Synthesis and magnetic properties of nanocrystalline Y1 ? xCdxFeO3 ? δ (0 ≤ x ≤ 0.2)

We report the synthesis of Y_{1 − x} Cd _x FeO_{3 − δ} nanocrystals in the range x = 0–0.2. The Y_{1 − x} Cd _x FeO_{3 − δ} materials were shown to be single-phase by X-ray diffraction, with an average crystallite size from 23 to 34 nm, depending on composition. With increasing cadmium oxide content, the size of the Y_{1 − x} Cd _x FeO_{3 − δ} nanocrystals decreases and their magnetization rises.     

Electrical conductivity of LaCoxFe1 ? xO3 ? δ and LaLi0.1CoxFe0.9 ? xO3 ? δ (0 ≤ x ≤ 0.4) oxides

We have studied the effect of Co and Li concentrations on the phase composition and electrical conductivity of LaCo _x Fe_{1 − x} O_{3 − δ} and LaLi_0.1Co _x Fe_{0.9 − x} O_{3 − δ} perovskite-like oxides synthesized in air at 1470 K. Single-phase materials with an orthorhombic crystal structure were obtained in the range 0 ≤ x ≤ 0.3. The composition dependences of conductivity have a minimum at x _c = 0.1 and 0.2, respectively. In the range x > 0.1, the conductivity of LaCo _x Fe_{1 − x} O_{3 − δ} increases with increasing Co concentration for T > 700 K and decreases for T < 600 K. The conductivity of La(Li_0.1Co _x Fe_{0.9 − x} )O_{3 − δ} in the range 0 ≤ x ≤ 0.1 and for x ≥ 0.2 increases with Co concentration throughout the temperature range studied.     

Phase composition and structure of La1 ? x Ca x MnO3 + δ (0 ≤ x ≤ 0.2) solid solutions

A structural phase diagram of La_{1 − x} Ca _x MnO_{3 + δ} (0 ≤ x ≤ 0.2) solid solution in air has been constructed for the first time, and the equilibrium T-x fields of the monoclinic, orthorhombic, and rhombohedral phases in this system have been outlined. The transitions between these phases are accompanied by sharp changes in lattice parameters, suggesting that they are first-order. Original Russian Text ? S.Kh. Estemirova, A.M. Yankin, S.G. Titova, V.F. Balakirev, Yu.E. Turkhan, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 11, pp. 1387–1392.     

钙钛矿型Gd1-xDyxMnO3（0≤x≤1）的水热合成及磁性表征

通过环境友好的水热法制备了钙钛矿型稀土锰酸盐Gd1-xDyxMnO3(0≤x≤1),该系列化合物具有正交结构(属于pbnm空间群)。在合成反应中,Mn(OH)2在强碱体系下被空气中O2氧化生成包含Mn3+的反应前驱物;锰酸盐的晶体生长、反应温度和碱度对其有明显的影响。磁性表征结果显示Dy3+对Gd3+的取代引起了化合物低温磁有序的竞争。     

Valence Charge Fluctuations and Tc Retention in Tl1?xPbxSr1+xLa1?xCuO5?y (0.0 ≤ x ≤0.5) System

Structural and x-ray photoelectron spectroscopy (XPS) studies of the Tl_1–xPb_xSr_1+xLa_1–xCuO_5–y (0.0x0.5) system have been carried out. The unit cell parameters increase with x. Irrespective of x the T_c is retained in this series and the optimum hole concentration (n_h) is maintained for x 0.5. An increase in Tl 4f and O ls binding energy with x suggests a reduction in their oxidation state. Origin of holes is discussed in terms of charge transfer between Tl, Pb and CuO₂ layers.     

Spin Gap Effects on Bulk R1+xba2?x Cu3O7?δ (R=Eu or Nd and 0≤x≤0.4)

Spin gap effects on the underdoping states of the bulk system of R_1+x Ba_2–x Cu₃O_7– (R = Eu or Nd and 0 x 0.4) were investigated through transport property measurements. The underdoping states were achieved by, alternatively substituting R³⁺ for Ba²⁺ ions in the system rather than adjusting the oxygen deficiency. The excess R³⁺ ions were to occupy the Ba sites of the crystalline lattice as revealed from Rietveld analysis for powder X-ray diffraction. The underdoped materials were observed to first undergo spin pairing transition in the temperature range well above T _c, and come across with superconducting transition at T _c. The increasing feature observed for spin gap temperature and the decreasing one for T _c, as the concentration of holes decreases, are in qualitatively good agreement with theoretical predictions from the mean-field RVB model.     

The penetration depth of HgBa2CuO4+δ with 0.07 ≤ δ ≤ 0.35

The magnetic penetration depth (T) of three HgBa₂CuO₄₊ samples with 0.16 < 0.27 has been determined from the reversible magnetization. The obtained follows a BCS-like correlation of 1/² 1–(T/T_c)² over whole measured temperature range in an underdoped sample with T_c 90 K, but deviates significantly from similar fits in an overdoped sample with the same T_c and an optimum doped sample, whose 1/² 's depends on T nearly linearly below T_c/2. This asymmetry between the underdoped and overdoped samples suggests that the T-dependence of 1/² is affected by doping in a complicated way.     

Emissivity and Optical Properties of Thermochromic Material La0.7Ca0.3?xSrxMnO3?(0 ≤ x ≤ 0.3)

La_0.7Ca_0.3−x Sr _x MnO₃ (0 ≤ x ≤ 0.3) (LCSMO) is a thermochromic material. The material can show a phase transition from ferromagnetic-metal to paramagnetic-insulator under the appropriate doping level (x). In this paper, LCSMO compounds were synthesized by a conventional solid-state reaction method. The normal emissivity and the spectral reflectance of LCSMO with different doping levels (x) are experimentally investigated. Based on the spectral reflectance data, the optical constants (refractive index n and extinction coefficient k) are calculated by using Kramers–Kronig (K–K) relations. Then, the emissivity changing mechanism is discussed. The experimental results show that the emissivity of LCSMO increases with increasing temperature. For the samples with x = 0.1 and 0.15, their emissivity has a sudden change in the vicinity of the phase transition temperature T _p.     

Self-propagating combustion synthesis of Pb1?xSrxZrO3 (0 ≤ x ≤ 0·20) ceramics and their dielectric properties

Lead strontium zirconate, Pb_1−x Sr _x ZrO₃ (0 ≤ x ≤ 0·20) ceramics, were prepared by novel glycinenitrate self-propagating combustion technique. The crystal structure of the ceramics was investigated as a function of composition via X-ray diffraction (XRD). The XRD patterns obtained on these powders showed the formation of pure orthorhombic phase of lead strontium zirconate without impurities and all the compounds retained the orthorhombic structure. The samples were sintered at 900–1100°C for 2 h. It has been observed that the dielectric constant decreases with increase in strontium content (100 kHz). In all compositions, dielectric constant showed a peak at transition temperature and the magnitude of the peak was found to decrease with strontium doping level.     

La3+ effect on dipole ordering in Pb1 ? xLax[Zr0.7Sn0.2Ti0.1][1 ? x/4]O3(0 < x ≤ 0.03) solid solutions

We have studied temperature- and electric-field-induced phase transitions in ceramic samples of Pb_{1 − x} La _x [Zr_0.7Sn_0.2Ti_0.1]_{1 − x /4}O₃ (0 < x ≤ 0.03) solid solutions. The results indicate that La³⁺ doping to x > 0.005 impedes long-range dipole-dipole interactions and stabilizes nonpolar phases below the Curie temperature. At a constant La³⁺ concentration, lowering the temperature facilitates a field-induced transition to a ferroelectric state. In thermally depoled samples, the first antiferroelectric → ferroelectric switching usually requires a higher bias voltage than do subsequent switchings. Original Russian Text ? E.A. Bikyashev, E.A. Reshetnikova, M.I. Tostunov, 2009, published in Neorganicheskie Materialy, 2009, Vol. 45, No. 8, pp. 990–995.     

Conduction in nanostructured La1?x Sr x FeO3 (0 ≤ x ≤ 1)

We investigated electrical properties of nanostructured La_1?x Sr _x FeO₃ (0 ?? x ?? 1) from 300 K?C400 K. The nanostructured La_1?x Sr _x FeO₃ (0 ?? x ?? 1) was synthesized by citrate gel method requiring no pH control. X-ray diffraction pattern showed that single phase LaFeO₃ with an orthorhombic structure was formed. The structure changed into rhombohedral for x = 0.5 and it became cubic for x = 1.0. For x ?? 0.5, our material showed non-linear current-voltage characteristics and for x > 0.5 it showed linear current-voltage characteristics. Poole Frenkel type conduction mechanism was found to be operative in LaFeO₃ from 300 K?C400 K. The experimental values of field-lowering coefficient were by 2.56?C6.41 times higher than the predicted value and were attributed to the presence of localized fields. The increase in conductance with Sr content was due to formation of Fe⁴⁺ ions in addition to Fe³⁺ with the increase in Sr content. Impedance spectroscopy and ac conductivity analysis of La_1?x Sr _x FeO₃ (0 ?? x ?? 1) was also carried out in the temperature range from 300 K?C400 K and frequency was varied from 20 Hz - 2 MHz. The ac conduction followed the correlated barrier hopping model in La_0.9Sr_0.1FeO₃.     

Electronic Properties and Superconductivity of Electron-Doped La1?x/2Pr1?x/2CexCuO4

La_1−x/2Pr_1−x/2Ce _x CuO _y (LPCCO) samples with doping level up to 20% have been synthesized and their electronic and superconductive properties are studied. X-ray diffraction revealed that the LPCCO system is a pure phase system with a T’214 structure. Magnetic and resistive measurements show that the system is superconducting at 0.08≤x<0.20 with T _cmax=25 K at x=0.12. An anti-ferromagnetism transition was also observed in under-doped PLCCO (x=0.05) with the window width of the anti-ferromagnetism phase being significantly narrower than that NCCO and PCCO systems. The behavior of the Ce doping is compared with Sr doping in this system, and the mechanism is discussed.     

Effect of magnetic field on the temperature gradient in Y1Ba2Cu3O7 ? δ + Eu1Ba2Cu3O7 ? δ rods

A method for growing Y₁Ba₂Cu₃O_{7 − δ} + Eu₁Ba₂Cu₃O_{7 − δ} (YBCO-EBCO) high-temperature superconductor rods is described. The temperature dependences of the resistance of rods in a magnetic field of B = 0.6 T and in the absence of the field (B = 0 T) are presented. The current-voltage characteristics of YBCO-EBCO rods have been measured at liquid nitrogen temperature have been measured in the absence and presence of a magnetic field. It is shown that the magnetic field significantly decreases the temperature gradient arising when the rod leaves the superconducting state.     

Synthesis, structural and ferromagnetic properties of La1?xKxMnO3 (0·0 ≤ x ≤ 0·25) phases by solution combustion method

We describe the solution combustion synthesis and characterization of La_1–x K _x MnO₃ (0·0 ≤ x ≤ 0·25) perovskite phases, which is a low temperature initiated, rapid route to prepare metal oxides. As-synthesized compounds are amorphous in nature; crystallinity was observed on heating at 800°C for 5 min. Structural parameters were determined by the Rietveld refinement method using powder XRD data. Parent LaMnO₃ compound crystallizes in the orthorhombic structure (space group Pbnm, No. 62). Potassium substituted compounds were crystallized with rhombohedral symmetry (space group R-3c, No. 167). The ratio of the Mn³⁺/Mn⁴⁺ was determined by the iodometric titration. The Fourier transform infrared spectrum (FT-IR) shows two absorption bands for Mn-O stretching vibration (ν _s mode), Mn-O-Mn deformation vibration (ν _b mode) around 600 cm⁻¹ and 400 cm⁻¹ for the compositions, x = 0·0, 0·05 and 0·10. Four-probe electrical resistivity measurements reveal a composition controlled metal to insulator transition (T _M–I), the maximum T _M–I was observed for the composition La_0·85K_0·15MnO₃ at 287 K. Room temperature vibrating sample magnetometer data indicate that for the composition up to x = 0·10, the compounds are paramagnetic whereas composition with x = 0·15, 0·20 and 0·25 show magnetic moments of 27, 29 and 30 emu/g, respectively.     

Y1?xPrxBa2Cu3O7: Charge redistribution between planes and chains?

A qualitative discussion is given of the electronic structure and properties of the system Y_1–x Pr _x Ba₂Cu₃O₇ in which there is a transition from a high-T _c superconductor to a magnetic insulator. To reconcile the apparently contradicting experimental data, it is suggested that the progressive hole redistribution between CuO₂ planes and chains occurs with increasingx so that for large Pr content all the holes are in chains and none remain in planes. In this picture one can naturally explain the main properties of this system; notably, one gets an insulating state for pure PrBa₂Cu₃O₇, the valence of Pr being still Pr³⁺. Many other properties of Y_1–x Pr _x Ba₂Cu₃O_7– are naturally explained as well, and several predictions are made.     

层状LixCo1/3Ni1/3Mn1/3O2（0．5≤x≤1）的结构转变及其热稳定性研究

采用固相合成法制备了具有良好层状结构的LiCo1/3Ni1/3Mn1/3O2.通过化学方法对其进行去锂处理,制备了LixCo1/3Ni1/3Mn1/3O2(0.5≤≤1)系列样品,并利用XRD、TEM以及HR-TEM等方法对其微观结构进行了系统表征.计算与实验结果表明.当0.778≤x＜1时LixCo1/3Ni1/3Mn1/3O2的结构依旧保持O3结构,而当0.5≤x＜0.778时其结构由初始的六方结构转变为单斜结构,同时电子衍射花样模拟及高分辨像模拟证明其对称性由R3m转变为P2/m.锂离子与去锂后形成的空位的有序排列是其对称性发生转变的主要原因.DSC/TG实验表明,LixCo1/3Ni1/3Mn1/3O2的热稳定性随去锂程度的不断加深而减弱;当加热至300～400℃时发生了由单斜结构向尖晶石结构转变的放热反应.     

Effect of nonstoichiometry on the structure and microwave dielectric properties of Ba1 ? x(Zn1/2W1/2)O3 ? x and Ba(Zn1/2 ? yW1/2)O3 ? y/2

We have synthesized Ba_{1 − x} (Zn_1/2W_1/2)O_{3 − x} and Ba(Zn_{1/2 − y} W_1/2)O_{3 − y/2} barium tungstates with different deviations from cation stoichiometry (x = 0.01–0.05, y = 0.01–0.05), determined the phase composition of ceramics fabricated from the tungstates, and investigated their electrical properties. Even slight deviations from cation stoichiometry in Ba(Zn_1/2W_1/2)O₃ lead to the formation of the scheelite phase BaWO₄, and its content increases with heat-treatment temperature. Barium or zinc deficiency in the systems studied improves the sintering behavior of Ba(Zn_1/2W_1/2)O₃ and increases the degree of 1: 1 B-site cation ordering, which in turn ensures an increase in microwave quality factor, Q.     

Specific Heat of LaMnO3 + δ at 50 K ≤ T ≤ 160 K

We have developed a shell model, which includes the long-range coulomb, van der Waals interaction, and the short-range Hafemeister–Flygare repulsive interaction operative up to second neighbor atom to study the cohesive and thermal properties of LaMnO_{3 +} . The results on cohesive energy obtained by us are in good agreement with that of calculated value by DeSouza et. al. (R. A. DeSouza, M. S. Islam, and E. I. Tiffee, J. Mater. Chem. 9, 1621 (1999)). In addition, we have also calculated molecular force constant (f), compressibility (), restrahlen frequency (_o), Debye temperature (_D), and the low temperature specific heat at 50 K T 160 K. Our results on Debye temperature and specific heat for the temperature range 50 K T 160 K are closer to the recently measured data with an automated quasi-adiabatic pulse technique.     

Microwave properties of the systems Ba1?xSrx(Zn1/3Ta2/3)0.94T{i}0.06 O3 and Ba(Zn1/3Nb2/3)1?xZrxO3

By means of a solid-phase synthesis two types of microwave dielectric materials are obtained as follows: Ba_1–xSr_x(Zn_1/3Ta_2/3)_0.94Ti_0.06O₃, where x = 0.20, 0.25, 0.30, 0.35 and 0.40 at sintering temperature T_S = 1350, 1400 and 1450 C; Ba(Zn_1/3Nb_2/3)_1–xZr_xO₃, where x = 0.04, 0.06, 0.08 and 0.10 at T_S = 1300, 1350, and 1400 C. The microwave characteristics of the materials are investigated at f = 10 GHz. The composition Ba(Zn_1/3Nb_2/3)_1–xZr_xO₃ demonstrates _r = 38, Q = 6100 and _f = +15 ppm C^–1 and the composition Ba_0.80Sr_0.20- (Zn_1/3Ta_2/3)_0.94Ti_0.06O₃ has _r = 42, Q = 8200 and _f = –13 ppm C^–1. The composition Ba_0.75Sr_0.25(Zn_1/3Ta_2/3)_0.94Ti_0.06O₃ has _r = 40, Q = 6500 and low _f = –13 C^–1 ppm. This composition could be used successfully for realisation of dielectric microwave resonators for the satellite television.     

Structure of Sr1 ? xPbxFeO3 ? δ (0 < x < 0.5) perovskite-like materials

We have synthesized Sr_{1 − x} Pb _x FeO_{3 − δ} (x = 0, 0.05, 0.1, 0.15, 0.2, 0.3, 0.5) perovskite-like materials and studied their structure by X-ray diffraction, M?ssbauer spectroscopy, and electron microscopy. According to the X-ray diffraction data, the Pb solubility limit in the perovskite structure is x ≈ 0.15. The materials with x = 0.05 and 0.1 contained Pb_1.33Sr_0.67Fe₂O₅ inclusions 10–30 nm in size. Using chronopotentiometry and temperature-programmed desorption, we have estimated oxygen mobility in the materials with x = 0.05 and 0.1. The results demonstrate that Pb doping increases oxygen mobility in the strontium-ferrite-based materials.