Al掺杂NdFeO_3体系的晶体结构精修与磁特性研究

利用固相反应法制备了Al掺杂的NdFe1-xAlxO3系列化合物。通过X射线粉末衍射和结构精修分析发现,随着Al掺杂量的增加,样品晶胞参数变小,晶胞内Fe—O键长、Fe—O—Fe键角也发生了很大程度的改变,并且在a、b、c方向上存在不同的变化规律。Al掺杂导致样品结构上的改变对其磁学性质具有重要影响。磁测量结果表明,随着Al掺杂量的增加,由dzyaloshinsky-moriya(D-M)相互作用导致的宏观磁性逐渐减弱;由Nd离子磁晶格与Fe离子磁晶格耦合作用导致的体系自旋重取向相变温度向低温方向移动,样品的饱和磁化强度随着Al掺入浓度的增加呈减小趋势。表明Fe位非磁性元素Al的掺入,使得样品内部由D-M相互作用所引起的倾角反铁磁结构受到了明显的调制。     

La2/3Sr1/3MnO3掺杂RE(RE=Pr、Eu、Y、Tb)的结构、红外及磁学性质

采用空气中固相反应烧结法制备了一系列钙钛矿结构的(La1-xREx)2/3Sr1/3MnO3(RE=Pr、Eu、Y、Tb;x=0、0.3或0.4)掺杂稀土锰氧化物多晶样品.X射线衍射(XRD)分析表明随着RE离子半径的减小,样品XRD的衍射峰位置普遍向高角度偏移,2θ增大0.02～0.62°.扫描电镜(SEM)观测的结果表明掺杂RE离子的半径越小,形成多晶样品的晶粒越小,未掺杂RE的La2/3Sr1/3MnO3在所有的样品中晶粒最大.红外吸收光谱测量发现样品在599～629cm-1范围出现了吸收峰并且峰的位置随掺杂RE离子半径的减小而向低频方向偏移.样品的磁性质测量表明掺杂稀土离子的半径及磁矩对材料的磁电阻有明显影响.     

La0.6Sr0.15Na0.1□0.15MnO3+xAgNO3复合体系的结构、磁性及磁电阻的温度稳定性研究

采用固相反应法制备了La0.6Sr0.15Na0.1□0.15MnO3+xAgNO3(x=0.08、0.16、1.00,x为物质的量比,□代表空位)系列复合材料样品,对复合样品的相结构、磁性质及其磁电阻效应进行了研究。通过相结构的研究发现:复合样品近似呈现La0.6Sr0.15Na0.1□0.15MnO3/Ag/Mn3O4的特殊复合结构。通过对磁电阻的研究发现:复合样品不同程度地提高了母体样品的MR峰值,降低了峰值温度,使其更接近室温。在204～280K的温度范围内和1.8T外磁场作用下,当x=0.08时,MR保持在(4.70±0.25)%;x=0.16时,MR保持在(7.20±0.28)%。所以,复合样品较之母体样品,磁电阻的温度稳定性有了很大提高。     

空穴掺杂Sr2FeMoO6的输运性质研究

采用扫描电子显微镜和四探针技术研究了空穴掺杂系列样品Sr2-xKxFeMoO6(0≤x≤0.04)的输运性质。结果表明,空穴掺杂提高了该系列样品的结晶度,使颗粒均匀,空洞变少,晶粒尺寸由未掺杂时的约为2μm变化至掺杂量x=0.04时的约为1μm。四探针输运结果表明该系列样品的金属-绝缘体转变温度(TS-M)由未掺杂时的170K变化至掺杂量x=0.04时的72K。晶粒尺寸、阳离子有序、载流子浓度是影响Sr2-xKxFeMoO6输运性质的重要因素。     

Zn2+、Cr3+掺杂对水热合成纳米CoAl2O4尖晶石色料的影响

以CoCl2·6H2O、ZnCl2、AlCl3和CrCl3·6H2O为原料,采用水热法合成了CoAl2O4(AB2O4)尖晶石型纳米钴蓝色料.采用色度分析、X射线衍射(XRD)、透射电镜(TEM)以及高分辨透射电镜(HRTEM)等研究了A位掺杂Zn2+和B位掺杂Cr3+时不同掺杂量以及不同水热合成温度对样品呈色、晶相组成及CoAl2O4尖晶石的晶粒大小、发育程度和晶面间距的影响.结果表明,掺杂Zn2+、Cr3+所得固溶体型钴蓝色料晶粒发育均不完整,颗粒较于相同水热条件下获得的未掺杂样品更细小.A位掺杂Zn2+可降低CoAl2O4色料的合成温度,在230℃便能制得呈色较佳的Co0.95Zn0.05Al2O4钴蓝色料.随着Zn2+掺杂量的增加,合成产物由蓝色转为绿色,且呈色逐渐变浅.B位Cr3+掺杂则随着掺杂量的增加,产物从蓝色逐步转为绿色,但呈色逐渐变深.就两者相比较,A位掺杂Zn2+更有利于色料明度值的提高而呈色鲜亮.     

Mn掺杂快淬NdFeB永磁体磁性能研究

在前期研究工作的基础上,从热磁重(TMA)测量出发对快淬Nd9Fe85-xMnxB6(x=0～2)的相关磁性能及交换耦合效应作了进一步的研究.发现在最佳的热处理条件下,一定的Mn掺杂能提高快淬NdFeB的磁性能,特别是矫顽力最大能提高20%左右,但是更高的Mn掺杂量会导致矫顽力和最大磁能积的明显下降.XRD显示快淬态的NdFeB样品的晶化程度随Mn掺杂量提高而提高,但在最佳的热处理条件下所有的快淬NdFeB样品都包括硬磁性相Nd2Fe14B和软磁性相α-Fe.热磁重(TMA)测量显示一直随着Mn掺杂量提高到2%(原子分数),硬磁性相Nd2Fe14B的居里温度(Tc)在不断下降,但是α-Fe的Tc却随Mn掺杂量提高而提高.认为磁性能和居里温度改变是因为形成了δ-Mn和R2Fe23B3相.当Mn掺杂量较低时高温下有δ-Mn形成并和α-Fe产生交换耦合作用导致α-Fe的居里温度升高,而当Mn掺杂量提高到2at%时形成的R2Fe23B3相固溶δ-Mn相才导致α-Fe的居里温度下降.     

Al掺杂对自旋梯子化合物Sr14Cu24O41电输运性质的影响

利用固相反应法制备了Al掺杂的Sr14(Cu1-xAlx)24O41(x=0,0.01,0.02,0.03)系列多晶样品。X射线衍射结果表明所有样品均为单相,Al掺杂使样品晶格常数a、b发生涨落,但使晶格常数cladder逐渐减小。X射线光电子能谱结果表明Al掺杂对体系内Sr、Cu、O离子价态不存在影响,并且Al离子以+3价的形式替代了Sr14Cu24O41体系内的Cu2+,不存在其他混合价态。电阻率测量结果表明所有样品均呈半导体性,Al掺杂使体系电阻率升高。进一步分析表明所有样品存在一渡越温度Tρ,Al掺杂使Tρ发生微弱涨落。在Tρ以上,自旋梯子中单个空穴热激活对体系电导存在贡献。在Tρ以下,自旋梯子中空穴的变程跳跃电导对体系电导存在贡献。实验数据拟合结果表明Al掺杂使体系内单个空穴热激活能Δ以及局域态势垒参数T0逐渐增大。     

合金元素对块体纳米晶Fe3Al材料磁学性能的影响

为了研究合金元素对块体纳米晶Fe3Al材料磁学性能的影响,通过铝热反应熔化法制备了纳米晶Fe3Al以及分别含Ni质量分数10%、Cr质量分数10%、Mn质量分数10%和含Ni质量分数10%-Cu质量分数2%的块体纳米晶Fe3Al.在振动样品磁强计(VSM)上测得合金的磁滞回线,分析其磁性能,采用X射线衍射仪进行结构分析和平均晶粒尺寸计算.结果表明:各样品的磁滞回线呈倾斜状且狭长,磁滞损耗很小;含Ni质量分数10%的样品饱和磁化强度Ms较大,剩余磁化强度Mr和矫顽力Hc较其他样品最小,具有较好的软磁性能;添加合金元素后几种材料的晶粒尺寸变小,磁性能有较大变化,合金元素对纳米晶Fe3Al块体材料的磁性能影响明显.     

热处理温度对纳米CoFe2O4/SiO2复合材料结构和磁性的影响

采用溶胶2凝胶法制备了纳米 Co Fe 2O 4/ SiO 2复合材料。利用 X射线衍射(XRD) 、 透射电镜( TEM) 、 振动样品磁强计(VSM)和 Mssbauer 效应研究了纳米复合材料结构、 晶粒尺寸及磁性。结果表明 , 样品中 Co Fe 2O 4的晶粒尺寸随着热处理温度的提高而增加 , 非晶态 SiO 2的存在有效地抑制了 Co Fe 2O 4晶粒的生长。VSM结果表明 , 样品的比饱和磁化强度和矫顽力随 Co Fe 2O 4晶粒尺寸的增加而变大。Mssbauer 效应结果表明 , 随着热处理温度的提高 , 样品从超顺磁和磁有序的混合状态转变为完全的磁有序状态。     

La空位和Sr离子掺杂对La-Ca-MnO材料磁性能的影响

用溶胶-凝胶法制备了La位空位掺杂La_(0.7-x)Ca_(0.28)Sr_(0.02)MnO_3(x=0.00~0.10)系列样品和Sr离子掺杂La_(0.77-x)Ca_(0.2)Sr_xMnO_3(x=0.00~0.10)系列样品,研究了La位空位掺杂和Sr离子掺杂对样品相结构、居里温度和磁熵变的影响。结果表明,两个系列样品都在近室温有较大磁熵变,对于钙钛矿La-Ca-MnO_3型材料,在La位含少量空位的基础上进行Sr离子掺杂,对居里温度和磁熵都有较积极的调节作用。     

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.