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.     

三次系统x′=-y+8x+mxy+ny~2+a_1x~3+a_3xy~2,y′=x的极限环研究

本文研究了E_3~1系统,x=-y+δx+mxy+ny~2+a_1x~3+a_3xy~2,y=x的极限环,其中m≠0,a_1≠0,a_3≠0,利用Dulac函数法及地形系法得到了一系列无环性条件,并证明了系统在一定条件下至少可以存在一个及两个极限环,同时通过构造Poinear'e—Bendixson环域得到了系统存在大范围的极限环的条件。     

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.     

Structural and electrical properties of nanostructured fluorite-like R2 + x TiO5 + 1.5x (R = Y, Er; 0 �� x �� 1)

We have studied the detailed structure and electrical properties of single-crystal and polycrystalline fluorite-like R_{2 + x} TiO_{5 + 1.5x} (R = Y, Er; 0 ?? x ?? 1) materials and found the first evidence for the formation of nanodomains ? 40?C1000 nm in size, which are coherent with the matrix and have various degrees of structural order. The formation of the nanodomains is driven by internal stress. Using impedance spectroscopy, we have determined the electrical conductivity of the materials in air at temperatures from 300 to 1000°C. The 1000°C electrical conductivity of Y₂TiO₅ (Er₂TiO₅) and Y_2.44TiO_5.67 (Er_2.44TiO_5.67) is 1.86 × 10^?3 (1.35 × 10^?3) and 9.98 × 10^?4 (8.13 × 10^?4) S/cm, respectively. The effective activation energy for electrical conduction in Y₂TiO₅ (Er₂TiO₅) and Y_2.44TiO_5.67 (Er_2.44TiO_5.67) is 1.16 (1.21) and 1.25 (1.21) eV, respectively.     

UO2+x芯块低温烧结的活化机理

报道了UO2+x芯块低温烧结实验的结果.12组芯块在N2+CO2组成的部分氧化气氛下于立式钼丝炉中低温烧结.UO2芯块要获得密度为10.41g/cm3(94.98％理论密度)需在氢气氛中于2073～2273K下烧结,而UO2+x芯块实现该密度的烧结温度可降低400K以上.建立了超氧化铀缺陷模型来研究低温烧结的活化机理.研究发现铀离子扩散系数与气氛中氧分压或是UO2+x中x成正比.利用铀离子的扩散系数,可预测UO2+x芯块在1073、1273、1473和1673K温度下的烧结密度；还可算出x=0.04时,UO2+x芯块在部分氧化气氛下的理论烧成温度.计算所得烧结密度和烧成温度与实验结果符合得很好.     

New Perspectives for Cuprate Research: (Ca x La1?x )(Ba1.75?x La0.25+x )Cu3O y Single Crystals

We report the successful growth of a large (Ca _x La_1?x )(Ba_1.75?x La_0.25+x )Cu₃O _y (CLBLCO) single crystal. In this material, x controls the maximum of T _c ( $T_{c}^{\max }$ ), with minimal structural changes. Therefore, it allows a search for correlations between material properties and $T_{c}^{\max }$ . We demonstrate that the crystals are good enough for neutron scattering and cleave well enough for Raman scattering. These results open new possibilities for cuprate research.     

非线性方程x=Ax+λBx的可解性

X是实Banach空间,FX是楔形,(0,1)X是闭单位球,Ω,DX是两个有界开集,D;用和分别表示D_F≡D∩F关于F的闭包和边界,A:→F是半紧1—集压缩,B:(—Ω)_F→F全连续,当F∩(0,1)非紧或F是锥以及A和B满足某些补充假设时,本文证明了固有向量集∑={x∈(-Ω)_F|x∈Ax+λBx,对采个λ∈[0,m/β]}中有一连通分支C使得C∩F(A)≠φ,C∩≠φ,这里F(A)={x∈(-Ω)_F|x=Ax}。     

Synthesis, microstructure and thermal expansion studies on Ca0·5+x/2Sr0·5+x/2Zr4P6−2x Si2x O24 system prepared by co-precipitation method

We report on the synthesis, microstructure and thermal expansion studies on Ca_0·5?+?x/2Sr_0·5?+?x/2Zr₄P_6???2x Si_2x O₂₄ (x = 0·00 to 1·00) system which belongs to NZP family of low thermal expansion ceramics. The ceramics synthesized by co-precipitation method at lower calcination and the sintering temperatures were in pure NZP phase up to x = 0·37. For x ≥ 0·5, in addition to NZP phase, ZrSiO₄ and Ca₂P₂O₇ form as secondary phases after sintering. The bulk thermal expansion behaviour of the members of this system was studied from 30 to 850 °C. The thermal expansion coefficient increases from a negative value to a positive value with the silicon substitution in place of phosphorous and a near zero thermal expansion was observed at x = 0·75. The amount of hysteresis between heating and cooling curves increases progressively from x = 0·00 to 0·37 and then decreases for x > 0·37. The results were analysed on the basis of formation of the silicon based glassy phase and increase in thermal expansion anisotropy with silicon substitution.     

Low-temperature thermoelectric and magnetic properties of Ca3−x Bi x Co4O9+δ (0 ≤ x ≤ 0.30)

Polycrystalline samples of Ca_3?x Bi _x Co₄O_9+δ (x = 0.00, 0.05, 0.10, 0.15, 0.20 and 0.30) have been prepared by conventional solid-state synthesis. Thermopower of all the samples is positive, indicating that the predominant carriers are holes over the entire temperature range. The resistivity of all the samples, except the one with x = 0.30, exhibits nonmetal to metal transition (T _MI) in the low temperature regime. The resistivity results indicate that all the doped samples obey the variable range hopping in the low temperature regime. The T _MI and T ^* (transition temperature from Fermi liquid metal to incoherent metal) increase, and the slope of A value (Fermi-liquid transport coefficient) decreases with the increasing Bi content due to an increase in chemical pressure in the lattice. Among the samples, Ca_2.7Bi_0.3Co₄O_9+δ has the highest dimensionless figure of merit of 0.091 at 300 K. This value represents an improvement of about 135 % compared to the undoped Ca₃Co₄O_9+δ . Magnetic measurements indicate that all the samples exhibit a low-spin state of cobalt ion. The ferrimagnetic transition temperature is suppressed by the Bi dopant. These results suggest that Bi is an effective doping element for improving the thermoelectric properties of Ca₃Co₄O_9+δ .     

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.     

Preparation of Thick LaCu1 – x Ni x O2.5 + δ Films Exhibiting a High-Temperature Metal–Semiconductor Transition

The conditions for producing thick LaCu_{1 – x} Ni _x O_{2.5 +} films on different substrates were optimized. The effects of the heat-treatment conditions, substrate material, and the nature of the liquid organic binder on the composition, structure, and properties of the films were studied. Single-phase coatings obtained on MgO, ZrO₂, BaSO₄, and Ni substrates 50 to 200 m in thickness were close in properties to bulk LaCu_{1 – x} Ni _x O_{2.5 +} and exhibited a metal–semiconductor transition at about 500°C.     

NMR of 89Y in the Copper-Oxide Spin-Chain Compound Ca2+x Y2−x Cu5O10

We report NMR lineshape, spin-lattice relaxation time T ₁, and spin-spin relaxation time T ₂ data at 17 MHz (8.07 T) for ⁸⁹Y in the copper-oxide spin-chain compound Ca_2+x Y_2–x Cu₅O₁₀. For x=0, a broad, asymmetric line with width 90 kHz is observed for T=250–300 K. The spectra exhibit an appreciable average shift (H/H+0.7%) and sharpen at lower temperature, possibly due to increasing intrachain ferromagnetic correlations. T ₁ and T ₂ decrease with decreasing temperature. The Tl data imply a short correlation-time limit, with _e=3–5×10^–11 s. The T ₂ data apparently include a contribution from dipolar interactions with copper nuclei. Relaxation time data for a doped (x=0.5) compound surprisingly show more rapid relaxation.     

Microwave Surface Impedance of Nd-rich Nd 1+x Ba 2−x Cu 3 O 7−δ Thin Films

Surface impedance measurements on highly c-axis epitaxial Nd _1+x Ba _2–x Cu ₃ O ₇ (x=0, 0.09 and 0.12) films grown by d.c. magnetron sputtering on LaAlO ₃ substrates are presented. It is found that the zero temperature London penetration depth correlates well with the critical temperature of the films and with the corresponding number of carriers. The low temperature penetration depth follows a linear T law for optimally doped Nd123 sample and a T ² law in Nd-rich samples. In the case of the heavily underdoped samples (T _c < 60K) the T ² law extends to temperatures higher than T _c/2. The possible role of the Nd/Ba ions substitution on the penetration depth and surface resistance is discussed.     

Optical and electrical properties of Ba1−x Sr x TiO3 nanopowders at different Sr2+ ion content

Barium strontium titanate (BST) Ba_1?x Sr _x TiO₃ nanopowders have been successfully synthesized using oxalate precursor route. The effect of Sr²⁺ ion content from 0.3 to 0.7 on the crystal structure, crystallite size, microstructure, electrical and optical properties was systematically studied. The results revealed that well crystalline single BST phase was formed by annealing the oxalate precursor at 1,000 °C for 2 h. The crystallite size of the BST powders was decreased with increasing the Sr²⁺ ion molar ratios. The crystallite size was decreased from 56.0 to 33.1 nm when the Sr²⁺ ion content increased from 0.3 to 0.7. Additionally, the lattice parameter (a), unit cell volume and X-ray density of BST ware decreased whereas the porosity, % were increased with Sr²⁺ ion concentration. The BST phase appeared as cubic-like structure. The spectrophotometer measurement results demonstrated that the room temperature band gap energy varied with the Sr²⁺ ion composition x. The band gap energy was shifted to low energy and it was decreased from 3.6 to 3.2 eV with increasing the Sr²⁺ ion content from 0.3 to 0.7. Moreover, the DC resistivity was enhanced with increasing the Sr²⁺ ion ratio. The dielectric response obtained for the stressed samples corresponds to a true resonance rather than a dispersion process with a characteristic frequency around 1 GHz at room temperature. However, the peaks commonly observed at GHz frequency were changed with varying the Sr²⁺ ion composition. The high imaginary components of dielectric permittivity for x = 0.3 was found at higher frequency region around 1.6 GHz compared with the samples with x values of 0.5 and 0.7 in which the frequency regions were around 1.25 and 1.15 GHz, respectively.     

Pb1−x Bi x /Bi/Pb1−x Bi x Josephson junction

A superconductor/semimetal/superconductor (S/SM/S) Josephson junction has been developed. We have used an alloy of Pb_1–x Bi _x (0x 0.6) as the superconductor and Bi as the semimetal. By irradiating at X-band microwave of 10 GHz, Shapiro steps were observed for various bismuth barrier thicknesses inÅ and bismuth weight ratiosx. Finally, we obtained the empirical relationship for barrier thickness, below which microwaves could be detected for various bismuth weight ratiosx at the temperature of 4.2 K.     

Lattice-matched epitaxial Pb1 − x Mn x Se/PbSe1 − x S x heterojunctions

This paper examines the possibility of producing lattice-matched p-n heterojunctions based on epitaxial n-Pb_{1 ? x} Mn _x Se (x = 0.02) and p-PbSe_{1 ? x} S _x (x = 0.04) films. The heterojunctions have been grown by molecular beam epitaxy in a single processing cycle, without breaking the vacuum, using a compensating Se vapor source in the growth process. Optimal conditions have been found for the growth of structurally perfect (W _1/2 = 90″-100″) epitaxial films and fabrication of lattice-matched heterojunctions based on such films, photosensitive in the IR spectral region.     

Crystal structure of (Ba1−x Lax) [Mg(1 + x)/3Nb(2−x)/3]O3 ceramics

The crystal structure of (Ba_1–x La _x )[Mg_{(1 + x)/3}Nb_(2–x)/3]O₃ (BLMN) ceramics with 0 x 1 was investigated using X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). When the La content, x, was above 0.1, the 1:2 ordered hexagonal structure found in Ba(Mg_1/3Nb_2/3)O₃ (BMN) was transformed into the 1:1 ordered cubic structure. The 1:1 ordered cubic structure was maintained up to x = 0.7. When x exceeded 0.7, however, BLMN exhibited a 1:1 ordered monoclinic structure, rather than a 1:1 ordered cubic structure. La(Mg_2/3Nb_1/3)O₃ (LMN) has a 1:1 ordered monoclinic P2₁/n structure with a = 5.6004 Å, b = 5.6414 Å, c = 7.9346 Å, and = 89.9819°. The monoclinic LMN has the in-phase and the anti-phase tilt of oxygen octahedra. The anti-parallel shift of A-site cations was also found in LMN.     

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.