Reinvestigation of Phase Equilibria in the V2O5–ZnO System

A diagram of phase equilibria established in a two-component oxide system V_{2 5}–ZnO has been worked out applying differential thermal analysis and X-ray phase analysis as well as depending on investigations carried out with the aid of high-temperature X-ray attachment and scanning electron microscope linked to an X-ray microanalyser. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermodynamic Analysis of Phase Equilibria in the System Cyclohexane—Methanol

The phase diagram of cyclohexane-methanol was thermodynamically modeledin the range of 150 T/K 360 and at a pressure of 1 bar on the basis ofavailable experimental data. The Gibbs energy functions of four pure solid andtwo mixture phases were taken into consideration. The liquid phase was describedby a model based on mole fraction statistics and the simplified assumption ofmethanol tetramers mixed with cyclohexane monomers. The gas phase was treatedas a nonideal mixture with a Gibbs energy modeled on the basis of the virialcoefficient formalism considering only monomers. The Gibbs energies of the twosolid modifications of pure methanol, as well as pure cyclohexane, were fixedusing literature data. The pressure dependence of the Gibbs energies of the liquidand solid phases were neglected. The complete T-x phase diagram includinggas/liquid equilibria as well as p-x phase diagrams in the range of 20 and 55°C werecalculated. Experimental and calculated data were found to agree reasonably well.     

The Effect of Interactions between γ-AlOOH and SiO2 Hydrosols on the Phase Formation in Their Mixed Products during Thermal Treatment

The effect of the sign and the value of a relative change in the -potentials of -AlOOH and SiO₂ sols on the composition homogeneity of the products of their mixing, as well as on the phase formation during thermal treatment of the latter is studied. A sample prepared by mixing -AlOOH and SiO₂ sols at pH 2.5 demonstrates the highest homogeneity of mixed gels and forms the only phase of mullite 3Al₂O₃ · 2SiO₂ during its thermal treatment (1350°C). At this pH value, a slow heterocoagulation of the sol particles with different signs of the -potential takes place. The coagulation of the sols at pH 1.5 and 5.0 results in the preparation of more or less heterogeneous mixed products and the formation of several phases during thermal treatment.     

Formation,Phase, and Elemental Composition of Micro- and Nano-Dimensional Particles of the Fe–Ti System

X-ray fluorescence, X-ray phase analysis, and transmission Mössbauer and NGR spectrometry are used to study the formation, phase, and elemental composition of Fe–Ti particles. The interaction between Fe(III) ions and dispersed titanium in an aqueous solution containing chloride ions and HF is studied. It is shown that the resulting Fe–Ti samples are a set of core–shell microparticles with titanium cores coated with micro- and nanosized α-Fe nucleation centers with the thinness outer layer of iron(III) oxide characterized by a developed surface.     

Structural Aspect of a Thermal Activation Effect in the MnO x /γ-Al2O3 System

Solid-phase reactions in the aluminum–manganese oxide system, including the structural mechanism of the thermal activation of catalysts, were studied at temperatures up to 1100°C. It was found that the solid-phase reaction at 900–1000°C occurred via two pathways because of the diffusion of manganese ions to aluminum oxide and aluminum ions to manganese oxide. Nanoheterogeneous state of the active component, which was observed in the range 25–600°C, is the product of incomplete decomposition of the high-temperature aluminum–manganese phase Mn_{2.1 – x} Al_{0.9 + x} O₄ (0 x 0.6) with a cubic spinel structure; this phase was equilibrium at the synthesis temperature but metastable below 650°C.     

Refining the Phase Diagram of the System 3Al2O3·2SiO2-ZrO2

The quasi-binary section mullite-zirconium dioxide in the ternary system Al₂O₃-SiO₂-ZrO₂, described by an eutectic phase diagram with T _{e u t} = 1750°C, was studied experimentally.     

Phase Diagram of the Ethylene Glycol–Dimethylsulfoxide System

The phase diagram of ethylene glycol (EG)–dimethylsulfoxide (DMSO) system is studied in the temperature range of +25 to ?140°C via differential scanning calorimetry. It is established that the EG–DMSO system is characterized by strong overcooling of the liquid phase, a glass transition at ?125°C, and the formation of a compound with the composition of DMSO · 2EG. This composition has a melting temperature of ?60°C, which is close to those of neighboring eutectics (?75 and ?70°C). A drop in the baseline was observed in the temperature range of 8 to ?5°C at DMSO concentrations of 5–50 mol %, indicating the existence of a phase separation area in the investigated system. The obtained data is compared to the literature data on the H₂O–DMSO phase diagram.     

Mechanism of Polymer Formation in the System Oligoester Aery late—Sodium Naphthalene

The formation of living soluble and network polymers during anionic polymerization of α, ω-methacrylbis(triethylene glycol) phthalate leads to the two types of the equlibria in the system: the equilibrium distribution of electrons between groups with electron affinity and equilibrium between living soluble and network polymers and oligomer. The equilibrium state can be reached both by direct (polymerization) and reverse (depolym-erization) reactions.     

Determination of High Pressure Phase Diagrams of the Ternary Alloy System

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Phase Relationships in the U – Np – O System

U – Np – O phase equilibria was experimentally studied by X-ray diffraction in reducing and oxidizing conditions. Both (U1yNpy)O2 stoichiometric and hyper-stoichiometric compounds were characterized after a heating treatment and resulting lattice parameters were compared to that of previous studies. Synthesized stoichiometric compounds are monophasic and their lattice parameters as a function of Np content are in nice agreement with the Vegard's law between UO2 and NpO2 end-member. Resulting compounds after an oxidizing heat treatment of the stoichiometric samples confirm previous reported U – Np – O relationship. For low Np content, a biphasic hyper-stoichiometric compound is observed: a (U1-y’Npy’)O2+x phase (space group fm-3m) and a (U1-y”,Npy”)3O8 phase (space group C2 mm). For higher Np content (with starting material y = 0.7), only one monophasic hyper-stoichiometric phase (U1-y’Npy’)O2+x appears. Lattice parameters of the (U1-y”,Npy”)3O8 phase differ from the ones of pure U3O8, indicating some Np solubility in this compound. Although Np might remain tetravalent in the (U1y”,Npy”)3O8 phase, this result is in conflict with the assumption of Yamashita et al. (1994).     

Specific Features of Radical Formation in the Trialkylborane–Oxygen System and the Gluing Mechanism of Acrylate Composites

Russian Journal of Applied Chemistry - Fundamental study of how radicals are generated, with involvement of trialkylboranes combined with oxygen and organoelement peroxides, was carried out. It was...     

Phase Diagram of the AgNO3–CsNO3 System

The phase diagram of the binary AgNO₃–CsNO₃ system was constructed using differential thermal analysis (DTA) technique in the range 300–700 K. The apparatus is described briefly. The results exhibit a congruently melting compound CsNO₃·AgNO₃ (m.p.=453 K) characterized by two allotropic varieties and , an incongruently melting compound AgNO₃·CsNO₃ (m.p.=450 K) with three forms , and , two eutectics (16 mol% CsNO₃, 442 K and 32.5 mol% CsNO₃, 445 K) and a peritectic (38mol% CsNO₃, 450 K). The occurrence of the transitions of intermediates was confirmed by X-ray diffraction at variable temperatures. The phase diagram exhibits also two plateaus at 429 K and 435 K corresponding to the phase transitions of CsNO₃ and AgNO₃, respectively.This revised version was published online in November 2005 with corrections to the Cover Date.     

Phase Equilibria in the System Fe2O3–V2O5 –WO3 in the Solid State

DTA and X-ray phase diffraction methods were used to construct a solidus area projection onto the component concentration triangle plane of the system Fe₂ O₃-V₂ O₅-WO₃. This revised version was published online in August 2006 with corrections to the Cover Date.     

Phase Equilibria in the Ternary System Fe-Gd-Mo at 600 °C

 Phase equilibria in the ternary system Fe-Gd-Mo at 600 °C were determined. The phase composition for different element concentrations were quantitatively determined from the diffraction patterns by means of the multi-phase Rietveld-refinement as well as through evaluation of the microstructure images obtained by the scanning electron microscopy. Both methods are compared with each other with respect to their precision and limitations. The complete isothermal section at 600 °C includes one ternary phase τ (ThMn₁₂-type of structure), four pseudo-binary phases (Fe,Mo)₁₇Gd₂, (Fe,Mo)₂₃Gd₆, (Fe,Mo)₃Gd and (Fe,Mo)₂Gd and binary phases Fe₂Mo and μ-(Fe,Mo). The ternary phase τ forms the tie-lines with the solid solutions α-Fe, (Mo)-, Fe₂Mo and μ-(Fe,Mo) phases as well as with the pseudo-binary Fe-Gd compounds. Three phases (Fe,Mo)₂Gd, (Mo) and Gd coexist in a wide concentrations range. The homogeneity region of the ternary phase τ as well as the solubilities of the third element in the binary phases were determined.     

Melt–Vapor Phase Diagram of the Te–S System

The values of partial pressure of saturated vapor of the constituents of the Те–S system are determined from boiling points. The boundaries of the melt–vapor phase transition at atmospheric pressure and in vacuum of 2000 and 100 Pa are calculated on the basis of partial pressures. A phase diagram that includes vapor–liquid equilibrium fields whose boundaries allow us to assess the behavior of elements upon distillation fractioning is plotted. It is established that the separation of elements is possible at the first evaporation–condensation cycle. Complications can be caused by crystallization of a sulfur solid solution in tellurium.     

Study on the Phase Behavior of Supercritical CO2／Dynol—604／Water System and Solubilization of Methyl Orange in the Microemulsions

It was found that Dynol-604, a non-fluorous and no silicon-containing nonionic surfactant,was soluble in supercritical (SC) CO2. The phase behavior of SC CO2/Dynol-604/water system was studies. The results showed that one-phase water-in-CO2 microemulsions could be fromed. The solubilization of methyl orange in the microemulsions proved further the existence of water domain in the microemulsions.     

NOx—Catalyzed Gas—Phase Activation of Methane： the Formation of Hydrogen

NOx-catalyzed oxidation of methane without a solid catalyst was investigated, and a hydrogen selectivity of 27% was obtained with an overall methane conversion of 34% and a free O2 concentration of 1.7% at 700℃.     

Mechanism of Bi−Ni Phase Formation in a Microwave-Assisted Polyol Process

Typically, intermetallic phases are obtained in solid-state reactions or crystallization from melts, which are highly energy and time consuming. The polyol process takes advantage of low temperatures and short reaction times using easily obtainable starting materials. The formation mechanism of these intermetallic particles has received little attention so far, even though a deeper understanding should allow for better synthesis planning. In this study, we therefore investigated the formation of BiNi particles in ethylene glycol in a microwave-assisted polyol process mechanistically. The coordination behavior in solution was analyzed using HPLC-MS and UV-Vis. Tracking the reaction with PXRD measurements, FT-IR spectroscopy and HR-TEM revealed a successive reduction of Bi³⁺ and Ni²⁺, leading to novel spherical core-shell structure in a first reaction step. Bismuth particles are encased in a matrix of nickel nanoparticles of 2 nm to 6 nm in diameter and oxidation products of ethylene glycol. Step-wise diffusion of nickel into the bismuth particle intermediately results in the bismuth-rich compound Bi₃Ni, which consecutively transforms into the BiNi phase as the reaction progresses. The impacts of the anion type, temperature and pH value were also investigated.