Sol-gel preparation of wavelength-selective reflecting coatings in the system ZrO2SiO2

Multilayer, wavelength-selective reflecting coatings were prepared by alternate stackings of amorphous zirconia and silica by the sol-gel spinning technique; alkoxide-derived, polymeric sols were used. A detuned, i.e. non-λ/4 stacking system was applied. The spectrum showed a transmission minimum (∼ 4%) at a wavelength of 430 nm, with a bandwidth of 72.5 nm after deposition of the 17th layer.     

Composition analysis of glasses in the PbBr2–PbCl2–PbF2–PbO–P2O5 system

Composition change during the melting process of some glasses in the PbBr₂–PbCl₂–PbF₂–PbO–P₂O₅ system melted at 450–470°C for 15 min was studied. Results show that there was a remarkable difference between the batch composition and the analyzed composition. Large amount of P, Br, Pb, and Cl were lost mainly in the form of PbBr₂, PbCl₂ and P₂O₅. The content of O is influenced by two factors. The incomplete decomposition of NH₄H₂PO₄ or the reaction between P₂O₅ and H₂O in the atmosphere increases the content of O, while the volatilization of P₂O₅ decreases the content of O.     

X-ray diffraction study of Na2OGeO2 melts

The structure of Na₂OGeO₂ melts in the temperature range from 1100 to 1150°C has been investigated with the high temperature X-ray diffraction technique. Comparing the radial distribution functions obtained for the melts with those for the corresponding glasses, the first peak due to the GeO interatomic distance is invariant upon melting, although it becomes broader due to thermal vibration. The second peak for the GeGe interatomic distance for melts shifts toward the large distance, which is explained by broadening of the GeOGe bond angle, not by the thermal expansion of the GeOGe bond. The composition dependences of GeO distances and coordination numbers of the Ge⁴⁺ ion of the melts are found to be almost the same as the corresponding glasses, indicating that even in melts at such high temperatures 6-fold coordinated Ge⁴⁺ ions are present and their content changes with the Na₂O content as in the case of the corresponding glasses.     

Spectroscopic studies of tungsten ions in PbO–PbF2–SiO2 glasses

40PbO–(10 ? x)PbF₂–50 SiO₂:xWO₃ (where x = 1 to 7 mol%) glasses are prepared in the glass forming region. Spectroscopic studies (UV–Vis absorption, ESR, IR) are carried out for these glasses. Interesting changes are observed in the spectroscopic parameters of these glasses when the concentration of WO₃ is changing in the glass matrix. Two absorption bands are observed around at 830 and 620 nm. ESR signal are measured at room temperature for these glasses, the strength of the signal is increased and hyperfine splitting is resolved with increasing the concentration of WO₃ in the glass matrix. IR transmission gives valuable information about the nature of bonds in the glass matrix. The physical parameters along with spectroscopic parameters are measured.     

Infrared spectra and structure of superionic conducting glasses in the system AgIAg2OMoO3

Thin blown films of glasses with the mole ratio Ag₂O/MoO₃ = 1 in the system AgIAg₂OMoO₃ (or the pseudobinary system AgIAg₂MoO₄) show three absorption bands in the range 4000-200 cm^?1; 875 cm^?1 (w), 780 cm^?1 (s), and 320 cm^?1 (m, b), which are characteristic of tetrahedral MoO₄^2? ions. The glasses with the ratio Ag₂O/MoO₃ < 1 have two additional bands at 600 cm^?1 (w) and 450 cm^?1 (vw), which are characteristic of condensed ions of MoO₄ tetrahedra, probably Mo₂ O₇^2? ions. These glasses are thus composed of Ag⁺, I^?, MoO₄^2?, and probably Mo₂O₇^2? ions, and classified as “ionic” glasses containing one type of cations. The presence of partial covalency in the Ag⁺… ^?OMo link and the influence of ion exchange of Ag⁺ with K⁺ on IR spectra are discussed. The molar volume of the glasses with the ratio Ag₂O/MoO₃ = 1 is primarily determined by a fairly dense packing of the constituent anions, I^? and MoO₄^2?.     

Nuclear magnetic resonance studies of the glasses in the system K2OB2O3P2O5

B¹¹ NMR spectra have been used to study the structure of glasses in the system K₂OB₂O₃P₂O₅. The results indicate that the glasses do not contain an appreciable number of boron atoms in BO₃ units with one or two non-bridging oxygens. The fraction N₄ of boron atoms in BO₄ units is measured and analyzed according to a structural model containing the following elements. (1) If the binary borophosphate system forms glasses, they consist of a borophosphate (BPO₄) network and a borate network for K<1, or a borophosphate (BPO₄) network and a phosphate network for K>1, where K = mol.% P₂O₅/mol.% B₂O₃. (2) The conversion rates of BO₄ units (i.e. the rate of production or destruction by added oxygens) in the borate network and the borophosphate (BPO₄) network are given as (+2) and (?0.38), respectively. (3) K⁺¹ ions are proportionally shared between the two networks; (i.e. between the borate and borophosphate (BPO₄) networks for K<1, and between the phosphate and borophosphate (BPO₄) networks for K>1).     

Ionic conductvity and NMR investigation of quaternary glasses in the ZrF4BaF2ThF4LiF system

The existence of glasses involving large amounts of LiF (up to 60%) within the ZrF₄BaF₂ThF₄LiF quaternary systems has allowed the authors to study the evolution of transport properties with varying LiF content.A minimum of ionic conductivity bound to a maximum of activation energy has been detected when the atomic Li/F ratio is equal to ≅ 0.07. In the Li-low concentration domain, σ increases regularly and ΔE decreases simultaneously when the BaF₂ concentration increases; on the contrary in the Li-high concentration region log σ and ΔE are quasi-linear functions, increasing and decreasing respectively, of the LiF rate.A ⁷Li and ¹⁹F NMR investigation has shown that Li⁺ and F⁻ ions are simultaneously mobile and the temperature dependence of the number of mobile F⁻ ions has been determined. In the Li-low concentration domain transport properties result from mixed contributions of mobile Li⁺ and F⁻ ions, for high Li concentrations they depends only on the Li⁺ rate.Glasses with high Li-content have good electrical performnces (e.g. σ_175°C ≅ 2.10⁻⁴ω⁻¹ cm⁻¹ for Zr_0.20Ba_0.10Li_0.60Th_0.10F₂).     

The leaching behavior of PbOSiO2 glasses

The leached layer of PbOSiO₂ glasses formed by diluted nitric acid solution has been investigated by ellipsometry and Auger electron spectroscopy (AES). The leaching behavior of PbOSiO₂ glasses in 10^?4 N aqueous solution of NHO₃ at 30°C was measured in real time using a Nikon auto-ellipsometer.The results were applied by curve fitting to the two-layer model from the concentration profile obtained by AES, and the refractive index profile against the film thickness was determined.The leached layer is inhomogeneous and consists of a low refractive index region and a transition region. The gradient of the refractive index in the former region is extremely small and the refractive index becomes nearly constant between 1.42 and 1.44. The shape of latter region becomes stable with its thickness at 100–310 Å, and moves in the direction of depth without changing the shape as the leaching proceeds.     

Sensitivity of the photo-darkening effect in CuAsSe glasses

When CuAsSe glasses are irradiated, they exhibit higher concentrations of darkening than AsSe glasses. Since darkening depends on the composition, the darkening centers in CuAsSe glasses to be of the same kind as those in AsSe glasses, i.e. arsenic clusters. Concerning the kinetics of erasing, it was found that the activation energy and the rate constant of erasing in CuAsSe are almost equal to those in AsSe glasses, but for the kinetics of darkening, it was found that the activation energy of darkening is equal to that of AsSe but α₀, which is proportional to the number of latent darkening centers, and the darkening rate constant k₁ are about twice as high as the corresponding constants of AsSe glasses. This may be the reason for the greater darkening in CuAsSe glasses. The high value of α₀ was attributed to the generation of more AsAs bonds on the addition of Cu to the AsSe glass network. The high value of k₁ was attributed to the increase in efficiency of photo-decomposition because of the many impurity levels in the band gap and also because of the narrow optical energy gap in the CuAsSe glasses.     

Effect of V2O5 addition on the crystallisation of glasses belonging to the CaO–ZrO2–SiO2 system

The crystallisation of CaO–ZrO₂–SiO₂ glasses doped with V₂O₅ (0.1–5 mol%) has been investigated in terms of microstructure and thermal parameters. Results indicate that crystallisation is predominantly controlled by a surface nucleation mechanism, even though a partial bulk nucleation has been encountered in compositions containing more than 2 mol% of doping oxide. As detected from differential thermal analysis curves, glass transition temperature and crystallisation temperature, are strongly dependent upon V₂O₅ content varying from 0.0 to 2.0 mol%, while the crystallisation activation energy values decrease with a parabolic trend from B-glass (0.0 mol% V₂O₅ content, 495±7) to V-0.7 (0.7 mol% V₂O₅ content, 420±6) composition, increasing again to 442±5 kJ/mol K with higher amount of V₂O₅. The microstructure of the glass-ceramic materials clearly showed a marked dependence upon the amount of V₂O₅, also due to the presence of phase separation for content higher than 0.7 mol%. Wollastonite, CaO·SiO₂, and a calcia–zirconia–silicate, 2CaO·4SiO₂·ZrO₂, are the main crystalline phases whose ratio slightly varies with vanadium oxide content. The glass ceramics obtained from the studied materials are greenish and bluish coloured, so it is possible to use the studied glasses as coloured frits for tile glazes.     

Photoconductivity of oxychalcogenide glasses in the system As2Se3CdO

The photoconductivity of oxychalcogenide glasses in the system As₂Se₃CdO was investigated. When 2–3 mol % CdO was added, the photoresponse peak of the parent glass As₂Se₃ in the vicinity of 740 nm became broader and a little weaker. The addition of more than about 4 mol % CdO brought about a sharp and strong peak at 720 nm and a broad peak at 860 nm. X-ray diffraction and electron microscopic observations revealed the presence of crystalline CdSe in the glass matrix, indicating that the reaction As₂Se₃ + 3CdO → As₂O₃ + 3CdSe took place in the melting process of these glasses. Tempeature and light intensity dependences of the photocurrent lead to the conclusion that the above spectral photoresponse is greatly affected by the presence of the dispersed crystalline CdSe.     

Formation of glass in the GeSiS system

The formation of glass in the GeSiS system was investigated. After synthesis of material with the general formula Ge_1?xSi_xS_y, where x was chosen to be 0.05, 0.1, 0.2, 0.3 and y was in the range 1.28–3.6, cylindrical samples were prepared and used for the characterization of glass by means of DTA. It was found that the substitution of germanium with silicon does not lead to any expressive change of the glass transition temperature, crystallization and the onset of melting.     

Structure of V2O5–P2O5 glasses by X-ray and neutron diffraction

The atomic structures of two V₂O₅–P₂O₅ glasses and vitreous (v-) V₂O₅ were investigated by X-ray and neutron diffraction. The V=O double bond is a common characteristic of the VO_n units that constitute the structures of the glasses. VO₅ square pyramids with elongated bonds of ~ 0.190 nm to the pyramidal base are found for the 50V₂O₅–50P₂O₅ glass. These weaker V–O bonds are balanced in V–O–P bridges by overbonded P–O bonds. The V^(IV) sites, which account for 19.7% and 35.2% of the total V sites in the 73V₂O₅–27P₂O₅ and 50V₂O₅–50P₂O₅ glasses, respectively, form similar pyramids in agreement with the structure of crystalline (VO)₂P₂O₇. The short-range structure of v-V₂O₅ and the 73V₂O₅-27P₂O₅ glass is formed of mixtures of VO₅ and VO₄ pyramids. A significant amount of V···O distances > 0.22 nm found for all glasses belong either to linkages V=O···V or to three-coordinated O sites.     

Nuclear magnetic resonance studies of the glasses in the system Na2OB2O3SiO2

The ¹¹B NMR spectra have been used to study the structure of glasses in the system Na₂OB₂O₃SiO₂. The fraction of BO₄ units, and the fraction of BO₃ units with one or two nonbridging oxygens, are measured and analyzed according to a structural model. The results indicate that: (1) for a sodium oxide to boron oxide ratio of 0.5 or less, the Na⁺¹ ions are attracted primarily by the borate network; therefore, the ternary glasses can be viewed as binary sodium borate glasses diluted by SiO₂; (2) when the sodium oxide to boron oxide ratio exceeds 0.5, the additional Na₂O results in the formation of [BSi₄O₁₀]^?1 units at the expense of diborate and SiO₄ units. In this process, Na⁺¹ ions are still taken up only by the borate network. After all the available SiO₄ units are consumed to form [BSi₄O₁₀]^?1 units, additional Na⁺¹ ions are proportionally shared between the borate and silicate networks.     

Raman scattering study of BaF2ZrF4FeF2 glasses

Several BaF₂ZrF₄ glasses containing 5 mol% FeF₂ have been studied to elucidate the fraction of nonbridging fluorine atoms (−F⁻) in a ZrF₆ octahedron constituting a zigzag chain. A continuous increase in the fraction of nonbridging fluorine atom in a ZrF₆ octahedron is deduced from the increase in the integrated peak intensity of the symmetric stretching-vibrational mode (ν^s) for the Zr-nonbridging fluorine atom when the BaF₂ (+ FeF₂) content is lower than 38 mol%, i.e., in the composition region where the average coordination number of Zr is regarded as six. This result is well consistent with the previous results obtained from Raman studies of binary BaF₂HfF₄ glasses, and also with those of Mössbauer and Raman studies of ternary BaF₂ZrF₄FeF₂ glasses. A drastic decrease in the symmetric-stretching vibrational mode (ν^s) in 42BaF₂·53ZrF₄·5FeF₂ glass suggests that a friction of ZrF₆ octahedron is reduced when BaF₂ (+FeF₂) content is close to 50 mol%. The zigzag chain is therefore considered to be constituted of ZrF₇ units in such glasses.     

Thermal expansion of glasses in the As2Se3–AsI3 system

Thermal expansion coefficients (α) of glasses in the As₂Se₃–AsI₃ system are measured in the glass transition region and temperature dependence of the fictive temperature is calculated on the basis of relaxation model. It is found that the increase of AsI₃ content results in: an increase of α, decrease of the glass transition temperature (T_g), increase of the α change at T_g, an effect of quenching rate on α, and also changes in the structural relaxation times spectrum. The data are discussed within the framework of the assumption that the addition of AsI₃ to As₂Se₃ results in: (1) destruction of the As₂Se₃ glass network, (2) structural inhomogeneity of the glasses increase, (3) the temperature dependence of chemical–structural equilibria occurring in the liquid state increases.     

Influence of various alkali and divalent metal oxides on phase transformations in NiO-doped glasses of the Li2O–Al2O3–SiO2–TiO2 system

Regularities of phase transformations in glasses of the Li₂O–Al₂O₃–SiO₂–TiO₂ system doped with up to 2.5 mol% of alkali- and divalent metal oxides were studied by X-ray diffraction analysis, Raman scattering and optical spectroscopy. Ni(II) ions were used as spectral probes of phase transformations because Ni(II)-ions enter the inhomogeneous regions formed during the phase separation and crystallization, and their absorption spectra change with heat-treatment temperature reflecting formation of aluminotitanate amorphous regions, spinel nanosized crystals and β-quartz solid solutions, consequently.It was demonstrated that the technological additives do not change the sequence of the phases' formation but accelerate the liquid phase separation and crystallization. Addition of MgO and ZnO leads to increasing the temperature range of spinel precipitation. Addition of CaO, BaO and PbO results in increasing the light scattering of prepared glass-ceramics.In selection of the technological additives for decreasing the melting temperature of glass-ceramics for optical and photonic applications the influence of the additives on the structure and optical properties of the prepared material should be considered.