柠檬酸溶胶-凝胶法制备Ca3Co4O9粉体及结构表征

以柠檬酸为络合剂,采用溶胶凝胶法,制备了Ca3Co4O9 粉体,通过差热分析(TG DTA)、红外光谱(FT IR)、扫描电子显微镜(SEM)、选区电子衍射(SAD)、高分辨电子显微镜(HRTEM)、能谱(EDX)等手段对Ca3Co4O9 进行表征。实验结果表明,干凝胶的煅烧温度在750~900℃之间,时间2h,可制备纯相Ca3Co4O9 粉体。该粉体为粒径100~200nm 的片状单晶。     

Ce掺杂Ca3Co4O9的高温热电性能

利用二次固相反应方法制备了Ce掺杂的Ca3Co4O9热电材料(CexCa3-xCo4O9,x=0、0.1、0.3),并测试了样品的微观结构和高温热电性能。测试结果表明,Ce替代Ca可有效调制Ca3Co4O9的热电参数;随着温度的升高,样品的电阻率和热导率降低,See-beck系数增大。在973K的温度下,Ce0.1Ca2.9Co4O9具有最高的热电性能(ZT=0.23)。     

EDTA络合溶胶-凝胶法制备Ca3Co4O9粉体

钴基氧化物Ca3Co4O9是一种新型的中高温热电材料。本文以金属醋酸盐和乙二胺四乙酸(EDTA)为原料,利用EDTA络合溶胶-凝胶法制备了Ca3Co4O9粉体,通过X射线衍射(XRD)、热重-差示扫描量热分析(TG-DSC)、傅利叶变换红外光谱(FT-IR)、X射线能谱仪(EDX)和扫描电子显微镜(SEM)等手段对Ca3Co4O9进行表征。实验结果表明,干凝胶在700-900℃条件下恒温煅烧2h,即可获得纯相Ca3Co4O9片状晶体,其晶粒尺寸约为1-2μm。     

Ca_3Co_4O_(9+δ)热电陶瓷的晶粒细化及其电学性能研究

以乙二醇(EG)为溶剂,采用柠檬酸溶胶-凝胶法成功制备了晶粒细化的Ca3Co4O9+δ粉体,结合SPS烧结技术烧结成陶瓷块体,分析了晶粒尺寸对Ca3Co4O9+δ电学性能的影响。研究发现,以EG为溶剂能有效降低晶粒尺寸,XRD和SEM表征结果表明所制备的粉体及块体均为纯相Ca3Co4O9+δ;随着溶剂中EG比例的增加,粉体粒径由1000nm降低至100nm,相应Ca3Co4O9+δ块体的层状晶粒厚度也由1000nm降低至约120nm。电性能测试结果表明,晶粒细化提高了试样的电性能,虽晶粒细化影响了电导率的提高,但Seebeck系数增加,最终试样功率因子增大,当晶粒尺寸为120nm、880K时其功率因子可达299.4×10-6 W/(m·K2)。     

Ca3Co4O9基热电材料的研究进展

Ca3Co4O9是一种很有潜力的氧化物热电材料。本文从Ca3Co4O9的结构出发,讨论了利用不同工艺制备Ca3Co4O9的粉体材料、块体材料和薄膜材料的方法。并针对块体材料和薄膜材料的热电性能进行了一定的分析,提出了提高热电材料性能的途径。     

Sm掺杂对Ca3Co4O9+δ基化合物高温热电性能的影响

用溶胶-凝胶法合成了Ca3-xSmxCo4O9+5(x=0,0.15,0.3和0.45)化合物粉体,并用SPS(Spark Plasma Sintering)烧结方法制备出相对密度＞95%的块体材料.研究了Sm掺杂对其高温热电性能的影响.结果表明在Ca位用Sm替代后材料的Seebeck系数和电阻率都增大,热导率降低.当Sm的掺杂量为10%(即x=0.3)时可获得最佳的热电性能,1000K时它的ZT值可达0.3.     

溶胶-凝胶法制备单相Ca2Co2O5粉体

以Co（N03）2.6H2O，Ca（NO3）2.4H2O为原料，柠檬酸为络合剂，利用溶胶-凝胶法（Sol-gel）制备出Ca2CO2O5粉体。采用TG-DSC、XRD和ESEM等测试方法对干凝胶体的热分解过程、样品的物相以及形貌进行了表征。实验结果表明：干凝胶体在700-900℃煅烧，煅烧2h后均能得到单相的Ca2CO2O5粉体，颗粒尺寸分布均匀，范围在1-2μm。在同一配比浓度、同一煅烧时间下，适当提高煅烧温度有利于Ca2CO2O5晶体的生长。     

Ca3Co4O9的电子结构、化学键及热电性能

Ca3Co4O9是一类很有希望的新型氧化物热电材料,用离散变分密度泛函方法(DFT-DVM)计算了失配层钴酸盐Ca3Co4O9的电子结构和化学键,讨论了它们与热电性能之间的关系.结果表明,Ca3Co4O9属于窄带半导体,在费米能级附近Co 3d主要对导带贡献,O 2p主要对价带贡献.Ca2CoO3层中Co-O键表现出明显的各向异性特征,在c轴方向上化学键比ab-面方向上强.Ca连接了CoO2和Ca2CoO3层的相互作用,Ca与周围O原子的弱结合有可能导致材料的低热导率.     

Ca3Co4O9热电材料及其Ca位掺杂改性

氧化物热电材料Ca3Co4O9与传统热电材料相比具有其独特优势,因而引起了广泛的关注.评述了Ca3Co4O9热电材料的主要结构、热电特性及其Ca位掺杂研究的进展(掺入Na,Bi,Ag等),并对Ca3Co4O9热电材料的应用前景进行了展望.     

负载磷钼杂多酸/La0.7Ca0.3Fe0.25Co0.75O3/聚吡咯的制备及光催化性能研究

采用甘氨酸-硝酸盐燃烧法成功制备了La0.7Ca0.3Fe0.25Co0.75O3钙钛矿型复合氧化物,以(NH4)2S2O8为氧化剂,运用化学氧化法合成La0.7Ca0.3Fe0.25Co0.75O3/聚吡咯薄膜,然后通过静电自组装方法制备了一种新的表面负载修饰型复合光催化剂La0.7Ca0.3Fe0.25Co0.75O3/PPy/PMO12。采用XRD、SEM、FT-IR对催化剂的物化结构进行了表征。光催化性能测试是以亚甲基蓝染料的水溶液为降解目标,结果表明,PMo12的负载修饰改进了La0.7Ca0.3-Fe0.25Co0.75O3/PPy光催化剂的催化活性。     

Magnetic coupling in La0.67Ca0.33MnO3/La0.67Sr0.33CoO3/La0.67Ca0.33MnO3 sandwiches

La_0.67Ca_0.33MnO₃ (LCMO)/La_0.67Sr_0.33CoO₃ (LSCO)/LCMO trilayer films are fabricated on single-crystal substrates NdGaO₃ (110) and the interlayer coupling are investigated. Compared with LCMO single layer, sandwiches showed the enhanced metal-insulator transition temperature of LCMO layers. The magnetoresistance is dependent on spacer thickness and the peak value dramatically decreases when LSCO layer is thick enough because of shorting by the LSCO layer. The magnetic coercivity H_C shows a nonmonotonic behavior with changing spacer layer thickness and the waist-like hysteresis indicates that there is an indirect exchange coupling between the top and bottom LCMO layers across the spacer layer.     

Varistor properties of ZnO-Pr6O11-CoO-Cr2O3-Y2O3-In2O3 ceramics

The varistor properties of the ZnO-Pr₆O₁₁-CoO-Cr₂O₃-Y₂O₃-In₂O₃ ceramics were investigated for different concentrations of In₂O₃. The increase of In₂O₃ concentration slightly increased the sintered density (5.60-5.63 g/cm³) and slightly decreased the average grain size (3.4-2.9 μm). The breakdown field increased from 6023 to 14822 V/cm with increasing concentration of In₂O₃. The nonlinear coefficient increased from 17.6 to 44.6 for up to 0.005 mol%, whereas the further doping caused it to decrease to 36.8. In₂O₃ acted as an acceptor due to the donor concentration, which decreases in the range of 1.02 × 10¹⁷ to 0.24 × 10¹⁷/cm³ with increasing concentration of In₂O₃.     

Nanocrystallization of SrBi2Nb2O9 from glasses in the system Li2B4O7---SrO---Bi2O3---Nb2O5

Transparent glasses in the system (100−x)Li₂B₄O₇–x(SrO---Bi₂O₃---Nb₂O₅) (10≤x≤60) (in molar ratio) were fabricated by a conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via X-ray powder diffraction (XRD) and differential thermal analyses (DTA) respectively. Glass–ceramics embedded with strontium bismuth niobate, SrBi₂Nb₂O₉ (SBN) nanocrystals were produced by heat-treating the as-quenched glasses at temperatures higher than 500 °C. Perovskite SBN phase formation through an intermediate fluorite phase in the glass matrix was confirmed by XRD and transmission electron microscopy (TEM). Infrared and Raman spectroscopic studies corroborate the observation of fluorite phase formation. The dielectric constant (_r) and the loss factor (D) for the lithium borate, Li₂B₄O₇ (LBO) glass comprising randomly oriented SBN nanocrystals were determined and compared with those predicted based on the various dielectric mixture rule formalism. The dielectric constant was found to increase with increasing SBN content in LBO glass matrix.     

Syntheses of hollandite type Rb2Cr8O16, K2Cr2V6O16 and K2V8O16

Hollandite-type compounds, Rb₂Cr₈O₁₆, K₂Cr₂V₆O₁₆ and K₂V₈O₁₆, were synthesized under high P-T conditions up to 1200°C and 7GPa. The structural refinement using a single crystal of Rb₂Cr₈O₁₆ confirms that the structure is similar to that of K₂Cr₈O₁₆. Magnetic measurements indicate that Rb₂Cr₈O₁₆ is ferromagnetic below 295K, K₂Cr₂V₆O₁₆ paramagnetic down to 77K and K₂V₈O₁₆ has susceptibility anomaly at 175K. These compounds are all semiconductive and show discontinuities in temperature-resistivity curves at points corresponding to magnetic anomalies.     

PbSbBiS4-Sb2S3 and PbSbBiS4-Bi2S3 joins in the PbS-Sb2S3-Bi2S3 system

Phase equilibria along the PbSbBiS₄-Sb₂S₃ and PbSbBiS₄-Bi₂S₃ joins of the PbS-Sb₂S₃-Bi₂S₃ system have been studied for the first time using differential thermal analysis, X-ray diffraction, microstructural analysis, microhardness tests, and density measurements, and the phase diagrams of the joins have been mapped out. The joins are shown to be pseudobinary with limited series of terminal solid solutions. The solid solutions are p-type semiconductors.     

Microstructures of YBa2Cu3O7/La0.7Ca0.3MnO3 and La0.7Ca0.3MnO3/YBa2Cu3O7 bi-layers grown on (001)LaAlO3

Epitaxial YBa₂Cu₃O₇/La_0.7Ca_0.3MnO₃ (YBCO/LCMO) bi-layers and La_0.7Ca_0.3MnO₃/YBa₂Cu₃O₇ (LCMO/YBCO) bi-layers were grown on (001)LaAlO₃ by pulsed laser deposition, and their microstructures were compared by transmission electron microscopy investigation. In the YBCO(100 nm)/LCMO(150 nm) bi-layers, the LCMO layer consists of columnar grains of ~ 17 nm in diameter and contains mixed orientation domains of [100]_c, [010]_c and [001]_c. The YBCO layer is totally c-axis oriented and the YBCO lattices are tilted − 2.5° to + 2.5° as they grew on the rough surfaces of LCMO columnar grains. For the LCMO(140 nm)/YBCO(140 nm) bi-layers, the LCMO/YBCO interface is sharp and flat. The initial 12-nm thickness of the YBCO layer is composed of c-axis oriented domains, and the upper part of YBCO layer is [100] oriented. The LCMO layer was predominantly [001]_c oriented while [100]_c-oriented domains were occasionally observed.     

Vapour-liquid equilibria in the ternary mixtures N2---CH4---C2H6 and N2---C2H6---C3H8

A systematic study was performed with mixtures consisting of N₂, CH₄, C₂H₆ and C₃H₈, to investigate experimentally phase equilibria and caloric properties and to test the accuracy of thermodynamic correlations. The first part of this Paper reports results of T---p---x---y measurements on ternary systems in the range 20 < p < 120 bar and 140 < T < 220 K. The results are compared with data calculated by generalized equations of state.     

Characterization of YBa2Cu3O7/PrBa2Cu3O7 superlattices

We investigated the structural and superconducting properties ofc-axis oriented (YBa₂Cu₃O₇) _nY /(PrBa₂Cu₃O₇) _npr superlattices with thicknesses of the individual layers down to one unit cell (10nY1; 18>nPr 1). By transmission electron microscopy and X-ray diffraction we find an excellent structural quality of the samples, though the quantitative analysis shows the existence of defects. In superlattices with decoupled YBa₂Cu₃O₇ layers of two unit cell thickness we find a highT _c value of 75 K. We probed the flux line structure in the superlattices by measurements of the critical current density in magnetic fields. The experiments show that the flux-line dynamics is dominated by the movement of pancake vortices.     

Structural study of Sr0.3Ba0.7Nb2O6 and La0.030Sr0.255Ba0.700Nb2O6 ceramic systems

Sr_0.3Ba_0.7Nb₂O₆ (SBN) and La_0.030Sr_0.255Ba_0.700Nb₂O₆ (LSBN) ceramic compounds have been prepared using the traditional ceramic method at two different calcination temperatures (900 and 1000 °C) and later sintered both at 1400 °C. A study of the effects of the calcination temperatures and La substitution on the morphological, compositional, and structural properties of SBN and LSBN is presented using scanning electronic microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD) analysis. From Rietveld refinement processes, the XRD patterns were interpreted to evaluate such effects in the structural parameters and the site occupation factors of the heavy metals and oxygen atoms. The effect of the incorporation of La resulted in a 0.25% cell contraction and turned out to be higher than the 0.08% dilation effect produced by the increase of calcination temperature. The La ion with similar effective ionic radius and higher electronegativity is incorporated into the structure occupying the A₁ site just like the Sr ions in the SBN compound. Differences in the site occupation factors between the SBN and LSBN samples lead to substantial changes in the physical properties such as temperature of relative dielectric constant maximum, relative dielectric constant, and dielectric loss, correlated with the distortion and the relative orientation of the oxygen octahedra.     

The effect of Bi1.5Zn0.5Nb0.5Ti1.5O7 cover layer on the dielectric and tunable properties of Ba0.6Sr0.4TiO3/Bi1.5Zn0.5Nb0.5Ti1.5O7 bilayered thin films

Bi_1.5Zn_0.5Nb_0.5Ti_1.5O₇ (BZNT) thin films with different thicknesses as cover layers were deposited on the Ba_0.6Sr_0.4TiO₃ (BST) thin films on the Pt/Ti/SiO₂/Si substrates by radio frequency magnetron sputtering method. The microstructure, surface morphology, dielectric and tunable properties of BST/BZNT heterogeneous bilayered films were investigated as a function of the thickness of BZNT films and the effect of BZNT films on the asymmetric electrical properties of BST/BZNT bilayered films was discussed. It was found that BZNT cover layer significantly improved the leakage current and the dielectric loss, and the dielectric constant and tunability of BST/BZNT bilayered thin films simultaneously decreased with the increasing thickness of BZNT films. The BST/BZNT bilayered thin film with a 50 nm BZNT cover layer gave the largest figure of merit (FOM) of 33.48 with the upper tunability of 55.38%. The asymmetric electrical behavior of BST/BZNT bilayered films is probably related to an internal electric field caused by built-in voltages at Pt/BST and BZNT/Au interfaces.