Static bismuth disorder in Bi2−x(CrTa)O7−y

The crystal structure of the pyrochlore Bi_2−x(CrTa)O_7−y has been refined by the Rietveld method from powder neutron and synchrotron X-ray diffraction data. Using the ideal pyrochlore structural model, anomalously high atomic displacement parameters (APD), which could not be satisfactorily explained with anisotropic ADP, of both Bi and O′ sites were observed. The structure was successfully refined with a model that incorporated static displacive disorder of both the Bi and O′ atoms. Using this model physically reasonable ADP parameters for both the Bi and O′ atoms, and improvement in the various measure of fit were obtained. The underbonding of the Bi atoms, observed in ideal pyrochlore model, but removed in the disordered structure, is believed to be the main driving force for this disorder.     

Photoconductivity in single crystals of (TlGaSe2)1−x(TlInS2)x alloys (0−0.45 ≤ x ≤0.55-1)

The spectral distribution of the photoconductivity in (TlGaSe₂)_1−x(TlInS₂)_x single crystals has been studied at 77 K and 300 K. At O ≤ x ≤ 4, Eg is observed to vary linearly with x. Eg(x) deviates from linearity at x = 0.6. This deviation is attributed to the effect of disorder in the composition. Over the range 0.6 to 2.2 eV pronounced impurity photoconductivity is detected at 77 K and 300 K. Deep impurity levels and their neighbourhood in this alloy are established to preserve their positions with the variation in the composition. The analysis of the obtained results indicates that the impurity centres are mainly connected with the cation neighbourhood.     

Superstructures exhibited by oxides of the aurivillius family, (Bi2O2)2+ (An−1BnO3n+1)2−

Bi₅Ti₃FeO₁₅ and Bi₇Ti₃Fe₃O₂₁ which are n=4 and n=6 members of the family of oxides of the general formula (Bi₂O₂)²⁺(A_n−1B_nO_3n+1)²⁻ show unusual superstructures, possibly due to cation ordering.     

Critical thermistors based on VnO2n−1 (n=3−6)

New types of critical thermistors are proposed, based on V₃O₅, V₄O₇, V₅O₉, and V₆O₁₁. It is shown that they can be prepared from Magnelli-phase single crystals, which do not decompose during the phase change. Volt-ampere characteristics and switching voltage-temperature curves were obtained.     

Phase diagram and some properties of Cu2−xSe(2.01≥2−x≥1.75)

The temperatures of phase transformation from low-temperature -phase to high-temperature -phase were measured for copper selenide Cu_2–x Se in the composition range 2.012–x1.75. The -phase was found to be unstable in air, and further experiments should be performed in a good vacuum. The phase diagram of Cu_2–x Se was redetermined by the X-ray parametric method and the possible reasons why the phase diagrams reported by several authors do not coincide with each other are discussed.     

Ionic conductivity in the ternary system (ZrO2)1−0.08x−0.12y–(Y2O3)0.08x–(CaO)0.12y

The total electrical conductivity of the samples in the ternarysystem (ZrO₂)_{1-0.08x-0.12y} –(Y₂O₃)_0.08x –(CaO)_0.12y was measured by adirect current four-probe method in the temperature range 773 to1673 K. It was found that partial replacement of Y₂O₃ by CaO in thesystem ZrO₂–Y₂O₃ may enhance the electrical conductivity at highertemperatures. At lower temperatures, however, doping CaO as the thirdcomponent into the system ZrO₂–Y₂O₃ depresses the conductivity. Theobserved mixed dopant effect was then analyzed by considering thecombined effect of both parameters appeared in the traditionalArrhenius equation, the activation energy, E, and the preexponentialfactor, ₀, on the temperature-dependence of the measured conductivity.     

Growth of perfect-crystal Si-Si1−x Gex-(Ge2)1−x (InP)x structures from the liquid phase

Structures comprising Si-Si_1−x Ge_x-(Ge₂)_1−x (InP)_x with an intermediate Si_1−x Ge_x buffer layer were grown on silicon substrates. Morphological examinations, scanning patterns and diffraction spectra, and also the electrophysical and luminescence properties of the heterostructures were used to show that the crystal perfection of these structures depends on the choice of liquid-phase epitaxy conditions. Pis’ma Zh. Tekh. Fiz. 25, 37–40 (December 26, 1999)     

The orthorhombic-to-tetragonal phase transition in YBa2(Cu1−xFex)3O7−y

The phase transition YBa₂(Cu_1–x Fe _x )₃O_7–y (0x0.05) prepared through solid-state reaction was studied with X-ray diffraction analysis and optical microscope. It was found that the orthorhombic-to-tetragonal phase change was induced between x=0.02 and x=0.03 by X-ray diffraction. The phase transition was also identified by the disappearance of striations in plate-like grains under polarized light. The microstructures of the specimens with compositions of x=0.01 and x=0.02 showed faint striation images. It is considered that a mixture of the orthorhombic and tetragonal phase exists in these compositions.     

Hole distribution in La2−xSrxCu1−yZn(Ni)yO4 (x ⩽ 1/8)

Simulation with interacting-potentials has been performed to investigate hole distribution in La_2−xSr_xCu_1−yZn(Ni)_yO₄ (y = 1/32 and x ⩽ 1/8). It is found that the orderly distributed hole configurations are more energetically favorable than the randomly distributed hole configurations. Moreover, the doped Zn²⁺ and Ni²⁺ ions can both act as stabilizing centers to localize the holes in their vicinity leading to an atomic-scale inhomogeneous distribution of holes. This atomic-scale inhomogeneities of holes obtained from our simulation is similar to that predicted by the “Swiss Cheese” model.     

Mixtures of (N2)1−x : (O2) x at High Pressures and Low Temperatures

We performed Raman measurements at 18 K and pressures up to 25 GPa in order to construct a tentative phase diagram of the (N ₂)_1–x :(O ₂)_x –system at low temperatures. We varied the composition of the mixed system over the whole concentration range. Here we focused on the systems with high nitrogen concentration and pressures above 2 GPa. It is known that at room temperature oxygen is highly solvable in the –phase of N ₂. The experimental results show that oxygen suppresses the disorder–order transition –N ₂.     

Synthesis and properties of LiZr2(AsO4)3 and LiZr2(AsO4) x (PO4)3 − x

The LiZr₂(AsO₄)₃ arsenate and LiZr₂(AsO₄) _x (PO₄)_{3 ? x} solid solutions have been prepared through precipitation followed by heat treatment, and characterized by X-ray diffraction, X-ray structure analysis, IR spectroscopy, and impedance spectroscopy. We have established conditions for the crystallization of the arsenate and a continuous series of arsenate phosphate solid solutions (0 ≤ x ≤ 3), which have been obtained as two polymorphs: monoclinic and hexagonal. Using the Rietveld method, we have refined the crystal structures of the polymorphs of LiZr₂(AsO₄)₃ (sp. gr. P2₁/n, a = 9.1064(2), b = 9.1906(2), c = 12.7269(3) Å, β = 90.844(2)°, V =1065.03(5) ų, Z = 4; sp. gr. R $\bar 3$ c, a = 9.1600(4), c = 22.9059(13) Å, V = 1664.44(14) Å, Z = 6) and LiZr₂(AsO₄)_1.5(PO₄)_1.5. Their structural frameworks are built up of AsO₄ tetrahedra—or (As,P)O₄ tetrahedra occupied by arsenic and phosphorus atoms at random—and ZrO₆ octahedra, with the lithium atoms in between. The ionic conductivity of the materials has been measured. The cation conductivity of monoclinic LiZr₂(AsO₄) _x (PO₄)_{3 ? x} with 0 ≤ x ≤ 1 has been shown to exceed the conductivity of lithium zirconium phosphate.     

Synthesis and Para-conductivity Analyses of TlBa2(Ca 3 − y Mg y )Cu4 O 1 2 − δ Superconductors

TlBa ₂(Ca _3?yMg _y)Cu ₄ O _12?δ (y=0,0.5,1.0, 1.5,2) superconductors are synthesized at normal pressure, and the influence of doped Mg atoms on the superconductivity parameters at the microscopic level is investigated by carrying out para-conductivity analyses of conductivity data. The samples have shown tetragonal structure, and the unit cell volume decreases with increased Mg doping. The onset temperature of superconductivity [ T _c(onset)] and zero resistivity critical temperature [ T _c(R=0)] decreases with Mg. Maximum magnitude of diamagnetism is observed in the samples with Mg of y=2. The apical oxygen mode of the type Tl-O _A-Cu(2) and CuO ₂ planar oxygen modes are softened as observed in fourier transform infrared spectrometer (FTIR) absorption measurements. The fluctuation-induced conductivity (FIC) analyses of conductivity data have shown the enhancement of inter-plane coupling and coherence length along the c-axis. These analyses have shown an increase in the coherence length along the c-axis and the inter-layer coupling J. The enhancement of inter-plane may possibly be arising due to a small decrease in the value of the order parameter of the carriers from ∣ψ∣ ²=1 in the CuO ₂ planes in Mg-doped samples. The values of B _c0(T), B _c1(T), J _c(0) are suppressed with the increased incorporation of Mg, which most likely arises due to the weak coupling of the grains induced by Mg doping.     

Magneto-resistance and Excess Conductivity Studies of Tl(Ba2−y Mg y )Ca 2 Cu 3 O 10−δ Samples

The flux pinning characteristics of T l(B a _2?y M g _y )C a ₂ C u ₃ O _10?δ(0.0≤y≤ 1.5) samples have been studied under the influence of various dc magnetic fields in the light of thermally activated flux flow model. It was observed form the magneto resistivity measurements that the activation energy U has been increased in the sample with Mg incorporation of y=0.5, however, it is decreased in the samples with higher Mg doping. This shows that lower Mg doping concentration promotes enhancement, whereas its higher concentration suppresses the flux pinning characteristics of Tl(Ba _2?yMg _y )Ca ₂Cu ₃ O _10?δ (0.0 ≤y≤1.5) samples. The excess conductivity analysis of Tl(Ba _2?yMg _y )Ca ₂Cu ₃ O _10?δ (0.0 ≤ y ≤ 1.5) samples has shown that the coherence length along the c-axis ξ _c(0), the interlayer coupling J, the phase relaxation time of the carriers τ _? , and the Fermi velocity v _F of the carriers are suppressed with Mg doping. However, the values of B _c0(T), B _c1(T), and J _c(0) are enhanced which complement the magnetoresistivity analysis. These results showed that the flux pinning characteristics are enhanced for lower doping concentration of Mg at the charge reservoir layer sites.     

Ti−6Mo−5V−3Al−2Fe−2Zr合金热变形行为及热加工图

目的 建立近β钛合金Ti−6Mo−5V−3Al−2Fe−2Zr(质量分数)的热变形本构方程,绘制热加工图,确定该合金的流变失稳区和适宜加工区,为其在工业生产中热加工工艺参数的制定提供指导。方法 在变形温度700~ 850 ℃、应变速率0.000 5~0.5 s⁻¹、真应变0.7的条件下,对近β钛合金Ti−6Mo−5V−3Al−2Fe−2Zr进行热压缩实验;基于Arrhenius方程建立该合金的热变形本构方程,并对方程进行验证;根据Prasad失稳准则,构建该合金的热加工图。结果 该合金的流变应力随着变形温度的升高而减小,随着应变速率的增大而增大;其热变形激活能为226.29 kJ/mol,本构方程为;通过热变形本构方程得到的峰值应力计算值与实验值平均误差为4.21%。结论 建立的热变形本构方程预测了流变应力,描述了该合金的热变形行为;通过叠加合金的能量耗散图和流变失稳图,获得了该合金的热加工图。基于热加工图确定该合金的流变失稳区为变形温度700~755 ℃与784~850 ℃、应变速率0.5~0.05 s⁻¹,最佳加工区为变形温度836~850 ℃、应变速率0.000 5~0.005 s⁻¹。     

Microwave dielectric properties of Ba(Sn x Zn(1−x)/3Nb(1−x)2/3)O3 (0 ⩽ x ⩽ 0.32) ceramics

The dielectric properties of the (1–x)Ba(Zn_1/3Nb_2/3)O₃–xBaSnO₃ (0 x 0.32) composition at microwave frequencies were investigated in this study. With the addition of BaSnO₃, the dielectric Q(Q _d) value of Ba(Zn_1/3Nb_2/3)O₃ (BZN) can be improved and a small temperature coefficient of resonant frequency (_f) can be achieved. When 22.6 mol % of Sn is added to BZN, the characteristics of the Ba(Sn_0.226Zn_0.258Nb_0.516)O₃ ceramics sintered at 1500°C are as follows: dielectric constant _r = 32, _f = + 12 p.p.m.°C¹ and high Q _d value of 9700 at 10 GHz. Based on the classical dispersion theory and the logarithmic mixing rule, the effects with additions of substitutional element of BaSnO₃ on the microwave dielectric properties of Ba(Zn_1/3Nb_2/3)O₃ can be mostly explained.     

Composite dielectrics (1−x)(Mg0.97Zn0.03)2(Ti0.95Sn0.05)O4−xCaTiO3 suitable for microwave applications

(Mg_0.97Zn_0.03)₂(Ti_0.95Sn_0.05)O₄ ceramics by adding CaTiO₃ have been prepared via the solid-state reaction method. The microstructures of samples are systematically studied in order to establish the effects of sintering temperature and additives on microwave dielectric properties of (Mg_0.97Zn_0.03)₂(Ti_0.95Sn_0.05)O₄ ceramics by X-ray diffraction and scanning electron microscopy. A fine combination of microwave dielectric properties (ε_r = 14.57, Q × f = 183,468 GHz, τ_f = ?43.7 ppm/°C) was achieved for (Mg_0.97Zn_0.03)₂(Ti_0.95Sn_0.05)O₄ ceramics sintered at 1,390 °C for 4 h. CaTiO₃, as a τ_f compensator, was added to form a temperature-stable ceramic system. For (1?x) (Mg_0.97Zn_0.03)₂(Ti_0.95Sn_0.05)O₄?xCaTiO₃ system, 0.93(Mg_0.97Zn_0.03)₂(Ti_0.95Sn_0.05)O₄?0.07CaTiO₃ ceramic sintered at 1,390 °C had optimal dielectric properties (ε_r = 18.32, Q × f = 94,715 GHz, τ_f = ?4.1 ppm/°C) which satisfied microwave applications in resonators, filters and antenna substrates.     

N2O decomposition over (Mg6−xAx) MnO8 (A = Li, Al)

Two different murdochite-type mixed oxides, (Mg_6–x Li _x )MnO₈ (x = 0, 0.1, 0.2 and 0.3) and (Mg_6–x Al _x )MnO₈ (x = 0, 0.2, 0.4, 0.6) were examined for the catalytic decomposition of N₂O in order to make clear the effects of mixed valencies of pairing manganese ions and oxygen vacancies. The valence of manganese ions and the amount of surface oxygen vacancies have been examined with X-ray photoelectron spectroscopy (XPS). (Mg_6–x Li _x )MnO₈ had mixed valence manganese ions and oxygen vacancies on the surface after the substitution. The substituted (Mg_6–x Al _x )MnO₈ had a mixed valence state but oxygen vacancies decresed with x and excess oxygen over stoichiometry was observed at x = 0.4 and 0.6. The reaction rate of N₂O decomposition increased after substitution with lithium but hardly increased after the substitution with aluminum in (Mg_6–x A _x )MnO₈. We assumed that the presence of oxygen vacancies on the surface along with pairing altervalent manganese ions affected strongly to enhance the reactivity of N₂O decomposition.     

Superconductivity and spin correlation study by Fe3+ - ESR in (La1−xSrx)2Cu1−yFeyO4−z

Fe³⁺-ESR measurements are carried out for the samples of (La_1–xSr_x)₂Cu_1–yFe_yO_4–z. Peak-peak width H_pp of the signals decreases with falling temperature until minimum value and rises sharply with further decreasing temperature, which is approximated by H_pp = C₀ +C₁/T + BT. The H_pp behavior at high temperature and at low temperature can be analyzed by Korringa mechanism and slowing down of Fe₃₊ spin fluctuation, respectively. From the analysis of coefficient B's of Korringa terms, C₀ and g-shift, it is revealed that the magnetic interaction of Fe³⁺ with hole carriers and Ce²⁺ spins depends strongly on hole density.     

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.