ISSN 1753-3562
June 2012 Volume 53 Number 3
Physics andChemistry ofGlasses
Welcome in Prague The International Commission on Glass was created in 1933 in order to promote international collaboration and to disseminate information throughout the entire glass community. One way to achieve this mission, consists in the triennial organization of the International Glass Congress. The last time that this event occurred in Czech Republic was in 1977. Czech Glass Society is honoured to organize the next International Congress on Glass in the Czech Republic in 2013.
European Journal of Glass Science and Technology Part B
Conference Site Prague is one of the most beautiful cities in Europe. Built between the 11th and 18th centuries, the Castle District, the Old Town, the Lesser Town and the New Town demonstrate the great architectural and cultural influence enjoyed by this city since the Middle Ages. The historic centre of Prague has been included in the UNESCO World Heritage List. The congress will be held at the at the Prague Congress Centre, the largest conference centre in the Czech Republic.
Topics Plenary talks, invited talks, contributed papers and posters sessions will cover all topics in glass science, technology and production. In addition to the common topics, the Congress will focus on new directions for glass developments and applications: Main topics covered (but not limited): Glass transition and relaxation, entropy of glass, theoretical modelling Glass structure (computer modelling, experimental) New glasses (preparation, properties, and their applications) Metallic, organic and hybrid glasses Glass properties (optical, mechanical, thermal, electrical, etc.) Glass surfaces (modelling, properties, tayloring) Phase separation, nucleation, and crystallization Glass melting and forming Glass technology Furnace technology and refractories Raw materials and glass components Enviromental issues in the glass production Archeological glass
Congress Secretariat Registration, hotels, other services Exhibition Payments
www.icg2013prague.cz
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Malé nám. 1, 110 00 Praha 1 Czech Republic Contact E-mail:
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June 2012
Online Manuscript Submission, Tracking and Peer Review System for
Physics and Chemistry of Glasses
The European Journal of Glass Science and Technology
Volume 53 Number 3
European Journal of Glass Science and Technology B Contents
The European Journal of Glass Science and Technology is a publishing partnership between the Deutsche Glastechnische Gesellschaft and the Society of Glass Technology. Manuscript submissions can be made through Editorial Manager, see the inside back cover for more details. Senior Editor Professor R. J. Hand Regional Editors Professor J. M. Parker Professor L. Wondraczek Professor A. Duran Professor R. Vacher Dr A. C. Hannon Professor M. Liška Professor S. Buddhudu Professor Y. Yue Abstracts Editor Professor J. M. Parker Managing Editor D. Moore Assistant Editor S. Lindley Society of Glass Technology 9 Churchill Way Chapeltown Sheffield S35 2PY, UK Tel +44(0)114 263 4455 Fax +44(0)8718754085 Email
[email protected] Web http://www.sgt.org The Society of Glass Technology is a registered charity no. 237438. Advertising Requests for display rates, space orders or editorial can be obtained from the above address. Physics and Chemistry of Glasses: European Journal of Glass Science and Technology, Part B ISSN 1753-3562 (Print) ISSN 1750-6689 (Online)
61 Phase separation and crystal precipitation in supercooled sulphophosphate ionic melts S. Reibstein, N. Da, J.-P. Simon, E. Spiecker & L. Wondraczek 68 Tin oxide solubility in soda–lime–silica melts P. Gateau, C. Petitjean, P. J. Panteix, C. Rapin & M.Vilasi 74 Dissolution of copper slag glasses Hans Roggendorf, Thomas Pfeiffer, Sebastian Müller & Antje Schilling 79 Glass-forming ability and structure of glasses in the ZnO–WO3–P2O5 system Ladislav Koudelka,* Jiří Šubčík, Petr Mošner, Ivan Gregora, Lionel Montagne & Laurent Delevoye 86 Structure and properties of lead tungstate phosphate glasses Ladislav Koudelka, Ivana Rösslerová, Zdeněk Černošek, Petr Mošner, Magdalena Lissová, Marek Liška, Lionel Montagne & Laurent Delevoye 93 Crystallization and microstructure of Na2O–CaO–Nb2O5–P2O5 glasses Agnese Stunda-Zujeva, Guna Krieke, Dmitrijs Jakovlevs, Liga Berzina-Cimdina 99 Dependence of crystallization processes of glass-forming melts on melt history: a theoretical approach to a quantitative treatment Jürn W. P. Schmelzer* & Christoph Schick 107 Fluctuation inhomogeneities of glasses and melts studied by light scattering spectroscopy and high temperature acoustic methods A. Anan’ev, V. Bogdanov, L. Maksimov & O. Yanush 115 A non-dimensional approach to computing the global relative glass forming ability of oxides Boubata Nouar, Moussaoui Islam & Roula Abdelmalek 121 SpectraFit: a new program to simulate and fit distributed 10B powder patterns – application to symmetric trigonal borons Victor Khristenko, Kevin Tholen, Nathan Barnes, Evan Troendle, David Crist, Mario Affatigato, Steve Feller, Diane Holland, Thomas F. Kemp & Mark E. Smith 128 Mechanochemical synthesis of BaO–B2O3 glass and glass-ceramic phosphor powders containing europium ions Atsuko Shinomiya, Akitoshi Hayashi, Kiyoharu Tadanaga & Masahiro Tatsumisago 132 Double rotation 11B NMR applied to polycrystalline barium borates Oliver L. G. Alderman,* Dinu Iuga, Andrew P. Howes, Diane Holland & Ray Dupree 141 Conference diary A25 Abstracts
The journal is published six times a year at the beginning of alternate months from February. Electronic journals: peer reviewed papers can be viewed by subscribers through Ingenta Select http://www.ingentaconnect.com The editorial contents are the copyright © of the Society. Claims for free replacement of missing journals will not be considered unless they are received within six months of the publication date.
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From January 2006 the journals of the Society of Glass Technology (SGT) and the Deutsche Glastechnische Gesellschaft (DGG) were combined as the European Journal of Glass Science and Technology. Published in two parts Glass Technology: European Journal of Glass Science and Technology Part A and Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part B. This venture builds on the successes and traditions of the journals of both societies to produce two high quality scientific and technical journals with essential reading for all those working in the fields of glass science and technology. Both journals are published six times per year. Papers appearing in Glass Technology are concerned with glass making, glass fabrication, properties and applications of glasses or glass ceramics and other related topics. Physics and Chemistry of Glasses accepts papers of a more purely scientific interest concerned with glasses and their structure or properties. Thus the subject of a paper will normally determine the journal in which it will be published. Papers on structure of glass, for example will always appear in Physics and Chemistry of Glasses while those on furnace operation will appear in Glass Technology. In some cases, the way in which a subject is discussed determines the appropriate journal and the Editors will advise authors in such cases. Open Access The Society of Glass Technology is able to offer authors the Open Access route to publication. This option is now available to our authors, on payment of an appropriate up-front one-off fee to meet the costs of electronic production. The fee will be payable by the author after paper acceptance and prior to publication. The fee is £800 for members of the SGT and DGG; for nonmembers the fee is £1000. VAT is applicable to residents in the EU. Open Access papers are licenced under the Creative Commons licence BY-NC-ND: http://creativecommons.org/licenses/by-nc-nd/3.0/ Editorial Manager At the start of 2009, a new online manuscript submission, tracking and peer review system was introduced. Using the Editorial Manager platform: Authors may submit manuscripts and track their progress through the system, hopefully to publication. Reviewers can download manuscripts and submit their opinions to the editor. Editors can manage the whole submission/review/revise/publish process. Publishers can see what manuscripts are in the pipeline awaiting publication. Email is sent automatically to appropriate parties when significant events occur. Glass Technology: European Journal of Glass Science and Technology Part A: http://www.editorialmanager.com/gt/
Cover: A detail taken from Figure 1 of the paper: Dependence of crystallization processes of glass-forming melts on melt history: a theoretical approach to a quantitative treatment by Jürn W. P. Schmelzer & Christoph Schick (Phys. Chem. Glasses: Eur. J. Glass Sci. Technol. B, June 2012, 53 (3), 99–106)
Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part B: http://www.editorialmanager.com/pcg/ All manuscript preparation software will be supported by Editorial Manager. Files submitted will be converted to Acrobat PDF file format for distribution to editors and reviewers.
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Phys. Chem. Glasses: Eur. J. Glass Sci. Technol. B, June 2012, 53 (3), 107–114
Fluctuation inhomogeneities of glasses and melts studied by light scattering spectroscopy and high temperature acoustic methods A. Anan’ev,a V. Bogdanov,b L. Maksimova* & O. Yanushc Research and Technological Institute of Optical Material Science, Ul.Babushkina 36 Bld.1, Saint Petersburg 192171 Russia b Saint Petersburg State University, Universitetskaya nab. 7/9, Saint Petersburg 199034 Russia c Saint Petersburg State Technological University of Plant Polymers, Ul. Ivana Chernykh 4, Saint Petersburg 198095 Russia a
Manuscript received 1 September 2011 Revised version received 27 February 2012 Accepted 28 February 2012
Fluctuation inhomogeneities of inorganic glasses are considered based on light scattering spectroscopy and high temperature acoustic data. The dependencies of the Landau–Placzek ratio on glass composition were determined from Rayleigh and Mandel’shtam–Brillouin scattering (RMBS) spectra. The dependencies of the ultrasound velocities of glasses and their melts on temperature and frequency were found. Results are discussed in terms of “freezing” refractive index fluctuations during glass melt cooling. Constant stoichiomentry groupings (CSG) were found from specially processed Raman scattering spectra of glasses. In particular, highly electro-optic sensitive niobate glasses contain CSGs with stoichiometries of well-known electro-optical crystals. Selective entering, i.e. segregation, of dopants (Nb, Pb, rare earths, etc.) into inhomogeneities of a glass host causes growth of Rayleigh scattering losses and increases the probability of transfer of electron excitation energy between luminescent rare earth ions. The data obtained opens a route for developing low scattering multicomponent glasses for optical and electro-optical fibres, laser and radiation converting glasses.
1. Introduction Recent decades have been characterized by a revolution in our understanding of the structure of inorganic glasses from the first well-known speculative hypothesis of a disordered network and crystallites to a set of models describing glass structure on scales from nanometres to hundreds micrometres.(1,2,3) This progress was caused by the demand to manufacture glass products with operational parameters that strictly depend the on nano- or microstructure of the glass. This relates to a wide assortment of glass materials from glasses for optical fibre drawing,(4) nonlinear,(5) optically resistant,(6) electro-optical,(7) laser,(8) radiophotoluminescent,(9) magneto-optic(10) glasses, glasses for immobilization of radioactive waste,(11) glassy fuel elements,(12) bioactive glasses,(13) glassy fertilizers,(14) etc. In spite of a powerful arsenal of structure sensitive methods being applied to glasses in the main glass forming systems some aspects of glass inhomogeneity have remained unknown in detail. The paper is aimed at analysis of compositional dependencies of inhomogeneities in glasses using Rayleigh and Mandel’shtam–Brillouin scattering (RMBS) spectroscopy, Raman scattering spectroscopy and high temperature acoustic data. It is expected that general * Corresponding author. Email
[email protected] Presented during the International Conference on the Chemistry of Glasses and Glass-Forming Melts, Oxford, September 2011
relationships between peculiarities of inhomogeneous glass structure and Rayleigh scattering losses, electro-optical sensitivity, and spectral–kinetic parameters of rare earth dopants can be determined.
2. Background 2.1. Rayleigh and Mandel’shtam–Brillouin scattering spectroscopy
Although Mandel’shtam–Brillouin scattering is widely used in studying the physics of substances in equilibrium states, that is gases, liquids, crystals(15) its use for studying the inhomogeneous structure of glasses by RMBS spectroscopy seems to be underestimated. This can be explained by difficulties related to glass sample requirements and interpretation of the measurement results. The theory of RMBS is published elsewhere and it will be briefly reviewed here.(16,17) For binary glasses the intensities of RMBS spectrum components can be written as V (∂n / ∂ρ )C2 〈∆ρ 2 〉 (1 + cos 2 θ ) (1) I R ~ I inc 4 λ + (∂n / ∂C )PT 2 〈∆C 2 〉 I MBS ~ I inc
I t ~ I inc
V 4 −1 (n p12 ) 2 kTc11 (1 + cos 2 θ ) (2) λ4
V 4 (n p44 ) 2 kTc−441 (1 + cos 2 θ ) (3) λ4
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Proc. Int. Conf. on Chemistry of Glasses and Glass-Forming Melts, Oxford, UK, September 2011
where IR, IMBS and It are the intensities of the Rayleigh, Mandel’shtam–Brillouin longitudinal and tranverse components of a spectrum, respectively. Iinc and λ are the intensity and wavelength of incident radiation, V is the scattering volume, n is the refractive index, ρ is the density of scattering medium, C is the concentration of the second component in the glass and ·Δρ2Ò and ·ΔC2Ò are the mean square density and concentration fluctuations. θ is the scattering angle, T and P are the temperature and the pressure, respectively, k is the Boltzmann constant, p12, p44 are the Pockels coefficients, c11=ρνl2, and c44=ρνt2 are the longitudinal and transverse elastic moduli, and νl and νt are the longitudinal and transverse hypersonic velocities. The Landau–Placzek ratio is given by RL–P=IR/(2IMBS) (4) Rayleigh scattering loss coefficient, αs, can be expressed via the Landau–Placzek ratio as αs = ( RL-P + 1)
8π 3 kT 4 −1 (5) (n p12 )2 c11 3 λ4
Spectral shifts Δνl and Δνt for the longitudinal and transverse components of the spectrum can be written as ∆ν l v θ = 2n l sin (6) c 2 ν
∆ν t v θ = 2n t sin (7) ν c 2
where ν=1/λ, and с is the velocity of light in a vacuum. RMBS spectroscopy opens the way to determine both macroscopic (e.g. phonon propagation velocities) and microscopic (Landau–Placzek ratio) parameters of a glass. As was found in Refs 16, 18 as a rule IMBS varies monotonically with glass composition. This means that it may be used as an inner reference and the composition dependence of Rayleigh scattering losses can be extracted from the composition dependence of the Landau–Placzek ratio. The main obstacle of studying glass by RMBS spectroscopy lies in the great difference between Landau–Placzek ratios of liquids and glasses (see Table 1). This result was plausibly explained by the model of “freezing” of fluctuations caused by translaTable 1. Experimental values of Landau–Placzek ratios of some inorganic compounds in crystalline, liquid, and glassy states Substance State
Temperature Landau–Placzek (K) ratio, RL-P=IR/(2IMB)
Ref.
Water SiO2 SiO2 (Homosil) SiO2 (quartz) Al2O3 (sapphire) KBr
298 ~1900 298 298 298 298
21 22 19 23 23 24
Liquid Liquid Glassy Crystal Crystal Crystal
0·006–0·038 7·50±0·01 23·0±0·7 0·06 0·6 0·599±0·19*
Note: * Minimum value chosen from a set of nine crystals
tional motion of species during melt cooling when the increase of melt viscosity prevents nucleation. This means that Rayleigh scattering intensity of a glass at room temperature should correspond to its value at the glass transition temperature while the intensity of Mandel’shtam–Brillouin scattering is proportional to the glass sample temperature. In general, the Landau–Placzek ratio of a single component substance should be written as(16) RL–P=IρR/(2IMB)+IanisR/(2IMB)=Rρ+Ranis (8) where IρR, IanisR, and Rρ, Ranis are the contributions of “frozen-in” density and anisotropy fluctuations to the Rayleigh scattering intensity and the Landau–Placzek ratio, correspondingly. Ranis may be estimated from the depolarization coefficient of the Rayleigh scattering component, ΔV=IVVR/IVHR, where IVVR and IVHR are Rayleigh scattering intensities measured with VV and VH polarization. For a 90° scattering angle(19,20) IisoR=IVVR−(4/3)IVHMBS (9) where IisoR is the isotropic Rayleigh scattering intensity. Using Macedo–Schroeder’s formalism Rρ can be written as (16) Rρ =
Tg T
(β0,Tg c11 − 1) (10)
where Tg and T are the glass transition and measurement temperatures, correspondingly, β0,Tg=(ρv02)Tg−1 is the static isothermal compressibility, ρ and v0 are the density and the value of the sound velocity in the low frequency limit at Tg. Taking into account that, as a rule, results of density measurements performed at T and Tg differ by not more than 5% it is possible to use Equation (10) in the form Tg
[(v0,Tg / v)2 − 1)] (11) T In the case of multicomponent glasses Rayleigh scattering depends both on “frozen-in” density fluctuations and concentration fluctuations, that is Rr ≈
RL–P=Rρ+Ranis+RC (12) RC=ICR/(2IMB) (13) where ICR and RC are the contributions of “frozen-in” concentration fluctuations to the Rayleigh scattering intensity and the Landau–Placzek ratio, respectively. In the case of a binary glass RC can be written as: 2 Tf (¶ n/¶ C )PT 〈∆C 2 〉 (14) 2 I MBS where Tf is the temperature at which concentration fluctuations are “frozen in”. In accordance with Ref. 16 Tg
