The system copper-tellurium

The system copper-tellurium was investigated by DTA, DSC, and X-ray methods. A phase diagram with the phases Cu_2?xTe (33.5–36.2 mole% Te), Cu_3?xTe₂ (40–41 mole%), and CuTe was constructed. In the homogeneity ranges of the nonstoichiometric phases several superstructures were observed. The lattice parameters and d values of some of these phases are given.     

Influence of iron addition on the oxygen-deficient Sr0.85Bi0.15Co1−xFexO3−δ (0.0?x?1.0) perovskites

A series of oxygen-deficient Sr_0.85Bi_0.15Co_1−xFe_xO_3−δ (0.0?x?1.0) perovskite phases were prepared using solid-state reaction. Results of neutron powder diffraction analyses show that the introduction of Fe onto the B-site severely effects the long range coherence of the oxygen vacancy ordered, I4/mmm supercell, observed for the x=0.0 sample. For x=0.1 a smaller, a=b≈a_p, c≈2a_p, P4/mmm supercell gives the best agreement to the diffraction data, whilst phases in the range 0.2?x?0.6 adopt disordered cubic perovskite structures. Pseudo-cubic, a=b≈a_p, c≈a_p, structures are found for x?0.8. Evidence of weak superstructures, reflecting local oxygen ordering, is also obtained from electron diffraction. For all oxygen-annealed phases the average structure reverts to cubic Pm3¯m. The as-prepared samples show G-type antiferromagnetic order at room temperature. The oxygen annealed x=0.10, 0.25 and 1.0 samples display low-temperature spin-glass transitions.     

Pressure-induced phase transitions in mercury chalcogenides

Polymorphic transitions of HgSe_xTe_{(1 ? x)} induced by pressure were investigated for 0 <- x <- 1. The transitions were followed by both volume and resistivity measurements on samples of different alloy compositions and of different textures. The transition pressure seems to be a linear function of the alloy composition.     

Polytype phase transition in the series GaSe1−xSx

The structure of crystals GaSe_1?xS_x, grown by the iodine transport method, has been investigated with X-ray diffraction techniques. Between x = 0.2 and 0.3 a phase segregation has been found, which is indicative of the first-order nature of the ? to β polytype transitions, which occur in this composition region with increasing sulfur content.     

NMR, DTA, and impedance spectroscopy studies of ion mobility, phase transitions, and ionic conductivity in K1 − x (NH4) x SbF4 crystals

The ion mobility, phase transitions, and ionic conductivity in the crystal phases in the KF-NH₄F-SbF₃ system were studied by NMR, DTA, and impedance spectroscopy. An analysis of the ¹⁹F and ¹H NMR spectra showed how the character of ionic motions in the fluoride and proton sublattices changed with temperature. The types and temperature ranges of ionic motions were determined. Diffusion of the fluoride and partially ammonium ions was found to be the dominant form of ionic motion in the high-temperature modifications formed as a result of phase transitions. According to the electrophysical data, the high-temperature K_{1 ? x} (NH₄) _x SbF₄ phases (0.05 ≤ x ≤ 0.75) are superionic, their conductivity reaching ～10^?2–10^?3 S/cm at 450–500 K.     

Synthesis and study of cesium-containing phosphates with a β-tridymite structure

Complex phosphates CsMg_{1 ? x} M _x PO₄ (M = Mn, Co, Cu, Zn), containing cesium and metals in the oxidation state +2, have been synthesized, and their structure and thermal behavior have been studied. Continuous solid solutions (0 ?? x ?? 1) of the ??-tridymite structure type are formed in the CsMg_{1 ? x} Mn _x PO₄, CsMg_{1 ? x} Co _x PO₄, and CsMg_{1 ? x} Zn _x PO₄ systems, whereas limited solid solutions (0 ?? x ?? 0.4) are formed in the CsMg_{1 ? x} Cu _x PO₄ system. Based on DTA data, phase transitions have been revealed in the cobalt-, copper-, and zinc-containing phosphates, and the orthorhombic or monoclinic crystal system has been identified. Unit cell parameters of the solid solutions have been calculated. Thermal expansion of the CsMPO₄ phosphates has been studied.     

Photocatalytic hydrogen generation using glucose as electron donor over Pt/Cd x Zn1−x S solid solutions

Cd _x Zn_1?x S solid solution photocatalysts were prepared by a hydrothermal process. The photocatalysts were characterized by X-ray diffraction (XRD), UV–vis diffusive reflectance spectroscopy (DRS), and transmission electron microscope (TEM) measurements. Using glucose as an electron donor, photocatalytic hydrogen generation over Pt/Cd _x Zn_1?x S was investigated. The results show that glucose not only improves the efficiency of photocatalytic hydrogen generation but prevents photocorrosion of Cd _x Zn_1?x S. Glucose was degraded effectively with the hydrogen generation. The factors which affect photocatalytic hydrogen generation, such as composition and structure of Cd _x Zn_1?x S solid solutions, irradiation time, initial concentration of the glucose, and concentration of NaOH were studied.     

Phase relationships of the lithium halide spinels Li2MCl4-Li2MBr4 with M = Mn,Fe, Cd

The sections Li₂MCl_4?4xBr_4x of the quaternary systems LiCl-LiBr-MCl₂-MBr₂ with M = Mn, Cd, and Fe were studied by high-temperature X-ray diffraction patterns and DTA and DSC measurements. In the quasibinary lithium manganese halide system complete series of solid solutions exist between the inverse spinels Li₂MnCl₄ and Li₂MnBr₄. Li₂MnBr₄ and solid solutions with x > 0.54 undergo phase transitions to tetragonal spinels at lower temperatures. In the nonquasibinary system with M = Cd, only at temperatures near 400°C a complete series of mixed crystals is formed. At lower temperatures the system is mainly two-phase with rock salt-type Li_1?yCd_0.5yCl_1?xBr_x and cadmium chloride-type Cd_1?yLi_2yCl_2?2xBr_2x solid solutions in equilibrium. The lithium iron halide system is similar to that of cadmium, but spinel-type Li₂FeBr₄ does not exist at any temperature. The manganese and cadmium halide spinels and spinel solid solutions undergo phase transitions to NaCl defect structures at elevated temperatures.     

Effect of mechanical activation on the hydrogen reduction kinetics of magnetite concentrate

The combined thermal analysis techniques thermal expansion: and differential scanning calorimetry were used to characterize various phase transitions that exist in the solid solutions of PbZr_1?xSn_xO₃. Using thermodynamic quantities, i.e., thermal expansion and specific heat to distinguish first-order transitions from second-order ones, we demonstrate that some perovskite antiferroelectrics can exhibit continuous transition at their Curie temperature T _C. We observed such a transition in antiferroelectric crystals of solid solutions based on PbZrO₃. Although pure PbZrO₃ is a classical example of antiferroelectric crystal with a first-order transition at T _C, the solid solutions of PbZr_1?xSn_xO₃ in the range of composition of x > 0.25 seem to exhibit a second-order phase transition.     

Magnetic susceptibility and the spin-glass transition of Cd1−xMnxS and Zn1−xMnxS at low temperatures

Low-field magnetic susceptibility of the diluted magnetic semiconductors Cd_1?xMn_xS and Zn_1?xMn_xS was measured between 4.2 and 30 K for the Mn concentration range 0.25 < x < 0.40. When x > 0.25, both of these ternary systems show a spin-glass transition in the above temperature range, as evidenced by a somewhat rounded cusp in the susceptibility and by the presence of irreversible effects. Because these materials are insulators at low temperatures, and the interactions between the Mn ions are only antiferromagnetic, the observed spin-glass behavior is attributed to frustration inherent in the hcp lattices of these compounds. The phase diagrams for the boundary of the paramagnetic and the spin-glass phases are presented for the two alloy systems, and the difference between the two phase diagrams is discussed.     

Phase transitions and electroconducting properties of BIMEVOX solid electrolytes

Ceramic solid solutions Bi₄ (V_{1 ? x} Me _x )₂O_{11 ? y} (x= 0?0.3, Me = Zr, Ga, Fe) were obtained by solid-state synthesis. The homogeneity regions, x ≤ 0.3 for Me = Ga, Fe and x ≤ 0.15 for Me = Zr, were established. Structure parameters, microstructure, and the thermal, dielectric, and conducting properties of the samples were studied. The concentration and temperature ranges of the existence of different polymorphs and the concentration ranges x over which the high-conductivity phase was stable at ～20°C were established. Using DTA, DSC, and dielectric spectroscopy, the α?β and β?γ phase transitions were revealed. It was found that the electrical conductivity of the solid solutions decreased as x increased.     

Eu+2 fluorescence in BaCl2

The Ba_1?xEu_xCl₂ system was studied over wide ranges of x, particularly regarding the fluorescent emission of Eu²⁺. In addition to the commonly observed 5d → 4f band emission sharp line, f → f transitions were observed. Single crystals of Eu²⁺ containing BaCl₂ were grown via the Czochralski technique and many of the optical properties, such as transmission, fluorescence, and excitation, were measured. X-ray and thermal parameters for the Ba_1?xEu_xCl₂ system are also reported.     

Étude experimentale et théorique de la polarisation des PZT durs dopes au niobium

This paper deals with phase transitions of niobium-doped PZT ceramics. Phase diagrams of PbZr_1?xTi_xO₃ + yNb₂O₅ for x = 0,035 and 0,045 with 0 < y < 0,01 are given. An apparatus for remnent polarization measurement is described and experimental conditions are specified. Experimental results are interpreted with the help of a modified molecular field theory in which the molecular field coefficient is supposed to be a function of electric polarization. A discussion on phase transition order and on the theory validity is undertaken.     

Electronic structure and molecular properties of [Re6−x Os x Se8Cl6](4−x)− (x = 0–3) clusters: A study based on time-dependent density functional theory including spin-orbit and solvent effects

Relativistic time-dependent density functional (TDDFT) calculations including spin-orbit interactions via the zero order regular approximation (ZORA) and solvent effects are carried out on the [Re_6?x Os _x Se₈Cl₆]^(4?x)? (x = 0–3) cluster. These calculations indicate that the lowest energy electronic transitions of the MMCT and LMCT type are similar to those observed in strongly luminescent 24-electron hexanuclear rhenium chalcogenide clusters [Re₆Se₈Cl₆]^4?. Thus our calculations predict that [Re_6?x Os _x Se₈Cl₆]^(4?x)? (x = 0–3) clusters could be luminescent.     

Cesium-cation conduction in the systems Cs3−x P1−x E x O4 (E = S, Cr, Mo, W)

Solid solutions on the basis of cesium orthophosphate in the Cs_3?x P_1?x E _x O₄ (E = S, Cr, Mo, W) systems are synthesized. The temperature and concentration dependences of the systems’ electroconductivity are studied. The cesium-cation character of conduction in the systems is confirmed. Factors that bear upon the transport properties of the synthesized phases are analyzed.     

Interstitial superstructures in the TaD system

Ordered deuterium arrangements and order-disorder transformations of the tantalum deuterides in the range TaD_0.50TaD_0.78 have been studied by neutron diffraction and calorimetry at temperatures between ?170 and 120°C. In addition to the disordered phase (α), three ordered phases based on the superstructures Ta₂D_1+x (β₁), Ta₄D₃, (γ), and TaD (δ) are clarified. The Ta₂D_1+x structure is a nonstoichiometric from of the Ta₂D superstructure over the rangex < 0.5. The γ-phase is formed below ?70°C near Ta₄D₃, and transforms into theβ₁and δ-phases, respectively, in the hypo and hyperstoichiometric compositions. The δ-phase that exists beyond TaD_0.75 changes to the disordered α-phase around 100°C.     

Defect structure of anion-excess fluorite-related Ca1−xYxF2+x solid solutions

On the basis of the transformation of a cube within a fluorite-type matrix into an archimedean antiprism of the kind found in numerous ordered anion-excess fluorite-related superstructures, a new polyhedral cluster, labeled 4:4:3, [according to B. T. M. Willis, Proc. Br. Ceram. Soc.1, 9 (1964) and A. K. Cheetham, B. E. F. Fender, and M. J. Cooper, J. Phys. C4, 3107 (1971)], is proposed to explain the defect structure and short-range order in Ca_1?xY_xF_2+x solid solution. In agreement with the spectroscopic, dielectric, and electric experiments, this new structural model fits perfectly well the measured occupation numbers for normal F and interstitial F′ and F″ fluorine atoms for the whole range of compositions without requiring the too short F′F′ distances generated by the previously proposed 2:2:2 or 3:4:2 clusters. Such 4:4:3 clusters and nearly identical 4:4:4 or 4:4:5 ones, are probably present in the other highly and moderately doped Ca_1?xLn_xF_2+x solid solutions; they could be precursors for the largest clusters, i.e., ordered microdomains, observed for samples annealed for a long time.     

Synthesis of Ba(V1−xTix)S3 (0 ≦ x ≦ 1.0) compounds and their structural transitions

The two-layer hexagonal perovskites Ba(V_1?xTi_x)S₃ (0 ≦ x ≦ 1.0) are prepared in a H₂S stream. A in a H₂S stream. A structural phase transition from a hexagonal to an orthorhombic form takes place for the powder samples with 0 ≦ x ≦ 0.4 and their transition temperatures are determined to be 250 K for x = 0, 240 K for x = 0.1, 222 K for x = 0.2, 195 K for x = 0.3, and 160 K for x = 0.4, respectively. The phase transformation does not occur down to 90 K for the materials above x = 0.5.     

Composition-induced structural phase transitions in the (Ba1−xLax)2In2O5+x (0?x?0.6) system

Composition-induced structural phase changes across the high temperature, fast oxide ion conducting (Ba_1−xLa_x)₂In₂O_5+x, 0?x?0.6, system have been carefully analysed using hard mode infrared (IR) powder absorption spectroscopy, X-ray powder diffraction and electron diffraction. An orthorhombic brownmillerite to three-dimensionally disordered cubic perovskite phase transition in this system is signalled by a drastic change in slope of both wavenumber and average line widths of IR spectra as a function of composition. Some evidence is found for the existence of an intermediate tetragonal phase (previously reported to exist from electron diffraction data) around x∼0.2. The new spectroscopic data have been used to compare microscopic and macroscopic strain parameters arising from variation in composition. The strain and spectroscopic data are consistent with first-order character for the tetragonal→orthorhombic transition, while the cubic→tetragonal transition could be continuous. Differences between the variation with composition of spectral parameters and of macroscopic strain parameters are consistent with a substantial order/disorder component for the transitions. There is also evidence for precursor effects within the cubic structure before symmetry is broken.     

New strategy for band-gap tuning in semiconductor nanocrystals

In the last decade, the main efforts have focused on the preparation of different sized binary II–VI group semiconductor nanocrystals to obtain different color-emitting luminescence. However, the tuning of physical and chemical properties by changing the particle size could cause problems in many applications, in particular if unstable small particles are used. Recent advances have led to the exploration of tunable optical properties by changing their constituent stoichiometries in ternary alloy nanocrystals. High-quality Zn _x Cd_1?x Se alloy nanocrystals have been successfully prepared at high temperature by incorporating stoichiometric amounts of Zn and Se into pre-prepared CdSe nanocrystals or embryonic CdSe nuclei. With increasing Zn content, a composition-tunable emission across the whole visible spectrum has been demonstrated by a systematic blue-shift in emission wavelength. High-quality alloy Zn _x Cd_1?x S nanocrystals have been obtained by the conucleation and co-growth of the constituents through the reaction of a mixture of CdO- and ZnO-oleic acid complexes with sulfur at elevated temperatures. The obtained Zn _x Cd_1?x S alloy nanocrystals possess superior optical properties with photoluminescence quantum yields of 25–50%, especially the extremely narrow emission spectral width (fwhm=14 nm).