be verified by the variation of some glass properties over time. We investigated
the structural relaxation of silver phosphate glass (AgPO3) by analyzing the variation in electrical conductivity
over time. Electrical conductivity was measured by impedance spectroscopy during isothermal heat treatments.
Data were collected at regular time intervals, with atotal heat treatment up to 48h. The change in the electrical
conductivity of anon-annealed glass, measured at 150C (30C below the glass transition), is well fitted by the
Kohlrausch expression, indicating that the change in conductivity can be attributed to structural relaxation. The
conductivity of an annealed glass increased when measured above the annealing temperature and decreased
when measured below this temperature.

Structure and properties of the ferriferous

nano porous vitreous matrixes
Antropova T.1, Anfimova I.1, Drozdova I.1, Polyakova I.1,
Pshenko O.1, Cizman A.2, Rysiakiewicz-Pasek E.2, Poprawski R.2
1
2

Grebenshchikov Institute of Silicate Chemistry RAS, Saint Petersburg, Russia

Institute of Physics Wrocaw University of Technology, Wrocaw, Poland

It is known that composite materials with nanostructured elements possess unique functional properties. Interest represents creation of the nano composites with magnetic and ferroelectric ordering which can be applied in
microelectronics. One of perspective ways of the decision of this problem is an introduction of the ferroelectric
phase into pore channels of the artificial nano porous magnetic matrixes.
In our work new ferriferous nano porous vitreous matrixes (porous glasses) are synthesized by through chemical etching of the phase-separated alkali borosilicate the glasses modified by iron oxide. The structure of initial
two-phase and porous glasses is investigated by transmission electronic microscopy and X-ray analysis. Also the
magnetic and electric properties of glasses are studied.
In the initial glasses against of two-frame structure, and also in porous matrixes the inclusions of nano particles
of magnetite Fe3O4 are found out thanks to what the glasses possess of magnetic properties. The iron mainte-

286 Poster Contributions

nance in high silica (8090 wt. % SiO2) porous matrixes (in recalculation on Fe2O3) makes 515 . %. Depending on structure of initial glass and conditions of their leaching the average pore sizes of the received matrixes
D=550nm, porosity W = 0.30.6.
Work was carried out under financial support of Russian Foundation for Basic Research (project No. 11-03-00747a)
and including within the limits of the Polish Russian joint research project Porous magnetic glasses and composite multiferroic materials on their basis (the Inter Academic Cooperation Program 2012/2013, theme 61).

368

Effects of Al2O3 addition on the thermal properties

and structure of CaO-Al2O3-SiO2 glasses
Takahashi S., Takebe H.
Ehime University, Matsuyama, Japan

Aluminosilicate glasses are composed of SiO2, Al2O3, R 2O and RO where R 2O and RO are alkali and alkaline oxide, respectively. These glasses have good thermal and mechanical properties. The roles of Al2O3 as an amphoteric
oxide for network former and/or modifier are considered to be changed with glass composition. It is reported that
amolar ratio of [Al2O3]/[R 2O + RO] is adeterminant of thermal properties. We have prepared CaO-Al2O3-SiO2
glasses in the molar ratio range of 0.1 and 1.5.
Glass transition temperature Tg and thermal expansion coefficient were obtained by use of athermo-mechanical analyser. Intermediate structure was evaluated by IR and Raman spectroscopes. As aresult, Tg showed atendency to increase while decreased with increasing Al2O3 concentration. Moreover, the compositional dependences of Tg and were classified into two regions due to the slopes of the properties with the molar ratio at [Al2O3]/
[CaO]=0.70.9. IR and Raman spectroscopes also showed that the chemical shift of Si-O vibration bands in the
range of 930 and 1,020cm-1 occurred at [Al2O3]/[CaO]=0.8. The results suggested that the Al2O3 addition promoted the formation of ((Si, Al)nO3n)2n ring structure including AlO4 tetrahedra.

378

Use of the glass cullet in the production

of cementitious materials
ak R., Goek .
AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Department of
Building Materials of Technology, Cracow, Poland

The recycling of the waste glasses poses amajor problem for the worldwide. Waste glasses creates serious environmental problem, mainly to the inconsistency of waste glass streams. With increasing environmental pressure to
reduce solid waste and to recycle as much as possible, the concrete industry has adopted anumber of methods to
achieve this goal. The use of recycled waste glasses in cement and concrete has attracted alot of interest worldwide
due to the increased disposal and environmental concerns. The researches of the domestic glassware and window
glass used in the concrete industry have been conducted for along time. Being amorphous and containing large
quantities of silicon and calcium, relatively, glass is, in theory, pozzolanic or ever cementitious in nature when it is
finely ground. Up till now the research works have mainly concerned utilization of the glass cullet as aaggregate,
that had been connected with necessity of resolving the problem of expensive alkali metals silicates forming.
This paper summarizes the progresses and point out the directions for the proper uses of glass cullet in cement. Furthermore, the work contained the results of examination made on two kinds of pastes, whom the main component is
aPortland cement clinker and grinded glass cullet, as asource of the active silica. Obtained results of researches indicate the possibility of using this kinds of materials to produce acheap bonding materials of the special application.

ICG Prague 2013 287

381

Synthesis and structural study

of sonora wollastonite glasses
Zayas Ma. E.1, Garca-Amaya I.2, Palafox J. J.2,
Alvarado-Rivera J.1, Acosta-Enrquez M. C.1, Lozada R.3, Daz G. C.4, Rincn J. Ma.5
1

Departamento de Investigacin en Fsica, Universidad de Sonora, Hermosillo, Sonora, Mxico;

Departamento de Geologa, Universidad de Sonora, Hermosillo, Sonora, Mxico;
3
Facultad de Ciencias Fsico Matemticas, Benemrita Universidad de Puebla, Puebla, Mxico;
4
Facultad de Ciencias Qumicas e Ingeniera UABC, Tijuana, B.C. Mxico;
5
Instituto Eduardo Torroja de Ciencias de la Construccin, Madrid, Espaa
2

389

Vanadium oxide (V2O5) based glasses are of importance due to their semiconducting properties and electrical
conduction which is due to the electron hopping on account of the available reduced states of the TM ions. In this
study, V2O5-wollastonite glasses were synthesized at 1,200C by the conventional melt quenching method using
ahigh alumina crucible on aThermolyne electric furnace in air atmosphere. Several glasses were obtained with
different wollastonite content from 10 to 40% wt. The wollastonite is obtained from The Pilares Mine (Mining
Nyco), located at northwest from Hermosillo city, in Sonora state in Mexico, this mine produces 450,000 tons
per year of wollastonite with a5565% purity. The obtained glasses are of atransparent brilliant brown colour.
Structural studies by XRD showed that all the samples are amorphous with the presence of well-defined peaks
for the VO2, SiO2 and wollastonite crystalline phases. Raman spectroscopy also detected amorphous phases in
these glasses. XPS spectra of the glasses revealed some iron, aluminium and chromium impurities resulting from
wollastonite as araw material. Furthermore, high resolution spectra of the O 1s and V 2p spin orbit doublet were
taken to perform curve fitting to determine the bridging/non-bridging oxygen ratio (BO/NBO) and vanadium
oxidation states, respectively. The BO/NBO ratio shows information about the role of the wollastonite on forming
glass in combination with vanadium oxide for the materials obtained in this study.

Analysis of nucleating agents

for lithium silicate glass-ceramics
Villas-Boas M. O. C.1, Soares V. O.2, Zanotto E. D.1
1

Postgraduate Program in Materials Science and Engineering at the Federal University of So Carlos
DEMa/UFSCar, So Carlos-SP, Brasil;
2
State University Maringa, Maring-PR, Brasil

Lithium silicate glass-ceramics (GCs) have great commercial importance. For instance, their excellent biocompatibility, mechanical strength, color stability, thermal conductivity similar to dental tissues and strong potential
to simulate the appearance and hardness of natural teeth have allowed their widespread application as dental
prostheses. This combination of positive features makes this system one of the most extensively studied at university laboratories and companies. However, it is still important to carry out more detailed studies on the effect
of nucleating agents and their influence on the microstructures of the resulting GCs. In this study we compared
several formulations of Li2Si2O5 GCs with the nucleating agents P2O5, Pt, ZrO2 and combinations. Glass compositions were melted and crystallized at different temperatures and the glass-ceramics were characterized by
X-ray diffraction, scanning electron microscopy and Vickers indentations. We concluded ZrO2 combined with
P2O5 increases the nucleation efficiency. The nucleating agents also determine the crystalline phase obtained, for
instance while Pt favors lithium metasilicate which is good for machinability the frequently used P2O5 favors
the formation of the disilicate phase which leads to higher fracture toughness.

288 Poster Contributions

395

Dehydration study on phosphate

glasses for optical fibers
Mura E.1 , Annoscia A.1 , Lousteau J.2 , Boetti N. G. 1 , Milanese D. 1
1
2

Institute of Materials Physics and Engineering, DISAT, Politecnico di Torino, Torino, Italy
Istituto Superiore Mario Boella, Torino, Italy

Phosphate glass is avery promising host material for manufacturing lasers and optical amplifiers operating at wavelengths in the near infrared spectrum. As arare-earth ion host matrix, phosphate glass possess properties more attractive than those of silica glass for these applications. Nevertheless, one of the key parameter to exploit the potential of
phosphate glass as an optical active medium is the glass concentration in OH radicals. Actually OH tends to degrades
severely the luminescence properties of the rare-earth ions used as optical active medium within the glass.
This work reports the comparison of different synthesis methods of Er/Yb co-doped phosphate glass composition
(P2O5 Al2O3 Li2O B2O3 BaO PbO La2O3) with the aim of reducing the OH concentration. Three types of
synthesis routes have been studied: melting in laboratory atmosphere, flowing dry gas during melting and adding
fluoride to the batch. Thermo-mechanical and optical properties of the glasses are presented and discussed with
respect to different preparation methods. Comparison of the processes carried out in laboratory atmosphere and
performed by bubbling dry air through the melt evidences an increase of the lifetime of Er3+ ions from 4.5 (melting in air) to 7.7ms (flow of dry air), respectively. The confrontation of these lifetime with FTIR analysis results
confirm the decrease in OH radicals as the main factor for the luminescence lifetime improvement. Actually,
bubbling dry air during the melting process, adding fluorides or acombination of these two methods has lead to
aconsiderable decrease of hydroxyl-groups concentration. The decrease in concentration of OH-groups in the
glass was confirmed also by the FTIR spectra and analysis. Our results suggest that insufflating and bubbling dry
air during the melting process provided the most suitable results for the optical applications foreseen. In fact, this
method ensures high optical quality glass with low OH concentration while the glass produced presents thermo-mechanical properties well adapted for glass engineering. Although the addition of fluorinated chemicals to
the batch leads to astrong reduction of the OH concentration, the process compromises the thermo-mechanical
properties of the phosphate glass system.

397

A new equation to describe crystal

growth rates in glasses
Rodrigues B. P1, Zanotto E. D.2, Wondraczek L.1
1
2

Otto-Schott-Institut fr Glaschemie, FSU, Jena, Germany;

LaMaV Vitreous Materials Laboratory, UFSCar, So Carlos, Brazil.

In our on-going work to further test and perhaps improve the Guided Random Parameterization Method for critical cooling rate calculation, recently proposed by Xu et al. [Appl. Phys. Lett. 97, 024102, 2010], we found ourselves
with acomputational problem: because of the decoupling of the effective diff usivity that controls crystal growth
from the viscosity at about 1.1Tg, the classical crystal growth models do not describe the experimental crystal
growth data in the entire temperature range from liquidus to Tg. To facilitate our computations we needed an
equation that can describe the crystal growth rates throughout the entire temperature range. Therefore, in this
work we propose anew, semi-empirical equation and show its application to asuccessful analysis of experimental
growth rate data for most of the ten oxide glass-forming systems tested.

ICG Prague 2013 289

400

Lithium self-diffusion and electrical

conductivity in lithium silicate glasses
Bauer U.1, Welsch A.-M.1, Behrens H.1,2, Horn I.1, Rahn J.3
1

Institute of Mineralogy, Hannover, Germany

ZFM Centre for Solid State Chemistry and New Materials, Hannover, Germany
3
Institute of Metallurgy, Clausthal, Germany

401

Aimed to improve the understanding of lithium migration mechanisms, this study focuses on defining the dynamic parameters in two types of binary Li-silicate glasses. The isotope exchange experiments and conductivity
measurements yielded the activation energies and diff usion coefficients of lithium transport processes in Li2Si3O7
and Li2Si6O13 glasses. The influence of thermal history on glass properties was studied on thermally unrelaxed
and relaxed glasses. To experimentally investigate the kinetic isotope effect between 6Li and 7Li isotopes the glass
samples were prepared with different Li-isotopy, including the natural lithium composition (7.42% 6Li, 92.58%
7
Li) and nearly isotopically pure glasses (94 % 6Li and 6% 7Li; 99% 7Li and 1% 6Li). The glass samples of same
composition but different isotopy were combined for diff usion experiments in couples and triples. The diff usion
profi les developed in the temperature range between 511 and 664K were analyzed applying the femtosecond laser
ablation coupled with plasma mass spectrometry (fs LA-MC-ICP-MS) technique and confirmed by secondary ion
mass spectroscopy (SIMS). The experimentally obtained self-diff usion coefficient, DLi,IE , and the ionic diff usivity,
D,Li derived out of specific conductivity data can be used to provide information about the prevailing correlated
nature in Li-diff usion. Thereby it is indicated that ~70 % of displaced lithium ions are successful for long-range
transport in Li2Si3O7, in contrast to only ~30% in Li2Si6O13, suggesting atendency for an increased correlated
Li-migration coupled with the decreasing Li-concentration. In comparison, about the half of jumps are successful
for long-range transport of ions in LiAlSi2O6 glass.

The role of Al in the potential

landscape of Li-Al-Si glasses
Welsch A. M.1, Ross S.1, Behrens H.1,2
1
2

Institute for Mineralogy, Hannover, Germany;

ZFM Centre for Solid State Chemistry and New Materials, Hannover, Germany

Li-containing aluminosilicate glasses and nanocrystalline materials are well-known for their negative thermal
expansion coefficient, and are as such broadly used in high precision thermo and electro-optics. They exhibit
high chemical and mechanical stability and feature high lithium mobility. However, the mechanisms governing
the transport processes of lithium ions in silicate-based networks are insufficiently understood. The exact nature
of the interaction of light mobile Li-cations and tetrahedrally coordinated Al bound within the potential landscape is yet to be determined. The sensitivity of glass properties such as density, viscosity, refractive index, electrical conductivity etc, relative to the degree of polymerization and the Al/Si substitution has been well established.
This work is focused on studying the interdependency between the local potential landscape formed by Al and Si
tetrahedra and the transport of lithium, as the only mobile species. For this purpose we have primarily concentrated on studying Li-dynamics in the aspects of Al-content in the local structure and the degree of polymerization in the two series of synthetic Li-Al-Si glasses. Raman spectroscopic analysis was used to determine the local
structure in polymerized and depolymerised samples, quantifying the individual Q-species abundance. For both
polymerized and depolymerised glass samples, impedance spectroscopy measurements indicated linear dependency of specific conductivities and exponential dependency of activation energies with the Al-content, contrary
to only partial dependencies observed as afunction of Li-content. Additionally, in contrast to [AlO4] sites, the
negative potentials localized around non-bridging oxygens appear to require more energy in mobilizing lithia.

290 Poster Contributions

403

Light-field induced surface patterning

of chalcogenide glasses
Reinfelde M, Jirgensons M, Teteris J.
Institute of Solid State Physics, University of Latvia, Latvia

Recently anumber of studies on direct surface structure formation by holographic recording were carried out
in thin layers of chalcogenide semiconductors. This phenomenon is due to photoinduced mass transport during
comparatively long light illumination. Dependence on recording light polarization as well on grating period was
studied. Efficiency of recording is defined by distribution of electric field vector of resulting interference pattern
inside the recording media. In this work we will present the results obtained on bulk 1mm thick As2S3 and As-SSe samples. Employing the very stable large period polarization modulated pattern (period d>40m) it is possible
to achieve surface reliefs as high as ~12m.

405

Synthesis and characterization

of a phosphate low melting glass
Eftimie M., Dima V., Volceanov A., Dima R.
University Politehnica, Bucharest, Romania

The stannous-fluoro-chloro-phosphate glasses are avery new field of research that is treated with great interest
because it opens very interesting and promising perspectives, especially in the optical and electronic fields. In
the ternary system P2O5 SnCl2 PbF2 the 40%P2O5 55%SnCl2 5%PbF2 molar composition was selected. For
the studied melt the density, thermal expansion, basicity and IR absorption were determined. The IR absorption
spectra highlight the existence of the absorption bands which are characteristic for the P-O- and Sn-O-P-bonds
vibration. These bonds contribute to increased chemical durability, since it seems that Sn acts as anetwork former
that strengthens the structure of these glasses.

Stoch P.1, Ciecinska M.1, Zachariasz P.2, Stoch A.3

1

AGH University of Science and Technology, Krakow, Poland;

National Centre of Nuclear Research, Otwock, Poland
3
Institute of Electron Technology Krakow Division, Krakow Poland

The P2O5 Fe2O3 glass system is of great interest for scientific reason and because it is being considered as amatrix for the storage of different types of radioactive waste. Conventional phosphate glasses have poor chemical
durability which could limits their potential applications. However increasing iron content improves significantly
durability of the glasses by replacing weak P O bonds by much stronger Fe O. The 60P2O5 40 Fe2O3 glass
was chosen as abase glass for vitrification of asimulated waste composed of Al2O3, Na2O and Cs2O. Structural
changes of the local iron environment of the base glass caused by vitrification of different amounts of waste were
investigated using 57Fe Mssbauer spectroscopy. The obtained spectra are composed of paramagnetic doublets
which were assigned to Fe3+ and Fe2+ and changes in redox ration were observed. The more detailed analysis of
the measured spectra revealed at least two different Fe3+ sites which were described as aFe3+ in tetrahedral and
octahedral symmetry. The average hyperfine interaction parameter were obtained. The structural role of the iron
and their changes during vitrification is discussed.

ICG Prague 2013 291

409

Mssbauer efect studies of iron phosphate

glasses for radioactive waste immobilisation

411

Crosstalk and fiber fuse

on hole walling multi core fibers
Sekiya E. H.1, Saito K.1, Bing Y.2, Ogura A.2, Ohsono K.2
1
2

Toyota Technological Institute, Nagoya, Japan;

Hitachi Cable, Ltd., R&D Laboratory, Hitachi-shi, Japan

416

Recently, it has been pointed out that the transmission capacity for systems based on conventional single-core
single-mode optical fiber (SMF) is growing to reach its fundamental limit in near future. To overcome these
limitations new technologies have been developed and multi core fibers (MCFs) with different designs has been
propose and developed to realize MCFs with high core density and low cross-talks. In this work, radial line arrayed holes walling between adjacent cores has been proposed to minimize the crosstalk. To observe the influence
of holes walling, MCFs with 3 conventional single mode cores intercalated with 3 dispersion compensation cores
without and with holes walling were fabricated. The measured crosstalk between adjacent cores through 6.7km
of MCF without holes walling and then extrapolated to 100km varies from 11.8 to 44.3dB. In the other hand,
the measured crosstalk through 3.5km of MFC with holes walling and then extrapolated to 100km varies from
43.4 to 53.9dB. The present results confirm that the holes walling is effective to suppress crosstalk. The fiber
fuse experiment has been carried out using an Erbium doped fiber laser (EDFL) operating at 1,550nm. In MCF
without holes walling, the fuse threshold power (Pth), which is the minimum power that the plasma propagate, are
almost the same in the 3 SM cores and around 1.45W. The Pth in conventional single core was around 1.4W. Other
parameters such as plasma propagation speed, bubbles interval also are similar in MCF and SMF. The crosstalk
and fiber fuse measurements in other MCFs has been carried out to investigate its influence on the fiber fuse
parameters, and will be reported also.

Preparation of sintered silica glass

using mesoporous SiO2/PVA composite
Fujino S1., Ikeda2 H.,Kida1
1
2

Kyushu University, Fukuoka, Japan;

Institute for Electronic Science, Hokkaido University, Sapporo, Japan

427

We researched glass preparation process by use of inorganic/organic nanocomposite. To obtain monolithic transparent silica glass by sintering SiO2 nanoparticles, we prepare an SiO2/PVA mesoporous material.
We demonstrated fabrication of submicron patterns on silica glass by roomtemperature imprinting method.
Micropatterns on the n anocomposite are fabricated by imprinting a mold at room temperature for 5MPa in
air atmosphere. The nanocomposite has astrong network made of hydrogen bonding interactions between the
silanol groups of SiO2 nanoparticles and the hydroxyl groups of PVA. This strong network structure prevents
destruction of the nanocomposite due to compressive stress during imprinting. After sintering the nanocomposite at 1,100C, micropatterned silica glass is obtained. The process described, herein, provides an attractive,
low-temperature alternative to fabricate micropatterns on silica glass. And Nano metals such as Cu, Au, Pt can
be printed on the surface or inside of nanocomposite and can form circuit pattern by sintering. Thus circuit on
glass can be formed. The novel transparent glass we prepared would be conducive to its use in optical sensor, light
guide, optical lens, and microchip.

Formation of nuclei over liquidus temperature

and their influence on the properties of glass melt.
They may have an influence on glass strength?
Smrek J.
Electroheat s.v.p.d. Praha, Czech Republic

When measuring the light transmission in molten glass was observed an increase in the extinction within temperatures 1,0001,300C, well above the liquidus temperature, when measured with increasing temperature,
while the measurements at decreasing temperature extinction is low in temperatures up to 1,0001,100 C. Since

292 Poster Contributions

the similar phenomenon is also observed in measuring the viscosity, aexamination was made in the described
high temperature viscosity measurement also. Initial investigation was performed on sufficient in detail measured standard glasses of ASTM. Seems that the deviation from astraight line of viscosity in Arrhenius form
log =A + B / T comes with most glass melts at viscosity of 60Pas (log=1.62). Since Arrhenius curve applies
to unassociated liquid, it can be assumed that the higher viscosity leads to formation of associated departments
fluctuations (or fluctuants?) which increases the viscosity by jump. From equations for the viscosity of suspensions can be calculated concentration of these nuclei around 1% vol. Further was used the latest available measurements and measurements concentrated in Sciglass, soft and hard glasses. Was investigated both viscosity and
electrical conductivity, but it seems that, in the sufficiently accurately measured density of molten glass, its linear
temperature dependence deviates away from alinear dependence on the temperature as well.
It offers the presumption that the formation of these nuclei concentration fluctuations can cause low tensile strength
of the glass. Because viscosity of 60Pas correspond to temperatures 100200K above the temperature of forming, it is
the question how quickly is necessary to cool to this temperature. It is now managed only by fibers drawing.

431

Decoupling between crystal growth

and viscosity in barium disilicate glass
Rodrigues A. M., Zanotto E. D.
Vitreous Materials Lab, PPG-CEM, Federal University of So Carlos UFSCar, So Carlos, Brazil.

We performed an analysis to find experimental evidence to confirm or not whether the diffusion coefficients calculated
from viscosity data (using the Eyring equation) fails to describe the temperature dependence of crystal growth rates. It
is noteworthy that previous studies, principally based on literature data (mostly conducted by our own group), indicate
that this correlation fails for oxides glasses at about1.1-1.2Tg resulting in aphenomenon often denominated decoupling
or breakdown. In this work we calculate and compare the diffusion coefficients obtained via crystal growth kinetics
and viscous flow from data measured in awide undercooling range for astoichiometric barium disilicate glass (BaO.
2SiO2). The data analysis was performed using the VFT and MYEGA viscosity equations and by the Screw Dislocation
growth model. For this particular glass aclear decoupling was observed at approximately 1.1Tg.

438

Kinetics of leaching of 725 QN glass grains

under flow-through conditions in distilled
water and in borate coolant solution
Michlkov J.1, Vlkov P.1, Faturkov K.1,
Kakov H.1, Vokelov J.1, Chromkov M.1, Soltsz V.2, Lika M.1
1
2

Vitrum Laugaricio Joint Glass Center of IIC SAS, TnUAD, FChPT STU, and RONA, Trenn, Slovakia
VUEZ, a.s., Levice, Slovakia

The corrosion resistance of 725 QN glass grains with the composition of 725 QN fibrous insulation used in nuclear
power plants was tested at flow-through conditions during 336 hours in distilled water and in borate coolant solution (H3BO3/NaOH) at the flow rate of 12ml/hour, at temperatures (55, 70, 80, and 90)C. For each temperature
four parallel experiments were performed. The concentration of leached elements (Al, Ca, Fe, K, Mg, Mn, and
Si) in the solution was determined by optical emission spectroscopy with inductively coupled plasma (VARIAN
Vista MPX/ICP-OES). The observed time dependences of the normalized amount of leached elements were
described by the empirical Helebrants empirical kinetic equation. The stationary leaching rates at different temperatures were obtained by this method.
Acknowledgement
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project ZDESJE, ITMS code 26220220084, of the Operational Program Research and Development funded
from the European Fund of Regional Development.

ICG Prague 2013 293

439

Kinetics of leaching of 725 QN glass fibers

under static conditions in distilled water
and in borate coolant solution
Vlkov P.1, Faturkov K.1, Kakov H.1, Chromkov M.1, Soltsz V.2, Lika M.1
1
2

Vitrum Laugaricio Joint Glass Center of IIC SAS, TnUAD, FChPT STU, and RONA, Trenn, Slovakia
VUEZ, a.s., Levice, Slovak Republic

443

Corrosion resistance of 725 QN glass fibers commonly used as thermal insulation in nuclear power plants was
studied under static conditions. Experiments have been conducted during 720 hours in distilled water and in
borate coolant solution (H3BO3/NaOH) at temperatures of 55C, 70C, 80C and 90C. Concentrations of elements extracted from the glass into the solution were analyzed by atomic emission spectrometry with inductively
coupled plasma (VARIAN Vista MPX). Time dependences of the total amount of leached elements Al, Ca, Fe,
K, Mg, Mn, Na, andSi from glasses into the solution were determined. The experimental results were described
by Helebrants kinetic model. The obtained parameters of the kinetic model can be used for prediction of glass
corrosion under different experimental conditions.
Acknowledgement
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project ZDESJE, ITMS code 26220220084, of the Operational Program Research and Development funded
from the European Fund of Regional Development.

Raman spectra and structure of glasses

for Chrompic vitrification
Chromcikova M.1, Liska M.1, Teplanova M.1, Vokelova J.1, Gavenda T.2
1
2

Vitrum Laugaricio Joint Glass Center of IIC SAS, TnUAD, FChPT STU, and RONA, Trencin, Slovakia;
Institute of Chemical Technology, Prague, Czech Republic

Vitrification is utilized for the processing of cooling medium of stored fuel assemblies in A1 nuclear power plant
in Jaslovsk Bohunice in Slovakia. The so-called chrompic (a mixture of potassium chromate and potassium
dichromate) is fi xed into aboro-alumino-silicate glass matrix. The present contribution deals with the Raman
spectra and structure of glasses with chemical composition close to the contemporary used glass for chrompic
vitrification. The chemical composition of 7-components studied glasses can be characterized (in weight%) as:
(3.5 3.5)% Li2O(9.0 5.0)% Na 2O(14.5 3.5)% B2O3(5.5 5.5)% Al2O3(5.5 5.5)% TiO2(4.5 4.5)% Fe2O3
(57.5 5.5)% SiO2. The Principal Component Analysis is used for determination of the number of spectral active
independent components in the studied set of glasses. An attempt is made to assign these components to particular structural motifs defined by the Shakhmatkin Vedishcheva thermodynamic model of studied glasses.
Acknowledgement
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project ZDESJE, ITMS code 26220220084, of the Operational Program Research and Development funded
from the European Fund of Regional Development.

294 Poster Contributions

447

Kinetics of leaching of 725 QN glass fibers

under flow-through conditions in distilled
water and in borate coolant solution
Vokelov J.1, Vlkov P.1, Faturkov K.1,
Kakov H.1, Michlkov J.1, Chromkov M.1, Soltsz V.2, Lika M.1
1
2

Vitrum Laugaricio Joint Glass Center of IIC SAS, TnUAD, FChPT STU, and RONA, Trenn, Slovakia
VUEZ, a.s., Levice, Slovakia

Glass fibers are commonly used as thermal insulator in nuclear power plants. The corrosion resistance of 725
QN glass fibers was tested at flow-through conditions during 336 hours in distilled water and in borate coolant
solution (H3BO3/NaOH) at the flow rate of 12ml/hour, at temperatures (55, 70, 80, and 90)C. For each temperature four parallel experiments were performed. The concentration of leached elements (Al, Ca, Fe, K, Mg, Mn
and Si) in the solution was determined by optical emission spectroscopy with inductively coupled plasma (VARIAN Vista MPX/ICP-OES). The observed time dependences of the normalized amount of leached elements
were described by the empirical Helebrants empirical kinetic equation. The stationary leaching rates at different
temperatures were obtained by this method.
Acknowledgement
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project ZDESJE, ITMS code 26220220084, of the Operational Program Research and Development funded
from the European Fund of Regional Development.

449

Study of glasses in the Sb2O3-Li2O-MoO3

system by Raman and NMR
Hamzaoui M.2, Lebullenger R.1, Poulain M.1, Soltani M. T.2, Trebosc J.3, Moreac A. 4
1

UMR 6226-ISCR-Verres et Cramiques, Rennes, France;

Laboratoire de Chimie Applique, Universit Biskra, Algeria
3
UMR 8181 UCCS, ENSC, Lille, France
4
UMR 6251 IPR Rennes, France
2

Antimony oxide based glasses belong make aspecial group of Heavy Metal Oxide glasses (HMO). They have been
the subject of many researches in recent years for their low phonon energy, high refractive index, non linear optical properties and large optical transmission spectrum. These antimony based glasses have potential applications
in active and passive devices.
By using classical routes (melting casting), novel glasses synthesized in silica crucibles were obtained in the
combination of Sb2O3, Li2CO3 and MoO3 precursors. The limits for glass formation have been investigated and the
characteristic temperatures such as glass transition Tg, onset of the crystallization Tx, and maximum of crystallization Tp have been measured using differential scanning calorimetry (DSC). Several physical characterizations
have been carried out on these new glasses. They concern the glass densities, molar volumes, elastic and mechanical measurements and viscosity of bulk samples.
Non monotonous behaviours were observed when molybdenum concentration increase. Structural characterisations by NMR and Raman permit to explain these latter behaviours.

ICG Prague 2013 295

450

Kinetic model of 725 QN glass leaching

under static conditions in distilled water
and in borate coolant solution
Faturkov K.1, Vlkov P. 1, Kakov H. 1, Chromkov M. 1, Soltsz V. 2, Lika M. 1
1
2

Vitrum Laugaricio Joint Glass Center of IIC SAS, TnUAD, FChPT STU, and RONA, Trenn, Slovakia
VEZ a.s., Levice, Slovakia

455

Leaching tests were performed on grained glass samples prepared from melted bulk glass with chemical composition of 725 QN glass fibers used as the insulating material in nuclear power plants. The static leaching tests were
performed at four temperatures 55C, 70C, 80C and 90C within 30 days. Distilled water and coolant solution
(H3BO3/NaOH) were used as corroding medium. Concentration of leached elements Al, Ca, Fe, K, Mg, Mn, Na,
and Si in the corrosion medium was analyzed by ICP optical emission spectroscopy. The composition of the
leaching solution was described by the time dependencies of normalized leached amounts of elements. Obtained
experimental results were described by the Helebrants kinetic model and the initial leaching rates of individual
elements were determined this way. Obtained kinetic model allows characterizing the partial processes involved
in the glass corrosion by its activation energy and quantifying of the glass chemical durability.
Acknowledgement
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project ZDESJE, ITMS code 26220220084, of the Operational Program Research and Development funded
from the European Fund of Regional Development.

Novel barium-free alkali based glass-ceramic

compositions for application as SOFC sealants
De Miranda A. C.1, Smeacetto F.1, Salvo M.1, Chrysanthou A.2, Ferraris M.1
1
2

Department of Applied Science and Technology, Politecnico di Torino, Torino, Italy

School of Engineering and Technology, University of Hertfordshire,UK

457

The development of sealants for solid oxide fuel cells (SOFCs) is asignificant challenge as they must meet very restrictive requirements; they must withstand the severe environment of the SOFC (i.e., be resistant to oxidative and
reducing gas environments) and be thermo-chemically and thermo-mechanically compatible with the materials
to which they are in contact with. This study focuses on the preparation and characterization of two barium-free
glass compositions with self-healing behaviour, labelled as SACNKMg and KMBY, and based on the Ca-Al-NaSi-O system. Each glass had slightly differences in the Ca-Al-Na-Si proportion, as well as in the amount of K2O,
B2O3,Y2O3 and MgO as additives. The glasses were characterized by heating stage microscopy, differential thermal
analysis, dilatometry, X-ray diffraction, and Vickers microhardness. Both new glass-ceramic sealant compositions
showed excellent compatibility with Crofer22APU coated with Mn1.5Co1.5O4 (obtained by thermal co-evaporation
method) and anode supported electrolyte (YSZ), as revealed by SEM and EDS measurements. No reactions, failure
or cracks formation were observed at the Mn1.5Co1.5O4 coated Crofer22APU/glass-ceramics interface and between
the glass-ceramics and YSZ after thermal cyclic tests at 800C for 500 hours in air atmosphere.

Innovative testing solutions adapted

to the new challenges of the glass industry
Ballon A.2, Boistel P.2, Cabodi I.2, Citti O.1, Fourcade J.1, Gaubil M.2, Gleize V.2, Massard L.2
1
2

Saint-Gobain Northboro R&D Center, Northborough, USA;

Saint-Gobain CREE, Cavaillon, France

Several glasses have been developed in recent years for new applications (touch screen, thin films) or to improve
performance of existing applications (display, wind blades, lighting, photovoltaic panels ). Even though they

296 Poster Contributions

have different compositions (low iron sodalime, alkali free borosilicate, alkali aluminium silicate) they all have
in common their need for superior glass quality with minimum defects and tighter tolerances. Glass makers had
to modify furnace operating conditions to adapt to new melting and forming temperatures. New glass compositions and different operating temperatures have adirect impact on performances of refractories, such as corrosion resistance, stoning potential, blistering potential and thermo-mechanical resistance.
For the past 10 years, SEFPRO R&D has put together innovative testing methods to help assess and study the wear
mechanisms of our refractories under these new conditions and when needed develop new refractories that answer the need of glass makers for higher quality materials and longer lasting furnaces. In this paper, we propose
to present some of these tests and the progresses they have helped making for the glass industry.

458

The thermodynamic model of leaching of 725 QN

glass in distilled water and borate coolant solution
Kakov H.1, Vlkov P. 1, Faturkov K. 1, Chromkov M. 1, Soltsz V. 2, Lika M. 1
1

Vitrum Laugaricio Joint Glass Center of the Institute of Inorganic Chemistry,

Slovak Academy of Sciences, Alexander Dubek University of Trenn, Faculty of Chemical
and Food Technology, Slovak Technical University, and RONA, j.s.c., Slovakia Republic;
2
VUEZ, a.s., Levice, Slovak Republic

Chemical durability of 725 QN glass in distilled water and in coolant solution (H3BO3/NaOH buffering solution)
was experimentally tested and compared with the results of thermodynamic model in present work. The static
leaching tests without replacement of media were realized at temperatures 55C, 70C, 80C and 90C during 30
days. The dissolution was followed by ICP OES. Thermodynamic model of equilibrium composition of liquid
phase was obtained by the PHREEQC soft ware for different amounts of dissolved glassy phase. Different assumptions were put on particular crystalline phases with respect to their ability to precipitate from oversaturated
solution. Such way the experimentally obtained time evolution of liquid phase was interpreted.
Acknowledgement
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project ZDESJE, ITMS code 26220220084, of the Operational Program Research and Development funded
from the European Fund of Regional Development.

Jonov .1, Clov Z.2, Klouek J.1

1

Laboratory of Inorganic Materials, Joint Workplace of the Institute of Chemical Technology Prague,
Technick 5, 166 28 Prague 6, and the Institute of Rock Structure and Mechanics ASCR, v.v.i.,
Holeovikch 41, 182 09 Prague 8, Czech Republic
2
Department of Glass and Ceramics, Institute of Chemical Technology Prague, Technick 5, 166 28 Prague 6

The glass button was found at archaeological research Salmas palace in Prague in 2009. This finding with its specific appearance and techniques processing ranks among unique discoveries and it was unambiguously worked of
handy glassmaker. There wasnt found any similar analogy in reasonable publications up to now. The aim of work
was to scrutinize the chemical composition of object and find out way and technology of his production. The glass
button is decorated not only with different types of soda-calcium opaque and transparent glass, but even with
gold (determined by method SEM/EDS). The pipe from blue-violet transparent glass (depth 1,3001,500m) was
winded up on incurvature metal stick. The pipe served as basis for other decorative elements. On basis of X-ray
image was designed the probable manufacturing process of the main load-bearing button and was read length
two iron sticks intervening to glass. The precision of production and using gold argue that button had to belong
to ostentatious clothing wearing evidently by very important person. We can conclude from established chemical
composition that object was not made in Bohemian glassworks.

ICG Prague 2013 297

459

Hand-decorated Renaissance glass button survey

and assessment technology of production

464

Doped tin fluorophosphates glasses:

A joint computationalexperimental effort to improve
solar cell efficiency through up and down conversion
Oelgoetz J. 1, Tanner T.1, York-Winegar J. 1,
Kovalskiy A. 1, Harper T. A. 2, Ulery H. 2, Brennan C. 2
1
2

Department of Physics & Astronomy, Austin Peay State University, Clarksville, TN, United States of America;
Department of Chemistry, Austin Peay State University, Clarksville, TN, United States of America

466

Solar cell efficiency is limited, in part, because only alimited range of the electromagnetic spectrum can be converted into electrical current. One way to improve this efficiency, without developing an improved photo-voltaic
cell, is to cover the cell with alayer of glass which can convert unusable parts of the electromagnetic spectrum
into usable light via photon up and/or down conversion. We are currently investigating the use of tin fluorophosphates glasses, which have been doped with organic dyes for such applications. This poster presents the latest
results of our efforts to model tin fluorophosphates glasses doped with organic dyes using the computational
chemistry program NWChem. Results from both ground state calculations, using density functional theory, and
excited state calculations, using time-dependent density functional theory will be presented along with comparisons to experimental spectroscopy.

Physicochemical essence of subendoeffect

(sub-Tg endoeffect) in glassforming substance
Minaev V.
National Research University of Electronic Technology

467

Tammans (1933) glass transition region lies between the transformation temperature of viscous flow liquid to
the solid fragile glassy state Tg and the temperature of its conversion to anormal fluid Tf. In the middle of this
area Tamman located the temperature Tw the temperature of bend on the property-temperature dependence
curve. Tammans Tg is below Tw. After the Lindigs (1959) works, Tammans Tg Tg(T) has been forgotten, and
his Tw was unreasonably called the glass transition temperature Tg. According to Winter-Klein (1953), Nemilov
(1971), Mazurin and others (1987), the glass transition region lies within the viscosity of cooling liquid =1078
...101416Pas. Common today Tg (Tammans Tw) characterizes the viscous-flow liquid at =1012,3Pas, ie located
approximately in the middle of the glass transition area. Subendoeffect in glass is located from 10 to 70C below
the conventional Tg (Ping Chen et al). Below this Tg at =10141016Pas the true glass transition temperature
Tammans Tg(T) is located, at which in the glass when temperature increases the heat capacity dramatically increases. This process requires additional energy generated during the heating of the glass free energy of viscous
flow activation E* (Nemilov, 1976). Exactly that energy we detect as subendoeffect when the brittle glassy solid
state transforms into viscous flow liquid at viscosity 1015Pas.

Structure and relaxation processes

of chalcogenide glasses of As-Se system
Minaev V., Kalugin V., Timoshenkov S., Mukimov D.
National Research University of Electronic Technology;

Experiments based on chalcogenide glasses of As-Se system are very common in the scientific literature. However, despite
this, many key questions regarding the structure and relaxation processes of these glasses still remain unanswered.
In this paper we have analyzed the system by studying such glasses as AsSe and As2Se3 that have agreat interest
among researchers. Analysis of the processes occurring in the glass at its vitrification and annealing carried
out based on the concept proposed by Minaev in 1987. According to the concept of polymeric-polymorphoid
structure of glass and glassforming liquid of individual chemical substances (ICS), glass is acopolymer of crystal

298 Poster Contributions

lattice structure fragments of different polymorphic modifications (PM) polymorphoids with no translational symmetry (long-range), but with short and intermediate-range orders of these modifications. For example,
for As2Se3 such modifications include: -modification high temperature PM (HTPM) formed at atemperature
of ~390C and atmospheric pressure and low temperature polymorphic modification (LTPM) of high pressure,
which was obtained only at pressure of 3070kbar.
The content of different PM structure fragments in the glassforming liquid dramatically affects the properties of
obtained glass. Thus, changes in the structure and properties of glasses of the As-Se can be predicted based on
changes in the concentration ratio of polymorphoids (CRP) HTPM:LTPM by external conditions such as temperature, pressure, time, etc.

468

Changing function into art by creating new trend

in designing shower cabinets by glass fusing technique
Elhammamy W. O.
Faculty of Applied arts, Giza, Egypt;

The new trend is initiated when it comes to bath enclosures with many challenges as how to add anew artistic
touch without using an extra space. So, the first direction was the thinking of creating anew look and design to
the shower cabinet to be not only afunctional but also an enjoyable artistic glass piece which is created by the
Glass fusing technique that relying mainly on customization satisfying different taste and styles. The shower cabinets may customize with the different bath elements as (Ceramic tiles, flooring style, and paint scheme).Also, the
design may comes up with creating different textures inside the glass showers to have the relief sculpture touch
and look. And the shower cabinet now becomes an artistic functional glass piece in the bathroom.

470

New antimony-tungstate oxide glasses

Soltani M. T.1, Poulain M.2
1
2

Dpartement de physique, Facult des sciences, Universit M. Khider BP 145 RP, 07000 Biskra, Algrie.
UMR 6226 Verres et Cramiques Campus de Beaulieu, Universit de Rennes1, 35042, Rennes, France.

Antimony oxide as one of the HMO glasses attracted researches recent years for their low phonon energy, high
refractive index and large optical transmission spectrum. By using classical routes, glasses synthesized in vitreous carbon and silicate crucibles were obtained in the binary Sb2O3-WO3 and in the ternary Sb2O3-WO3-M2O
(M=Li, Na or K) glass system The ternary glasses contain up to 70 (mol%) of WO3. The incorporation of alkali
oxides M2O in ternary systems gives large vitreous area and enhances the stability of antimony glasses. Samples
are red orange in binary Sb2O3-WO3 and turn yellow by the addition of the alkali oxide. Several physical characterization are carried out such as DSC measurements, elastic modules, micro-hardness, thermal expansion and
optical measurements and are discussed in term of the structural role of tungsten in these glasses. These highly
stable glasses suggested having potential application as low phonon energy glasses for infrared transmission and
hosts for rare earth ions in active devices.

Kostka P.1, Klucka M.1, Dvorsky D.1, Kohoutkova M.1, Zavadil J.2
1
2

Institute of Rock Structure and Mechanics, AS CR, Prague, Czech Republic

Institute of Photonics and Electronics, AS CR, Prague, Czech Republic

Glass formation within TeO2PbCl2MO3 systems, where M=Mo or W, was investigated by melting of small quantities of raw materials. Glass forming area falls into the TeO2 rich corner in both systems. It turns out that the
glass forming ability is much better for WO3 containing system. Glass transition temperatures were determined by
thermal analysis performed on DSC at heating rate of 10C/min. They fall in ranges of 250350C and 250300C

ICG Prague 2013 299

471

TeO2 based oxy-chloride glasses containing WO3 or MoO3

480

for WO3 and MoO3 containing systems, respectively. In some cases the experimental setup allowed also the determination of crystallization onset and crystallization peak. Bulk samples were prepared by melting in open silica/
alumina/platinum crucibles in air atmosphere; poured glasses were annealed at Tg and cooled to room temperature.
Density of annealed glasses was determined (5.56.5g/cm3, higher density values belonging to WO3 system) and
correlated with molar volumes of starting compounds. Transmission spectra were recorded and short wavelength
and infrared absorption edges were determined. Glasses are transparent in broad wavelength range with high energy absorption edge at 440 and 480nm; and the infrared absorption edge at 6.5 and 7.0 microns for WO3 and MoO3
systems, respectively. Band gap was determined from short wavelength absorption edge and correlated with the
broad luminescence band that could be observed by low temperature photoluminescence spectroscopy. This broad
band luminescence is mediated by deep energy states in the gap. WO3 containing glasses appear more promising for
further investigation, for doping with rare earths elements and for use in photonics applications.

Physical properties of selected

boro-alumino-silicate glasses for HLW vitrification
Teplanov M., Chromkov M., Faturkov K., Lika M.
Vitrum Laugaricio Joint Glass Center of IIC SAS, TnUAD, FChPT STU, and RONA, Trenn, Slovakia

490

Vitrification is ahigh-temperature process of fi xation of liquid radioactive waste, originally used for cooling of
fuel elements after their removal from reactor of A1 nuclear power plant into (Jaslovsk Bohunice in Slovakia)
aglass matrix. The so-called chrompic (a mixture of potassium chromate and potassium dichromate) is fi xed into
aboro-alumino-silicate glass matrix. The present contribution deals with the compositional dependence of selected physical properties of glasses with chemical composition close to the contemporary used glass for chrompic vitrification. The chemical composition of 7-components studied glasses can be characterized (in weight%)
as: (3.5 3.5)% Li2O(9.0 5.0)% Na2O(14.5 3.5)% B2O3(5.5 5.5)% Al2O3(5.5 5.5)% TiO2(4.5 4.5)%
Fe2O3(57.5 5.5)% SiO2. The thermal expansion coefficient, glass transition temperature, glass density, viscosity,
molar volume, and water resistance were measured for 15 studied glasses. The empirical functions describing the
compositional dependence of particular physical properties were found.
Acknowledgement
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project Centre of excellence for ceramics, glass, and silicate materials ITMS code 26220120056, based on
the Operational Program Research and Development funded from the European Fund of Regional Development.

Bubble nucleation temperature and intensity

of bubble nucleation in the glass melt
Cincibusova P.1, Vernerova M.1, Maehara T.2
1

Laboratory of Inorganic Materials, Joint Workplace of the Institute of Chemical Technology Prague,
Technick 5, 166 28 Prague 6, and the Institute of Rock Structure and Mechanics ASCR, v.v.i.,
Holeovikch 41, 182 09 Prague 8, Czech Republic;
2
Asahi Glass Co., LTD., Tokyo, Japan

Nucleation of bubbles is an important physico-chemical process with converse effects on glass melting. The bubbles nucleated at fining temperatures prolong the fining process or even evoke volume glass foaming and other
bubbles, arising as aconsequence of temperature, pressure or composition reboil, are the important source of
glass defects. On the other side, the bubbles nucleated, grown on undissolved sand particles or chemical inhomogeneities produce the melt microconvection which enhances the dissolution process. It is therefore worth dealing
in detail with the bubble nucleation process in glass melts. The direct observation of the nucleation process under
defined condition seems to be the proper way to define the values of nucleation parameters. The relevant experiments were realized by the high temperature observation method, consisting in observation and recording the
melt with the immersed Pt wire under slowly rising temperature (2C/min) by CCD camera and in evaluation

300 Poster Contributions

of the acquired record. The value of the nucleation temperature represents the state, under which the supersaturation of the melt is sufficient to produce the first nuclei and consequently, the growing bubbles. Because the
nucleation temperature is the first chance for bubbles to be nucleated by the heterogeneous mechanism, the nucleation intensity at nucleation temperature is low. Technology of glass melting needs nevertheless knowledge of
the intensity of bubble nucleation at temperatures higher than nucleation temperature because the numbers of
nucleated bubbles and the volume of the evolved gas give the fundamental information about the occurrence of
potential bubble defects and about the degasing of the melt.

491

The semiempirical model

of the bubble behaviour in molten glass
Nmec L.1, Jebav M.1, Cincibusov P.1, Vernerov M.1, Klouek J.1, Trochta M.2, Brada J.2
1

Laboratory of Inorganic Materials, joint workplace of the Institute of Chemical Technology Prague
and the Institute of Rock Structure and Mechanics ASCR, v.v.i., Prague, Czech Republic
2
Glass Service, Inc., Vsetn, Czech Republic

A semiempirical model of the bubble growth or its dissolution in glass melts containing afining agent has been derived.
This model applies the experimental data from bubble observation at melting and fining temperatures. The experimental data needed for the model involved the temperature dependences of the average growth rate of the bubble radius
and the average concentration of the fining gas in bubbles. Both sets of values were measured in the laboratory in the
float glass. The measurements of the solubilities and diffusion coefficients of the gases present in the glass needed
for the complete analytical model of multicomponent bubbles were thus avoided. The course of the partial bubble
absorption with the temperature decreasing was simulated by means of two factors modifying the experimental values
of the bubble growth rates at constant temperature. The modelled temperature dependence of the bubble growth rate
corresponding to the experimental observations in the soda-lime-silica glass will be presented.

Trnovcov V.1, Kostka P.2, Laba V.1, Podoliniakov J.3, Pedlkov J.2, Bok O.4
1

Faculty of Education, Catholic University, Ruomberok, Slovakia

Institute of Rock Structure and Mechanics, Academy of Sciences of the Czech Republic, Prague, CR
3
Faculty of Natural Sciences, Constantine the Philosopher University, Nitra, Slovakia
4
Faculty of Materials Science and Technology, Slovak University of Technology, Trnava, Slovakia
2

Influence of the crucible material (Pt, Al2O3), chemical form of one constituent (PbO, Pb3O4), and doping with Nd3+
ions (500wt-ppm Nd2O3) on ac and dc conductivities, static permittivity, dielectric relaxation, short wavelength
optical edge, and infrared (IR) absorption of binary and ternary glasses of the system PbO-Ga2O3-Bi2O3 is presented
and discussed. The experimental results obtained for glasses prepared in Pt crucibles with non-damaged surfaces
and in those with damaged surfaces are also compared.
IR absorption of all glasses prepared in Pt crucibles is almost the same, showing vibrational bands of H2O and CO2,
and the absorption edge near 6.57m. Melting procedure in Al2O3 crucibles is not suitable; the transmittance of
glasses is low due to scattering losses. An influence of crucible on short wavelengths absorption edge is very pronounced. Preparation in an Al2O3 crucible shifts the absorption edge to ashorter wavelength significantly.
Temperature dependences of the dc conductivity are Arrhenius-like, all having the same conduction activation
energy (1.200.03eV). All binary glasses PbO-Ga2O3 have almost the same dc conductivity; the dc conductivity of
ternary glasses PbO-Ga2O3-Bi2O3 is about 100 times higher. The type of crucible and the chemical form of Pb have
only anegligible influence on the dc conductivity. Doping with Nd3+ ions slightly enhances the dc conductivity. Static permittivity of glasses prepared at 300C in Pt crucibles ranges from 22.2 up to 26.3, in dependence on the chemical form of lead. Binary glasses are stable up to 300C, ternary glasses change their properties irreversibly at 270C.

ICG Prague 2013 301

493

Influence of preparation conditions

on some physical properties of PbO-Ga2O3-Bi2O3 glasses

495

Materials determinants of bioactivity

and osteoinductivity of gel-derived
bioglasses of CaO-P2O5-SiO2 system
Cholewa-Kowalska K.1, Pawlik J.1, Osyczka A. M.2, Filipowska J.2, czka M.1
1

AGH University of Science and Technology, Faculty of Material Science and Ceramics,
Department of Glass Technology and Amorphous Coatings, Mickiewicza Ave. 30, 30-059 Cracow;
2
Jagiellonian University, Faculty of Biology and Earth Sciences, Institute of Zoology,
Department of Cell Biology and Imaging, Cracow, Poland

497

Bioactivity and osteoinductivity are the two important features of biomaterials. They predetermine of implant
integration with the living tissue as well as the stimulation of tissue to faster regeneration. Gel-derived glasses of
various content of silica SiO2 and calcium oxide CaO were obtained in the form of sintered tablets and powders.
Bioglasses in the form of powders were also used as amodifier of composites of PLGA and TiO2 matrix. Bioactivity test in vitro in simulated body fluid SBF was conducted as well as the responses of human bone marrow
mensenchymal stem cells (BMMSCs) examined. It has been found that the content of both SiO2 and CaO decides
on bioactivity and osteoinductivity of examined biomaterials but in different way. CaO promotes the surface
crystallisation of HAp in contact with SBF while the silica SiO2 effects favourably on positive cells responses.
Moreover, there is no simple correlation between HAp formation on materials surface in contact with SBF and
promote the bone mineral matrix creation. Materials factors may in various ways effect on this two phenomena.

Gel derived bioglasses modified by SrO2 addition

Cholewa-Kowalska K., Pawlik J., Laczka M.
AGH University of Science and Technology, Fac. of Mat. Sci. and Ceramics Krakow, POLAND;

498

Bioactivity and chemical reactivity of bioactive glass offer the ability to bond for soft and hard biological tissues.
Strontium (Sr) plays aspecial role in bone remodelling, being associated with both the stimulation of bone formation and areduction in bone resorption. Thus, the modification of bioglasses by partial substitution by Sr is
expected to increase biocompatibility without reduction bioactive properties. The present study investigates the
influence of SrO on structure, apatite-forming ability and physico-chemical degradation of bioactive glasses from
the CaO-SiO2-P2O5 system with the compositions (mol.%): A2: (54-x) CaOxSrO6P2O540SiO2; S2: (16-x) CaO
xSrO4P2O580SiO2, where x varies between 0 and 5. Bioglasses were prepared by Sol-Gel method and obtained
in the form of powders. The structural analysis of the glasses was made by FTIR and Raman spectroscopy. In vitro bioactivity of the samples was evaluated by soaking them in simulated body fluid (SBF) followed by structural
characterization using XRD, FTIR and SEM techniques. The results showed that the substitution of 5% Sr for Ca
in the glass composition slightly reduces the rate of formation of apatite layer onto the A2 glasses surfaces, but in
case S2 glasses apatite-like layer formation occurs only after 2 weeks in SBF. We expect that glasses with 15mol%
of SrO2 can exhibit bioactivity connect with optimal proliferation and differentiation of osteoblastic cells.

Characterisation of compositional
photosensitivity dependence of rare earth doped
RF-sputtered silica-germania thin films
Chiasera A.1, Chiappini A.1, Speranza G.2,
Ferrari M.1, Berneschi S.3,4, Calzolai R.3, Pelli S.3, Scarpelli I.3, Righini G. C.3,4
1

IFN CNR, Via alla Cascata 56/C, Povo, 38123 Trento, Italy
FBK, Via Sommarive 18, Povo, 38123 Trento, Italy
3
IFAC CNR, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy
4
Centro Studi e Ricerche Enrico Fermi, Piazza del Viminale 2, 00184 Roma (Italy)
2

Since the discovery of light-induced refractive index changes in silica materials, UV-writing of gratings in Gedoped optical fibres has become an important technological field for telecommunications and optical sensors.

302 Poster Contributions

Germanosilicate glass thin fi lms have also attracted aconsiderable interest in integrated optics, thanks to the
proof of stability of structures, like channel waveguides and diff raction gratings, obtained by UV photoimprinting. Various techniques have been used to deposit Ge-doped silica thin films, including plasma enhanced chemical vapour deposition (PCVD), flame hydrolysis deposition (FHD), and radio-frequency (RF)-sputtering. The
latter technique is particularly attractive due to the easiness of changing the film composition by co-sputtering
from different targets or simply by introducing adopant on top of the target. Previous works had shown that
RF-sputtered SiO2-GeO2 thin fi lms are highly photo-refractive and that the refractive index changes are positive
when the GeO2 content is around 25%. It is generally assumed that, for low doping levels, the photosensitivity increases linearly with germanium content. At higher doping levels this dependence is no more valid and some authors have also reported that the photoinduced variation of the refractive index changes sign when GeO2 content
is higher than athreshold value around 25%. With the aim of further investigating the dependence of refractive
index on the composition, we produced aset of RF-sputtered silica-germania thin fi lms, with germania concentrations in the range 0.18 to 0.47mol%, doped with erbium or co-doped with erbium and ytterbium. The fi lms
have been characterized by absorption and fluorescence spectroscopy; the photoinduced change of refractive
index n has been measured in areas irradiated by an excimer laser at doses up to 20kJ/cm2. Values of n of the
order of 210-3 were obtained in all the samples, thus showing only avery little dependence on the composition.
This index change, however, has been sufficient to photo-imprint channel waveguides having width in the range
4to 9m, and integrated optical structures like 14 splitters. Propagation losses were less that 1dB/cm at 1,300nm.

506

External coating methods for glass containers

Czarnacki K.1, Wasylak J.2
1
2

PolAmPack S.A. Oddzia Huta Szka ORZESZE w Orzeszu, ul. Gliwicka 59,43180, Poland,
AGH University of Science and Technology, Faculty of Materials Science and Ceramics,
Department of Glass Technology and Amorphous Coatings, av. Mickiewicza 30, 30-059 Cracow, Poland

For many years there has been scientific and industrial research into how to increase the mechanical resistance
of glass packaging. Factors influencing the correction of resistance parameters of packaging were the application
of heat treatment, glass digestion, and also different hot-end and cold-end coating. The aim of the following
investigations was to evaluate the effect of discovered coating application methods on mechanical resistance of
glass containers. I will attempt various ways of external coating of the bottle and also the application of hardened
polymer UV for cold end coating. The following results could be used as guidelines for future container weight
and the decrease of wall thickness.

Ivanova Z. G.1, Zavadil J.2,Hamzaoui M.3, Soltani M. T.3

1

Institute of Solid State Physics Bulgarian Academy of Scinces, Sofia, Bulgaria

Institute of Photonics and Electronics AS CR, Prague, Czech Republic
3
Dpartement de physique, Universit de Biskra, Algeria

Er-doped bulk glasses of the system Sb2O3-Na2O-ZnO have been investigated by transmission and photoluminescence (PL) spectroscopy. Two series of (Sb2O3)90-x(Na2O)10(ZnO)x and (Sb2O3)80-x(Na2O)20(ZnO)x compositions
have been chosen for this study. The doping level for both groups of samples was 0.25, 0.5 and 1.0mol% Er2O3.
The glasses studied have relatively high glass transition temperatures (Tg ~290C) and high thermal stability, the
maximum being at 0.5mol% Er2O3 (the difference between the crystallization and glass transition temperatures
has been found to be 185C). The transmission spectra exhibit sharp absorption bands of Er3+ centred at 489, 521,
652, 800, 980 and 1,530nm, and according to the energy level diagram of Er3+ ions, they are attributed to the optical transitions from the ground state 4I15/2 to the excited states 4F7/2, 2H11/2, 4F9/2, 4I9/2, 4I11/2 and 4I13/2, respectively.
Samples doped with Er concentration of 0.25mol% were studied in more detail by low-temperature PL spectroscopy. The fine structure of PL bands at 1,530 and 980nm measured at low temperature (4K) have been evaluated
in terms of Stark level splitting of corresponding Er3+ manifolds as afunction of glass composition and compared
with room temperature PL data.

ICG Prague 2013 303

507

Compositional dependences of photo luminescence

in antimonite Er-doped Sb2O3-Na2O-ZnO glasses

513

The microwave synthesis

of sodium silicate from perlite
Baghramyan V. V. 1, Sargasyan A. A. 1, Ghazaryan A. A. 1, Harutyunyan R. V. 1,
Petrosyan G. X. 1, Meliksetyan A. M. 1, Ponzoni C. 2, Rosa R. 2, Leonelli C. 2
1

Stone and Silicates Scientific-Industrial and Projecting Closed Joint-Stock Company,

Acharyan Str. 40a, 0040 Yerevan, Armenia, Fax: + 374 10 615842, E-mail: v_bagramyan@mail.ru
2
Universita degli Studi di Modena e Reggio Emilia, Via Vignolese 905/A, 41125, Modena, Italy,
Fax: +39 059 2056243,E-mail: cristina.leonelli@unimore.it

516

One of the most important tasks of contemporary inorganic chemistry and materials science is the development
of new methods for the synthesis of materials, which allow reducing energy costs and decreasing reaction time.
To these promising methods relates the microwave (MW) heating of reaction mixture. The microwave processing has several advantages in comparison with conventional methods of heating condensed matter (solids and
liquids): speed and lower inertia of heating, the lack of contact between heating material and heater, uniformity
of the heating material over the whole volume, the possibility of selective heating of components substances mixture and the high coefficient of efficiency. The study presents asystematic investigation of possibilities of using
microwave energy to obtain silicate solutions from perlite rocks, i.e. natural silica source, using astrong basic
environment by sodium hydroxide. Several hydrothermal synthetic protocols were carried out in amicrowave
oven (ETHOS, Milestone, Bergamo, Italy) at frequency of 2.45GHz and power of 600W. For sake of comparison,
parallel synthesis was carried at the solution boiling temperature, without microwave processing. The influence
of various factors on the degree of extraction of silicon dioxide, silica modulus and the reaction rate have been
studied. It has been evaluated that compositions of intermediate and desired products of synthesis of sodium silicatesolutionsare identical, irrespective of the method of heating microwave or thermal. Additionally, the use of
microwave radiationenergy allows considerably intensification (34 times)of process time for the hydrothermal
treatments of perlite in comparison with conventional heatingmethod.

Erbium-doped active optical fibers

with nanostructured host matrix
Kak I.1, Cajzl J. 1,2, Podrazk O. 1, Mrzek J. 1,
Aubrecht J.1, Peterka P.1, Nekvindov P.2, Matjec V.1
1
2

Institute of Photonics and Electronics ASCR, Prague, Czech Republic

Department of Inorganic Chemistry, Institute of Chemical Technology, Prague, Czech Republic

Erbium-doped fiber amplifiers (EDFA) are the most widely used optical amplifiers in photonics and optoelectronics. Er3+ ions are used because of their three-level radiative transition I11/2 I15/2 with emission around the wavelength of 1.5m. Emission at 1.5m falls into the 3rd telecommunication window where the silica optical fibers
exhibit the lowest optical attenuation. Nowadays, the attention is given to the development and characterization
of nanostructured optically active materials. Special optical fibers with the nanostructured rare-earth doped
matrix are known for their interesting optical properties. In this contribution we demonstrate the effect of the
nanostructured matrix doped with erbium ions on the optical properties of prepared active fibers. Several optical
fibers with nanostructured core were drawn from preforms prepared by different techniques, i.e. by common
doping from solution of erbium and aluminium ions, by deposition of the dispersed alumina nanoparticles with
either Er3+ ions or Er2O3, and by deposition of sol with the composition of erbium-doped YAG. Prepared optical
fibers were analyzed by structural and spectroscopic techniques such a Raman spectroscopy, absorption and
emission spectroscopy etc. The structural data were related to the luminescence properties of Er3+ ions to evaluate
the effect of the matrix structure to the luminescence properties of Er3+ ions. It was found that the presence of nanocrystals inside the fiber core improves the fiber-core homogeneity and decreases the optical background losses.
The presence of nanostructured alumina inside the core matrix enhances the luminescence properties of Er3+ ions.
The effect of nanostructure to the further optical properties is discussed in the contribution.

304 Poster Contributions

517

Properties of Eu2Ti2O7 nanocrystals

dispersed inside a silica matrix
Mrzek J.1 , Kak I. 1 , Podrazk O. 1 , Matjec V.1 , Bursk J.2
1
2

Institute of Photonics and Electronics ASCR, Prague, Czech Republic

Institute of Physics of Materials AS CR, Brno, Czech Republic

Lanthanide-titanium oxides crystallizing in apyrochlore structure RE2Ti2O7 have been extensively investigated in
recent years. According to the incorporated rare earth element (RE), formed materials provide us with awide range
of phenomenal physico-chemical properties; from anti-ferromagnetic behaviour to so called spin-ice materials or
novel optical materials. However, the final properties of these materials strongly depend on their crystalline structure. Moreover, their potential application in an opto-electronic industry requires acompatibility with the technology of thin-films. The common synthesis of RE2Ti2O7 results into the formation of thin films with poor optical and
mechanical quality. The properties of thin films can be improved by an encapsulation of RE2Ti2O7 nanocrystals
inside asilica matrix which improve the mechanical properties allowing the processing of thin films.
In this contribution we present aSol-Gel synthesis of nanocrystalline Eu2Ti2O7 encapsulated inside asilica matrix.
The starting sol was prepared by mixing the precursors of Eu2Ti2O7 with pre-hydrolyzed tetraethylorthosilicate.
Formed sol was treated to xerogel or deposed as thin films on planar optical substrates. Prepared samples were
thermally treated. The structural evolution of Eu2Ti2O7 nanocrystals inside asilica matrix was analyzed by structural and spectroscopic techniques such aX-ray diffraction, Raman spectroscopy, absorption and emission spectroscopy etc. Optical and luminescence properties of formed materials were related to their structural properties.
Presented approach allows us to prepare powders and thin films with tailored size and morphology of formed
nanocrystals in an excellent optical quality.

518

Surface tension of zirconium silicate glass melts

Gaprekov E., Lika M., Chromkov M.
Vitrum Laugaricio Joint Glass Center of Institute of Inorganic Chemistry SAS, Alexander Dubcek University of Trencin and Rona Lednicke Rovne, Studentska 2, Trencin SK-911 50, Slovak Republic

Surface tension of five-component glasses with as weighted composition xNa2O(15-x)K2OyCaO(10-y)ZnOzZrO2(75-z)SiO2 (x=0, 15; y=0, 10; z=0, 1, 3, 5, 7) were measured. The surface tension was determined over the
temperature range 1,2501,500C by the sessile and pendant drop method using the melt density value obtained by
independent experiment. The profile of drops was analyzed using the numerical integration of Laplaces equation. The
composition and temperature dependences of the surface tension were investigated. Linear temperature dependence of
measured surface tension was found for all studied glass melts. The effect of substitution K2O / Na2O, ZnO / CaO was
discussed. Also, the influence of increasing content of zirconia on the surface tension was analyzed.
Acknowledgement
This work was supported by the Slovak Grant Agency for Science under the grant VEGA 1/0006/12 and by the
Slovak Research and Development Agency Project ID: APVV-0487-11. This publication was created in the frame
of the project PVTECHSKLO, ITMS code 26220220072, of the Operational Program Research and Development
funded from the European Fund of Regional Development.

520

The chemistry and applications

of oxynitride phosphate glasses
Muoz F., Mascaraque N., Durn A., Muoz-Senovilla L.
Instituto de Cermica y Vidrio, Kelsen 5, 28049 Madrid, Spain

The substitution of nitrogen for oxygen in phosphate glasses might have opened the door for their application
in many fields, from the soldering or energy storage technologies to the optics and even in biomaterials science.
The main improvement in the properties of phosphate glasses as aresult of the nitridation has been the drastic
increase of their chemical durability. However, there are still many requirements from the processing point of

ICG Prague 2013 305

525

view that have not been dealt with, much less solved. The easiest way to perform nitridation is accomplished by
the thermal ammonolysis of the phosphate melt at moderate temperatures, being the viscosity of the melt akey
parameter that influences the feasibility of the process. This is determined by the composition of the melt and
so this will directly influence whether the substitution reaction can be accomplished or not. Furthermore, the
introduced nitrogen content and the way the oxynitride glass network is distributed within the oxide one are
also governed by the composition, and both will influence the final properties of the oxynitride glass. Therefore,
the knowledge of the structure at the short and intermediate ranges becomes also arelevant point to understand
and control the nitridation in phosphate glasses. The potential applications of phosphate glasses will require of
particular compositions that might, or might not, be suitable for nitridation. Hence, if one wants to improve their
chemical resistance by introduction of nitrogen, the processing of the glasses should be adequately changed to get
the desired properties. This talk will explore the requirements that must be fulfi lled in the nitridation of phosphate glasses, focusing on the viscosity of the melt as well as the secondary reactions that may take place during
the ammonolysis, and paying special attention to the properties needed for their final application.

Characterization of amorphous Sb2Se3 thin film

ernokov E.1, Todorov R.2, Holubov J.3, ernoek Z.3
1

JLSSC of IMC ASCR, v.v.i., and University of Pardubice, Faculty of Chemical Technology, Studentsk 84,
532 10 Pardubice, Czech Republic, eva.cernoskova@upce.cz.
2
Institute of Optical Materials and Technologies Acad. G. Bonchev Str., bil. 109, 1113 Sofia, Bulgaria
3
Department of General and Inorganic Chemistry, Faculty of Chemical Technology,
University of Pardubice, Studentsk 573, 532 10 Pardubice, Czech Republic

534

The amorphous Sb2Se3 film was prepared by thermal evaporation. Some thermoanalytical properties and Raman
scattering were studied. The film compositions were confirmed using of the energy dispersive X-ray analysis. The
powder XRD analysis revealed that the as-deposited films are amorphous. The optical gap of the amorphous film
Egopt was found to be 1.32eV. The glass transition temperature was not found by either DSC techniques or by thermomechanical analysis. Crystallization of film was characterized using quasi-isothermal DSC. The temperature
dependence of Cp is monotonous and no drop over the course of crystallization was observed. The temperature
modulated thermomechanical analysis discovered the temperature T=133C which can be assumed to be the temperature of the structural reorganization beginning. Raman spectra of amorphous Sb2Se3 were measured for the
first time. The vibrations of crystalline and amorphous Sb2Se3 were compared and it was found that the energies of
the vibrations are nearly the same for both. It can be concluded that the short and the medium-range order of the
amorphous and the crystalline phases are in principle extremely close each other. Acknowledgements: This work was
funded by Joint Research Project between BAS and ASCR No 9: Hybrid structures from chalcogenide glasses and
optical polymers for sensors applicationand by the grant P204/11/0832 from the Czech Science Foundation.

VITREA-the spectrochemical analyses

database of historic and prehistoric glass
Hulinsky V 1., Venclova N2., Gedeon O1., Cerna E3., Jonova S1., Tomkova K2.
1
2

Institute of Chemical Technology, Prague, Czech Republic

Institute of Archeology of the Academy of Sciences of the Czech Republic, UAPP SZC, Most, CR

This paper contains results of about 800 spectrochemical analyses of archaeological glass mostly realized by means
of SEM-EDS sometimes completed by other spectral methods as NAA, LA-ICP and XRF. These analyses are the
part of the project Glassmaking in prehistoric and medieval age realized by the 3 institutions presented above and
supported by the Grant Agency of Czech Academy of Sciences in the years 20092011. The aim of this project was to
work out the continuous chronologic sequence of the glass technologies in connection to archaeological and historic
assessment of the glass production and its economical and cultural significance. The prerequisite for the succesful
realization of this project was the close cooperation of the glass scientists and archeologists. The data presented indicate at least six groups of glass composition connected with given historic period. This database is in the Europe
obviously extraordinal covering not only analyses but all necessary archeological data and coloured photographs
of individual artefact. It is presented under the name VITREA on the websites of the Institute of Archeology of the
Academy of Sciences of the Czech Republic http://www.arup.cas.cz/cz/VITREA/Index.htm

306

Poster Contributions

562

Experimental studies of structural and stress

relaxation in glasses of CMAS system
Prokhorenko O. A., Tarakanov S. V., Pevzner B. Z., Eroshkin R. A.
Laboratory of Glass Properties, LLC St. Petersburg, Russia

Accurate mathematical modeling of quick heating or cooling of silicate glass within the glass transition range represents aquite challenging task. In order to take the challenge one needs to have two elements available. One is an
accurate thermal and visco-elastic models taking into account delay of current (at agiven rate of heating or cooling)
values of anumber of key physical properties from their equilibrium values. Two is reliable data on constants of
structural and stress relaxation, and physical properties of agiven glass within the whole glass transition range. The
present paper describes mathematical routines used for calculation of quick (up to 100K/min) non-isothermal heating and cooling of aflat glass plates accompanied by their deformation under the force of gravity, so aquick cooling
(up to 109K/min) of adrop of the molten glass. It is clear that for correct calculation of the processes in question the
model must be capable in calculating of release and/or formation of stresses in the glass in the course of non steadystate processes. Experimental setups and methods, which allow studying parameters of structural relaxation (dilatometric hysteresis loops), stress relaxation (stretching-compression multi-mode relaxometer), and physical properties
(viscosity, CTE, elastic modulus) are described as well. Examples of use of relaxation constants along with the data
on physical properties within the glass transition range sensitive to the rates of heating and cooling (viscosity, specific heat, elastic modulus, shear modulus, and others) are presented as well.

563

Cu+ Sol-Gel layers for utilization in waveguide

lasers and non-linear optical devices
Tresnakova-Nebolova P., Horkavcova D.
Institute of Chemical Technology, Prague, Czech Republic

This work is concerned to design and experimentally verify anew cheap and feasible approach to fabricate optically active Cu+ containing thin layers deposited onto the surface of common silicate glasses and having the parameters for using in active photonics devices. Basic copper-silicate layers were prepared by Sol-Gel dip-technique
on two kinds of commercially available glass substrates and they were covered by the silicate Sol-Gel layer for
protection of the copper-silicate layer and to prevent oxidation of Cu+ ions. Considerable effects on the quality of
the prepared optical layers had stirring and aging time of the fabricated sol. The best quality (good homogeneity,
crack free, smooth and flat surface) showed the layers prepared from the Cu-Si I sol were stirred for 30min and
aged for six days. Luminescence spectra of those samples showed emission peaks at blue-green region. It was
demonstrated that by adjusting the conditions of fabrication Cu+ containing homogeneous optical layers can be
prepared (with emission in blue-green region) and some of them containing nanoparticles.

566

Mesoporous bioactive glasses

as Drug Delivery Systems
Shruti S.1, SalinasA. J.2,3, Ferrari E.1, Malavasi G.1,
Lusvardi G.1, Doadrio A. L.2, Menabue L.1, Vallet-Regi M.2,3
1

Dept. of Chemical and Geological Sciences, University of Modena and Reggio Emilia,
Via G. Campi 183, 41125 Modena, Italy,
2
Departamento de Quimica Inorgnica y Bioinorgnica, Facultad de Farmacia,
Universidad Complutense de Madrid, 28040 Madrid, Spain
3
Networking Research Center on Bioengineering,
Biomaterials and Nanomedicine (CIBER-BBN), Madrid, Spain

Drug delivery systems (DDS) are carriers that efficiently and in control rate deliver drug to specific area of the
body without causing any side effects. Silica based Sol-Gel mesoporous materials are promising candidates where
drugs can be confined. These bioceramics exhibit high surface area, high degree of porosity, is chemically and

ICG Prague 2013 307

576

thermally stable, highly hydrophilic and biocompatible. Recently, these key features of silica mesoporous glasses
were exploited as DDS for curcumin and they produced beneficial results. Curcumin is the main component of
turmeric (Curcuma longa L) which is being used since centuries due to medicinal benefits with no side effects.
80%SiO215%CaO5%P2O5 mesoporous bioactive glass (MBG) containing 1.0 and 2.0% Ce2O3 or Ga2O3 and 2.0
and 4.0% ZnO (in mol.%) are synthesized by evaporation induced self-assembly method to investigate their potential as DDS for curcumin. Impregnation method was applied for incorporating curcumin into MBGs and
in vitro release was performed in simulated body fluid. The synthesized MBG exhibited mesostructure having
textural properties good enough for drug delivery. Drug loading results indicated increase in substitutent content
in MBG increases the loading of curcumin. Highest Ga and Ce substituted MBG incorporated drug more than
unsubstituted MBG due to high affinity of curcumin towards hard Lewis acids. But only unsubstituted MBG and
lowest Ce, Ga and Zn substituted MBG showed in vitro curcumin release as strong interaction between curcumin
and substitutent caused negligible release from the other set of MBGs. Furthermore, MBGs loaded with curcumin
showed quick in vitro response except 4.0%ZnO. Hence, lowest Ce, Ga and Zn substituted MBG could be used as
DDS whereas the highest Ce, Ga and Zn substituted MBG retaining curcumin in their system could find potential
application in scaffold preparation for tissue engineering with anti-oxidant and reduced inflammatory properties.

Foaming of CRT panel glass powder with Na2CO3

Petersen R. R.1, Koenig J.1,2, Smedskjaer M. M.1, Yue Y. Z.1
1
2

Section of Chemistry, Aalborg University, DK-9000 Aalborg, Denmark;

Advanced Materials Department, Joef Stefan Institute, SI-1000 Ljubljana, Slovenia

578

Recycling of cathode ray tube (CRT) glass remains achallenging task. The CRT glass consists of four glass types
fused together: Funnel-, neck-, frit and panel glass. The three former glasses contain toxic lead oxide, and therefore have alow recycling potential. The latter on the other hand is lead-free, but since barium and strontium oxide
are present, panel glass is incompatible with most common recycling methods. However, foam glass production is
apromising approach for the recycling of panel glass waste, since the process parameters can be changed according to the glass waste composition in question. In this work, we foam panel glass cullet using sodium carbonate
(Na2CO3) as afoaming agent, and study the foaming mechanism. When heat treating Na2CO3 powder with cullet
powder, Na2CO3 reacts with the glass melt and is decomposed into Na2O and CO2. The released CO2 foams the
glass melt, while Na2O becomes incorporated into the glass structure. We have quantified the melt expansion
through density measurements and the Na2O incorporation is indicated by the decrease of the glass transition
temperature (Tg) of the final foam glass. The glass foaming quality depends on the foaming temperature (i.e., the
melt viscosity) and the concentration of Na2CO3. We reveal the origin of these dependencies.

Preparation of chalcogenide glass hollow

core microstructured fibers
Shiryaev V. S.1, Kosolapov A. F.2,
Snopatin G. E.1, Kolyadin A. N.2, Pryamikov A. D.2, Biriukov A. S.2
1

G. G. Devyatykh Institute of Chemistry of High-Purity Substances of the Russian Academy of Sciences,

49 Tropinin Str., 603950 Nizhny Novgorod, Russia
2
Fiber Optics Research Center of the Russian Academy of Sciences, Moscow, 119333, Russia

Hollow core microstructured optical fibers (HC MOF) are promising to achieve ultra low optical losses, expansion
of transmission range and transmission of power laser radiation. In this work we developed apreparation method
of chalcogenide glass HC MOF. The fiber preform was manufactured by the stack and draw technique from asubstrate tube and 810 capillaries with agiven geometry and thickness of the walls, arranged in aspecific configuration to create aphotonic band gap. The high purity As30Se50Te20, As2S1.5 Se1.5, As2S3 and Ge10As22Se68 glasses transparent in the 110m spectral range and having alow tendency to crystallize were used for HC MOF. Special methods
of chalcogenide glass purification used chemical gettering and multi-stage vacuum distillation were applied. The
impurity content in the pure samples was as follows: hydrogen <0.01ppm, Si 0.1ppm, carbon 0.25ppm, transition metals < 0.1ppm. Substrate tubes (outside diameter 16 mm, internal diameter 11mm, length up to 165mm)

308 Poster Contributions

were obtained by centrifugal casting of chalcogenide glass melt inside an evacuated silica ampoule. Capillaries with
an outside diameter of 3 mm and aratio of inner/outer diameters of 0.80.94 were fabricated by melt extraction
from adouble crucible. HC MOFs with diameter of 700900m were drawn. Investigation of prepared HC MOF
has shown their transparency in the range of 211m and possibility to transfer of 2-laser radiation. Minimum
optical losses in the hollow core PCF fiber from As-Se-Te glass were 4dB/m at 10.6m; from As-S-Se glass 30dB/m at
10.6m and 10dB/m at 2m, from As-S glass 4dB/m at 6.4m. To improve the optical transmittance of chalcogenide
HC MOF, the optimization of its design and improvement of geometric perfection are needed.

579

A cryogenic vacuum facility for characterisation

of optical glasses for space applications
Van Nijnatten P. A.
OMT Solutions BV, Eindhoven, Netherlands

Advances in optical instrumentation for Space Infrared Astronomy and Earth Observation rely on the availability
of optical properties of awide range of optical glasses under operating temperatures applicable in space.
OMT Solutions has developed aunique Cryogenic Vacuum facility for measuring reflection, transmission and
refractive index of glasses at cryogenic temperatures. The sample temperature can be set in the range 35375K
and the wavelength range covered using acombination with different instruments is 18025,000nm.
The paper gives ashort description of the facility and some results obtained on optical glasses that where selected
by the European Space Agency for instrument development for future scientific missions.

581

Effect of substituting alkaline earth metals for SiO2

on the mechanical properties and connectivity
of alkali-alkaline earth-silicate glasses
Kilinc E., Hand R. J.
Department of Engineering Materials, University of Sheffield, Mapping Street, Sheffield S1 3JD, UK

Two different glass series have been produced by altering the CaO:SiO2 or MgO:SiO2 ratios in the base glass composition 72SiO2.13.5Na2O.10CaO.3MgO.1.5Al2O3. The mechanical properties of these series of glasses were measured
and it is found that increasing CaO as SiO2 is lowered reduces the indentation fracture toughness of the glasses.
Meanwhile increasing MgO up to 4mol% increases indentation fracture toughness but further MgO additions lower fracture toughness. Additions of either MgO or CaO increase Vickers hardness and density of the glasses. The
connectivity of these series of glasses has been investigated using Raman and Fourier transform infra-red (FTIR)
spectroscopy. In Raman studies, degree of connectivity was measured in terms of the polymerization index given
by the ratio of the areas of the peaks at 500cm1 and 1,000cm1. Addition of CaO and MgO reduced polymerization
index reflecting the role of these oxides as network modifiers. This was also shown by the broadening of the band
at ~1,050cm1 band. Overall Vickers hardness and density tend to decrease as connectivity of the glasses increases;
however the link between indentation fracture toughness and connectivity is less clear cut.

Wang H., Dongyun Ma D., Yaogang Li Y., Zhang Q.

Engineering Research Center of Advanced Glasses Manufacturing Technology, MOE,
College of Materials Science and Engineering, Donghua University, Shanghai 201620, P. R. China.

Electrochromic (EC) devices are capable of reversibly and persistently changing their optical properties on application of an external voltage. This can be used in energy-saving smart windows, antiglare mirrors, high-contrast
displays, and active camouflage. Tungsten oxide (WO3) is one of the most promising EC materials and is widely used

ICG Prague 2013 309

583

Vertically aligned WO3 nanostructure films

for highly enhanced electrochromic performance

587

in EC devices. Compared to the organic EC materials, however, the response time and coloration efficiency still need
to be further improved. It has been reported that the response speed, i.e., the time constant of the ion-intercalation
reaction, is limited by both the diffusion coefficient and the length of the diffusion path. The CE is often observed to
have astrong dependence on the surface morphology. Thus, designing ananostructure with proper crystal structure
and unique surface morphology is the key to obtaining amaterial with enhanced EC performances.
We have demonstrated that vertically aligned WO3 nanostructure fi lms can be fabricated on FTO-coated glass
substrates using atemplate-free hydrothermal technique. Detailed mechanistic studies revealed that avariety
of WO3 nanostructures (including nanowires, nanorods, nanoflakes and nanorod-flowers) could be obtained by
tuning the composition of the precursor solution, where the urea content, oxalic acid content and solvent composition played important roles in controlling the shape and size of the WO3 nanostructures, respectively. These
nanostructure fi lms exhibited enhanced electrochromic performance, and we drew a map for the correlation
between the morphology and the electrochromic performance of the as-synthesized WO3 fi lms. For the vertically
aligned nanorod array films, hexagonal windows and four-coordinated square windows in the hexagonal WO3
led to alarge diff usion coefficient, and the open-pore voids between the nanorods reduced the diff usion path
lengths of the Li+ ions. Fast switching speeds of 6.7 s and 3.4 s for coloration and bleaching, respectively, were
therefore achieved. While the vertically aligned nanoflake fi lms self-woven by the nanowires give acoarse surface,
making alarger active surface available for reactions in electrochemical processes and allowed asufficient number of Li+ ions to be intercalated into the WO3 fi lm. ahigh CE of 134.4cm2 C-1 was achieved.

Enhancement of the properties

of glass fibers modified by SiO2 on the surface
Wang Q.1,2, Wang H.1,2, Wang W.2, Jiang W.1,2, Wu X.1
1

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,
Donghua University,Shanghai 201620, P. R. China)
2
Engineering Research Center of Advanced Glasses Manufacturing Technology,
MOE, Shanghai 201620, China

589

With the development of information,vehicle,wind-power industries, the higher requirements were put forward
on the mechanical properties of glass fiber/resin composite materials. The interface between the glass fiber and
resin plays an important role in improving the mechanical properties of the composites, so how to improve the
interface properties between glass fibers and resins is necessary.
Recently our research carried out on the colored glass fiber had found that the properties of composites were
changed when glass fibers were modified in the surface. This study probe into the efficient coating technology of
the sizing modified by SiO2 particles by mean of controlling the size and surface modification of SiO2 particles.
Through analyzing the relationship between the best morphology or concentration of SiO2 particles and the properties of the composite materials, the effects of SiO2 particles on glass fiber/resin composite materials is expected
to be verified, which definitely contributes to the enhancement of the strength of composites.
By aid of the single glass fiber testing line and 200 fibers line peculiarly belonged to State Key Laboratory for Modification of Chemical Fibers and Polymer Materials (Donghua University), the study is to apply online coating
technology to prepare glass fibers covered with the modified sizing, with the goal of acchieving an increase of 8%
for the tensile strength of composites.

Spatial distribution of thulium in Tm3+-doped

oxyfluoride glasses and glass-ceramics
de Pablos-Martin A.1,2, Patzig C.1, Hche T.1, Durn A.2, Pascual M. J.2
1
2

Fraunhofer Institute for Mechanics of Materials IWM, Walter-Huelse-Strae 1, 06120 Halle, Germany;
Instituto de Cermica y Vidrio (CSIC), C/Kelsen 5, Campus de Cantoblanco, 28049 Madrid, Spain

Rare-earth (RE) doped oxyfluoride glass-ceramics combine the properties of fluoride crystals (LaF3, NaLaF4,
NaYF4), like low phonon energy and good solubility of RE ions, which enhance the radiative optical-emission
processes (like up and down-conversion emissions), while keeping the good mechanical properties of silicate
matrices. Until now, the verification of the incorporation of RE ions in nanocrystalline phases in glass-ceramics
is mainly based on luminescence spectroscopy techniques. Thus, the aim of this work is to perform elemental

310 Poster Contributions

distribution mappings of RE ions, by using Transmission Electron Microscopy techniques (TEM) and Energy
Dispersive X-Ray Spectroscopy (EDXS). aglass of composition 55SiO220Al2O315Na2O10LaF3 (mol%), doped
with 1mol% Tm2O3, and the corresponding glass-ceramic were structurally characterized through TEM, STEM
and EDXS. The elucidation of the LaF3 nano-crystallisation mechanism in this glass has been improved through
these techniques: The parent glass contains amorphous La and F-enriched phase separation droplets of ca.
30nm, also containing Si and Al. Tm3+ ions are partly incorporated in the phase-separation regions. Upon annealing, 1020nm LaF3:Tm crystals growth within these phase separation droplets. The remaining volume not
occupied by the crystals is fi lled with Al, while silicon relocates itself towards the periphery. Thus, the viscosity
increases in the periphery of the crystals, inhibiting further crystal growth. The possibility to being able to map
the distribution of Tm is well worth mentioning. Thanks to the advance STEM/EDSX analysis it was possible to
discern between athin aluminum layer around the crystals, and asecond shell of Si. The verification of the inclusion of Tm3+ ions into the LaF3 structure is agreat advance in the development of RE doped glass-ceramics, since
it is the key feature of these materials for their application in optical devices.

592

Qualimetric approach to evaluation

of the accuracy of glass property measurements
Mazurin O. V.1, Priven A. I.2
1
2

Thermex Joint Stock Company, St. Petersburg, Russia;

Institute of Theoretical Chemistry, Newton, MA, USA

During the last decades, intentions of many glass specialists publishing new results of glass property measurements considerably changed. Now saving time and cost of experimental studies is often considered more important than accuracy and reliability of obtained results. Thus the risk of obtaining erroneous data considerably
increases, which might misinform the authors and readers of apaper about real behavior of studies glasses. General solution of this problem is the independent evaluation of the accuracy and reliability of new experimental
data. The problems are (1) to find the alternative data in avariety of sources (journals, books, patents, etc.), and
(2) to evaluate the reliability and accuracy of these data themselves. Our approach is borrowed from qualimetry
ascientific discipline that concerns itself with the methods and problems of quantification of the quality of any
object in general and quantitative evaluation of expert estimates in particular. Qualimetric approach suggests
comparison of earlier estimates of aparticular expert made in similar situations with consolidated opinions of
multiple independent referees. By transferring this approach to the above-described situation, we suggest the use
of existing methods of calculation of glass properties from chemical compositions as analogs of expert estimates.
The property values calculated by each method should be compared with earlier published experimental data
for compositions similar to the composition of the studied glass. Obtained standard deviation can be used as
aquantitative measure of quality of acalculation method applied to this particular glass composition. The test
dataset of earlier published data can be taken from aglass property database such as SciGlass where the published
experimental data for about 400,000 glass compositions are presented. On the base of the qualimetric approach,
we suggest acompletely automated procedure for evaluation of reliability of experimental data. We suggest to include such evaluation into the standard procedure of reviewing new papers before publishing. The authors whose
data were evaluated as suspicious ones should be asked to focus on their experimental procedure and to explain
the reasons of found differences between their results and results of earlier publications.

Neves E.
Laboratory of New Materials and Packaging, Unemat, Mato Grosso, Brasil

An aluminosilicate calcium glass was prepared. The sample contained 1.8% wt. of K 2O. The glass composition is
not stoichiometric to anorthite phase. The glass crystallization parameters were studied. The controlled crystallization was carried out at anucleation rate maximum temperature. The glass crystallization kinetics was studied
and defined. The controlled crystallization of glass was followed by an analysis of the phases obtained. Charac-

ICG Prague 2013 311

594

Orthoclase crystallization in the crystallization

process glass of chemical composition
in the region of phase anorthite

596

terization of glass-ceramic was carried out by XRD. The phases were obtained Orthoclase, KAlSi3O8, Anorthite,
CaAl2Si2O8 and rutile. TiO2 was used as nucleating agent. The study shows that for the glass composition, orthoclase could not have made if it had not preferred in the reaction with SiO2 and Al2O3. The calculations are based,
with athermodynamic approach. The chemical nature of atoms K and Ca are related to the atomic mobility and
reactivity. The reagent limit was defined as Al2O3. The preferential reaction of this oxide with CaO and SiO2 would
have prevented the formation of KAlSi3O8. The conclusion of this study suggests solutions to promote the preferential formation of CaAl2Si2O8. The mechanical properties are aconsequence of the reactions in the glass field.
Therefore, the entire study is related to theoretical comments on structural defects not control phases.

Modelling of optimal melt flow

character in a melting space
Dyrkov P., Polk M., Nmec L.
Laboratory of Inorganic Materials, Joint Workplace of the Institute of Chemical Technology Prague
and the Institute of Rock Structure and Mechanics ASCR, v.v.i.

597

The goal of this work was to propose an optimal character of glass melt flow in amodel melting space with the
industrial soda-lime-silica glass. The glass melting space was proposed having the T-shape and both sides charging of the batch in order to support the transversal circulations of the melt in the below-batch region. Different
modifications of glass heating and flow conducting were tested as setting up the high ratio between the transversal to longitudinal temperature gradient or application of solid barriers and electrode barriers. The simulations
were focused on setting up the character of glass flow with the high space utilization for the sand dissolution and
bubble removal phenomena. The sufficient supply of energy in the batch region which ensures adequately hot
glass leaving the region is the prerequisite of the beneficial character of melt flow.

Energy transfer process in Pr3+-Yb3+ codoped

gallium-germanate glasses and glass ceramics,
and their enhanced luminescence properties
Zhang S.1,2,*, Xu M.1, Zhang Y.1, Jin Y.1, Zhang X.2
1

Key Laborotory of Chemical Laser, Chinese Academy of Sciences/Dalian Institute of Chemical Physics,
116023, Dalian, China
2
Laboratory of glass and ceramics, UMR CNRS 6226, University of Rennes I, 35042 Rennes cedex, France

598

Pr3+-Yb3+ codoped 65GeO215Ga2O310BaO10LaF3 glasses were prepared. Infrared cross relaxation involving Yb3+:
2
F5/2 2F7/2 emission was achieved on the excitation of the 1G4 state level of Pr3+. Visible up-conversion and multi-phonon assisted emission was obtained originating from Pr3+: 3P0 and 1D2 state level thanks to Yb3+ sensitizer.
It is also found that the quantum efficiency could be increased by heat treatment of glass ceramics precipitation.

Ion-exchanged glass with high damage resistance

Wilantewicz T. E., Reiman K. B., Pesansky J. D., Saha C. K.
Corning Incorporated, Corning, USA2

The damage resistance and retained strength after damage introduction of several ion-exchanged alkali aluminosilicate glasses subjected to sharp contact is shown to be superior to that of conventional ion-exchanged soda-lime
silica glass. It is proposed that the maximum surface compressive stress (CS) and depth of compressive stress layer
(DOL), are responsible for the greater damage resistance and retained strength after damage introduction. In
addition, the base composition of one of the glasses with no ion-exchange leads to greater resistance to sharp contact damage compared to other glasses. Indentation testing was used to quantify damage resistance, and abraded
ring-on-ring testing to quantify the strength after damage introduction.

312 Poster Contributions

Author Index

ICG Prague 2013 313

 314

A
Abdelouas A. _____________ 168
Aben H. _________________ 109
Abrahams I. _______________ 32
Acosta-Enrquez M. C. _____ 288
Adamietz F. _______________ 87
Adichtchev S. V. __________ 256
Agarwal A. ______________ 148
Ainsworth R. I. ___________ 102
Akerman M. _____________ 213
Akiyama R. ______________ 258
Akmaz F. ________________ 214
Akola J. __________________99
Al Saghir K. _______________ 62
Alahrache S. ______________ 62
Aleksandrov L. I. __________260
Alekseeva I. _______________ 72
Alexeiko L. N. _________ 64, 256
AlHamdan K. ____________ 253
Alizadeh P._______________ 123
Allan D. C._______________ 110
Alleno E. _________________ 53
Allix M. ______________ 62, 166
Almeida R. M. _____________ 33
Almuhamadi J. ____________ 68
Alvarado-Rivera J. _________ 288
Anfimova I. ______________ 286
Annoscia A. ______________ 289
Anton J. _________________ 109
Antropova T. _____________ 286
Arai Y. ________________ 45, 77
Arbuzov V. I. ______________ 75
Armellini A. _____________ 147
Aseev V. A. ___142, 143, 278, 278
Aso K. ___________________54
Aubrecht J. _______________ 304
Avakyants L. I._________ 75, 257
Aydin S. _______________ 24, 25

B
Babich A. V._______________ 57
Babina T. O. __________ 75, 257
Bagga R. ________________ 166
Baghramyan V. V. _________ 304
Bachvarova-Nedelcheva A. D. 266
Bailey P. __________________ 79
Baldin J. M. C._____________66
Ballon A. ________________ 296
Bankhead M.______________ 24
Barbosa L. C. _____________ 137
Barboux P. ________________ 94
Baret B. _________________ 219
Barney E. R. _____________ 104
Bartk J. _________________ 26

Barthel E. _______________ 177

Bau L. __________________ 242
Bauer U. ________________ 290
Bazakutsa A. P. ____________ 82
Beall G. H. ________________46
Beerkens R. __________ 197, 204
Behrens H. __________ 290, 290
Bei R. _______________ 191, 192
Belanon M. P. ___________ 137
Beldiceanu A. ____________ 269
Bloubkov T. ____________ 124
Benmore C. J. _____________99
Brar J.-F. ________________ 31
Berbano S. S. ______________ 72
Bergmann G._________ 204, 241
Bernardo E. __________ 225, 258
Berndt S. _________________ 68
Berneschi S.__________ 148, 302
Bertolin M. ______________ 248
Bertrand A. ______________ 144
Bertuzzi P. _______________ 173
Berzina-Cimdina L. ________24
Bezdika P. ______________ 274
Bianchin O. S. ____________ 120
Bielikov B. __________ 268, 268
Bing Ai __________________ 76
Bing Y. __________________ 292
Bingham P. A. _________ 32, 160
Biriukov A. S. ____________ 308
Blach J. F.______________ 21, 52
Blaanovi H. _____________ 55
Blondeau J.-P. ____________ 111
Boccaccini A. R. ______ 159, 278
Bocker C._________________ 70
Bodi R. _____________ 195, 195
Bodiov K. ____67, 283, 284, 285
Boehm P. ________________ 203
Boetti N. G. ______________ 289
Bogdanov V. N. ____________ 25
Boistel P. ________________ 296
Boller E._________________ 220
Boroica L. ___________ 269, 285
Boschetti C. ______________ 152
Bok O. ________________ 301
Botelho M. B. S. __________ 123
Boulard B. ___________ 147, 148
Boulay E. _________________ 67
Bourhis K. ________________ 82
Bousquet N.______________ 165
Boussard-Pledel C. _________ 55
Bouvry B. _______________ 191
Bouznik V. M. ____________ 256
Brada J. _________________ 301
Bragatto C. B. ____________ 286
Brauer D. ________________ 117
Brauer D. S. _______________34
Brazda L. ____________ 116, 119

Brems D. ____________ 151, 151

Brennan C. ______________ 298
Bretschneider J. ____________80
Bren M. _______________ 275
Brokmann U. _____________80
Brun C. __________________48
Bubnov M. M. ____________ 283
Bufetov I. A. __________ 78, 139
Buchkremer H. P. _________260
Bujnoch M. ______________ 275
Bureau B. _________________ 55
Bursk J. _________________ 305
Burt T. C. ________________ 88
Burtan B. _________________ 79
Buso D. _________________ 124

C
Cabodi I. ____________ 191, 296
Cabrall A. A. ______________ 61
Cadars S. _________________ 36
Caillaud C. _______________ 55
Cajzl J. __________________ 304
Calahoo C. ______________ 179
Calas G. ______ 39, 39, 41, 84, 131
Calver A. _________________ 36
Calvez L. _____________ 78, 179
Calzolai R._______________ 302
Campayo L. ______________ 165
Cardinal T. ______82, 83, 87, 144
Carney S. _________________ 47
Carreaud J. ___________ 78, 144
Carrillo E. G._____________ 276
Cartalade A. _____________ 172
Cassar D. R.___________ 66, 286
Castanie S._____________ 21, 52
Castaon Ma. C. __________ 276
Cattell M. J. _______________ 68
Caurant D. ____ 94, 166, 167, 167
Cavicchioli M. ____________ 126
Clari F ____________ 107, 108
Celikbilek M. __________ 24, 25
Chamma K. _______________64
Champagnon B. __________ 129
Chao Liu* ________________ 76
Charles J. C. _____________ 140
Charmasson L. ____________ 83
Charpentier T.______35, 167, 167
Chasse M. ________________ 39
Chechetkina E. A. ______ 22, 272
Chen X. _________________ 116
Chen X. J. _______________ 115
Chenu S. _________________ 62
Chiappini A. ______147, 148, 302
Chiasera A. __________ 147, 302
Chiesa M. _______________ 145

ICG Prague 2013 315

Chigirinsky Yu. I. __________ 57

Chistokolova M. V. _________ 21
Cho Y. G. ________________ 126
Choi Y. G. _______________ 126
Choju K. _________________99
Cholewa-Kowalska K. ______108,
____________________ 302, 302
Chopinet M. H. ____ 51, 220, 220
Chotard T. ________________ 78
Chouard N. ______________ 172
Chouffart Q. _____________ 241
Christie J. K. _____________ 102
Chromcikova M. ____ 94, 95, 275,
________________ 293, 294, 294,
_________ 295, 296, 297, 300, 305
Chrysanthou A. __________ 296
Chung W. J. ______________ 126
Churbanov M. F. ______ 267, 273
Ciccotti M. _______________48
Ciecinska M. _________ 284, 291
Clov Z. ________ 124, 281, 297
Cincibusova P. ________ 300, 301
Cisowski J. ________________ 79
Citti O. _____________ 192, 296
Cizman A. _______________ 286
Claireaux C. ______________ 51
Collin A. ________________ 242
Comerford J. ______________ 88
Conradt R.________ 94, 108, 132,
_____________ 203, 219, 237, 270
Consales T. ______________ 191
Conseil C. ________________ 55
Cook S. _________________ 247
Cormack A. N. ___________ 102
Cormier L.__________ 39, 39, 41,
__________________84, 131, 167
Couderc V. ______________ 144
Cremoux T. ______________ 144
Cumming A. _____________ 107
Czarnacki K. _____________ 303
astorlov M. ___________ 124
ern E._________________ 306
ernoek Z. ___________ 33, 262,
________________ 263, 270, 306
ernokov E. ________ 262, 306
ern M. ________________ 154

D
DAgostini M. D. __________ 231
DEste A. ________________ 110
Daguano J. K. M. F ________ 120
DallIgna R. ______________ 110
Dang D. D. ______________ 232
Danto S. ________________ 148
Dardar H. _______________ 144

316 Author Index

Dargaud O. ______________ 131

Dathe M. ______________ 93, 93
Davor R. ________________ 147
de Camargo A. S. S. _______ 123
de Diego Rincn J. ________ 233
de Leeuw N. H. ___________ 102
de Ligny D. ______________ 129
de Meo C. E. _____________ 277
De Miranda A. C. _________ 296
De Pablos-Martin A.________ 61,
____________________ 148, 310
de Queiroz T. B. __________ 123
De Sousa Meneses D. ___111, 191
de Wit E. ________________ 237
Death D. _________________ 88
Deepak K. L. N.____________ 83
De Ferri L. _______________ 125
Degiovanni A. _____________ 53
Degryse P. ___________ 151, 151
Deinhardt A. _____________ 147
del Campo L._____________ 191
Delaizir G. _________ 53, 78, 144
Delaporte P._______________ 83
Della Gaspera E. __________ 124
Dembsky S, ______________ 147
Dsvdavy F. ____________ 140
Desfeux R. _____________ 21, 52
Deshpande R. R. __________ 37
Deschamps T. ____________ 129
Detcheva A. ______________ 254
Deubener J. ______ 56, 64, 71, 71
Dianov E. M. ______ 78, 139, 273
Daz G. C. ___________ 276, 288
Dima R. _________________ 291
Dima V. _____________ 285, 291
Dimitriev Y. _____ 254, 260, 274
Dimitriev Y. D. ___________ 266
Dimitrova M. ____________ 274
Doadrio A. L. ____________ 307
Domanick A. ____________ 284
Donfeu T. R. ______________64
Dongyun Ma D. __________ 309
Donthu S. _______________ 247
Dorofeev V. V. ____________ 273
Dorosz D. _______________ 141
Dorosz J. ________________ 141
Drschner S. ______________80
Doweidar H. ______________34
Drbkov K. _____________ 281
Dronskowski R. __________ 108
Drozdova I. ______________ 286
Dublanche-Tixier C. ________ 78
Dubrovin V. D. ___________ 142
Duclre J. R. _______ 78, 84, 144
Dumitrescu O, ___________ 266
Dunkl M. ___________ 189, 190
Dunnett B. D. ____________ 171

Duran A. ___ 51, 69, 148, 305, 310

Dussauze M. _____82, 83, 87, 144
Dussossoy J. L. ___________ 165
Dutreilh-Colas M. _____ 78, 144
Duverger Arfuso C. ___ 147, 148
Dvorsky D. ______________ 299
Dymshits O. ______________ 72
Dyrba M. ________________ 147
Dyrkov P _________ 210, 312

E
Earl J. ___________________ 117
Ebert E. __________________ 61
Ebihara Y. ___________ 209, 285
Eckert H. __________ 37, 40, 123
Efimov A. M. ______________ 76
Eftimie M. ___________ 285, 291
Egorova O. N. ____________ 138
Echegut P. _______________ 191
Eisenga M._______________ 195
Elhammamy W. O. ________ 299
Elisa M. _________ 260, 269, 285
Elkhoshkhany N. _________ 279
Eltutar Z. ________________ 233
Endo J. ___________________ 37
Eng D. ___________________ 35
Enomoto T. ______________ 195
Ercole P._________________ 173
Erfurt D. _________________ 69
Eroshkin R. A. ___________ 307
Errapart A. ______________ 109
Ersundu A. E. __________ 24, 25

F
Faber A. J. ___________ 192, 232
Fagerlund S. _________ 116, 119
Falcone R. _______________ 173
Falconieri M. _____________ 166
Fargin E. __________ 83, 87, 144
Fargues A. ________________ 82
Fatome J. ________________ 140
Faturikova K. ___ 55, 94, 95, 293,
_________294, 295, 296, 297, 300
Feller S. A. _______________ 104
Feraru I. ________________ 269
Ferencz J. A. P. F. __________ 137
Ferlat G.__________________ 39
Fernandes H. _____________ 274
Fernandez-Hernandez J. M. _ 123
Fernie J. A. ______________ 118
Ferrari A. M. ______________ 69
Ferrari E. ________________ 307
Ferrari M. ________147, 148, 302

Ferraris M. ___________ 82, 296

Ferri A. __________________ 52
Ferrier A. _________________ 86
Filipowska J. _____________ 302
Firstov S. V ___________ 78, 139
Firstova E. G. _____________ 78
Fischer M. ________________20
Fleischmann B. ___________ 232
Florian P. _________________ 36
Fokin V. M. ______________ 282
Foret M.__________________ 23
Fourcade J. __________ 192, 296
Frosz M. _________________80
Frda F. _________________ 281
Fujino S. ________________ 292
Fujiwara A. _______________99
Fujiwara T. __ 20, 54, 65, 95, 142
Fukasawa Y. _____________ 101
Fukumi K. ________________ 38
Futagami T. ______________ 214
Fyodorov Yu. K. ___________ 75

G
Gaber M. _________________ 56
Gabrene A. __________ 258, 264
Gadret G.________________ 140
Gallo L. S. _______________ 277
Galoisy L. _____39, 39, 40, 41, 84
Galusek D. __________ 46, 66, 67,
________________ 283, 284, 285
Galuskov D. __________ 46, 283
Gandy A. ________________ 160
Gangadharini U. __________ 253
Gao G. J. ________________ 137
Gao W. _________________ 140
Garca-Amaya I. __________ 288
Gasnier E. _______________ 166
Gaprekov E. ___________ 305
Gatto C. __________________ 87
Gaubil M. ________191, 191, 296
Gavenda T. ___________ 45, 294
Gebavi H. _______________ 145
Gedeon O. _____45, 103, 133, 306
Gegova R. D. _____________ 266
Ghazaryan A. A. __________ 304
Ghribi N. _________________ 78
Giammarco J. ____________ 148
Giboire I. ____________ 165, 166
Giese A. _________________ 232
Gillam D.________________ 117
Giorgis F. ________________ 145
Girold C. ________________ 171
GlaCERCo Team __________ 258
Gladkov P. _______________ 146

Glebov L. B. ___________ 64, 139

Glebova L. ____________ 64, 139
Gleize V. ________________ 296
Godart C. _____________ 53, 53
Godehardt R.______________20
Godet S. __________________ 67
Golant K. M. ___________ 82, 82
Goldner P. ________________ 86
Goek ._________________ 287
Golubkov V. ______________ 72
Gonalves A. ______________ 53
Gonalves L. M. G. ________ 120
Goncharuk V. K. _______ 64, 256
Gonzlez J. C. ____________ 276
Gonzalez Rodriguez J. _____ 177
Gopal E. S. R. _____________ 57
Goruney T. ______________ 231
Goss S. _________________ 160
Gouillart E. __________ 220, 220
Grabchikov S. S. ______ 280, 280
Gravel J.-F._______________ 267
Greaves N. _______________ 133
Greiner-Wronowa E. ________ 47
Gribble N. R. _____________ 171
Griebenow P. _____________ 249
Grojo D. _________________ 83
Grschl Ch. _______________ 56
Grudin B. N. _________ 280, 280
Grundmann M. ___________ 61
Grynberg J. ______________ 220
Gueguen Y. ______________ 107
Guglielmi M. _____________ 124
Guin J. P. ____________ 168, 179
Guryanov A. N._______ 139, 283
Gutnikov S. I. ____________ 282

H
Habraken A. F. J. A. _______ 199
Haizheng Tao _____________ 76
Halbedel B. __________ 197, 204
Hammond G. D. __________ 107
Hamzaoui M. ________ 295, 303
Hamzawy E. A. M. _________ 69
Han K. __________________ 179
Hand R. J. _____ 24, 79, 159, 160,
_____________ 171, 172, 177, 309
Hannon A. C. ____________ 104
Hao Q. ___________________ 55
Harper T. A. _____________ 298
Harrison M. T. ___________ 265
Harutyunyan N. M. ____ 52, 271
Harutyunyan R. V. ________ 304
Hashimoto A. ____________ 261
Hayakawa T. ___________ 78, 84

Hayashi A._____ 54, 54, 263, 264

Hayashi Y. _______________ 261
Hayes S. A. _______________ 79
Heath P. G. ______________ 172
Hee P. ___________________ 87
Hein J. __________________ 143
Helebrant A. _____ 116, 119, 124,
_________________269, 274, 281
Hellmann K. _____________ 203
Henderson J. _____________ 152
Hensley J. _______________ 148
Heo J._____________ 75, 89, 138
Heo Jong _________________ 85
Herrmann A. ____________ 143
Hessenkemper H. _____ 189, 225,
____________________ 253, 253
Hickey, R. ________________ 33
Hijiya H. ___________40, 77, 101
Hill R. ____________68, 115, 117
Hill R. G. ____ 34, 36, 36, 115, 116
Hilmi M. M. Z. ___________ 171
Hind A. __________________ 88
Hirata S. _________________ 22
Hnatko M.________________46
Hobbs L. W. _____________ 130
Hoell A. __________________ 70
Hche T. _____________ 61, 310
Hland W. _____________ 46, 71
Holland D._______________ 104
Holubov J. __________ 262, 306
Honma T ___________ 62, 63, 63,
_____________178, 255, 259, 259
Hork M._________________ 45
Horkavcov D. _______ 124, 307
Horn I.__________________ 290
Hosokawa S. ______________ 31
Hota V._________________ 247
Htzel M. _______________ 253
Hough J. ________________ 107
Houizot P. _______________ 107
Hreglich S. ______________ 173
Hrma P. __________________ 18
Hruka B. _______________ 285
Hu J. ___________________ 148
Hubert M. ________________ 78
Hbner L. _______ 225, 253, 253
Huh C.___________________ 89
Hujova M. ________________90
Hulinsky V. ______________ 306
Hultstein E. _______________ 47
Hunault M. _______________84
Hupa L. ___ 82, 116, 116, 119, 119
Hupa M. _________ 82, 116, 119
Hwang J. _________________ 89
Hyatt N. C. ______ 159, 160, 172

ICG Prague 2013 317

Idriss M. ________________ 108

Idrissi H. _________________ 67
Ignatiev A. I. __________ 76, 142
Ignatieva L. N.____________ 256
Ignatov A. N. __________ 75, 257
Ihalainen H. ______________ 82
Ihara R. _________ 20, 54, 65, 95
Ihr A. ___________________ 154
Ikeda H. ________________ 292
Inaba S. __________________ 37
Inoue H. _____________ 81, 102
Inoue S. _____________ 209, 285
Inoue T. __________________ 63
Iordanescu R. ____________ 269
Iordanova R. S. ___ 255, 260, 266
Ishino T. ________________ 189
Iskhakova L. D. ___________ 138
Ito N. ____________________ 63
Ito S. _________________ 37, 58
Ito Y. ___________________264
Ivanda M. _______________ 148
Ivanova Y. _______________ 274
Ivanova Z. G._____________ 303
Iwamoto M.__________ 209, 285
yiel A. __________________ 214
zmirliolu B. ____________ 190

Kabadou A. _______________ 78
KAIWEN HU _____________48
Kalugin V. _______________ 298
Kaluza M. C. _____________ 143
Kamitsos E. I. _____ 35, 270, 277
Kakov H. ________ 94, 95, 293,
_____________294, 295, 296, 297
Kanwal N. ________________ 32
Karakurt G. ______________ 168
Karell R. _________________ 55
Karlsson S. _______________ 47
Karmakar B. _____________ 253
Karpukhina N. ___ 32, 34, 34, 36,
___________ 36, 68, 115, 115, 117
Kartashov A. A. __________ 282
Kasuga T._____________117, 118
Kak I. _____________ 304, 305
Kato M. _____________ 178, 214
Kavun V. Ya. __________ 64, 256
Kawaguchi M. ____________ 214
Kawashima H.____________ 140
Keding R. ________________80
Kent N. W._______________ 115
Kermouche G. ____________ 177
Kharchenko V. I. ___________64
Khopin V. F. _____________ 139
Khubetsov A. _____________ 72
Kibler B. ________________ 140
Kida ____________________ 292
Kilinc E. ________________ 309
Kim J. H. _________________ 89
Kim K. D. ___________ 213, 225
Kim M. S. _______________ 213
Kimerling L. C. ___________ 148
King E. A. _______________ 110
Kint M. __________________ 23
Kioka K. ________________ 259
Kirillov A. V. _____________280
Kitamura N. ______________ 38
Klement R. ____ 66, 67, 284, 285
Klimov M. ____________ 64, 269
Klpfel D. _______________ 143
Klouek J. ___________ 297, 301
Klucka M. _______________ 299
Knov M. ______________ 281
Knyazyan N. B. ________ 52, 271
Kobayashi H. __________ 22, 233
Kobayashi T. ______________ 77
Kocour V. _______________ 154
Korkov H. ____________ 196
Koenig J. ________________ 308
Koenraads A. ____________ 198
Kohara S. ______________ 38, 99
Kohoutkov M. _______ 146, 299
Kochanowicz M. __________ 141

J
Jablonsk E. ______________ 124
Jain H. ________________ 33, 56
Janiaud E. _______________ 219
Jatzwauk Ch. _____________ 249
Jeandel G. _______________ 242
Jebav M. ____________ 210, 301
Jiang S. _________________ 146
Jiang W. _________________ 310
Jianjun Han _______________48
Jin Y. ___________________ 312
Jirgensons M. ____________ 291
Jitwatcharakomol T. _______ 261
Jonov . __________ 297, 306
Jones R. _________________ 107
Jong Heo __________ 77, 80, 140
Jonson B. _____________ 47, 154
Jousseaume C. ____________ 131
Juhnevica I. __________ 258, 264
JUN XIE _________________48
Jursek I. ________________ 277
Jurek K. __________________ 45

318 Author Index

Kocharyan G. A. __________ 271

Kokumai H. _____________ 189
Kolobkova E. V. ___ 143, 278, 278
Kolyadin A. N. ___________ 308
Komatsu T. _____ 62, 63, 63, 178,
_____________255, 259, 259, 260
Kondo Y. ___________40, 77, 101
Konidakis I.______________ 277
Knig J. _________________ 226
Krner J. ________________ 143
Koshizawa Y. _____________ 209
Kosolapov A. F. _______ 273, 308
Kosseva I. I. ______________ 255
Kostka P. _________146, 299, 301
Kokov V. ______________ 214
Kol P. _________________ 26
Kothiyal G. P. ____________ 166
Koudelka L. ___________ 33, 263,
________________ 270, 273, 275
Koudelka M. ______________ 55
Koura A. _________________ 31
Kovik I. _______________ 275
Kovalskiy A. _____________ 298
Koynov S. ________________ 47
Kozyukhin S. A. ___________ 57
Kraev I. A. _______________ 273
Kraxner J. ___________ 266, 277
Kremr N. ______________ 275
Krekhova E. Y. ________ 75, 257
Kreski P. K. ______________ 102
Krieke G. _________________24
Krobot T. ________________ 196
Kroeker S. ________________ 87
Kruger A. A. _____________ 160
Krger S. _________________ 71
Kubeek V. _______________ 85
Kuciski G. ______________ 265
Kuerov I. ______________ 281
Kuhn S. _________________ 143
Khne R. ________________ 189
Kumar R.________________ 107
Kunicki-Goldfinger J. J. ____ 152
Kunugi T. _______________ 195
Kupriyanova T. A. _________ 272
Kusumoto H.______________ 36
Kynin A. T. _______________ 21

L
Laba V. _________________ 301
Lablonde L. ______________ 145
Labruyre A. _____________ 144
Lacroix R. _______________ 177
czka K.________________ 108
czka M. _______ 108, 302, 302
Lahodny F. _______________90

Laimbck P. _____________ 213

Lamberson L. _____________ 65
Lanagan M. T. _____________ 72
Lang J. B. ________________ 160
Lankhorst A. M. __________ 199
Laplace A. _______________ 160
Larink D. _________________40
Law R. V. ___________ 34, 36, 36
Lazarenko P. I. ____________ 57
Lazoryak B. I. ____________ 282
Le Corre B. ______________ 242
Le Losq C. _______________ 103
Leall V. S. ________________ 61
Lebedev R. V. ____________ 278
Leboeuf V. _______________ 111
Lebullenger R. _____179, 227, 295
Ledemi Y. ____________ 87, 267
Lee M. J. _________________ 89
Lee W. E. _________________ 17
Lefvre G. ________________ 94
Legouera M. _____________ 146
Lechevalier L. ____________ 191
Leitner M. ________________ 26
Lelong G. ________ 39, 39, 40, 84
Lemesle T. _______________ 165
Lenoir B. _________________ 53
Leonelli C. ________ 69, 152, 304
Lessard F. _______________ 267
Lessmann S. _____________ 192
Lever D. _________________ 247
Li H. ____________________ 35
Li N. ___________________ 116
Likhachev M. E. __________ 283
Lim T. Y. _________________ 89
Lima M. M. ______________260
Lin H. __________________ 148
Lin P-T _________________ 148
Lindig M. _______________ 238
Lipatov D. S. _____________ 283
Lisiecki M.___________ 265, 281
Lisiecki R. ________________ 79
Lissov M. ____________ 55, 275
Lika M. ___________ 55, 94, 95,
________________ 103, 133, 275,
____________ 293, 294, 294, 295,
____________ 296, 297, 300, 305
Liu C.______________75, 89, 141
Lixiong Han ______________48
Lber N.-H., _____________ 241
Lockerbie N. A. ___________ 107
Lochegnies D. ____________ 241
Loiseau P. _______________ 167
Lombard P. _______________ 53
Lombello C. B. ___________ 120
Lopes A. A. S. ____________260
Lopes E. B. _______________ 53
Lorenz M. ________________ 61

Lorenzi A. _______________ 125

Lottici P. P. ______________ 125
Lousteau J._______________ 289
Lozada R. _______________ 288
Lucas P. __________________ 55
Luedtke L. _______________ 197
Lukowiak A. _________ 147, 148
Lusvardi G. ______________ 307
Luzinov I. _______________ 148

M
M. Kilo _________________ 147
Mackov A. ___________ 85, 145
Maeda H._____________117, 118
Maehara T. __________ 213, 300
Maertin M. ______________ 232
Mahdy A. E. _____________ 254
Machacek J. ______________ 103
Machado M. M.____________ 23
Majcenovic Ch. ___________ 191
Majrus O._________94, 167, 167
Makrlik A._______________ 262
Maksimov L. V. ____________ 25
Malavasi G. ______________ 307
Mlek J. ______________ 26, 257
Malinsk P. ___________ 85, 145
Mallinson P. M.___________ 118
Malyarevich. A.____________ 72
Mandal A. K._____________ 226
Mandal S. _______________ 226
Manolescu G. _____________ 94
Manylov M. S. ____________ 282
Marangoni M. ____________ 225
Margueritat J. ____________ 129
Marchenko Yu. V. _________ 256
Markova T. S. _____________ 25
Martin S. W. ______________ 51
Martinet C. ______________ 129
Martinez V. ______________ 129
Martucci A. ______________ 124
Marzouk S. Y. _____________ 86
Masai H. _____________ 54, 142
Mascaraque N. ________ 51, 305
Maslennikova I. G. _________64
Massard L._______________ 296
Massera J. ____________ 82, 119
Massiot D. ____________ 36, 166
Masson O. _______________ 144
Massoni N. ______________ 166
Masuno A.____________ 81, 102
Matjec V. ___________ 304, 305
Matevosyan A. B. _________ 271
Matousek I. ______________ 243
Matsunaga M. ____________ 101
Matsuoka J. ______ 130, 178, 214

Matsuyama T. ____________ 263

Mattsson K. ______________ 145
Maty J. ________________ 160
Matzen G. ________________ 62
Mauro J. C. __________ 129, 132
Maxwell L. J. _____________ 171
Mazurin O. V. _________ 19, 311
McCarthy F. H. ___________ 118
McDonald N. ____________ 220
McKay I. J. _______________ 116
Mear F. __________________ 21
Mear F. O. ____________ 52, 165
Medianu R. ______________ 269
Meechoowas, E. __________ 261
Mechin D. _______________ 145
Meliksetyan A. M. ________ 304
Menabue L. ______________ 307
Menguy N. ___________ 39, 131
Menzler N. H. ____________260
Mercury J. M. R. ___________ 61
Mermet A. _______________ 129
Meshaka Y. ______________ 242
Messaddeq Y. _________ 87, 267
Messing M. _______________ 47
Meuleman R. R. ______ 198, 248
Meulemans J. _________ 53, 219
Meyer R. _________________ 56
Meynckens J.-P. _______ 189, 190
Mezinskis G. _________ 258, 264
Migt M. _________ 67, 283, 284
Michlkov J. ________ 293, 295
Michalkov K. ________ 268, 268
Michel F. _________________ 41
Mka M. ________ 80, 83, 85, 90
Milanese D. __________ 145, 289
Milanova M. K. ___________ 255
Miller J. A.________________24
Minaev V. ___________ 298, 298
Minami D._______________ 282
Mingareev H. ____________ 139
Mirsaneh M. ______________ 72
Mishkin V. P._____________ 138
Miura Y. ________________ 214
Miyajima T. ___________117, 118
Miyake Y. ___________ 209, 285
Miyasaka S. ______________ 261
Miyazaki S. ______________ 209
Mizerov Z. ______________ 124
Mneimne M. _____________ 117
Moaveni M. ______________ 249
Modin E. B. __________ 280, 280
Moeginger M. ____________ 248
Moeller A. _______________ 242
Mogu-Milankovi A.___ 55, 273
Moiseev A. N. ____________ 273
Molla A. R. ______________ 253
Mncke D. ________ 35, 255, 270

ICG Prague 2013 319

Monnier J. ________________ 53
Montagne L. ________ 21, 33, 52,
_____________100, 165, 263, 273
Montanari F. _____________ 152
Monteiro R. C. C. _________260
Montenero A. ____________ 125
Monteville A. ____________ 145
Montorsi M. ______________ 56
Montouillout V.___________ 166
Montoya D. ______________ 241
Moraes M. _______________ 126
Moreac A. _______________ 295
Moreau P. _______________ 241
Morena R. ________________ 65
Mori K. _________________ 125
Morinaga A. ______________ 22
Moner P. _________ 33, 55, 263,
________________ 270, 273, 275
Motorin S. E. _____________ 273
Mouawad O. _____________ 140
Mrzek J. ____________ 304, 305
Mueller R. _______________ 262
Mugoni C. _____________ 56, 87
Muijsenberg H. P. H. ___ 196, 231
Mukimov D. _____________ 298
Muller J. ____________ 195, 195
Muller M. ________________ 68
Mller R. ______________ 56, 69
Mller-Simon H. __ 203, 204, 241
Muoz F. __________ 19, 51, 305
Muoz-Senovilla L. ____ 19, 305
Mura E. _________________ 289
Mure S. _________________ 160
Musgraves J. D. ___________ 148

N
Nagakane T. ______________ 62
Nagao M.______________ 54, 54
Nakada Y. ___________ 209, 285
Nakamura A. ____________ 214
Nakamura K. _____________20
Nakamura R._____________ 261
Nakanishi T. ______________ 88
Naknikam U. ____________ 261
Nalbandyan K. A. __________ 52
Nalin M. _________________ 86
Naline S. ________________ 171
Nancy __________________ 166
Narushima T. _________117, 118
Nekrasova Y. A. __________ 143
Nekvindov P. _______ 80, 83, 85,
_________________ 90, 145, 304
Nmec L. _________210, 301, 312
Nemilov S. V. _____________ 17
Netusilova M. ____________ 269

320 Author Index

Neuville D. R. _________ 36, 103

Neves E._________________ 311
Nguyen H. P. ______________ 57
Nielsen K. H. ______________ 47
Nighogossian K. __________ 126
Nikolov V. S. _____________ 255
Nikonorov N. V. _______ 76, 142,
________________ 143, 278, 278
Nishchev K. N. ____________ 78
Nishida S. ________________99
Nishii J. __________________ 38
Nischev K. N. ____________ 138
Noi K. ___________________54
Novak P. ________________ 269
Novak S. ________________ 148
Novotn F.________________ 45
Nuryev R. K. _____________ 142

O
Obata A. _____________117, 118
Ocana Jurado M. ___________ 62
Oelgoetz J. _______________ 298
Ogata J. _____________ 209, 285
Ogawa K. _________________ 62
Ogura A. ________________ 292
Ohara K. ______________ 38, 99
Ohishi Y. ________________ 140
Ohji M. _______________ 62, 99
Ohkawa S. _______________ 209
Ohsono K. _______________ 292
Ohtake Y _________________ 22
Ohtomo T. _______________264
Ojovan M. I. __________ 17, 159
ktem D.________________ 214
Ollier N. ______________ 35, 86
nsel L. _________________ 233
Orain H. ________________ 107
Orman R. G. _____________ 104
Orzol D.__________________ 47
Osada M. _________________20
Ose Y. __________________ 195
Osipov A. A. ___________ 31, 31
Osipova L. M. __________ 31, 31
Oswald J. ______________ 85, 90
Osyczka A. M. ____________ 302
Owen A. T. ______________ 160
zdemir B. ______________ 190
zel Uar S. _____________ 233

P
Paemurru M. _____________ 109
Pagov J. _______ 55, 268, 268
Palafox J. J. ______________ 288

Palles D. ________________ 277

Panchartek Z. _____________ 45
Panov A. A. _______________ 78
Pantano C. _______________ 45
Pantano, C. G. _____________ 33
Papin S. _________________ 220
Park T. H. ________________ 89
Pascual M. J. ____58, 69, 148, 310
Patriarche G. _____________ 131
Patschger M. _____________ 109
Patzig C. ________________ 310
Pauo T._____________ 266, 277
Paulus G. G. _____________ 143
Pavese M. _______________ 145
Pawlik J. ____________ 302, 302
Pecoraro E. ______________ 126
Pedel J.__________________ 233
Pedlkov J. ______________ 301
Peitl O. _________________ 276
Pellerin N. _______________ 166
Pelli S. ___________147, 148, 302
Penelon B. _______________ 165
Peres M. F. S. _____________ 126
Perret D. ________________ 165
Pesansky J. D. ____________ 312
Peterka P.________________ 304
Peters-Niessen V. _________ 270
Petersen R. R. ________ 226, 308
Petit L. ___________________ 82
Petracovschi E. ____________ 78
Petrosyan G. X. ___________ 304
Pevzner B. Z. __________ 21, 307
Pfeiffer T. _________________64
Pfeiffer Th., _______________ 93
Pflaum S. _________________ 56
Philippart A. _____________ 278
Philippovskiy D. V. ________ 273
Philipps K._______________ 108
Piarristaguy A. ____________ 53
Pigeonneau F. ____________ 196
Pilgrim W.-C. _____________ 31
Pinet O. __________160, 165, 171
Piroux J. C. ______________ 171
Plotnichenko V. G. ____ 267, 273
Plotnikov V. S. ________ 280, 280
Plko A. ______ 55, 268, 268, 275
Pludons A. _______________264
Podoliniakov J. _________ 301
Podor R. _________________ 52
Podrazk O. _________ 304, 305
Poissonnet S. _____________ 166
Polk M. ________________ 312
Polian A. _________________ 23
Polyakova I. G. ________ 25, 286
Polyshchuk S. A. __________ 256
Ponsot I. ________________ 225
Ponzoni C. ______________ 304

Poprawski R. _____________ 286

Postnikov E. S. ____________ 76
Potuzak M. ______________ 132
Poulain M. __________ 295, 299
Poussou S. _______________ 231
Pozdnyakov A. E. ______ 75, 257
Pozdnyakov G. A. _________ 272
Pradel A. _____________ 53, 100
Prange A. ________________ 94
Priven A. I. _____ 19, 21, 268, 311
Prnov A. _____ 66, 67, 284, 285
Prochzkov O. ___________ 146
Prokhorenko O. A. _____ 21, 307
Prokhorenko S. O. _________ 21
Pryamikov A. D. __________ 308
Pshenko O. ______________ 286
Pukhkaya V. ______________ 86
Pustovalov E. V. ______ 280, 280
Pye L. D. _________________ 11
Pynenkov A. A. ____________ 78
Pytalev D. _______________ 167

R
Rademann K. ____________ 140
Radtke G. _______________ 131
Radu D. _________________ 266
Raedlein E. _______________80
Raghuwanshi V. S. ______ 70, 70
Raguenet B. ______________ 100
Rahn J.__________________ 290
Raj R. ____________________ 58
Rajbhandari P.____________ 100
Ramesh K. ________________ 57
Ramrez M. A.____________ 276
Ramon L. _______________ 173
Randkov S. ____________ 274
Randall C. A. _____________ 72
Rebai R. __________________ 78
Reben M. ______ 79, 265, 281, 281
Reibstein S. ______________ 130
Reid S. __________________ 107
Reiman K. B. _____________ 312
Reinfelde M. _____________ 291
Reinsch S. ________________ 69
Remy B. __________________ 53
Revel B. __________ 33, 263, 273
Ribeiro S. J. L. ____________ 126
Ribes M. _____________ 53, 100
Ribet I.__________________ 172
Ried P. ___________________ 56
Righini G. C. ______147, 148, 302
Richardson K. ____________ 144
Richardson K. A.__________ 148
Richter R. W. _____________ 153
Rincn J. Ma. ____________ 288

Rioux M. ________________ 267

Ristic D._________________ 148
Ritzberger C. ___________ 46, 71
Robin T._________________ 145
Rodrigues A. C. M. _ 23, 277, 286
Rodrigues A. M. ____ 61, 66, 293
Rodrigues B. P. _______ 134, 289
Rodriguez C. P. ___________ 160
Rodriguez V. _______ 82, 83, 144
Rodrguez-Lpez S._________ 69
Roggendorf H._______ 20, 93, 93
Rohanova D. _________ 269, 274
Rocherull J. _________ 179, 227
Roncalho L. ______________ 126
Rongen M. ___________ 204, 219
Rosa R. _________________ 304
Roskosz M. _______________ 51
Ross M. __________________ 26
Ross S. __________________ 290
Rssel A.-K.______________ 189
Rsslerov I. ______ 33, 262, 263
Roth, R. __________________20
Rothe S. __________________ 69
Roula A. _________________ 17
Rouxel T. ________ 107, 108, 129
Rouyer F. ________________ 196
Rowan S. ________________ 107
Ruedinger B. ______________64
Ruessel C. _____________ 70, 70
Ruffl B. __________________ 23
Russel C. _________________ 68
Rssel C. ____________ 109, 143
Russell P. St. J. _____________80
Rutkowski S. _____________ 248
Rysiakiewicz-Pasek E.______ 286

S
Saget A. _________________ 219
Saha C. K. _______________ 312
Saijo Y. _________________ 258
Saito K. _________ 275, 282, 292
Saitoh A. ______________ 38, 81
Saitzek S. ______________ 21, 52
Sakamoto A. ______________ 62
Sakamoto O. _____________ 209
Sakuda A. _____ 54, 54, 263, 264
Salama S. N. _____________ 254
Salanov A. N. ____________ 272
Salinas A. J. ______________ 307
Salman S. M. _____________ 254
Salmon P. S.______________ 131
Salvado I.________________ 274
Salvo M. ________________ 296
Sanders T. _______________ 232
Sangleboeuf J. C. __________ 227

Santos G. G. _____________ 282

Santos M. V. _____________ 126
Santowski K. _____________ 191
Sargasyan A. A. ___________ 304
Sato A. ___________________ 63
Sato K. ______________ 209, 285
Sauvage T. _______________ 168
Sava B. A. _______ 260, 269, 285
Savate B. J. ______________ 237
Savelyev E. A. _____________ 82
Savchenko N. N. __________ 256
Scarpelli I. _______________ 302
Scipioni U.________________ 58
Scott R. B. ___________ 151, 151
Sedlek J. _______________ 283
Sekiya E. H. ______ 275, 282, 292
Semjonov S. L.____________ 138
Sen R. __________________ 226
Sen S. ___________________ 226
Seo I. ____________________ 51
Sepiol B. _________________ 26
Setina J. _____________ 258, 264
Seungryeol Yi ____________ 140
Sgibnev E. M. ____________ 142
Sglavo V. M. __________ 58, 107
Sharma G. _______________ 166
Shashkin A. V. ____________ 75
Sherchenkov A. A. _________ 57
Shikin A. S. _______________ 82
Shimoda M. ______________84
Shimojo F. ________________ 31
Shin D. W. _______________ 126
Shinohara N. _____________ 209
Shinozaki K. _____________ 178
Shiryaev V. S. ________ 267, 308
Shortland A. _____________ 151
Shruti S. ________________ 307
Schadrack R. _____________ 262
Schick V. _________________ 53
Schmidtchen U. ___________ 56
Schneider J. _______________ 37
Schommers A. ____________ 152
Schreiber R.______________ 262
Schuller S. _______________ 165
Schweiger M. ______________46
Schweizer S, _____________ 147
Sidelnikova O. N. _________ 272
Sidorov A. I. _____________ 142
Sierka M. ________________ 133
Siligardi C. ____________ 56, 87
Silly G.__________________ 100
Silva R. R. _______________ 126
Silvestri M. ______________ 110
Simo A. _________________ 140
Simon P. ________________ 241
Singh V. _________________ 148
Sklepi K. ________________ 55

ICG Prague 2013 321

Skoptsov N. _______________ 72
Sluncik P.________________ 247
Smeacetto F. _____________ 296
Smedskjaer M. M. _____ 129, 308
Smektala F. ______________ 140
Smrek J. ____________ 214, 292
Smrok . _____________ 66, 67
Snopatin G. E. ____________ 308
So B. J. __________________ 138
Soares R. S. ______________260
Soares V. O __________ 120, 288
Soga N. _________________ 178
Sojref R. _________________ 262
Soliani A. P. ______________ 148
Soltani M. T. _____ 295, 299, 303
Soltsz V. __________ 94, 95, 293,
_____________294, 295, 296, 297
Sonneville C. _____________ 129
Soubeih S. _______________ 197
Souza M. T. ______________ 276
Speranza G. ______________ 302
Spirkova J. _______________ 145
Sroda M. _________________ 36
Stana M. _________________ 26
Stank S. ___________ 80, 83, 85
Star M. _________________ 45
Steele C. J. ___________ 171, 265
Stege H. _________________ 153
Stelwagen S. _____________ 198
Stennett M. C. ____________ 171
Stevens J. R. ______________ 160
Stoffel R. ________________ 108
Stoch A. _________________ 291
Stoch L. __________________ 18
Stoch P. _____________ 284, 291
Stoleriu S. _______________ 285
Stunda-Zujeva A. __________24
Sugawara T. __________ 130, 214
Sulcova J. ________________ 103
Sundaram S. K. ____________ 27
Surkova V. F. __________ 75, 257
Surovtsev N. V. ___________ 256
Suzuki F. _________________ 62
Suzuki Y. ________________ 258
Svecova B. _______________ 145
Svoboda R. ___________ 26, 257
Szemkus S. ______________ 286
Szotkwski P. ______________ 85
ajgalk P. ________________46
anda L._________________ 124
imon P. _________________ 67
imurka P. ___________ 266, 277
pirkova J. ________________ 83
ulcov J. ________________ 268
vecov B. _____________ 83, 85

322 Author Index

T
Taccheo S. _______________ 145
Tadanaga K. _____________ 125
Tagantsev D. K. ____________ 25
Takada A. _______________ 101
Takahashi H. ______________ 95
Takahashi S. _____________ 287
Takahashi Y. ___________ 20, 54,
__________________ 65, 95, 118
Takebe H. _________ 38, 81, 287
Taki Y. __________________ 255
Tamura K. _______________ 261
Tan S.___________________ 159
Tanabe S. _________________ 88
Tanaka A. _______________ 101
Tanaka C. _______________ 209
Tanibata N. _______________54
Tanner T. ________________ 298
Tao H. __________________ 141
Tapasa K. ________________ 261
Tarafder A. ______________ 253
Tarakanov S. V. ___________ 307
Tatchev D. ________________ 70
Tatsumisago M._____ 54, 54, 104,
________________ 125, 263, 264
Taylor T. ________________ 265
Teisseire J. _______________ 177
Telin I. A. ____________ 64, 256
Teplanova M. ________ 294, 300
Terrapon V. E. ____________ 241
Tessier F. ________________ 227
Tessier G. _________________48
Teteris J._________________ 291
Thiele S. _________________ 237
Thielen L.________________ 199
Thomas P. _________ 78, 84, 144
Tiegel M. ________________ 143
Timoshenkov S. __________ 298
Todorov R._______________ 306
Toffoli S. M. ______________ 213
Togashi T. ________________ 63
Tohidifar M. R. ___________ 123
Tojo S. __________________ 214
Tokmakov K. V. __________ 107
Tokuda Y. _______________ 142
Tomagov M. ________ 268, 268
Tomanov O. _____________ 274
Tomkova K. ______________ 306
Toplis M. J. _______ 51, 220, 220
Torkamani S., ____________ 233
Torres J. O. ______________204
Tourni A. ________________ 94
Tran Ngoc K. _____________ 148
Travis K. P. _______________24
Trebosc J. ________________ 295
Tregouet H. ______________ 167

Tresnakova-Nebolova P. ____ 307

Tricot G. ______ 33, 38, 100, 100
Tritschel D. ______________ 189
Trnovcov V. _____________ 301
Trochta M. ______________ 301
Tsenter M. ________________ 72
Tsuchida _________________ 37
Turrell S. ________________ 148

U
Ueda J. ____________88, 117, 118
Uchida M. ________________84
Ulery H. ________________ 298
Umesaki N. ______________ 104
Urata S. _________________ 195
Ushimaru Y. _____________ 189
Uteza O. _________________ 83

V
Vacher R. _________________ 23
Vaills Y _________________ 111
Valach J._________________ 154
Valle P. S. _________________ 86
Vallet-Regi M. ____________ 307
van Kersbergen M. ________ 232
van Limpt H. ______192, 219, 237
Van Nijnatten P. A. ________ 309
van Santen P. _____________ 198
Van Wllen L. ____________ 100
Vandembroucq D. __________48
Vaney J. B. ________________ 53
Varga Z. __________________ 70
Varshneya A. V. ___________ 102
Vaen R. ________________260
Vecstaudza J. ______________24
Velmiskin V. V. ___________ 138
Velinova R. ______________ 254
Venclova N. ______________ 306
Vercamer V. _______________40
Veres M. _________________ 57
Vernerova M._________ 300, 301
Veron E. _________________ 220
Vezin H._____________ 100, 167
Vezzalini G. ______________ 125
Viens J. _________________ 267
Viktorin P. _______________ 195
Villas-Boas M. O. C. _______ 288
Virga A. _________________ 145
Vivier H. ________________ 241
Vlkov P. _________ 94, 95, 293,
_____________294, 295, 296, 297
Voit E. I._________________ 256
Voitenko O. V. ____________280

Vojtech P. ________________ 231

Vokelov J. _______ 293, 294, 295
Volceanov A. _________ 285, 291
Vorokhta M. ______ 55, 270, 273
Vrbel P. ________ 266, 275, 277
Vytykacova S. ____________ 145

Wondraczek L. ____11, 11, 35, 47,

________________ 130, 134, 137,
_____________178, 255, 270, 289
Woon Jin Chung ____ 77, 80, 140
Wren J. E. C. ______________ 87
Wu X. __________________ 310
Wuthnow H. _____________ 232

Yoshida S. _______ 130, 178, 214

Yoshimoto K.______________ 81
Yuan Yao _________________48
Yue Y. Z. ________ 129, 226, 308
Yumashev K. ______________ 72

Z
W
X
Wachtel P. _______________ 148
Wallenberg R. _____________ 47
Wang H. ____________ 309, 310
Wang J. _________________ 231
Wang Q. ________________ 310
Wang W. ________________ 310
Wang Y. _________________ 259
Wanner A. _______________ 107
Wasylak J. ____________ 79, 265,
________________ 281, 281, 303
Watanabe Y. ______________ 81
Watson M. J. _____________ 231
Weber J. K. R. _____________99
Wegner S. _______________ 100
Weigand R. ___189, 225, 253, 253
Weigel C. _________________ 23
Welch R. C. ______________ 132
Welsch A. M. _________ 290, 290
Werner-Zwanziger U. ______ 179
Wilantewicz T. E. _________ 312
Wilantewicz T. W. _________ 178
Willberg M. ______________260
Wilson P. R. _______________ 79
Wilson R. M. _____________ 115
Winterstein A.______35, 137, 255
Wisniewski W. ____________ 68
Woelffel W. ______________ 220
Won Bin Im_______________80
Won Ji Park _______________ 77

Xin Mu __________________48
Xiujian Zhao ______________ 76
Xu K. ________________ 89, 138
Xu M.___________________ 312

Y
Yamamura S. _____________ 189
Yamaoka K. _______________ 65
Yamauchi H. ______________ 62
Yamazaki Y._______________ 65
Yamzaki H. ______________ 275
Yang G. ______________ 83, 144
Yano T. _____________ 209, 285
Yanush O. V. ______________ 25
Yaogang Li Y._____________ 309
Yaroshenko P. M. _________ 256
Yaroshenko R. M. __________64
Yi Z. ____________________ 148
Ying Huang _______________ 76
Yl Kwon Lee ______________80
Yoko T. _________________ 142
Yokoyama Y. _____________ 108
Yoo J. S. __________________ 89
Yordanova A. S. ___________ 255
York-Winegar J. ___________ 298
Yoshida K. ________________54

Zachariasz P. _____________ 291

Zainuddin N. _____________34
Zajc J. __________________ 214
ak R. __________________ 288
Zanotto E. D.__ 66, 120, 132, 276,
_________ 277, 282, 288, 289, 293
Zavadil J. ________ 146, 299, 303
Zayas Ma. E. _________ 276, 288
Zborowski J. _________ 189, 190
Zemanov V. ______________ 55
Zhang D. ________________ 116
Zhang G. ________________ 141
Zhang J. ______________ 85, 141
Zhang L. _________________ 94
Zhang Q. ________________ 309
Zhang S. ________________ 312
Zhang X. ________________ 312
Zhang X. H._______________ 78
Zhang Y. ________________ 312
Zhao D. _________________ 110
Zhao X. _________________ 141
Zhao X. J. ________________ 75
Zhilin A. _________________ 72
Zhiyong Zhao,_____________ 76
Zhou G. _________________ 179
Zmekal Z. ______________ 124
Zmojda J. ________________ 141
Zontek-Wilkowska J.___ 281, 281
Zwanziger J. W. ________ 41, 179

ICG Prague 2013 323

The 23rd International Congress on Glass Book of Abstracts

Published by Vydavatelstv esk sklsk spolenosti s.r.o., Stedov 1767/17 Teplice, Czech Republic
Printed by Macek a Kusala, U Rybnka 11 Jablonec nad Nisou, Czech Republic
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ISBN 978-80-904044-3-4.

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