Density, thermal expansion, glass transition temperature, refractive index, molar refractivity an... more Density, thermal expansion, glass transition temperature, refractive index, molar refractivity and chemical durability of fiveand six-component glasses with as weighted composition xNa2O·(15-x)K2O·yCaO·(10-y)ZnO·zZrO2·(75-z)SiO2 (x = 0, 7.5, 15; y = 0, 5, 10; z = 5, 7) were measured. The obtained experimental data were merged together with the previous results obtained for analogous glasses with lower zirconia content. The full set of glasses enabled the quantitative statistical estimation of possible mixed-oxide effects. The results of the multilinear regression analysis pointed out the ideal behavior of molar volume and molar refractivity. The strongest influence of mutual oxide interactions was found for chemical durability and glass transition temperature. The regression analysis of compositional dependence of metastable melt thermal expansion coefficient practically failed. The need of property-composition study based on the thermodynamic model was pointed out. Qualitatively th...
The glasses with composition xTiO 2-(100-x)[40Na 2 O-60SiO 2 ] (0 ≤ x ≤ 30 mol%) were studied usi... more The glasses with composition xTiO 2-(100-x)[40Na 2 O-60SiO 2 ] (0 ≤ x ≤ 30 mol%) were studied using Raman spectroscopy and thermodynamic modeling. According to the thermodynamic modeling results, the chemical structure of studied glasses is defined by seven chemical groups (TiO 2 , SiO 2 , Na 2 O⋅2SiO 2 , Na 2 O⋅SiO 2 , Na 2 O⋅3TiO 2 , Na 2 O⋅TiO 2 , Na 2 O⋅TiO 2 ⋅SiO 2), whereas the short-range order (SRO) structures are TiO 5 , TiO 6 , Q 4 , Q 3 and Q 2 species. Existence of all these SRO structures was confirmed by the analysis of measured Raman spectra. The equilibrium molar amounts of SRO groups calculated in the framework of the Shakhmatkin-Vedishcheva thermodynamic model and those derived from spectroscopic data exhibit a positive correlation.
The set of 34 baseline subtracted and thermally corrected Raman spectra of BaO-B 2 O 3 glassformi... more The set of 34 baseline subtracted and thermally corrected Raman spectra of BaO-B 2 O 3 glassforming melts with the composition x g BaO-(1 − x g)B 2 O 3 (x g = 0.20; 0.25; 0.30; 0.35; 0.40; 045; 0.50; 0.55; 0.60) measured at temperatures ranging from 600 to 1100 °C was analyzed. The thermodynamic model of Shakhmatkin and Vedishcheva was evaluated for each glass melt. Nine following system components (defined as stable crystalline phases of the BaO-B 2 O 3 binary phase diagram) were considered: BaO, B 2 O 3 , 2BaO•5B 2 O 3 (Ba2B5), 2BaO•B 2 O 3 (Ba2B), 3BaO•B 2 O 3 (Ba3B), 4BaO•B 2 O 3 (Ba4B), BaO•B 2 O 3 (BaB), BaO•2B 2 O 3 (BaB2), and BaO•4B 2 O 3 (BaB4). The equilibrium molar amounts of system components were used for the evaluation of the molar amounts of basic structural units T n (trigonal boron with n-bridging oxygen atoms, n = 0, 1, 2, 3) and Q 4 (tetragonal boron with 4-bridging oxygen atoms). Only three structural units (Q 4 , T 3 , and T 2) with the not negligible equilibrium molar amount were found. The significant correlation between equilibrium molar amounts of Q 4 and T 3 was found. Malfait's decomposition was performed for the most abundant units, i.e., T 3 and T 2. Multivariate curve resolution analysis performed for two components resulted in the Raman spectra (so-called loadings) and relative abundances (so-called scores) of each component. The obtained loadings were in good agreement with the partial Raman spectra obtained by the Malfait's decomposition. Keywords BaO-B 2 O 3 • Thermodynamic model • Raman spectra • Borate glass melts
The glasses of the xZnO-(1-x)[0.33BaO-0.67B2O3] system (0 x 0.35) were prepared by the melt q... more The glasses of the xZnO-(1-x)[0.33BaO-0.67B2O3] system (0 x 0.35) were prepared by the melt quenching technique. The FTIR and Raman spectroscopy were employed to study the influence of zinc oxide on the boron-oxygen network structure of the binary BaO-B2O3 glass matrix. Increasing ZnO content was found to induce progressive conversion of four-fold coordinated boron species to the trigonal borate units. The increase in the fraction of threefold coordinated borate units is primarily related to the transformation of [BØ4]tetrahedral units into BØ2Ometaborate units at x 0.15. The high-charged pyro-and orthoborate units are formed in the glass structure at further increase in x. These effects are discussed concerning the nature of the borate network at various ZnO contents. The density of the studied glasses was found to be gradually increased with increasing ZnO content, while the molar volume exhibits an opposite trend.
A simple mathematical model of thermal polishing of rough glass surface as observed by light beam... more A simple mathematical model of thermal polishing of rough glass surface as observed by light beam thermal analysis (LBTA) is presented. The rough surface is represented by a triangular profile used for calculation of the light beam intensity attenuation and an equivalent rectangular profile is used for the modeling of the time course of the thermal polishing. Computational results obtained for the NBS 711 viscosity standard glass showed that the characteristic temperature, obtained from the series of LBTA experiments after extrapolation to zero starting surface roughness, does not represent the glass transition temperature, but it corresponds to the viscosity value of about 10 9 dPa.s. The validity of the proposed model was confirmed by the comparison of simultaneous LBTA and viscosity measurements of CaO-Y 2 O 3-Al 2 O 3-SiO 2 glasses.
Viscosity, density, thermal expansion, glass transition temperature, refractive index, molar refr... more Viscosity, density, thermal expansion, glass transition temperature, refractive index, molar refraction, and chemical durability of compositional series of Na 2 O-K 2 O-ZnO-CaO-ZrO 2-SiO 2 glasses containing I and 3 mol. % ZrO 2 were measured and interpreted according to the network forming I modifying activities of particular oxides. The influence of ZrO 2 / SiO 2 , ZnO / CaO, and K 2 O / Na 2 O substitution on measured physical and chemical properties was detected. The regression formulae describing the temperature and composition dependence of the above properties were proposed.
High temperature viscosity and density of glass melts, glass transition temperature, and thermal ... more High temperature viscosity and density of glass melts, glass transition temperature, and thermal expansion coefficient of glasses from the system MgO-CaO-B2O3-Al2O3-SiO2 with composition close to the E-glass were measured and interpreted with respect to the effect of CaO and MgO content on their physical properties. The Andrade model was applied for description of the temperature dependence of the glass viscosity within studied temperature range. The regression formaulae describing the compositional dependence of the viscosity points T2 = T( η = 100 dPa.s), T3 = T( η = 1000 dPa.s), the glass transition temperature, Tg, thermal expansion coefficient of glass, αg , and of the viscous flow activation energy, Ea, were proposed.
Viscosity, density, thermal expansion, glass transition temperature, refractive index, molar refr... more Viscosity, density, thermal expansion, glass transition temperature, refractive index, molar refraction, and chemical durability of selected compositional series of Na2O-K2O-ZnO-CaOZrO2- SiO2 glasses containing 1 and 3 mol. % ZrO2 were measured and interpreted according to the network-forming / -modifying activities of particular oxides. The influence of ZrO2 / SiO2, ZnO / CaO, and K2O / Na2O substitution on measured physical and chemical properties was discussed.
An brief overview of the selected thermo-physical measurements realized in the VILA laboratories ... more An brief overview of the selected thermo-physical measurements realized in the VILA laboratories for the glass industry and for the fundamental research of glass is presented. Among the routine measurements realized for the glass industry the thermodilatometry for measuring the glass transition temperature, and linear thermal expansion coefficients of glass and metastable glassforming melt are described in detail. The fact that the glass transition temperature is not a single valued physical quantity is stressed in connection with the measurement time temperature schedule. The probably most important quantity related to the glass production technology is the viscosity. Its measurement in the range extending ten orders of magnitude is described. The combination of the falling ball method, the rotation viscosimetry and the thermomechanical analysis is needed to cover the above viscosity range. Among the methods used in the fundamental research of glass structure and properties the study of structural relaxation is overviewed. Here the own method of combined viscous flow and structure relaxation TMA measurement is described in detail.
Journal of Thermal Analysis and Calorimetry, Sep 14, 2017
The structural relaxation of Na 2 O-K 2 O-CaO-ZrO 2-SiO 2 (NKCZ), Na 2 O-K 2 O-ZnO-ZrO 2-SiO 2 (N... more The structural relaxation of Na 2 O-K 2 O-CaO-ZrO 2-SiO 2 (NKCZ), Na 2 O-K 2 O-ZnO-ZrO 2-SiO 2 (NKzZ), Na 2 O-CaO-ZnO-ZrO 2-SiO 2 (NCzZ), K 2 O-CaO-ZnO-ZrO 2-SiO 2 (KCzZ), and Na 2 O-K 2 O-CaO-ZnO-ZrO 2-SiO 2 (NKCzZ) glasses were studied by thermomechanical analysis. The structural relaxation was described by the Tool-Narayanaswamy-Mazurin model (TNMa). The relaxation function of Kohlrausch, Williams, and Watts (KWW) was used. The parameters of relaxation model were calculated by nonlinear regression analysis of thermodilatometric curves measured under cyclic timetemperature regime by thermomechanical analyzer under the constant load. The values of the exponent b of the KWW equation, modulus K, limit dynamic viscosity g 0 of the Mazurin's expression for relaxation time, and constant B of the Vogel-Fulcher-Tammann viscosity equation were optimized. It was found that TNMa relaxation model very well describes the experimental data. A more detailed analysis of the obtained results showed that the equimolar substitution of SiO 2 by ZrO 2 (i.e., the increase of the ZrO 2 content in the glass) decreases the parameter b, therefore the continuous distribution of the relaxation times spectrum is widening. A wider spectrum of relaxation times was obtained even in the case of substitution of ZnO for CaO and K 2 O for Na 2 O. Substitution of ZrO 2 for SiO 2 decreases the dynamic viscosity limit g 0 that corresponds to an activation energy increase of temperature dependence of isostructural viscosity. Increased content of ZrO 2 in the glass caused the increase of the value of the modulus K.
The structure of chalcogenide glasses of the pseudo-binary system As 2 S 3-Sb 4 S 4 was investiga... more The structure of chalcogenide glasses of the pseudo-binary system As 2 S 3-Sb 4 S 4 was investigated by comparing the results of the thermodynamic model of Shakhmatkin and Vedishcheva with the results obtained from the analysis of the Raman spectra of xAs 2 S 3 •(100 − x)Sb 4 S 4 (x = 100, 95, 90, 80, 70, 60, 50, 40) glasses performed by the Principal Component Analysis and the spectral decomposition by the method of Malfait. On the basis of the eigenvalues three independent components were identified in the studied spectral series. On the other hand, the thermodynamic modeling resulted in three components with significant abundance in the studied glasses, i.e. As 2 S 2 , As 2 S 3 , and Sb 2 S 3. Moreover, the correlation analysis proved the strong linear dependence between the concentrations of As, Sb, and Sb 2 S 3. Using the method of Malfait, partial Raman spectra of As 2 S 2 , As 2 S 3 , and the linear spectral combination (0.15 As + 0.20 Sb + Sb 2 S 3) were calculated. The experimental spectra were well reproduced. The obtained results confirmed the structural information acquired from the thermodynamic model.
The corroded surfaces of historical glass samples were studied by micro‐Raman spectroscopy. The s... more The corroded surfaces of historical glass samples were studied by micro‐Raman spectroscopy. The spectra acquired from lateral and stratified mapping were analyzed by principal component analysis providing the number of linearly independent spectral components and by multivariate curve analysis resulting in spectrum of native glass and spectra of different corrosion products (loadings) and their relative abundances (scores) in each measured spot. The obtained results were qualified by comparison of results obtained by stratified mapping with the results of lateral mapping. On the basis of dominant scores, the lateral distribution of various corrosion products was identified. The quality of corrosion products was only roughly identified by the spectral database (S.T. Japan spectral database).
• A refined application of the SVTD model has been developed for BaO-P 2 O 5 glasses. • Short str... more • A refined application of the SVTD model has been developed for BaO-P 2 O 5 glasses. • Short structure and properties of BaO-P 2 O 5 glasses estimated from SVTD model. • The activation energy of viscous flow in the equilibrium melts and in the undercooled liquids has been discussed.
Density, thermal expansion, glass transition temperature, refractive index, molar refractivity an... more Density, thermal expansion, glass transition temperature, refractive index, molar refractivity and chemical durability of fiveand six-component glasses with as weighted composition xNa2O·(15-x)K2O·yCaO·(10-y)ZnO·zZrO2·(75-z)SiO2 (x = 0, 7.5, 15; y = 0, 5, 10; z = 5, 7) were measured. The obtained experimental data were merged together with the previous results obtained for analogous glasses with lower zirconia content. The full set of glasses enabled the quantitative statistical estimation of possible mixed-oxide effects. The results of the multilinear regression analysis pointed out the ideal behavior of molar volume and molar refractivity. The strongest influence of mutual oxide interactions was found for chemical durability and glass transition temperature. The regression analysis of compositional dependence of metastable melt thermal expansion coefficient practically failed. The need of property-composition study based on the thermodynamic model was pointed out. Qualitatively th...
The glasses with composition xTiO 2-(100-x)[40Na 2 O-60SiO 2 ] (0 ≤ x ≤ 30 mol%) were studied usi... more The glasses with composition xTiO 2-(100-x)[40Na 2 O-60SiO 2 ] (0 ≤ x ≤ 30 mol%) were studied using Raman spectroscopy and thermodynamic modeling. According to the thermodynamic modeling results, the chemical structure of studied glasses is defined by seven chemical groups (TiO 2 , SiO 2 , Na 2 O⋅2SiO 2 , Na 2 O⋅SiO 2 , Na 2 O⋅3TiO 2 , Na 2 O⋅TiO 2 , Na 2 O⋅TiO 2 ⋅SiO 2), whereas the short-range order (SRO) structures are TiO 5 , TiO 6 , Q 4 , Q 3 and Q 2 species. Existence of all these SRO structures was confirmed by the analysis of measured Raman spectra. The equilibrium molar amounts of SRO groups calculated in the framework of the Shakhmatkin-Vedishcheva thermodynamic model and those derived from spectroscopic data exhibit a positive correlation.
The set of 34 baseline subtracted and thermally corrected Raman spectra of BaO-B 2 O 3 glassformi... more The set of 34 baseline subtracted and thermally corrected Raman spectra of BaO-B 2 O 3 glassforming melts with the composition x g BaO-(1 − x g)B 2 O 3 (x g = 0.20; 0.25; 0.30; 0.35; 0.40; 045; 0.50; 0.55; 0.60) measured at temperatures ranging from 600 to 1100 °C was analyzed. The thermodynamic model of Shakhmatkin and Vedishcheva was evaluated for each glass melt. Nine following system components (defined as stable crystalline phases of the BaO-B 2 O 3 binary phase diagram) were considered: BaO, B 2 O 3 , 2BaO•5B 2 O 3 (Ba2B5), 2BaO•B 2 O 3 (Ba2B), 3BaO•B 2 O 3 (Ba3B), 4BaO•B 2 O 3 (Ba4B), BaO•B 2 O 3 (BaB), BaO•2B 2 O 3 (BaB2), and BaO•4B 2 O 3 (BaB4). The equilibrium molar amounts of system components were used for the evaluation of the molar amounts of basic structural units T n (trigonal boron with n-bridging oxygen atoms, n = 0, 1, 2, 3) and Q 4 (tetragonal boron with 4-bridging oxygen atoms). Only three structural units (Q 4 , T 3 , and T 2) with the not negligible equilibrium molar amount were found. The significant correlation between equilibrium molar amounts of Q 4 and T 3 was found. Malfait's decomposition was performed for the most abundant units, i.e., T 3 and T 2. Multivariate curve resolution analysis performed for two components resulted in the Raman spectra (so-called loadings) and relative abundances (so-called scores) of each component. The obtained loadings were in good agreement with the partial Raman spectra obtained by the Malfait's decomposition. Keywords BaO-B 2 O 3 • Thermodynamic model • Raman spectra • Borate glass melts
The glasses of the xZnO-(1-x)[0.33BaO-0.67B2O3] system (0 x 0.35) were prepared by the melt q... more The glasses of the xZnO-(1-x)[0.33BaO-0.67B2O3] system (0 x 0.35) were prepared by the melt quenching technique. The FTIR and Raman spectroscopy were employed to study the influence of zinc oxide on the boron-oxygen network structure of the binary BaO-B2O3 glass matrix. Increasing ZnO content was found to induce progressive conversion of four-fold coordinated boron species to the trigonal borate units. The increase in the fraction of threefold coordinated borate units is primarily related to the transformation of [BØ4]tetrahedral units into BØ2Ometaborate units at x 0.15. The high-charged pyro-and orthoborate units are formed in the glass structure at further increase in x. These effects are discussed concerning the nature of the borate network at various ZnO contents. The density of the studied glasses was found to be gradually increased with increasing ZnO content, while the molar volume exhibits an opposite trend.
A simple mathematical model of thermal polishing of rough glass surface as observed by light beam... more A simple mathematical model of thermal polishing of rough glass surface as observed by light beam thermal analysis (LBTA) is presented. The rough surface is represented by a triangular profile used for calculation of the light beam intensity attenuation and an equivalent rectangular profile is used for the modeling of the time course of the thermal polishing. Computational results obtained for the NBS 711 viscosity standard glass showed that the characteristic temperature, obtained from the series of LBTA experiments after extrapolation to zero starting surface roughness, does not represent the glass transition temperature, but it corresponds to the viscosity value of about 10 9 dPa.s. The validity of the proposed model was confirmed by the comparison of simultaneous LBTA and viscosity measurements of CaO-Y 2 O 3-Al 2 O 3-SiO 2 glasses.
Viscosity, density, thermal expansion, glass transition temperature, refractive index, molar refr... more Viscosity, density, thermal expansion, glass transition temperature, refractive index, molar refraction, and chemical durability of compositional series of Na 2 O-K 2 O-ZnO-CaO-ZrO 2-SiO 2 glasses containing I and 3 mol. % ZrO 2 were measured and interpreted according to the network forming I modifying activities of particular oxides. The influence of ZrO 2 / SiO 2 , ZnO / CaO, and K 2 O / Na 2 O substitution on measured physical and chemical properties was detected. The regression formulae describing the temperature and composition dependence of the above properties were proposed.
High temperature viscosity and density of glass melts, glass transition temperature, and thermal ... more High temperature viscosity and density of glass melts, glass transition temperature, and thermal expansion coefficient of glasses from the system MgO-CaO-B2O3-Al2O3-SiO2 with composition close to the E-glass were measured and interpreted with respect to the effect of CaO and MgO content on their physical properties. The Andrade model was applied for description of the temperature dependence of the glass viscosity within studied temperature range. The regression formaulae describing the compositional dependence of the viscosity points T2 = T( η = 100 dPa.s), T3 = T( η = 1000 dPa.s), the glass transition temperature, Tg, thermal expansion coefficient of glass, αg , and of the viscous flow activation energy, Ea, were proposed.
Viscosity, density, thermal expansion, glass transition temperature, refractive index, molar refr... more Viscosity, density, thermal expansion, glass transition temperature, refractive index, molar refraction, and chemical durability of selected compositional series of Na2O-K2O-ZnO-CaOZrO2- SiO2 glasses containing 1 and 3 mol. % ZrO2 were measured and interpreted according to the network-forming / -modifying activities of particular oxides. The influence of ZrO2 / SiO2, ZnO / CaO, and K2O / Na2O substitution on measured physical and chemical properties was discussed.
An brief overview of the selected thermo-physical measurements realized in the VILA laboratories ... more An brief overview of the selected thermo-physical measurements realized in the VILA laboratories for the glass industry and for the fundamental research of glass is presented. Among the routine measurements realized for the glass industry the thermodilatometry for measuring the glass transition temperature, and linear thermal expansion coefficients of glass and metastable glassforming melt are described in detail. The fact that the glass transition temperature is not a single valued physical quantity is stressed in connection with the measurement time temperature schedule. The probably most important quantity related to the glass production technology is the viscosity. Its measurement in the range extending ten orders of magnitude is described. The combination of the falling ball method, the rotation viscosimetry and the thermomechanical analysis is needed to cover the above viscosity range. Among the methods used in the fundamental research of glass structure and properties the study of structural relaxation is overviewed. Here the own method of combined viscous flow and structure relaxation TMA measurement is described in detail.
Journal of Thermal Analysis and Calorimetry, Sep 14, 2017
The structural relaxation of Na 2 O-K 2 O-CaO-ZrO 2-SiO 2 (NKCZ), Na 2 O-K 2 O-ZnO-ZrO 2-SiO 2 (N... more The structural relaxation of Na 2 O-K 2 O-CaO-ZrO 2-SiO 2 (NKCZ), Na 2 O-K 2 O-ZnO-ZrO 2-SiO 2 (NKzZ), Na 2 O-CaO-ZnO-ZrO 2-SiO 2 (NCzZ), K 2 O-CaO-ZnO-ZrO 2-SiO 2 (KCzZ), and Na 2 O-K 2 O-CaO-ZnO-ZrO 2-SiO 2 (NKCzZ) glasses were studied by thermomechanical analysis. The structural relaxation was described by the Tool-Narayanaswamy-Mazurin model (TNMa). The relaxation function of Kohlrausch, Williams, and Watts (KWW) was used. The parameters of relaxation model were calculated by nonlinear regression analysis of thermodilatometric curves measured under cyclic timetemperature regime by thermomechanical analyzer under the constant load. The values of the exponent b of the KWW equation, modulus K, limit dynamic viscosity g 0 of the Mazurin's expression for relaxation time, and constant B of the Vogel-Fulcher-Tammann viscosity equation were optimized. It was found that TNMa relaxation model very well describes the experimental data. A more detailed analysis of the obtained results showed that the equimolar substitution of SiO 2 by ZrO 2 (i.e., the increase of the ZrO 2 content in the glass) decreases the parameter b, therefore the continuous distribution of the relaxation times spectrum is widening. A wider spectrum of relaxation times was obtained even in the case of substitution of ZnO for CaO and K 2 O for Na 2 O. Substitution of ZrO 2 for SiO 2 decreases the dynamic viscosity limit g 0 that corresponds to an activation energy increase of temperature dependence of isostructural viscosity. Increased content of ZrO 2 in the glass caused the increase of the value of the modulus K.
The structure of chalcogenide glasses of the pseudo-binary system As 2 S 3-Sb 4 S 4 was investiga... more The structure of chalcogenide glasses of the pseudo-binary system As 2 S 3-Sb 4 S 4 was investigated by comparing the results of the thermodynamic model of Shakhmatkin and Vedishcheva with the results obtained from the analysis of the Raman spectra of xAs 2 S 3 •(100 − x)Sb 4 S 4 (x = 100, 95, 90, 80, 70, 60, 50, 40) glasses performed by the Principal Component Analysis and the spectral decomposition by the method of Malfait. On the basis of the eigenvalues three independent components were identified in the studied spectral series. On the other hand, the thermodynamic modeling resulted in three components with significant abundance in the studied glasses, i.e. As 2 S 2 , As 2 S 3 , and Sb 2 S 3. Moreover, the correlation analysis proved the strong linear dependence between the concentrations of As, Sb, and Sb 2 S 3. Using the method of Malfait, partial Raman spectra of As 2 S 2 , As 2 S 3 , and the linear spectral combination (0.15 As + 0.20 Sb + Sb 2 S 3) were calculated. The experimental spectra were well reproduced. The obtained results confirmed the structural information acquired from the thermodynamic model.
The corroded surfaces of historical glass samples were studied by micro‐Raman spectroscopy. The s... more The corroded surfaces of historical glass samples were studied by micro‐Raman spectroscopy. The spectra acquired from lateral and stratified mapping were analyzed by principal component analysis providing the number of linearly independent spectral components and by multivariate curve analysis resulting in spectrum of native glass and spectra of different corrosion products (loadings) and their relative abundances (scores) in each measured spot. The obtained results were qualified by comparison of results obtained by stratified mapping with the results of lateral mapping. On the basis of dominant scores, the lateral distribution of various corrosion products was identified. The quality of corrosion products was only roughly identified by the spectral database (S.T. Japan spectral database).
• A refined application of the SVTD model has been developed for BaO-P 2 O 5 glasses. • Short str... more • A refined application of the SVTD model has been developed for BaO-P 2 O 5 glasses. • Short structure and properties of BaO-P 2 O 5 glasses estimated from SVTD model. • The activation energy of viscous flow in the equilibrium melts and in the undercooled liquids has been discussed.
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