On the fluctuation structure of single-phase glasses in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The structure of single-phase glasses in the SrO-B₂O₃-SiO₂ system has been studied by the small-and large-angle X-ray scattering technique. The glasses containing 35, 40, and 45 mol % SrO upon equimolar replacement of B₂O₃ by SiO₂ have been investigated. It has been demonstrated that the glasses do not contain chemical inhomogeneity regions. The inhomogeneity of the glasses is determined only by thermal density fluctuations. The isothermal compressibility varies insignificantly upon replacement of B₂O₃ by SiO₂ and decreases with an increase in the SrO content. The glass structure is consistent with the model of ideal associated solutions.     

Crystallization of glasses in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The crystallization of strontium borate glasses containing 16.7–43.0 mol % SrO is investigated. New crystalline compounds of the hypothetical compositions 2SrO · 3B₂O₃ (metastable) and SrO · 5B₂O₃ (stable below 750°C), as well as the metastable diborate modification β-SrO · 2B₂O₃, are revealed, and their X-ray powder diffraction data are obtained. It is demonstrated that, with a deficit of strontium oxide, the 4SrO · 7B₂O₃ compound forms solid solutions. Strontium triborate SrO · 3B₂O₃, which was previously prepared only through the dehydration of crystal hydrates, is produced using crystallization of glasses. The thermal stability of this compound is studied. The influence of the dispersity on the stability of different crystalline phases is discussed. Variants of the phase diagram for the SrO · B₂O₃-B₂O₃ system in the case of monolithic and dispersed samples are proposed from analyzing the experimental results and the data available in the literature.     

Synthesis and properties of flux-cast refractories in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Details are given of the synthesis and testing of flux-cast refractory materials in the alumina-rich region of the Al₂O₃-MgO-B₂O₃ system; XRD and petrography indicate that the main structure-forming phases are corundum and magnesian spinel. In subordinate amounts there are the boroaluminate 9Al₂O₃·2B₂O₃ and the previously unknown compound 4Al₂O₃·MgO·2B₂O₃, whose composition has been established by microprobe analysis. Corrosion tests showed that three-component systems containing magnesium and boron oxides at levels of 5–10% do not increase the corrosion resistance of refractories in molten sodium-calcium-silicate glass and electrovacuum borosilicate glass. __________ Translated from Novye Ogneupory, No. 3, pp. 161–163, March, 2008.     

Viscosity of glass melts in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The temperature dependences of the viscosity are investigated for three series of glass melts in the SrO-B₂O₃-SiO₂ system with a constant strontium oxide content equal to 35, 40, or 45 mol % in the viscosity range from 10¹⁰ to 10¹³ P.     

On the structure of glasses in the BaO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The structure of single-phase glasses in the BaO-B₂O₃-SiO₂ system has been studied by the large- and small-angle X-ray scattering techniques. The glasses containing 40 mol % BaO upon equimolar replacement of B₂O₃ by SiO₂ have been investigated. It has been demonstrated that the incorporation of barium ions into structural groupings fixes their position and provides ordering in the distribution of barium ions at interatomic distances up to at least 5 Å. The glasses under investigation are homogeneous, and their inhomogeneity is determined by thermal density fluctuations and fluctuations of the concentration of a part of barium ions distributed in a statistically random manner in the volume of the glass. The observed ordering in the distribution of barium ions is not reduced to the formation of local clusters with an increased concentration of barium ions but is most likely a characteristic feature of the bulk glass structure. The glass structure is consistent with the model of ideal associated solutions.     

Thermal expansion of glasses in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The linear thermal expansion coefficients below and above the glass transition range and the glass transition temperatures in the SrO-B₂O₃-SiO₂ system are determined using a quartz dilatometer.     

Density and microhardness of glasses in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The density d at a temperature of 25°C is measured by the hydrostatic weighing method, the Vickers microhardness H _V is determined, and the fluctuation free volume fraction f _g is calculated for glasses in the SrO-B₂O₃-SiO₂ system with a constant strontium oxide content in the range from 35 to 45 mol %. It is demonstrated that the quantities H _V and f _g decrease and the density d increases with an increase in the SrO content.     

Mechanism of formation of the complex oxide Na<Subscript>2</Subscript>Nd<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>10</Subscript>

The processes of phase formation in the Nd₂O₃-TiO₂-Na₂CO₃ system have been investigated in the temperature range 500–1100°C. The mechanism of the high-temperature solid-phase reaction of formation of the complex oxide Na₂Nd₂Ti₃O₁₀ has been studied. It has been established that the Na₂Nd₂Ti₃O₁₀ compound is formed from the intermediate product Na_0.5Nd_0.5TiO₃ with a perovskite structure in the temperature range 830–890°C and from the NaNdTiO₄ oxide with a perovskite-like layered structure in the temperature range 960–1100°C.     

The system SiC–W<Subscript>2</Subscript>B<Subscript>5</Subscript>–LaB<Subscript>6</Subscript>

Experiments and calculations have been applied to the structure of the triple eutectic system SiC–W₂B₅–LaB₆(T _eu = 1900 ± 40°C), composition in mol.%: 10 LaB₆, 44 SiC, 46 W₂B₅, error ±2–3%, which opens up prospects for making ceramic materials for various purposes.     

Synthesis of low-melting eutectic of the CaO–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system in a solid phase

Results are provided for a physicochemical study of processes that occur during synthesis of eutectic composition of the CaO–B₂O₃–SiO₂ system in a solid phase, and the possibility of their activation by using starting calcium-containing components with different chemical and thermal prehistory. It is established that independent of the form of starting components, in all cases there is formation of a crystalline eutectic phase, and the sequence of physicochemical processes that occur is determined by the reaction capacity of the calcium compound introduced.     

Preparation of surface-crystallized optical glass-ceramics SrO · 2B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The physicochemical features of the phase formation upon crystallization of monolithic glasses of the strontium diborate stoichiometric composition are investigated. It is demonstrated that the first phase crystallizing on the surface of the SrO · 2B₂O₃ glass is the strontium borate Sr₄B₁₄O₂₅, which plays the role of a precursor for the subsequent crystallization of the SrB₄O₇ borate. The temperature corresponding to the maximum crystal nucleation rate on the surface and the time of complete “operation” of nuclei are determined using differential thermal analysis. The optical glass-ceramics prepared by the two-stage crystallization are surface-crystallized glasses in which the filling density of the surface is approximately equal to 30% and the content of the main phase SrB₄O₇ is as high as ∼ 70%. No second harmonic generation of neodymium laser radiation in the glass-ceramics is observed because of both the absence of the preferred orientation of SrB₄O₇ nonlinear optical crystals and the small crystal sizes (considerably smaller than the coherence length of the SrB₄O₇ crystal) in the direction perpendicular to the glass surface.     

Study on the properties of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-BaO lead-free glass using in the electronic pastes

The Sb₂O₃ doping lead-free glass in Bi₂O₃-B₂O₃-BaO ternary system were prepared in the composition of several different subsystem, and the glass powder was produced through the process of water quenching. Glass transition temperatures (T _g ), glass soften temperatures(T _s ), the volume resistivity (ρ) in the temperature range of 80–200°C, and linear thermal coefficients of expansion in the temperatures range of 25–300°C (α_25–300) were measured for subsystems along with the different ratio of Bi₂O₃, B₂O₃ and BaO. For these subsystems, T _g ranged from 458 to 481°C, and T _s ranged from 490 to 512°C, both decreasing with the increasing of Bi₂O₃/B₂O₃ ratio, and increasing with the increasing of BaO/B₂O₃ ratio. The measured α_25–300 ranged from 65.3 to 76.3 × 10⁻⁷ K⁻¹, with values increasing with increasing Bi₂O₃/B₂O₃ and BaO/B₂O₃ ratio. The volume resistivity remains at a high standards, which may caused by it’s non-alkali composition, and it fluctuated from 10¹³ to 10¹¹ Ω cm with the temperature varied from 80–200°C. The structure of Bi₂O₃-B₂O₃-BaO ternary leadfree glass system was mearsured by FT-IR. The IR studies indicate that these glasses are made up of [BiO₆], [BO₃], and [BO₄] basic structural units, and it appears that Ba²⁺ acts as a glass-modifier in this ternary system, but the Bi³⁺ has entered the glass network when it is in relative high content so as to change the α_25–300, T _s and T _g .     

Volumetric nucleation of crystals catalyzed by Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> in glass based on furnace slags

The features of the volumetric nucleation of crystals in glass obtained by melting furnace slags with the additive of SiO₂, chromium sesquioxide Cr₂O₃, are studied by the methods of differential thermal and Xray phase analysis and optical microscopy. Upon the introduction of Cr₂O₃ as the catalytic additive, two phases are sequentially formed in the glass: magnesiochromite (MgO · Cr₂O₃) and diopside (CaO · MgO · 2SiO₂). The characteristics of homogeneous and heterogeneous crystallization are determined: the stationary nucleation rate, nonstationary nucleation time, crystal growth rate, and their temperature dependences are obtained. Practical recommendations on the use of the obtained glass are given.     

Thermomechanical properties of refractory materials of AL<Subscript>2</Subscript>O<Subscript>3</Subscript>–Si<Subscript>3</Subscript>N<Subscript>4</Subscript>–C compositions based on acpb after impregnation with a sol-gel composition

Comparative characteristics are presented for the physicomechanical properties and oxidation resistance of refractory materials of Al₂O₃–Si₃N₄–C composition based on an ACPB for the original materials (fired at 1400°C) and after impregnation with a sol-gel composition and heat treatment at 800°C. Areduction in material porosity, increase in strength and reduction in carbon burn-off are due to development of a glassy phase in the pore space and on graphite flakes due to SiO₂formation with thermal destruction of the organosilicon substance.     

Influence of pressure on the refractive index and relative density of glasses in the CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The pressure dependences of the refractive index for aluminosilicate glasses of the compositions 0.167CaO · 0.167Al₂O₃ · 0.666SiO₂ and 0.157CaO · 0.177Al₂O₃ · 0.666SiO₂ at pressures up to 6.0 GPa are determined using a polarizing interference microscope and an apparatus with diamond anvils. The compressibilities of the glasses are calculated from the measured refractive indices within the framework of the theory of photoelasticity. The structural-chemical parameters NBO/T (where NBO is the number of gram-ions of nonbridging oxygen atoms and T is the total number of gram-ions of network formers) are calculated for the glasses under investigation with allowance made for the formation of triclusters and highly coordinated aluminum.     

Sol-gel synthesis and features of the structure of Au-In<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposites

The specific features of the chemical state of gold and indium oxide in Au-In₂O₃ (0.01–1.0 wt % Au) nanocomposites have been investigated by the methods of X-ray diffraction analysis, electron microscopy, infrared and optical spectroscopy, electron paramagnetic resonance, and thermal analysis. Xerogels, powders, and films obtained by the introduction of HAuCl₄ into the indium hydroxide sol and thermal treatment at 50–700°C have been studied. The mutual influence of the components on the size of the Au and In₂O₃ particles and the state of their surface has been established. It has been shown that the synthesis of Au-In₂O₃ by the sol-gel method leads to the formation of nanosized indium oxide particles with the high concentration of hydroxyl groups on surfaces and favors the stabilization of gold in the form of nanoclusters and ion forms.     

Structure and crystallization of ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Structure and crystalline behavior of the ternary system ZnO-B₂O₃-P₂O₅ glasses were investigated by means of X-ray diffraction (XRD) and infrared Raman spectra. The research showed that number of the planar [BO₃] units increases with the increase of B₂O₃ content. When the B₂O₃ content is above ≥10 mol %, the relative content of planar [BO₃] units increases rapidly and causes weakening of the glass structure and decrease in the chemical stability. In the crystallized glasses the predominant crystal phase Zn₂P₂O₇ decreases with the increase of B₂O₃ content, while the crystal phase BPO₄ increases with it, which cause the declining of chemical stability and the decrease of thermal coefficients of expansion.     

Refractive index and compressibility of the KAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript> glass at pressures up to 6.0 GPa

The refractive index of potassium aluminosilicate glass of the KAlSi₃O₈ composition in the pressure range up to 6.0 GPa has been measured using a polarizing interference microscope and an apparatus with diamond anvils. The changes in the relative density, which characterize the compressibility of the K₂O · Al₂O₃ · 6SiO₂ glass, have been estimated in the pressure range under investigation from the measured refractive indices within the framework of the theory of photoelasticity. The results have been compared with the data previously obtained for the Na₂O · Al₂O₃ · 6SiO₂ glass. Although the molar contents of Al₂O₃ and M ₂O (where M = K or Na) are identical in these glasses, the KAlSi₃O₈ glass exhibits a higher compressibility, which agrees with the lower degree of depolymerization of this glass as compared to that observed in the NaAlSi₃O₈ glass. The pressure derivative of the bulk modulus K′ _t , which is calculated from the Birch-Murnaghan equation for the KAlSi₃O₈ glass (K′ _t = 7–9), is higher than that for the NaAlSi₃O₈ glass (K′ _t = 5.5–6.0). An increase in the pressure derivative of the bulk modulus K′ _t upon replacement of the Na⁺ cations by the K⁺ cations is explained by the inhibition of compression of the large K⁺ cations, which are located in cavities and have a considerably larger orbital radius than the Na+ cations. This manifests itself in the fact that the curves describing the dependences of the change in the relative density (d − d0)/d (compressibility) on the pressure P for the KAlSi₃O₈ and NaAlSi₃O₈ glasses converge at pressures above 4.0 GPa.     

Synthesis and characterization of zeolite mazzite analogue in Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–Piperazine–H<Subscript>2</Subscript>O

Zeolite Mazzite (MAZ) analogue was synthesized directly using piperazine as a structure directing agent. The reactive gel composition used was (5.0–7.0) piperazine:(6.0–7.0) Na₂O:Al₂O₃:20.0SiO₂:400H₂O. Using this composition, the reaction time was shortened greatly to 4 days and the crystallization time was reduced as well. The DTA data showed that piperazine, in as-synthesized zeolite omega decomposed easily. The decomposition of the piperazine occurred at 400–480°C. NH₃-TPD analysis proved that zeolite H-omega from piperazine had strong surface acidity with ammonia desorption temperature up to 590°C.     

Calculations of the Thermodynamic Properties of Glasses and Melts in the Na<Subscript>2</Subscript>O-SiO<Subscript>2</Subscript> and B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> Systems on the Basis of the Generalized Lattice Theory of Associated Solutions

The possibility of calculating the thermodynamic properties of binary glass-forming systems containing both modifier (Na₂O) and glass-former (B₂O₃) oxides with the use of the vacancy variant of the generalized lattice theory of associated solutions is demonstrated for glasses and melts in the Na₂O-SiO₂ and B₂O₃-SiO₂ systems.