EPR study of V2O5–P2O5–Li2O glass system

glass system, with 0 < x 50 mol%, was prepared and investigated by EPR method. For low content of V₂O₅ all the spectra present a hyperfine structure typical for isolated V⁴⁺ ions. With the increasing of V₂O₅ content, the EPR absorption signal showing hyperfine structure is superposed by a broad line without hyperfine structure characteristic for clustered ions. At high V₂O₅ content, the vanadium hyperfine structure disappears and only the broad line can be observed in the spectra. Spin Hamiltonian parameters g , g , A , A , dipolar hyperfine coupling parameters, P, and Fermi contact interaction parameters, K, have been calculated.The composition dependence of line widths of the first two absorptions from the parallel band and of the broad line characteristic to the cluster formations was also discussed.     

Thermoelectric properties of GdBaCo2−x Fe x O5+δ ceramics

The influence of Fe doping on the lattice structure and thermoelectric properties of GdBaCo_2?x Fe _x O_5+δ (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) ceramics was studied from room temperature to 525 K. The results show that presence of Fe will increase both electrical resistivity and Seebeck coefficients of the samples. Due to the lattice misfit and carrier concentration reduction caused by Fe, the thermal conductivity of the sample decreases. The activation energy of conductivity is larger than that of thermopower calculated in the semiconductive region, which means that the conduction mechanism may be determined as a small polaron hopping model. The optimum Fe doping amount is x = 0.6, which results in a ZT value 0.02 at 373 K.     

Investigation of the lithium-rich boundary of the Li1+x Mn2−x O4 cubic spinel phase in air

Several compositions of the cubic spinel Li_1+x Mn_2?x O_4?δ phase in the lithium–manganese–oxygen (Li–Mn–O) system were synthesized at 700, 750, and 800 °C in air ( $ p_{{{\text{O}}_{2} }} $  = 0.2 atm) to investigate the Li-rich boundary of the cubic spinel phase at these temperatures. The lattice parameters of the several compositions were determined by Rietveld analysis of the measured X-ray patterns, and the Li and Mn contents of the samples were measured using inductively coupled plasma with optical emission spectroscopy (ICP-OES). A Vegard-like dependence of the measured lattice parameter of the cubic spinel phase with Li to Mn ratio exists in the homogeneity range of the cubic spinel. This dependence could be used to derive the boundary of the single phase cubic spinel field in the Li–Mn–O system at 700 and 750 °C at $ p_{{{\text{O}}_{2} }} $  = 0.2 atm and to estimate the Li-rich boundary at 800 °C. The results of the present study are compared with two other experimental studies on the homogeneity range of the cubic spinel phase in an attempt to resolve the contradiction between these two studies.     

Ionic conductivity of Li x Na1 − x Ta y Nb1 − y O3 solid solutions

Experimental data demonstrate that Li _x Na_{1 ? y} Ta _y Nb_{1 ? y} O₃ (y ≠ 0) ferroelectric solid solutions near special concentration points (x = 0.125 and 0.25), which have increased degrees of short- and long-range order, undergo a superionic transition. In the Raman spectra of Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, the superionic transition shows up as a predominant “melting” of the alkali metal sublattice and broadening of the corresponding lines into a Rayleigh line wing, whereas the other sublattices in the structure remain relatively “rigid.” The temperature of the superionic transition can be tuned by varying the degree of static disorder of structural units in the Nb⁵⁺/Ta⁵⁺ sublattice.     

The nonstoichiometry and physical properties of the Nd1−x Ca1+x FeO4−y system

The solid solutions of the Nd_1–x Ca_1+x FeO_4–y system for compositions ofx=0.000,0.125, 0.250,0.375, and 0.500 are prepared by drip pyrolysis. XRD analysis shows all the solid solutions are tetragonal I_4/mmm. The Fe⁴⁺ ratio to the total Fe ions or value has a maximum for the compositionx=0.375. From the X-ray powder diffraction analysis and the Mössbauer spectroscopy, the distortion and symmetry change of oxygen octahedra of Fe ions are observed. The structural change of oxygen octahedra of Fe ions strongly affects the physical properties. The solid solution whenx=0.000 shows a weak ferromagnetic behaviour due to the spin canting of the distorted octahedra. The other solid solutions withx=0.125, 0.250, 0.375, and 0.500 show a paramagnetic behaviour over room temperature. The decrease of the magnetic transition temperature is due to the distortion of oxygen octahedra of Fe ions and the existence of the Fe⁴⁺ ion. The formation site of oxygen vacancies plays an important role in the conductivity of the Nd_1–x Ca_1+x FeO_4–y system. Although the oxygen vacancies in [Nd, Ca]-O layer have little effect on conductivity, the oxygen vacancies in the FeO₂ plane of the perovskite layer act as electron trapping sites and thus increase the activation energy.     

Thermodynamic properties of Ca1 − x Er x F2 + x and Ca1 − x Yb x F2 + x heterovalent solid solutions

The heat capacity of single crystals of the Ca_{1 ? x} Er _x F_{2 + x} (x = 0.05, 0.10) and Ca_0.95Yb_0.05F_2.05 fluorite solid solutions was determined by adiabatic calorimetry in the temperature range 55–300 K. The results were used to obtain temperature dependences of the Debye characteristic temperature, entropy, and enthalpy for the solid solutions.     

Crystal structure and magnetic properties of Sr1 − x Sm x Fe12 − x Co x O19 solid solutions

Sr_{1 ? x} Sm _x Fe_{12 ? x} Co _x O₁₉ (0 ≤ x ≤ 0.5) ferrites have been prepared by solid-state reactions in air at 1470 K using mixtures of samarium oxide, ferric oxide, Co₃O₄, and strontium carbonate. X-ray diffraction characterization showed that the samples with x < 0.2 were single-phase, whereas the samples with 0.2 ≤ x ≤ 0.5 contained α-Fe₂O₃ and those with 0.3 ≤ x ≤ 0.5 contained SmFeO₃, CoFe₂O₄, and Sm₂O₃ as well. The highest degree of Sm³⁺ and Co²⁺ substitutions for Sr²⁺ and Fe³⁺ (x) in the SrFe₁₂O₁₉ ferrite at 1470 K was determined to be slightly less than 0.2. This substitution only slightly decreases the a and c parameters of the hexagonal lattice and the Curie temperature (T _C) of the material. At temperatures of 5 and 300 K in magnetic fields of up to 14 T, we obtained magnetic hysteresis loops, which were used to evaluate the spontaneous magnetization (σ₀), specific saturation magnetization (σ_s), and coercive force (_σ H _c) of the ferrites. The experimentally determined 5-K spontaneous magnetization per formula unit (n ₀) of the x = 0.1 ferrite is 20.86μ_B, which coincides with the theoretical value calculated as n ₀ = (8 × 5) ? (3.9 × 5 ? 0.1 × 3) = 20.8μ_B. At 300 K, the n ₀ and _σ H _c of Sr_0.9Sm_0.1Fe_11.9Co_0.1O₁₉ exceed those of SrFe₁₂O₁₉ by 7.7 and 9.9%, respectively.     

Superconducting and normal state properties of Li1+x Ti2−x O4 spinel compounds. II. Low-temperature heat capacity

Heat capacity data are reported which confirm as a bulk effect the previously reported superconductivity in LiTi ₂ O ₄ . These data also establish LiTi₂O₄ as a weak couplingd-band superconductor with superconducting state properties well described by the Bardeen—Cooper—Schrieffer theory of superconductivity. The properties of LiTi ₂ O ₄ are compared with those of other superconducting spinel compounds, and the composition dependence ofT _c for Li _1+x Ti _2–x O ₄ is discussed. The disappearance of superconductivity forx0.1 was found to be correlated with a rapid decrease in the normal-state linear heat capacity coefficient.Research sponsored by the U.S. Energy Research and Development Administration under Contract No. ERDA E(04-3)-34 PA227.Research sponsored by the Air Force Office of Scientific Research, Air Force Systems Command, USAF, under AFOSR Contract Number AFOSR/F-44620-72-C-0017.     

Cation mobility in Li1 + x Hf2 − x Sc x (PO4)3 NASICON-type phosphates

Li_{1 + x} Hf_{2 ? x} Sc _x (PO₄)₃ (x = 0–0.3) NASICON-type mixed phosphates have been synthesized and characterized by X-ray diffraction, nuclear magnetic resonance, and impedance spectroscopy. The results demonstrate that the materials with 0 ≤ x ≤ 0.1 have a hexagonal structure, whereas in the range 0.1 < x ≤ 0.2 the materials consist of a mixture of hexagonal and orthorhombic phases. The x = 0.3 material has an orthorhombic NASICON structure. Doping with scandium leads to an increase in ionic conductivity in the range 0 < x ≤ 0.1.     

Composition range and physicochemical properties of La1 − x Ba x Mn1 − y Fe y O3 solid solutions

We have determined the extent of La_{1 ? x} Ba _x Mn_{1 ? y} Fe _y O₃ solid solutions with orthorhombically and rhombohedrally distorted perovskite structures. A partial phase diagram of the LaMnO_{3 + δ}-BaMnO₃-BaFeO_2.5-LaFeO₃ system in air at a temperature of 1373 K has been proposed for the first time. We have measured the relative length change of La_{1 ? x} Ba _x Mn_{1 ? y} Fe _y O₃ samples and calculated their thermal expansion coefficients.     

Investigation of Cs(H2PO4)1 − x (HSO4) x (x = 0.15–0.3) superprotonic phase stability

A detailed investigation of the highly conductive Cs(H₂PO₄)_1?x (HSO₄) _x (x = 0.15–0.3) proton electrolyte, its structural properties, and ageing behavior was carried out using X-ray diffraction, DSC, and impedance and NMR spectroscopy. The high conductivity of electrolytes (～2 × 10^?2 S/cm) remains stable during long-term ageing at 180–200°C due to stabilization of the high temperature phase to lower temperatures. The room temperature ¹H MAS NMR spectrum of (CsH₂PO₄)_1?x (CsHSO₄) _x demonstrates the predominantly highly mobile protons present in these materials with the residual low-mobile protons, which agrees with the XRD data. According to XRD and ¹H NMR data, the cubic phase of Cs(H₂PO₄)_{1 ? x} (HSO₄) _x (x = 0.15–0.3) that stabilizes at room temperature gradually transforms to a low-temperature monoclinic one. The kinetics of the phase transformation for mixed salt depends markedly on the relative air humidity. A possible stabilization mechanism of the Cs(H₂PO₄)_{1 ? x} (HSO₄) _x superionic phase with high proton mobility at low temperatures is discussed.     

Synthesis of Li x Na1 − x Ta y Nb1 − y O3 and LiTa y Nb1 − y O3 perovskite and pseudoilmenite solid solutions

This paper compares the solid-state reactions underlying the synthesis of LiTa _y Nb_{1 ? y} O₃ and Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions with the use of Ta_2y Nb_{2(1 ? y)}O₅ niobium tantalum pentoxides and a mechanical mixture of the Ta₂O₅ and Nb₂O₅ pentoxides. Our results demonstrate that the synthesis with the use of Ta_2y Nb_{2(1 ? y)}O₅ allows phase-pure solid solutions to be obtained at substantially lower temperatures in comparison with a mechanical mixture of Ta₂O₅ and Nb₂O₅.     

Tunneling Conductance of Ba1−x K x Fe2As2–GaAs Junction

We carried out point contact tunneling measurements by simply contacting degenerate GaAs semiconductor to polycrystalline Ba_1−x K _x Fe₂As₂ with T _c=31.1±1.0 K. The gap related structure was easily obtained. The gap value 2Δ determined from peak-to-peak voltage was 18.0 meV, and 2Δ/k _B T _c was 6.8. Small structures were observed at V∼±23 mV in the conductance curve separately from the gap edge structure. These values are included in phonon energy region and correspond to a peak of phonon density of states. Thus, the structures are attributed to phonon structure. We calculated d² I/dV ² and T _c, Δ in using Eliashberg equations by assuming α ² F(ω) from neutron phonon spectrum. The first phonon structure in calculated d² I/dV ² is comparable to experimental one.     

Decomposition of (Sn2xFe1−xSb1−x)O4 solid solutions with x≤0.50

Thermal stabilities of the rutile-type (Sn_2xFe_1−xSb_1−x)O₄ solid solutions with x≤0.5 were investigated by TG–DTA in flowing O₂ up to 1673 K. After thermal analysis the samples were characterised by means of powder X-ray diffraction analysis (XRD), optical and scanning electron microscopy (SEM) observation and electron dispersive spectrometry (EDS) analysis. The decomposition of the solid solution involves the formation of hematite and a volatile Sb oxide, probably Sb₄O₆. The decomposition temperature increases with the Sn content of the solid solution.     

Investigation of the functional properties of Mg x Ni1−x Fe2O4 ceramics

The paper presents a complex study of the effect of Mg substitution on the functional properties of Ni-ferrite ceramics prepared by self-combustion sol–gel method. The sintered ceramics have pure cubic spinel structures with an increase of the lattice parameter and the grain size with Mg content. The electrical properties of Mg _x Ni_1?x Fe₂O₄ (x = 0; 0.17; 0.34; 0.5; 0.66; 1) ceramics have been investigated. The complex impedance spectra suggest a grain boundary contribution in the conduction process and reveal that the real part of impedance and the imaginary component (reactance) increase with increasing the Mg amount. The temperature dependence of dielectric properties shows that the hopping of charge carriers is thermally activated. The resistivity as a function of frequency for different degree of humidity was also investigated. All the investigated samples show a typical ferrimagnetic character with a strong non-linearity, small coercitive field (~50 Oe) and a saturation field of ~1kOe, typical to the investigated Mg _x Ni_1?x Fe₂O₄ ceramics. The Curie temperature determined from magnetic susceptibility versus temperature dependences presents a decrease with the addition of non-magnetic Mg²⁺ ion concentration from 603 °C (for x = 0) to 384 °C (for x = 1).