Optical spectroscopy of Ca3Sc2Si3O12, Ca3Y2Si3O12 and Ca3Lu2Si3O12 doped with Pr

The silicates Ca₃Sc₂Si₃O₁₂, Ca₃Y₂Si₃O₁₂ and Ca₃Lu₂Si₃O₁₂, both undoped and doped with Pr³⁺ ions, have been synthesized by solid-state reaction at high temperature. The luminescence spectroscopy and the excited state dynamics of the materials have been studied upon VUV and X-ray excitation using synchrotron radiation. All doped samples have shown efficient 5d-4f emission upon direct VUV excitation of 5d levels, but only Ca₃Sc₂Si₃O₁₂:Pr³⁺ shows luminescence upon interband VUV or X-ray excitation. The VUV excited emission spectra of Ca₃Y₂Si₃O₁₂:Pr³⁺ and Ca₃Lu₂Si₃O₁₂:Pr³⁺ show features attributed to emission from two distinct sites accommodating the Pr³⁺ dopant. The decay kinetics of the Pr³⁺ 5d-4f emission in Ca₃Sc₂Si₃O₁₂:Pr³⁺ upon VUV excitation across the band gap are characterized by decay times in the range 25-28 ns with no significant rise after the excitation pulse. They appear to be faster upon X-ray irradiation than for VUV excitation. Weak afterglow components are attributed to defect luminescence.     

Structure and magnetic order in La0.7Ca0.3Mn0.5Co0.5O3 and La0.8Sr0.2Mn0.5Co0.5O3 perovskites

In this paper we report the study of the perovskites La_0.7Ca_0.3Mn_0.5Co_0.5O₃ and La_0.8Sr_0.2Mn_0.5Co_0.5O₃ by neutron powder diffraction at various temperatures and magnetization measurements in zero applied field and at low cooling regimes. The replacement of half Mn by Co in La_0.7Ca_0.3MnO₃ and La_0.8Sr_0.2MnO₃ destroys their long-range ferromagnetism exhibiting a cluster glass ferromagnetic order similar to the one observed in many cobaltites.     

The ν9 + ν11 − ν11, ν10 + ν11 − ν11 hot band system in allene-d4

The hot band system ν₉ + ν₁₁ ? ν₁₁, ν₁₀ + ν₁₁ ? ν₁₁ in allene-d₄ was studied at a resolution near 0.010 cm^?1. About 1500 partly overlapped hot band rotational lines were assigned and fitted to a model taking into account z-Coriolis resonance between the combination levels ν₉ + ν₁₁ and ν₁₀ + ν₁₁ as well as vibrational l-type resonances within these levels. Upperstate constants have been derived from an analysis in which the constants for the ν₁₁ level were constrained. A detailed study of rotational as well as vibrational l-type doublings occurring in the KΔK = ?1 subband is presented, and the sign of vibrational l-type doubling constants for the ν₁₀ + ν₁₁ level is determined. A localized (x, y)-Coriolis resonance between ν₁₀ + ν₁₁ and ν₄(B₁) + ν₁₁ is discussed and the interaction parameter is obtained as well as some constants for ν₄ + ν₁₁.     

Li4SiO4-Li3VO4赝二元系和Li4GeO4-Li4SiO4-Li3VO4赝三元系中新的锂离子导体

本文在室温到300℃的温度范围内研究了Li₄SiO₄-Li₃VO₄和Li₄GeO₄-Li₄SiO₄-Li₃VO₄体系中的离子导电性,发现γ_II相固溶体Li_3+xV_1-xSi_xO₄是好的锂离子导体。所研究的成分中Li_3.3V_0.7Si_0.3O₄的离子电导率最高,室温下为1×10^-5Ω^-1·cm^-1,在42—192℃的电导激活能为0.36eV,电子电导率可以忽略,因而这是迄今所发现的最好的锂离子导体之一。粗略确定了Li₄GeO₄-Li₄SiO₄-Li₃VO₄三元系中电导率高的范围,发现在Li_3.5V_0.5Ge_0.5O₄中Si部分取代Ge可以使电导率进一步提高,Li_3.5V_0.5Ge_0.4Si_0.1O₄的室温电导率可达1.3×10^-5Ω^-1·cm^-1,电导激活能为0.40eV。 关键词：     

X-ray study of phase transitions in the system of solid solutions K2Pb4Nb10O30-Na2Pb4Nb10O30-K6W4Nb6O30

Boundaries of morphotropic phase transitions region in the system of solid solutions K₂Pb₄Nb₁₀O₃₀-Na₂Pb₄Nb₁₀O₃₀-K₆W₄Nb₆O₃₀ with the structure of the tetragonal tungsten bronze have been specified. Presence of the second morphotropic phase transition, perpendicular to the first one has been revealed. The temperature dependences of the structural parameters of some compounds have been investigated. The compounds with high values of Curie temperatures and working temperatures have been obtained.     

Analysis of FTIR spectra of CH2BrCl; the ν4 and ν5 fundamentals and their hot-bands ν4+ν6−ν6 and ν5+ν6−ν6

The infrared spectrum of isotopically pure CH₂⁷⁹BrCl has been recorded at a resolution of 0.0023 cm⁻¹ (FWHM) in the range 550-800 cm⁻¹ with a Bruker IFS 120 HR Fourier transform spectrometer in Wuppertal. Here we report the full rotational analysis of the ν₄ and ν₅ fundamentals and of the hot-bands ν₄+ν₆−ν₆ and ν₅+ν₆−ν₆. Ground state combination differences were constructed for all bands, yielding improved ground state constants, up to quartic terms, as well as reliable rotational constants for the ν₄, ν₅, and ν₆ states.     

Appearance of an inhomogeneous superconducting state in La0.67Sr0.33MnO3-YBa2Cu3O7-La0.67Sr0.33MnO3 trilayers

An experimental study of proximity effect in La_0.67Sr_0.33MnO₃-YBa₂CU₃O₇-La_0.67Sr_0.33MnO₃ trilayers is reported. Transport measurements on these samples show clear oscillations in critical current (I _c) as the thickness of La_0.67Sr_0.33MnO₃ layers (d _F) is scanned from ∼50 ? to ∼ 1100 ?. In the light of existing theories of ferromagnet-superconductor (FM-SC) heterostructures, this observation suggests a long range proximity effect in the manganite, modulated by its weak exchange energy (∼2 meV). The observed modulation of the magnetic coupling between the ferromagnetic LSMO layers as a function of d _F, also suggests an oscillatory behavior of the SC order parameter near the FM-SC interface.      

Synthesis and crystallographic studies of garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

High-purity powder specimens of AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ have been successfully synthesized by solid-state chemical reaction. The Rietveld refinements from X-ray powder diffraction data verified that these compounds have the garnet-type structure (space group , No. 230) with the lattice constant of a=12.596(2) Å for AgCa₂Mn₂V₃O₁₂ and a=12.876(2) Å for NaPb₂Mn₂V₃O₁₂. Calculation of the bond valence sum supported that Mn is divalent and V is pentavalent in these garnets. Estimation of the quadratic elongation and the bond angle variance showed that the distortions of the MnO₆ octahedra and the VO₄ tetrahedra are significantly suppressed. Our new results of AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ are compared to those of AgCa₂M₂V₃O₁₂ and NaPb₂M₂V₃O₁₂ (M=Mg, Co, Ni, Zn).     

Glass formation in the As2Se3-As2Te3-Sb2Te3 system

Chalcogenide glasses from the As₂Se₃-As₂Te₃-Sb₂Te₃ system were synthesized for the first time. The glass-forming region was determined by X-ray diffraction and electron microscopic analyses.The basic physicochemical parameters such as density (d), microhardness (HV) and temperatures of phase transformations (glass transition T_g, crystallization T_cr and melting T_m) were measured. Compactness and some thermomechanical characteristics such as volume (V_h) and formation energy (E_h) of micro-voids in the glassy network as well as the elasticity module (E) were calculated. The glass-forming ability was evaluated according to Hruby's criteria (K_G). The correlation between composition and properties of the (As₂Se₃)_x(As₂Te₃)_y(Sb₂Te₃)_z glasses was established and comprehensively discussed.     

Preparation and characterization of co-doped (Ce0.80La0.15Al0.05O1.90) and multiple-doped (Ce0.80Sm0.10Gd0.05Al0.05O1.90 and Ce0.80Gd0.10Sm0.05Al0.05O1.90) ceria

Attempts have been made to synthesize a few compositions Ce_0.80La_0.15Al_0.05O_1.90, Ce_0.80Sm_0.10Gd_0.05Al_0.05O_1.90, and Ce_0.80Gd_0.10Sm_0.05Al_0.05O_1.90 by citrate–nitrate auto-combustion method. The aim of the present investigation was to study the effect of co-doping and multiple doping on the ionic conductivity of CeO₂ for its use as solid electrolyte in intermediate temperature solid oxide fuel cells. XRD patterns showed that all the samples have fluorite-type crystal structure similar to undoped ceria. Microstructures of thermally etched samples have been studied by scanning electron microscopy. Contributions of grains σ _g and grain boundaries σ _gb to the total conductivity σ _T, have been determined using impedance analysis. Impedance measurements were made in the frequency range 1 Hz–1 MHz and temperature range 250–500 °C. Our experimental results show that multiple doping is more effective than co-doping for improving the oxide ion conductivity of ceria in the materials investigated in the present study.     

Structural study of the Lu2Si2O7-Sc2Si2O7 system

Different compositions in the Lu₂Si₂O₇-Sc₂Si₂O₇ system have been synthesized following the ceramic method. All XRD patterns are compatible with the thortveitite structure (β-RE₂Si₂O₇ polymorph). Unit cell parameters change linearly with composition, which indicates a complete solid solubility of Sc₂Si₂O₇ in Lu₂Si₂O₇. ²⁹Si MAS NMR spectra show a decrease of the ²⁹Si chemical shift with increasing Sc content. A correlation reported in the literature to predict ²⁹Si chemical shifts in silicates is applied here to obtain the theoretical variation in ²⁹Si chemical shift values in the system Lu₂Si₂O₇-Sc₂Si₂O₇ and the results compare favourably with the values obtained experimentally. The FWHM values of the ²⁹Si MAS NMR curves indicate a random distribution of Lu and Sc in the structure of the intermediate members. Finally, the IR study of the system confirms the solubility of Sc₂Si₂O₇ in Lu₂Si₂O₇, showing the splitting of several modes in the intermediate members and a linear shift of the frequency on going from one end-member to the other.     

The ν2, 2ν2, 3ν2, ν4, and ν2 + ν4 bands of 15NH3

The ir absorption of gaseous ¹⁵NH₃ between 510 and 3040 cm^?1 was recorded with a resolution of 0.06 cm^?1. The ν₂, 2ν₂, 3ν₂, ν₄, and ν₂ + ν₄ bands were measured and analyzed on the basis of the vibration-rotation Hamiltonian developed by V. ?pirko, J. M. R. Stone, and D. Papou?ek (J. Mol. Spectrosc.60, 159–178 (1976)). A set of effective molecular parameters for the ν₂ = 1, 2, 3 states was derived, which reproduced the transition frequencies within the accuracy of the experimental measurements. For ν₄ and ν₂ + ν₄ bands the standard deviation of the calculated spectrum is about four times larger than the measurements accuracy: a similar result was found for ν₄ in ¹⁴NH₃ by ?. Urban et al. (J. Mol. Spectrosc.79, 455–495 (1980)). This result suggests that the present treatment takes into account only the most significant part of the rovibration interaction in the doubly degenerate vibrational states of ammonia.     

Research on charge-ordering state in La0.5Sr0.5MnO2.88 and La0.5Sr0.5Mn0.5Ti0.5O3 systems

The structural, magnetic and transport properties of La_0.5Sr_0.5MnO_2.88 and La_0.5Sr_0.5Mn_0.5Ti_0.5O₃ samples have been investigated systematically. Indeed, this series has been considered to understand the influence of physical parameters such as oxygen deficiency and titanium doping effect in undoped La_0.5Sr_0.5MnO₃ sample. Ceramic material based on La_0.5Sr_0.5MnO_2.88 exhibits interesting behaviours of charge-ordering (CO), ferromagnetic (FM) states and a good conductivity down to the lowest temperatures. The substitution of Ti for Mn destroyed drastically the CO, damaged the motion of itinerant e_g electrons and changed the local parameters of perovskite cell. A change of the structure from tetragonal to rhombohedral symmetry is observed causing a weakening of double-exchange interaction. The experiment results show that the suppression of the CO is sensitive to the variety of Mn³⁺/Mn⁴⁺ ratio. In a field of 8 T at 10 K, FM and CO phase can be evaluated to be ∼20:80 according to the μ_exp/μ_cal ratio for La_0.5Sr_0.5MnO_2.88, whereas the CO state is suppressed for La_0.5Sr_0.5Mn_0.5Ti_0.5O₃ sample, FM and anti-ferromagnetic (AFM) phase are coexisted and evaluated to be ∼54:46, respectively.     

BaB2O4-K2O和BaB2O4-K2B2O4赝二元系相图的研究

用X射线衍射和差热分析方法研究了BaB₂O₄-K₂O和BaB₂O₄-K₂B₂O₄赝二元系的相平衡关系。BaB₂O₄-K₂B₂O₄属共晶体系,共晶温度为850±3℃,共晶点成分为45mol％K₂O。在Ba 关键词：     

Antiferromagnetic phase transition in garnet-type AgCa2Co2V3O12 and AgCa2Ni2V3O12

Antiferromagnetic phase transition in two vanadium garnets AgCa₂Co₂V₃O₁₂ and AgCa₂Ni₂V₃O₁₂ has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature T_N=6.39 K for AgCa₂Co₂V₃O₁₂ and 7.21 K for AgCa₂Ni₂V₃O₁₂, respectively. The magnetic susceptibilities exhibit broad maximum, and these T_N correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χ_max). The magnetic entropy changes from zero to 20 K per mol Co²⁺ and Ni²⁺ ions are 5.31 J K⁻¹ mol-Co²⁺-ion⁻¹ and 6.85 J K⁻¹ mol-Ni²⁺-ion⁻¹, indicating S=1/2 for Co²⁺ ion and S=1 for Ni²⁺ ion. The magnetic susceptibility of AgCa₂Ni₂V₃O₁₂ shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μ_eff=3.23 μ_B Ni²⁺-ion⁻¹ and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa₂Co₂V₃O₁₂. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state ²E(t₂⁶e) and the first excited state is spin quartet state ⁴T₁(t₂⁵e²) which locates extremely close to the ground state. The low spin state S=1/2 for Co²⁺ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.     

Ti/Pr0.7Ca0.3MnO3/La0.67Sr0.33MnO3/Pt异质结电致电阻效应的改善

采用脉冲激光沉积技术制备了Ti/Pr_0.7Ca_0.3MnO₃/Pt和Ti/Pr_0.7Ca_0.3MnO₃/La_0.67Sr_0.33MnO₃/Pt异质结并研究了La_0.67Sr_0.33MnO₃功能插层对异质结电致电阻特性的影响. 实验结果表明La_0.67Sr_0.33MnO₃功能层的引入有效提高了器件的电阻转变特性,尤其是电阻转变率和疲劳性得到了极大的改善. 对La_0.67Sr_0.33MnO₃插层改善电致电阻转变特性的机理进行了定性的分析. 关键词： 电致电阻效应 电阻转变比率 疲劳特性     

Li3VO4-Li4SiO4-Li4GeO4赝三元系相图的研究

本文用差热分析法和高温、室温X射线衍射法对Li₃VO₄,Li₄SiO₄的相变过程,Li₃VO₄-Li₄SiO₄,Li₃O₄-Li-4GeO₄赝二元系相图以及Li₃VO₄-Li₄SiO₄-Li₄GeO₄赝三元系相图室温截面进行了研究。发现在Li₃VO₄-Li₄SiO₄,Li₃VO₄-Li₄GeO₄赝二元系中,由于Li₄SiO₄或Li₄GeO₄的加入而使Li₃VO₄的高温γ_II相稳定存在于室温,从而得到一种新的具有高电导率的锂离子导体。作者认为探寻使高温态稳定存在于室温的方法是探索新的离子导体研究中有效途径之一。 关键词：     

Increase in the diamagnetic response from low-density Bi1.8Pb0.3Sr1.9Ca2Cu3Ox high-temperature superconductors and Bi1.8Pb0.3Sr1.9Ca2Cu3Ox + Ag composites

Low-density polycrystalline Bi_1.8Pb_0.3Sr_1.9Ca₂Cu₃O _x high-temperature superconductors with a foamlike microstructure and composites consisting of this superconductor and silver in an amount of 20, 25, and 30 vol % are synthesized. The microstructure, as well as the temperature and field dependences of the magnetization, M(T) and M(H), are studied. It is found that, in Bi_1.8Pb_0.3Sr_1.9Ca₂Cu₃O _x high-temperature superconductors and Bi_1.8Pb_0.3Sr_1.9Ca₂Cu₃O _x + Ag composites, the diamagnetic response is enhanced and the screening properties are improved compared with high-temperature polycrystalline superconductors with the same composition that are prepared by the standard technology. The observed effect is explained by the features of magnetic flux penetration into a porous medium.     

Cation ordering and crystal structures in AGa2X4 compounds (CoGa2S4, CdGa2S4, CdGa2Se4, HgGa2Se4, HgGa2Te4)

Single crystals of some AGa₂X₄ compounds (CoGa₂S₄, CdGa₂S₄, CdGa₂Se₄, HgGa₂Se₄, HgGa₂Te₄) were prepared by chemical vapour deposition and flux method.The X-ray structural investigations indicated blende or defect chalcopyrite structures.A simple relationship is suggested between the c/a ratio and the cationic sublattice ordering.