Mechanisms of Interaction of Molybdenum and Tungsten Polyoxide with Aluminum Oxide Melt under Reducing Conditions

The main chemical reactions between Mo and W polyoxides and Al₂O₃ melt in a controlled Ar + H₂ atmosphere (T = 2400 K, P = 1 bar) during sapphire growth by horizontal directional solidification have been investigated. Under these thermodynamic conditions, the melt and products of its dissociative evaporation may actively react with the tungsten heater and molybdenum thermal screens of the crystallization system. It is shown that the polyoxides formed during evaporation do not directly interact with the melt; this interaction occurs only with participation of reagents exhibiting pronounced reducing properties (Al, H₂, H, WO, Al₂O, AlH, AlH₂, AlH₃). It is established that most of processes occur with participation of aluminum hydrides. A particular role of Mo(W) dioxide–W(Mo) polyoxide functional pairs in the interaction with the melt is determined.

     

Chemical processes in the Mo-W-Al2O3 system in vacuum (1 × 10?5 bar)

The behavior of the Mo-W-Al₂O₃ system at T = 2400 K and P = 1 × 10^?5 bar is considered, and the main chemical reactions that implement the oxidation of Mo and W by the products of dissociative evaporation of the melt are determined. The gas-phase composition is calculated for the equimolar ratio of the components of the system, both for the presence and absence of direct contact of W with Al₂O₃. It is established that in the first case the dominant components of the gas phase are Al and WO₃. In the second case, Al and Mo dominate, whereas the WO₃ concentration decreases by a factor of about 2.5.     

Some Aspects of Interactions in the Mo–W–Al2O3–H2 System: Formation of Polyoxides

The possibility of formation of molybdenum and tungsten polyoxides in the Mo–W–Al₂O₃–H₂ system at T = 2400 K and P = 1 bar in a controlled Ar + H₂ atmosphere has been investigated by the method of thermodynamic analysis. The formation of polyoxides is found to occur both due to the processes involving Al₂O₃ melt and in the absence of the latter. It is established that metals (Mo and W) and their mono-, di-, and even trioxides (in the latter case, mediated polymerization occurs) can be used as initial components to form polyoxides. It is shown that polyoxides themselves may interact with one of their main sources: Al₂O₃ melt.

     

Chemical transformations in the W-Al2O3 system under pressure P = 1 bar near the melting point of aluminum oxide

The W-Al₂O₃ system has been considered at a temperature of 2400 K and a pressure of 1 bar. The main chemical processes providing the interaction between the components of the system have been determined. It is shown that evaporation of Al₂O₃ into the gas phase gives rise to numerous reactions, which involve not only tungsten but also Al₂O₃ melt. It is concluded that such interactions can be reduced by decreasing the Al₂O₃ evaporation, which can be done by increasing the inert gas pressure. This approach makes it possible both to optimize the parameters of sapphire crystal growth and increase the lifetime of a tungsten heater and other units of crystallization systems.     

Growth of sapphire by the kyropoulus method

Single crystals of leuko-sapphire (α-Al₂O₃) are grown from the melt by an improved Kyropoulos technique using Mo or W crucibles. The influence of the temperature field on the structural and optical quality has been studied. Best results were obtained when heat losses from crystal and melt are minimized.     

Molybdenum and Tungsten Combined Oxidation by Dissociative Evaporation of Products during Refractory Oxides Crystal Growth from the Melt

The main chemical reactions and composition of gas and solid phases have been determined for the equimolar ratio Mo: W: O₂ = 1: 1: 2 at T = 2400 K in the pressure range of 1-1 x 10^-5 bar. It is established that the character of the main processes of combined oxidation depends significantly on the pressure and state of the oxidant (oxygen): at P > 7.52 x 10^-5 bar, oxidation reactions involve mainly molecular oxygen, whereas atomic oxygen dominates at lower pressures. At P ≥ 0.424 bar, the solid phase contains not only Mo but also MoO₂. At P = 1 x 10^-5 bar, the concentration of lower Mo and W oxides and elementary Mo and W in the gas phase sharply increases, which can negatively affect the main crystallization units.     

Thermodynamic analysis of the W-Al2O3 system near the melting temperature of Al2O3. I. Evolution of the system in the pressure range of 1 × 10−1−1 × 10−4 bar

The changes in the main chemical reactions occurring upon the interaction between tungsten and the evaporation products of Al₂O₃ melt are considered at a fixed temperature (2400 K). The concentrations of the components coexisting in equilibrium in a closed system under isobaric-isothermal conditions are determined by stochastic simulation for low (× 10⁻¹−1 × 10⁻³ bar) and high (1 × 10⁻⁴ bar) vacuum. It is shown that the gas-liquid-solid system is in heterogeneous equilibrium for the basic component ratio W: Al₂O₃ = 1: 1 in the entire pressure range under consideration. A detailed study of the chemistry of this system should facilitate the choice of the optimal conditions for growing leucosapphire crystals from melt.     

The chemical action of oxygen on a heater during growth of refractory oxide crystals from melt

The behavior of the W-O₂ system has been investigated at 2400 K in the pressure range from 1 to 1 × 10^?5 bar. The chemical composition of the solid and vapor phases for the ratio W: O₂ = 1: 1 was calculated by minimizing the Gibbs free energy. It is shown that the only solid phase in the system is metallic tungsten (0.333–0.355 mol), whereas trioxide WO₃ dominates in the vapor phase; its concentration may reach 99%. It is concluded that providing an inert atmosphere in the growth chamber with a pressure of 1 bar decreases the concentration of atomic and molecular oxygen in the vapor phase and decreases its effect on the tungsten heater.     

Chemical processes and composition of the gas and solid phases in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Mo system in the temperature range 2327–2500 K

The possibility of chemical reactions has been calculated and the composition of the gas and solid phases that are in equilibrium with an aluminum oxide melt is determined. It is shown that, for the Al₂O₃-Mo system in the pressure range 1?1 × 10^?5 bar, evaporation of Al₂O₃ is incongruent, and the fraction of this component in the gas phase decreases from 51.5 mol % (P = 1 bar) to 0.01 mol % (P = 1 × 10^?5 bar). The presence of molybdenum-containing compounds in the gas phase changes the balance of oxygen and aluminum in favor of the latter (the aluminum partial pressure increases by a factor of 1.5–3), as a result of which there may be an aluminum deficit in the solid phase of Al₂O₃ during crystal growth from a melt. The thermodynamic characteristics (K _p , ΔG, P _tot) of dominant chemical reactions have been calculated for the temperature range 2327–2500 K. Understanding of the chemical processes makes it possible to optimize the growth parameters of leucosapphire single crystals.     

Purity and doping possibilities of Al2O3 and YAG molten in Mo crucibles and crystals grown from this melt

Doping possibilities of Al₂O₃ and YAG crystals grown from the melt alternatively doped with alkali earth, silicon, iron group or molybdenum ions under 98% Ar – 2% H₂ or 98% He – 2% H₂ protective atmosphere are described. Alkali earth and particularly Si ions evaporate slowly from the melt. Reduction of iron group ions was observed. Mo may enter YAG phase using a wet protective atmosphere. Al₂O₃ phase contains Mo ions if grown from the electrolyzed melt.     

Chemical Processes in Al2O3-Mo and Al2O3-W systems in a weakly reducing atmosphere

Al₂O₃-Mo and Al₂O₃-W systems in a controlled Ar(95%) + H₂(5%) atmosphere at T = 2400 K and P = 1 bar have been calculated by the Monte Carlo method. It is established that the presence of hydrogen in these systems leads to the occurrence of OH, H₂O₂, HO₂, H₂O, AlOH, AlOOH, AlH, AlH₂, and AlH₃ components in the gas phase; aluminum hydrides are formed only through the interaction of hydrogen with melt evaporation products. The presence of reducing medium leads to a decrease in the free oxygen concentration by one to two orders of magnitude, which is expected to improve the quality of sapphire crystals.     

Structural chemistry of peroxo compounds of group VI transition metals: II. Peroxo complexes of molybdenum and tungsten: A review

The specific features revealed in the structure of the molybdenum and tungsten peroxo complexes with the ratios M: O₂ = 1: 1, 1: 2, and 1: 4 are considered. It is demonstrated that the geometry of the coordination polyhedron of the metal atom is primarily determined by the “metal: peroxo ligand” ratio. Formally, the pentagonal bipyramidal coordination polyhedra of the Mo(VI) and W(VI) oxo monoperoxo and oxo diperoxo complexes (the coordination numbers of the metal atoms are equal to seven) have different geometries, namely, the MO(O₂)A ₄ pseudooctahedral and MO(O₂)₂ A ₂ pseudotrigonal bipyramidal configurations.     

Growth and structure of α-Bi2B8O15 crystals

α-Bi₂B₈O₁₅ crystals (5-to 7-mm-thick, 2.7 × 2.7 cm² in cross section) have been grown by the Czochralski method from a melt of stoichiometric (Bi₂O₃: B₂O₃ = 20: 80) and nonstoichiometric (Bi₂O₃: B₂O₃ = 21.9: 78.1) compositions. It is established that there is a solid-solution range from 78.1 to 84.7 mol % B₂O₃ for α-Bi₂B₈O₁₅. The structure of a Bi₂(B₈O₁₅)(Bi₂O₃)_0.06 crystal, which was grown from a melt of nonstoichiometric composition and is an interstitial solid solution, has been refined (sp. gr. P2₁).     

Crystallization of a germanium melt in an external electric field

Data are presented on experimental studies of the influence of an external electric field on crystallization of a germanium melt under the layer of a B₂O₃ flux. It has been found out that with the field supercoolings of the melt sharply change. This effect is due to the change of the number of active nucleation centres at the germanium – B₂O₃ flux interface. The maximum supercoolings of the germanium melt ΔT⁻ = 190 K were obtained when a negative potential was connected to germanium. The dependences of supercooling on preliminary melt overheating were measured.     

Peculiarities of the behavior of the W–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system in a controlled reducing atmosphere

The W–Al₂O₃ system at T = 2400 K and standard pressure (controlled Ar + H₂ atmosphere) has been calculated by stochastic simulation. It is shown that the presence of hydrogen leads to the formation of aluminum hydrides, hydrogen oxides, and aluminum hydroxides; the compounds from the two latter groups (except for water) can interact directly with tungsten. The main chemical reactions occurring in the system are determined, based on which a conclusion about the cyclic character of the processes is drawn. Some recommendations on the composition and pressure of controlled atmosphere for growing sapphire crystals are given.     

Calculation of thermodynamic parameters of melts from experimentally determined liquidus‐curves

Thermodynamic parameters of melts (ΔH_S, A₀, A₁) in the system Anorthite‐Diopside and Bi₂O₃‐Bi₄B₂O₉ have been calculated by a rigorous application of solution thermodynamics. The data are internally consistent and yield values of ΔH_S for Anorthite = 133 kJ/mole, Diopside = 81 kJ/mole, Bi₂O₃ = 19 kJ/mole and Bi₄B₂O₉ = 39 kJ/mole. The activity of Anorthite and Diopside in an anorhtitic melt deviates negative from ideality, whereas a diopsidic melt behaves almost ideal. In a “Bi₂O₃” melt the activity of the Bi₂O₃ component is strongly positive, that of Bi₄B₂O₉ is strongly negative. The opposite is observed for the “Bi₄B₂O₉” melt. All calculated liquidi except the Bi₄B₂O₉ liquidus closely match the experimental ones. In contrast to the experimental liquidus the calculated Bi₄B₂O₉ liquidus has an inflection point. The crest of the metastable spinode (solvus) for a “Bi₂O₃” melt is close to the liquidus indicating melt separation at undercooling. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman scattering study of crystalline and melting states of BaO·2B2O3

Melting and crystallization scenarios of barium tetraborate BaB₄O₇ (BaO·2B₂O₃) are studied in situ by Raman spectroscopy. It is shown that the scenario depends on the temperature–time history of melt. Crystallization conditions of the beta modification of barium tetraborate (β-BaB₄O₇) from a stoichiometric glass structure BaO·2B₂O₃ were investigated.     

Low-temperature growth and doping of InP:S single crystals from melt-solution in microgravity

The effect of microgravity on the growth of bulk InP:S single crystals from a melt with an initial equilibrium composition (84 at % In, 16 at % P, and ～2.2 × 10¹⁸ at cm^?3 of S) on board the Foton-11 satellite was investigated. The growth of crystals on board the satellite and on Earth (a reference crystal) was carried out by the traveling heater method. The samples of the grown crystals were investigated by metallography, double-crystal X-ray diffractometry, single-and double-crystal X-ray topography, and secondary-ion mass spectrometry. It is shown that the mass transfer in the melt in microgravity is similar to the diffusion mode. Hence, the mass transfer in the melt results in the following: the formation of a nonstationary boundary layer, depleted in phosphorus; the constitutional supercooling at the crystallization front accompanied with the development of a cellular substructure in the early growth stage; and the hypothetical phase structurization of the transition layer with the formation of In-based associates (clusters), which were found in the grown crystals in the form of spherical defects 10–20 μm in diameter. The coefficients of sulfur distribution k₀ = 0.274 and k_eff = 0.43, the sulfur diffusivity in the melt D_S = 4.2 × 10^?7 cm²/s, and the effective thickness of the transition layer δ = 0.07 cm in terrestrial gravity are determined. The data obtained are necessary to develop a mathematical model of crystallization in zero gravity.     

Spectroscopy,oxidation-reduction behaviour and DC conductivity of a vanadium-containing barium aluminoborate glass

The vanadium(IV)-vanadium(V) equilibrium in a 37.5BaO, 5.0Al₂O₃, 57.5B₂O3 mol% + X mol% V₂O₅ (where X = 0.25?32.5) glass system has been studied as functions of temperature, partial pressure of oxygen and total vanadium concentration of the melt. The vanadium(V)/vanadium(IV) ratio in the melt increased with increasing partial pressure of oxygen, lowering temperature of melting, and with increasing total vanadium content of the melt. With X ? 10, the vanadium(V)/vanadium(IV) ratio became almost independent of the total vanadium content of the melt.With this knowledge of oxidation-reduction behaviour, a series of glasses containing 2.8?32.5 mol% V₂O₅ (at about 4 mol% intervals) and having a constant vanadium(IV)/vanadium(V) ratio (0.17) were prepared. Density, electronic absorption spectrum (both d-d and charge transfer transitions), and ESR of these glasses were measured. Optical and ESR spectra of these glasses indicated the vanadium(IV) to be present as vanadyl ion, VO²⁺; g| decreased monotonically with increasing vanadium content of these glasses, whereas gβ remained unchanged. The charge transfer transition energy due to vanadium(V) decreased, and the extinction coefficient increased by orders of magnitude with increasing vanadium content of the glass; the most striking changes occurred at X ≈ 10 mol%. DC conductivity of these glasses was measured at different temperatures; a plot of log (?/T) versus 1/T produced straight lines. The slope of these lines remained almost constant (39 ± 1 kcal/mol) for the glasses containing up to about 10 mol% V₂O₅; with further increase of V₂O₅ the slope decreased sharply.It has been concluded that the abrupt changes in properties like partial molar volume of V₂O₅, charge transfer spectrum of vanadium(V), activation energy of polaron hopping — all of which occurred around X ≈ 10 mol% — is due to a major change in the nature of vanadate groups rather than vanadium(IV) in these glasses.     

Mixed tetrahedral anionic framework in the K3Ga2(PO4)3 crystal structure

The crystal structure of a new synthetic potassium gallophosphate K₃Ga₂(PO₄)₃ grown from a solution in the melt of a mixture of GaPO₄ and K₂MoO₄ is determined using X-ray diffraction (Bruker Smart diffractometer, 2θ_max= 56.6°, R = 0.044 for 2931 reflections, T = 100 K). The main crystal data are as follows: a = 8.661(2) Å, b = 17.002(4) Å, c = 8.386(2) Å, space group Pna2₁, Z= 4, and ρ_calcd = 2.91 g/cm³. The synthesized crystals represent the third phase in the structure type previously established for the K₃Al₂[(As,P)O₄]₃ compound. It is shown that the structure consists of a three-dimensional anionic microporous tetrahedral framework of the mixed type, which is formed by PO₄ and GaO₄ tetrahedra shared by vertices. Large-sized cations K⁺ occupy channels of the zeolite-like framework. The crystal chemical features of the formation of structure types of compounds with mixed frameworks described by the general formula A ₃ ⁺ M ₂ ³⁺ (TO₄)₃ (where A = K, Rb, (NH₄), Tl; M = Al, Ga, Fe, Sc, Yb; T = P, As) are analyzed.