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1

Determination of ionic conductivity in the Bi-Si-O and Pb-Si-O glasses

Karczewski J., Miruszewski T., Bochentyn B., Kusz B.

Materials Science Poland

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2017

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Vol. 35, No. 4

681--686

EN

Impedance spectroscopy measurements in various gas atmospheres were carried out in order to explain the doubts about the type of carriers and the mechanism of electrical conductivity in Bi-Si-O and Pb-Si-O glasses. In bismuth silicate glass, a typical ionic conductivity with oxygen ions as charge carriers was observed. The level of electrical conductivity of the glass at 400 °C was 5 × 10-8 S·cm-1, with the activation energy of 1.3 eV and was independent of measuring atmosphere. In the case of lead silicate glasses, the conductivity changed with measuring atmosphere. Two types of charge carriers: oxygen ions and proton ions were postulated. Proton conductivity measured in wet argon at temperature 400 °C was estimated at the level of 4 × 10-8 S·cm-1 while the oxygen ions conductivity in such conditions was 78 × 10-8 S·cm-1. We suggest that both types of charge carriers are transported along the same conduction paths using oxygen defects in the glass structure.

2

Zastosowanie metody PALS do oceny stopnia zdefektowania struktury szkieł tlenkowych ołowiowo-bizmutowo-galowych

Golis E., Filipecki J., Reben M., Wasylak J.

Szkło i Ceramika

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2012

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R. 63, nr 3

26-28

PL

W pracy zaprezentowano badania struktury szkieł tlenkowych ołowiowo-bizmutowo-galowych z wykorzystaniem metody spektrometrii czasów życia anihilujących pozytonów PAL. Obliczone parametry wychwytu pozytonów w badanych szkłach pozwalają wyciągać wnioski dotyczące stopnia i charakteru zdefektowania struktury szkieł. Korelacja otrzymanych wyników z własnościami magnetooptycznymi pozwala na formułowanie hipotez dotyczących wpływu defektów struktury szkieł na ich własności magnetooptyczne. Otrzymane wyniki badań wskazują na postawienie hipotezy, że na własności magnetooptyczne badanych szkieł ma wpływ nie ilość a wielkość defektów oraz istnienie swobodnych objętości w strukturze szkła.

EN

Positron lifetime spectroscopy PALS has been applied to the investigation of lead-bismuth-gallium glass structure. The calculated parameters of positrons trapping in the studied glasses allow to draw conclusions about the defect degree and nature of glass structure. The correlation of obtained results with magneto-optic properties allows to formulate hypotheses concerning the influence of defects in the structure onto their magneto-optical properties. The obtained results of studied glasses suggest that size of defects and the existence of free volume in the glass have significant influence on magneto-optical properties.

3

Crystallochemical aspects of structure controlled processes in oxide glasses

Stoch L.

Optica Applicata

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2008

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Vol. 38, nr 1

225-235

EN

Nano size crystals formation in SiO2-Al2O3-MgO-TiO2(ZrO2) glasses as a structure controlled process is described. The applicability of the structure - chemical parameters for prediction and modelling of the middle range ordering in glass as a nanocrystals precursor are presented.

4

Rare earth ions doped aluminosilicate and phosphate double clad optical fibres

Dorosz D.

Bulletin of the Polish Academy of Sciences. Technical Sciences

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2008

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Vol. 56, nr 2

103-111

EN

The paper presents the result of investigations of aluminosilicate (low silica - 25 mol%) and phosphate optical fibres. The methods of glass preparation and their properties are showed. A set of physical measurements including: DTA, DSC, DL analysis, absorption spectroscopy, visible and infrared absorption edges and thermo-physical properties were determined. The stable glass compositions were doped with rare earth elements. Selected proper-ties of obtained glasses are: high transmission, refractive index 1.53-1.68, high solubility of RE ions (up to 10 wt%). Double-crucible and rod-in-tube drawing techniques were applied to obtain aluminosilicate and phosphate double clad optical fibres doped with neodymium and ytterbium ions. Luminescence spectra of manufactured glasses and fibres are presented.

5

The structure of rarefied and densified PbSiO3 glass: a molecular dynamics study

Bergmański G., Białoskórski M., Rychcik-Leyk M., Witkowska A., Rybicki J., Mancini G., Frigio S., Feliziani S.

TASK Quarterly : scientific bulletin of Academic Computer Centre in Gdansk

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2004

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Vol. 8, No 3

393-412

EN

The paper is a molecular dynamics (MD) study of the structure of rarefied and densified lead-silicate glass of the PbSiO3 composition. Simulations have been performed in the constant volume regime for systems with densities of 3000, 4000, 5000, 5970 (normal density), 7000 and 8000kg/m3, using a two-body potential (Born-Mayer repulsive forces and Coulomb forces due to full ionic charges). All the systems were initially prepared as well equilibrated hot melts, and then slowly cooled down to 300K. The information on short-range correlations was obtained in a conventional way (from radial and angular distribution functions), while the middle-range order was studied via cation-anion ring analysis, using our new programme for basal ring determination. The structure of rarefied and densified glasses is compared with the structure of the same glasses under normal conditions. Moreover, the present results on PbSiO3 glass are compared with the corresponding data previously obtained for rarefied and densified PbGeO3 glass (Rybicki et al. 2001 Comput. Met. Sci. Technol. 7 91-112).

6

The structure of Pb-PbO-SiO2 glass via molecular dynamics simulation

Rybicki J., Witkowska A., Bergmański G., Mancini G., Feliziani S.

TASK Quarterly : scientific bulletin of Academic Computer Centre in Gdansk

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2003

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Vol. 7, No 2

243-256

EN

The paper is dedicated to a molecular dynamics (MD) study of the structure of partially reduced lead-silicate glass of composition 1Pb 1PbO 1SiO2. The simulations have been performed in the constant volume regime, using a two-body potential (Born-Mayer repulsive forces, and Coulomb forces due to full ionic charges). The system was initially prepared as a well equilibrated hot melt, and then slowly cooled down to 300K. The information on short-range correlations were obtained in a conventional way (from pair and angular distribution functions), while the medium-range order was studied via cation-anion ring analysis. In the paper, the short- and medium-range order in the simulated system is discussed and compared with the structure of a glassy completely reduced system, i.e. 2Pb 1SiO2 and unreduced one, i.e. 2PbO 1SiO2 glass.

7

EXAFS study of glasses of the CaO-Ga2O3-GeO2 system

Chełstowski D., Witkowska A., Rybicki J., Padlyak B., Trapananti A., Principi E.

Optica Applicata

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2003

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Vol. 33, nr 1

125-132

EN

X-ray absorption spectroscopy (XAS) measurements for Ca3Ga2Ge3O12 and Ca3Ga2Ge4O14 glasses are presented. In particular, the extended X-ray absorption fine structure (EXAFS) spectra are analysed and local neighbourhood of Ga and Ge atoms is described in detail. The Ge/Ga atoms neighbourhood in considered glasses is compared with the data available for corresponding crystals. Performed comparative crystal-glass structural analysis confirms correlation between crystalline and glassy structures of the Ca3Ga2Ge3O12 and Ca3Ga2Ge4O14 compounds. Our results provide several new detailed data, and some general suggestions on the CaO–Ga2O3–GeO2 glass structure.

8

A Molecular dynamics study of the influence of chemical reduction on the structure of amorphous germania

Witkowska A., Murawski L., Bergmański G.

TASK Quarterly : scientific bulletin of Academic Computer Centre in Gdansk

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2002

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Vol. 6, No 2

273-281

EN

The contribution is dedicated to the molecular dynamics (MD) study of the structure of reduced germania glass of composition 1Ge 1GeO2. The work is inspired by a recent report on the formation of Ge clusters in hydrogen reduced germanate glasses containing oxides of heavy metals. The MD simulations have been performed in the microcanonical (NVE) ensemble, using a simple two-body Born-Mayer-Huggins interaction potential. A tendency of germanium atoms to agglomeration into clusters, observed in the present calculations, is compared with an analogous tendency of Bi and Pb atoms, observed previously in the xBi (1-x)GeO2 and xPb (1-x)GeO2 systems. The differences in the short and medium-range order in GeO2 system between the 1Ge 1GeO2 and GeO2 glasses are discussed.

9

Short- and medium-range order in bismuth-silicate glasses: a solecular dynamics study

Witkowska A., Rybicki J., Laskowski R., Mancini G., Feliziani S., Alda W.

TASK Quarterly : scientific bulletin of Academic Computer Centre in Gdansk

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1999

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Vol. 3, No 2

239-254

EN

We report on the results of classical molecular dynamics (MD) simulations of str ucture of amorphous 15 Bi2O3 85 SiO2 [% mol] and 40 Bi2O3 60 SiO2 [% mol], and their totally reduced forms, 15 Bi2 85 SiO2 [% mol], and 40 Bi2 60 SiO2 [% mol], respectively. The simulations have been perfo rmed in the isobaric-isoenthalpic ensemble, using a two-body interaction potential. The set of the potential parameters was constructed as a suitable com bination of the parameters which were previously proposed for pure Bi2O3, and SiO2. Both unreduced, and reduced sy stems were initially prepared as well equilibrated hot melts, and then slowly co oled down to 300K. The structural information from the MD simulations was obtained from radial and angular distribution functions, static structural factors, Voronoi polyhedra sta tistics, and ring analysis. The simulation results can be summarised as follows. In unreduced glass with 15% [mol] Bi2O3 contents, the silicon structural units (mainly regular tetrahedra) form continuous network, whereas in 40% [mol] Bi2O3 glass these units are disconnected. In both unreduced systems Bi ions have mainly six-fold oxygen co-ordination, and no dominating structural unit can be individuated. However, the distorted bismu th units form a continuous network. In both totally reduced glasses (15% Bi2 85% SiO2, and 40% Bi2 60% SiO2 [% mol]), the silica network is built entirely from corner shari ng SiO4 tetrahedra. The structure of the silica subsystem is similar to that of pure *-SiO2. After the reduction, the Bi-Bi co-ordination significantly increases, whereas the first neighbour distance decreases. Moreover, partial static structural fact ors for Bi-Bi pairs indicate that the medium-range order in reduced glasses exhi bits greater periodicity than in unreduced glasses. Neutral Bi atoms form small clusters within the silica matrix.

10

Ład w bezładzie, czyli kompleksy jonów metali przejściowych w szkłach i żelach tlenkowych

Kłonkowski A.M.

Wiadomości Chemiczne

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1998

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[Z] 52, 1-2

57-85

EN

The most basic difference between crystalline and non-crystalline solids is that a long range order (LORO) in the distribution of atoms (ions) or molecules exists only in crystalline materials [1]. This is indicated by diffraction patterns: the ideal crystal (the first extreme case) shows reflectants whose location and intensity obey three Laue conditions. The second extreme case is an ideally random structure. Scattering of radiation is impossible in the case of an ideally homogenous medium. Any real substance, including non-crystalline materials is inhomogenous regardless of its form or scale. Thus glasses can be thought of as assemblies of microcrystals (i.e. microcrystallites or paracrystals). Strain introduced due to lattice mismatch at grain boundaries, the presence of a disordered interfacial or matrix region, and defects such as dislocation, or stacking faults can be assumed to give rise to departures from periodicity at distances smaller than the average grain size [10]. In this sense glasses are interesting in the supramolecular science because they are intermediate objects in the way from random to organized matter [5]. The object of this article are such amorphous materials as inorganic oxide glasses with structural groups YO4, where Y = Si, P, and organically modified silicate gels. Among the studied glasses are ones of the type : R2O-SiO2 and R2O-Al2O3-SiO2, where R represents alkali atom (Li to Cs) [23, 25, 27], as well as M(II)O-P2O5, where M(II) is an alkaline earth atom (Mg to Ba) [28, 29, 32, 33]. Undoped glasses and those doped with copper (II) ions were investigated. These metal ions have played the role of probes. All the vitreous systems are classified according to their theoretical optical basicity [lambda] cal proposed by Duffy and Ingram [34]. Thanks to this method one can methodically observe and sensibly interpret changes of real measures of basicity as molar refractivity of oxide ions Ro (see Figs 9 and 10a), the so-called Imagawa's basicity (Fig.10b) and other physical and chemical properties of oxide glasses (Fig.11). The studied glasses are also classified according to their bond nature (Fig. 6)., taking into account their proximity to the onset of metallization [4]. Attention is also focused on the mixed alkali effect [22, 24]. A full understanding of the properties of colloids calls upon a wide range of physical and chemical ideas, while the multitude of colloidal systems presented to us in nature, and familiar in modern society, exhibits a daunting complexity. On the experimental side there is an ever-increasing emphasis on the application of modern physical techniques to colloidal problems. Colloid science is thus a truly interdisciplinary subject [3]. In the case of the xerogels there are described Cu(II) complexes existing on surface and in interior of the material [59-63]. Moreover, silica xerogels with immobilized supramolecular ligands show intensive luminescence (Fig. 17) which is effectively quenched by Cu(II) ions [64].