Magnetic diagram of CuCr<Subscript>2 – <Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Sе<Subscript>4</Subscript> solid solutions

Temperature-dependent magnetization was measured for CuCr_2–x Sb _x Sе₄ solid solutions in the range 300–5 K in a weak field (50 Oe) and a strong field (10 kOe) and in an ac magnetic field having a frequency of 100–10000 Hz and an amplitude of Н = 1 Oe. The type and character of magnetic transitions under investigation in the system were determined, and its magnetic phase diagram was constructed.     

Synthesis and magnetic properties of solid solutions In<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Sb〈Mn〉

Manganese-doped solid solutions In_1–x Ga _x Sb (x = 0.05, 0.1, 0.5, 0.9, 0.95) were synthesized. It was found that, in samples of the compositions In_0.95Ga_0.05Sb〈Mn〉 and In_0.05Ga_0.95Sb〈Mn〉, a homogeneous substitutional solid solution forms, into which manganese-containing clusters are incorporated. The clusters are mainly located at crystal lattice defects—grain boundaries and dislocations. The ferromagnetic properties of the obtained samples at room temperature and higher are caused by clusters Mn_1+x Sb, the effective size of which is about 180–300 nm.     

Ionic conduction of Li<Subscript>8 − 2<Emphasis Type="Italic">x</Emphasis></Subscript>Mg<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>ZrO<Subscript>6</Subscript> solid solutions

A boundary of existence of solid solutions in the Li_8−2x Mg _x ZrO₆ system is found to be 7 mol % MgO. The transport properties of Li_{8 − 2x} Mg _x ZrO₆ solid solutions (the electronic component of total conductivity, the temperature and concentration dependences of conductivity and activation energy) are studied. It is supposed that, for Li₈ZrO₆ phase and solid solution based on it, an abrupt change of conductivity in the temperature range from 663 to 713 K is caused by the transition of electrolyte into the superionic state.     

Potassium–conducting K<Subscript>1 − 2<Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>GaO<Subscript>2</Subscript> solid electrolytes

Solid electrolytes with potassium-cation conductivity in the K_{1 − 2x} Pb _x GaO₂ system were synthesized and studied. It was found that solid solutions based on potassium monogallate are formed in a wide range of compositions. They contain vacancies in the potassium sublattice that provide for high conductivity of electrolytes. The relationship is considered between electric characteristics of solid electrolytes and the composition and structure of solid solutions. The results are compared to the earlier obtained data for similar solid electrolytes based on potassium monoaluminate and monoferrite.     

Synthesis of (Ni<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>P (0 ≤ <Emphasis Type="Italic">x</Emphasis> ≤ 0.65) substitution solid solution

The phosphides (Ni_{1 ? x} Co _x )₂P (0 ≤ x ≤ 0.65) crystallizing in the hexagonal system, space group P \(\bar 6\)2m, were synthesized in two steps starting from the continuous solid solution (Ni_{1 ? x} Co _x )₃(PO₄)₂ · 8H₂O. The initial phosphates were first completely dehydrated at 800°C and then reduced with hydrogen at 900–1000°C for 1–2 h.     

Sol-Gel Synthesis and Properties of Y<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Ba<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>FeO<Subscript>3</Subscript> Nanocrystals

The sol-gel method was used to prepare Y_1–xBa_xFeO₃ (x = 0, 0.05, 0.1, 0.15, 0.2) nanocrystals. The influence of the dopant content on the particle size and magnetic properties of yttrium ferrite was examined.     

Films of supersaturated Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>S solid solutions: Composition prognostication,chemical synthesis,microstructure

Working conditions and the concentration regions of the joint precipitation of PbS and CdS at which substitution solid solutions Cd _x Pb_1–x can be formed were determined by calculation of ionic equilibria in the citrate-ammonia reaction mixture at 298 and 353 K with consideration for the conversion fractions of lead and cadmium sulfides into the corresponding sulfides. The hydrochemical precipitation onto glass-ceramic substrates was used to obtain Cd _x Pb_1–x S (0 < x ≤ 0.149) solid solution films with thicknesses of 0.5 to 1.7 μm and high supersaturation with the substituting component. All the films crystallize to form the B1 structure. The phase and elemental compositions and morphological specific features of the films were studied. It was shown that the thickness of the deposited layers is most strongly affected by the process temperature, ammonium hydroxide concentration, and relative amounts of the metal salts in the reaction mixture. It was found that there are oxygen and chlorine in the Cd _x Pb_1–x S solid solutions, and the distribution of these elements across the layer thickness was determined, with the layer-by-layer distribution of chlorine having a pronounced oscillatory nature. It was shown that, as the chemical precipitation temperature is raised, the content of CdS in the substitution solid solutions grows exponentially. The activation energies Ea.ic of the lead and cadmium interchange in the PbS crystal lattice were found to be, depending on the initial concentration of the lead salt, 75.3, 42.8, and 22.2 kJ mol^–1.     

Potassium-conducting solid electrolytes in K<Subscript>1 − 2<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>GaO<Subscript>2</Subscript> system

New solid electrolytes with a high conductivity by K⁺ ions in the K_{1 − 2x} Sr _x GaO₂ system are synthesized and studied. It is found that the introduction of Sr²⁺ ions into potassium monogallate leads to the formation of solid solutions with KGaO₂ structure in a wide range of additive concentration. These solid solutions exhibit a high conductivity; the conductivity increases monotonically with increasing concentration of strontium within the single-phase range. The electrical characteristics are related to the electrolyte structure. The results are compared with the earlier data for the gallate solid electrolytes with the additives of four-charged cations and the systems based on potassium monoferrite and monoaluminate.     

Storage performance of LiFe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> nanoplates (<Emphasis Type="Italic">x </Emphasis>= 0, 0.5, and 1)

Although LiFePO₄ (LFP) is considered to be a potential cathode material for the lithium-ion batteries, its rate performance is significantly restricted by sluggish kinetics of electrons and lithium ions. Several attempts have been made so far to improve the performance of LiFePO₄ by reducing the grain size, doping with aliovalent atoms, and coating conductive materials such as carbon or RuO₂. We report here synthesis of LFP nanoplates by solvothermal method, tailoring the thickness as well as carbon coverage at surfaces to explore their influence on the storage performance. Due to the fact that Li⁺ ion diffuses along the b-axis, solvothermal method was aimed to control the thickness of nanoplates across the b-axis. We synthesized several nanoplates with various plate thicknesses along b-axis; among those, nanoplates of LFP with ～30-nm-thick b-axis having thin (2–5 nm) and uniform layer of carbon coating exhibits high storage capacity as well as high rate performances. Thus, a favorable morphology for LiFePO₄ has been achieved via solvothermal method for fast insertion/extraction of Li⁺ as compared to spherical nanoparticles of carbon-coated LFP. Galvanostatic cycling shows a capacity of 164?±?5 mAh g^?1 at 0.1 C rate, 100?±?5 mAh g^?1 at 10 C rate, and 46?±?5 mAh g^?1 at 30 C rate, with excellent capacity retention of up to 50 cycles. Further attempts have been made to synthesize LiMnPO₄ (LMP) as well as Li(Fe_1???x Mn _x )PO₄/C (x?=?0.5) nanoplates using solvothermal method. Although LiMnPO₄ does not exhibit high storage behavior comparable with that of LiFePO₄, the mixed systems have shown an impressive storage performance.     

Obtaining nanostructured films of PbSe<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>S<Subscript>1–<Emphasis Type="Italic">y</Emphasis></Subscript> solid solutions by chemical deposition

We propose a technique for wet-chemical codeposition of lead sulfide and selenide using thiourea and selenourea to form films of PbSe _y S_1–y substitutional solid solutions. The synthesized nanocrystalline layers with NaCl (B1) structure simultaneously contain both PbS-based and PbSe-based PbSe _y S_1–y solid solutions (0 < y < 0.9).     

Thermodynamic investigation of the systems <Emphasis Type="Italic">Ln</Emphasis>Se<Subscript>2</Subscript>–<Emphasis Type="Italic">Ln</Emphasis>Se<Subscript>1.5</Subscript> (<Emphasis Type="Italic">Ln</Emphasis> = La,Nd)

A detailed thermodynamic study of the systems LnSe₂–LnSe_1.5 (Ln = La, Nd) was performed by static method of vapour pressure measurement using quartz membrane-gauge manometers within the temperature range 713–1,395 K. The p _Se–T–x dependences obtained in this study have shown that the phase regions in composition intervals studied consist of discrete phases: LnSe_1.95 LnSe_1.90, LnSe_1.85, LnSe_1.80 (Ln = La, Nd). The enthalpies and the entropies for the stepwise dissociation process were calculated from the experimental data. The standard enthalpies of formation and the absolute entropies were estimated for the compounds investigated using literature data.     

Chemical etching of Cd<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te solid solution single crystals with iodine solutions in methanol

Chemical etching of Cd_{1 ? x} Mn _x Te (0.04 < x < 0.5) solid solution (ss) single crystals in I₂ + CH₃OH etching mixtures was studied. Concentration and kinetic curves of etching rates were plotted. As the manganese concentration of the solid solution increases, the rates of their etching by iodine-methanol etchants increase, too. The etchant compositions and chemical-dynamic polishing protocols for Cd_{1 ? x} Mn _x Te single crystals were optimized.     

Transport and structural properties of compounds (1 − <Emphasis Type="Italic">x</Emphasis>)CsHSO<Subscript>4</Subscript>-<Emphasis Type="Italic">x</Emphasis>KH<Subscript>2</Subscript>PO<Subscript>4</Subscript>

The homogeneous substitution of cations (K⁺) and anions (H₂PO₄⁻) for CsHSO₄ is performed. The dependences of protonic conductivity and structure of (1 − x)CsHSO₄-xKH₂PO₄ (x = 0.05–0.9) compounds on the composition are studied. It is found that the introduction of KH₂PO₄ leads to the formation of a new highly conductive phase. At small amounts of introduced KH₂PO₄ (x = 0.05), a mixed salt forms; its low-temperature conductivity is by more than two orders of magnitude higher than that of the source salts. The thermal behavior of mixed salt (1 − x)CsHSO₄-xKH₂PO₄ of various compositions and the peculiarities of crystal structure are studied. The structural parameters of the salt at x = 0.05–0.5 are close to those of Cs₃(HSO₄)₂(H₂PO₄). At higher x, another phase forms, whose structure has yet to be determined. The thermal stability of the salt decreases with increasing fraction of KH₂PO₄ introduced. The conductivity of the composites based on the mixed salt and silicon dioxide (1 − y){xKH₂PO₄-(1 − x)CsHSO₄}-ySiO₂ (x = 0.05, 0.1; y = 0.1–0.7) is studied. It is shown that, in the low-temperature range, the conductivity of composite systems increases within an order of magnitude, passes through a maximum, and, then, decreases at y > 0.5 due to the percolation effect.     

Resonant photoemission and absorption spectroscopy study of the Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ti<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>2</Subscript> electronic structure

Solid solutions of 1T-Cr _x Ti_1?x Se₂ (x = 0?0.83) were synthesized for the first time. To study the electronic structure of Cr _x Ti_1?x Se₂ monocrystals, photoemission spectra of core levels, resonance spectra of valence bands, and absorption spectra of Ti and Cr were obtained. Titanium and chromium atoms were found to have the oxidation state 4+ and 3+, which is supported by atomic multiplet calculations for Ti and Cr in the octahedral environment. According to calculation of the local density of chromium electronic states, the Cr3d electrons are spin-polarized, and the density of chromium states is of half-metal nature. The calculation agrees well with the experimental data.     

Transport and thermal characteristics of Cs<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Rb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript>

The transport and thermal properties of Cs_{1 − x} Rb _x H₂PO₄ in a wide range of compositions were studied. The binary salts Cs_{1 − x} Rb _x H₂PO₄ (x = 0–0.9) contain solid solutions with a structure of CsH₂PO₄. The binary salts were synthesized by mechanically mixing the starting components and growing crystals by isothermal evaporation from aqueous solutions. The properties of Cs_{1 − x} Rb _x H₂PO₄ salts obtained by different procedures were found to differ considerably. At higher rubidium contents in compounds obtained by mechanical mixing, the superionic transition temperature rose insignificantly, the high-temperature phase conductivity decreased twofold, the low-temperature conductivity increased within the limits of the order of magnitude, and the system of hydrogen bonds was slightly weakened. In Cs_{1 − x} Rb _x H₂PO₄ crystals grown from solutions, the temperature of the superionic transition decreased along with its slowing down, and the low-temperature conductivity increased by more than three orders of magnitude because of the higher contents of residual acid aqueous centers in the structure of the salt. These systems are characterized by increased thermal stability.     

Electric conductivity of heterovalent substitution solid solutions of the (1–<Emphasis Type="Italic">x</Emphasis>)PbF<Subscript>2</Subscript>–<Emphasis Type="Italic">x</Emphasis>YF<Subscript>3</Subscript>–SnF<Subscript>2</Subscript> system

Heterovalent substitution solid solutions of tetragonal modification isostructural with β-PbSnF₄ and having fluoride anions localized in three structurally nonequivalent positions are formed in the (1–x)PbF₂–xYF₃–SnF₂ system in the concentration range 0 < x ≤ 0.17. The conductivity of the synthesized samples is provided by the interstitial fluoride anions and is independent of the concentration of the heterovalent substituent at temperatures below 300 K. The contribution of the surface conductivity of the crystallites of the synthesized samples to the total bulk conductivity was not found. The temperature dependences of electric conductivity of each of the synthesized samples show an inflection at 435–475 K, which is due to the increased mobility of fluoride anions at elevated temperatures. The transport numbers of the fluoride anions are close to unity over the whole range of concentrations of the synthesized samples and are almost independent of the YF₃ concentration. The electronic conductivity of the samples was two orders of magnitude lower than the ionic conductivity.     

Effects of lutetium doping on the X-ray-excited luminescence properties of the tungstate Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Lu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>WO<Subscript>4</Subscript>

Polycrystalline samples in the lutetium-doped zinc tungstate system Zn_1?x Lu _x WO₄ with 0 ≤ x ≤ 0.08 were synthesized using the coprecipitation method followed by thermal treatment at 1000 °C during 4 h. The polycrystalline samples were characterized by X-ray diffraction analysis, scanning electron microscopy (SEM), infrared spectroscopy, and luminescence analysis under X-ray excitation. Rietveld analyses were performed. The variation of the wolframite structure cell parameters in the range 0 ≤ x ≤ 0.05 were congruent with substitution of Zn²⁺ by Lu³⁺. SEM micrographs of the obtained samples presented improved crystallization with morphology depending on the lutetium fraction. The luminescence spectra obtained under X-ray excitation (E < 40 keV) were in the blue–green region, and their intensity increased with x up to x = 0.05. The differences in the intensities of the X-ray luminescence spectra could be related to additional cation vacancies resulting from substitution of Zn²⁺ by Lu³⁺.     

Pressure-induced zircon to monazite phase transition in Y<Subscript>1–<Emphasis Type="Italic">х</Emphasis></Subscript>La<Subscript><Emphasis Type="Italic">х</Emphasis></Subscript>PO<Subscript>4</Subscript>: First-principles calculations

Density functional theory was used to study pressure-induced phase transitions of zircon to monazite in doped yttrium orthophosphate, Y_1–х La _х PO₄, for х = 0, 0.0625, 0.125. The pressures of the phase transition, the elastic moduli and the universal elastic anisotropy index were calculated. It was shown that with increasing lanthanum concentration in Y_1–x La _x PO₄, the transition pressure increases. According to the Birch–Murnaghan equation of state, this effect is associated with a decrease in the critical volume. The increased stability of the doped zircon phase compared to YPO₄ is attributed to the more significant increase in the anisotropy and distortions of REO₈ polyhedra and RE–O–P chains found for the optimized structures at critical volumes.     

<Emphasis Type="Italic">T</Emphasis>–<Emphasis Type="Italic">x</Emphasis>–<Emphasis Type="Italic">y</Emphasis> Diagram of MgO–SiO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> System: Microstructure Design

A computer model of the T–x–y diagram of MgO–SiO₂–Al₂O₃ system is used to show the possibility of analysis of its microstructure constitution in terms of competition between primary and eutectic crystals by means of vertical mass balance diagrams calculated for a given centroid over the whole temperature range. The usefulness of horizontal mass balance diagrams is considered for studying phase relations at a fixed temperature along the chosen isopleth. Mass balances were used to determine the crystallization path at the quasi-peritectic liquidus point with the invariant reaction L + Al₂O₃ = 3Al₂O₃ · 2SiO₂ + MgO · Al₂O₃, whose composition was taken into account in giving a rationale to corundum armor element technology.