杂质对Gd_5(Si_xGe_(1-x))_4(x≈0.5)合金结构与磁熵变的影响

采用纯度分别为99.94%和99.2%的稀土金属Gd,配制了Gd5Si1.9Ge2.1和Gd5Si1.72Ge2.28两组合金,研究杂质对Gd5(SixGe1-x)4合金磁熵变的影响原因。粉末衍射结构分析表明,所研究的合金中都有Gd5Si2Ge2相,而采用低纯Gd配制的Gd5(SixGe1-x)4合金中还出现了明显的Gd5(Si,Ge)3相。磁性测量表明,杂质不改变合金中主相的居里温度,即没有改变合金中主相磁性原子的相互作用,但由于低温反铁磁性Gd5(Si,Ge)3相对室温Gd5Si2Ge2相的磁熵变没有贡献,导致Gd5(SixGe1-x)4合金在室温附近的磁熵变下降。     

GdsSi1．975Ge1.975T0，05（T=Ni，Fe，Cr，Mn，Co）合金的结构及磁热效应

研究了GdsSi1．975Ge1.975T0,05（为Ni,Fe,Cr,Mn,Co）合金的结构及磁热效应。XRD结果显示：当T元素的原子序数为偶数时,合金形成了单一的Gd5Si2Ge2单斜结构;而当原子序数为奇数时,则为Gd5Si2Ge2单斜结构和正交结构的混合相。在拥有单一相的合金中均发现了巨磁热效应,然而在具有混合相的合金中由于未能发生一级结构相变而导致了低的磁熵变。此外,GdsSi1.975Ge1．975Cr0.05合金的磁制冷量达到了112J／kg,相对于Gd5Si2Ge2合金提高了50％。     

Gd5Si1.975Ge1.975T0.05(T=Ni,Fe,Cr,Mn,Co)合金的结构及磁热效应

研究了Gd5Si1.975Ge1.975T0.05(T为Ni、Mn、Cr、Co、Fe)合金的结构及磁热效应.XRD结果显示:当T元素的原子序数为偶数时,合金形成了单一的Gd5Si2Ge2单斜结构;而当原子序数为奇数时,则为Gd5Si2Ge2单斜结构和正交结构的混合相.在拥有单一相的合金中均发现了巨磁热效应,然而在具有混合相的合金中由于未能发生一级结构相变而导致了低的磁熵变.此外,Gd5Si1.975Ge1.975Cr0.05合金的磁制冷量达到了112 J/kg,相对于Gd5Si2Ge2合金提高了50%.     

Sn合金化对Gd5Si2Ge2磁致冷材料结构和性能的影响

以商业纯Gd为原料,采用非自耗电弧炉氩气保护下熔炼了Gd5Si2Ge2-xSnx(x=0.2,0.5,1)和Gd5Si2-yGe2Sny(y=0.1,0.2,0.5)系列合金,研究Sn合金化对Gd5Si2Ge2晶体结构和磁热性能的影响.粉末XRD结果表明Sn代Ge样品具有正交Gd5Si4型结构;Sn少量代Si(y=0.1,0.2)的样品具有单斜Gd5Si2Ge2型结构;Gd5Si1.5Ge2Sn0.5则为单斜和正交的混合结构.用超导量子磁强计(SQUID)测定了样品的M-T和不同温度的M-H曲线,结果表明Gd5Si2Ge2-xSnx(x=0.2,0.5,1)不具有巨磁热效应;Gd5Si1 9Ge2Sn01合金的最大磁熵变达15.3 J/kg·K(0 T～5 T),具有巨磁热效应.     

磁致冷材料研究进展

介绍了磁致冷材料磁热效应的表征方法，概述了国内外各温度区间磁致冷材料的研究进展。在20K以下温区，磁致冷材料研究主要集中在具有高导热率、低点阵热容和极低有序化温度的石榴石，如Gd3Ga5O12(GGG)，Dy3Al5O12(DAG)，Gd3Ga5-xFexO12(GGIG)及Er基磁致冷材料；20K～77K温度区间，磁致冷材料研究主要集中在重稀土金属间化合物中，如(Dy1-xErx)Al2复合材料等；在室温附近，具有大磁热效应的磁致冷材料以稀土Gd，Gd5(SixGe1-x)4(0≤x≤0．5)和MnFeP1-xAsx(0．15≤x≤0．66)合金为代表，特别是Gd5Si2Ge2(Tc=274K)和MnFeP0.45As0.55(Tc=300K)合金，在磁场5T下具有巨磁热效应，是Gd的2倍以上。总结了各温度区间磁致冷材料的选择依据。重点评述了室温磁致冷材料的最新研究成果，展望了室温磁致冷材料的发展前景。     

原材料Gd对Gd-Si-Ge合金巨磁热效应影响的研究

采用国产钆制作Gd—Si—Ge合金，测量H-M曲线，计算磁熵变(-△Sm)判断其磁热效应。发现采用商业级钆配制合金时，由于杂质抑制了材料的一级相变，未发现巨磁热效应。经提纯后的钆尽管没有Ames实验室的纯度高，但配制的合金具有典型的一级相变，-△Sm值基本上达到Ames实验室报道的数据，而且居里点有所提高。     

Gd-Si-Ge磁致冷材料研究进展

介绍了Gd.Si.Ge磁致冷材料的晶体结构、磁相变、磁热效应、制备方法、防腐等方面的研究进展.室温磁致冷材料Gds(Si,Ge1-x)4在O≤x≤0.5、磁场H>5T时,呈现巨磁热效应;磁热效应的物理本质是一级磁晶相变;原材料Gd对Gd-Si-Ge系合金巨磁热效应的影响较大;Gd-Si-Ge磁致冷材料的成型方法主要有包覆法、复合法和真空扩散焊等.     

RE对（Gd1-xREx）5Si4合金晶体结构及居里温度的影响

用真空电弧熔炼制备（Gd1-xREx）5Si4（x=0．1，0．2，0．3，0．35）和（Gd1-xHox）5Si4（x=0．05，0．15，0．25）系列合金，在950℃下168h的真空热处理后，对其晶体结构、居里温度进行了研究。室温XRD分析发现该系列合金仍保持Gd5Si4的Sm5Ge4正交型结构，采用Rietveld法分析计算发现合金晶格常数随着X量的增加而逐渐减小。试样M-T磁化曲线测量结果表明：居里温度瓦在336K～260K连续可调，改变RE的含量可以得到不同的居里温度Tc;Tc近似呈线性变化，由此得出估计（Gd1-xREx）5Si4（RE=Dy，Ho）的Tc的计算公式。     

添加元素Sn对Gd5Si2Ge2合金磁热效应的影响

为了解决Gd5Si2Ge2磁制冷合金居里点低，制冷温区狭窄问题，采用合金化的方法，利用添加元素Sn代替Si或Ge，提高了Gd5Si1.9Ge2Sn0.1材料的居里温度，同时保持工质材料Gd5Si2Ge2的巨磁热效应，并相对于Gd5Si2Ge2合金的制冷温区有了很大的拓展。     

快速凝固Gd5Si2Ge2合金的显微组织与相组成

研究了在真空电弧炉和快淬炉2种快速凝固条件下制备的Gd5Si2Ge2合金的显微组织与相组成。结果表明，Gd5Si2Ge2合金亿电弧炉熔炼条件下，具有不同质蟹的样品可以获得不同的显微组织与相组成。不同速度下，快淬甩带实验表明，在小于40m／s的快淬速度下，Gd5Si2Ge2合金为单斜Gd5Si2Ge2-型晶体结构：在50m／s的快淬速度下Gd5Si2Ge2合金包含Gd5Si4-型和Gd5Si2Ge2-型两相。证实了冷却速度对Gd5Si2Ge2合金的相组成有重要影响。     

Crystal structures and structural relationships of KFe2(SeO2OH)(SeO3)3 and SrCo2(SeO2OH)2(SeO3)2

The new phases KFe₂(SeO₂OH)(SeO₃)₃ and SrCo₂(SeO₂OH)₂(SeO₃)₂ have been synthesized under low-hydrothermal conditions and their structures were determined by single-crystal X-ray methods. Both compounds are monoclinic; KFe₂(SeO₂OH)(SeO₃)₃: space group P2, A = 9.983(4), B = 5.270(1), C = 10.614(4) Å, β = 97.42(2)°, V = 553.7 ų, Z = 2; SrCo₂(SeO₂OH)₂(SeO₃)₂: space group P2ln, A = 14.984(2), B = 5.286(1), C = 13.790(2) Å, β = 94.72(1)°, V = 1088.5 ų , Z = 4. The refinements converged to R-values of 2.9 and 3.6% respectively.

The atomic arrangement in KFe₂(SeO₂OH)(SeO₃)₃ and SrCo₂(SeO₂OH)₂(SeO₃)₂ is based on isolated MO₆ octahedra (M = Fe³⁺, Co²⁺), which are corner-linked via trigonal pyramidal selenite groups to a framework structure. Interstitials are occupied by potassium or strontium atoms in ten- or eight-coordination respectively, and by the lone-pair electrons of the Se⁴⁺ atoms. Both compounds are not isotypic but are closely related and may be interpreted as different distortions of an idealized structure type in space group P2/m, which was modelled for a theoretical compound SrFe₂(SeO₃)₄ by distance least squares refinement (program ).     

Thermal expansion studies on Th(MoO4)2, Na2Th(MoO4)3 and Na4Th(MoO4)4

Thermal expansion behavior of Th(MoO₄)₂, Na₂Th(MoO₄)₃ and Na₄Th(MoO₄)₄ was studied under vacuum in the temperature range of 298–1123 K by high temperature X-ray diffractometer. Th(MoO₄)₂ was synthesized by reacting ThO₂ with 2 mol of MoO₃, at 1073 K in air and Na₂Th(MoO₄)₃ and Na₄Th(MoO₄)₄ were prepared by reacting Th(MoO₄)₂ with 1 and 2 mol of Na₂MoO₄, respectively at 873 K in air. The XRD data of Th(MoO₄)₂ was indexed on orthorhombic system where as XRD data of Na₂Th(MoO₄)₃ and Na₄Th(MoO₄)₄ were indexed on tetragonal system. The lattice parameters and cell volume of all the three compounds, fit into polynomial expression with respect to temperature, showed positive thermal expansion (PTE) up to 1123 K. The average value of thermal expansion coefficients for Th(MoO₄)₂, Na₂Th(MoO₄)₃ and Na₄Th(MoO₄)₄ were determined from the high temperature data.     

Kinetic study on Li2.8(V0.9Ge0.1)2(PO4)3 by EIS measurement

Kinetics for lithium ion transfers in the fast ionic conductor Li_2.8(V_0.9Ge_0.1)₂(PO₄)₃ prepared by solid-state reaction method has been studied by electrochemical impedance spectroscopy (EIS) at various temperatures and the results were correlated with observed cathodic behavior. The specific conductivities of Li_x(V_0.9Ge_0.1)₂(PO₄)₃ (x = 0.9–2.8) versus temperatures were analyzed from blocking-electrodes by Wagner's polarization method and the activation energy was calculated. It was observed that electronic conductivities of Li_x(V_0.9Ge_0.1)₂(PO₄)₃ increased with lithium contents in the materials. The compounds show a reversible capacity of 131 mAh g⁻¹ at low current density (13 mA g⁻¹). Modeling the EIS data with equivalent circuit approach enabled the determination of charge transfer and surface film resistances. The Li ion diffusion coefficient (D_Li⁺) versus voltage plot shows three valleys during the first charge cycle coinciding with the irreversible plateau of the voltage versus lithium content profiles reflecting the irreversible phase change in the compound. The obtained D_Li⁺ from EIS varies within 10⁻⁸ to 10⁻⁷ cm² s⁻¹, so Li_2.8(V_0.9Ge_0.1)₂(PO₄)₃ shows excellent chemical diffusion performance.     

Electrochemical performances of Ag–(Bi2O3)0.75(Y2O3)0.25 composite cathodes

The electrochemical performances of Ag–Y_0.25Bi_0.75O_1.5 (YSB) composite cathodes on Ce_0.8Sm_0.2O_1.9 (SDC) electrolytes have been investigated at intermediate temperature using AC impedance spectroscopy. The results indicated that the electrochemical performances of these composites are quite sensitive to the compositions and the microstructures of the cathode. The optimum YSB addition to Ag resulted in 10 times lower area specific resistance. The ASR of Ag-50 vol.% YSB was about 0.12 Ωcm² at 700 °C as compared to 3.9 Ωcm² for Ag cathodes. The observed high performance of Ag–YSB composite cathodes might be due to the high oxygen-ion conductivity of YSB and its high catalytic activity for oxygen reduction.     

Preparation and characteristic of spherical Li3V2(PO4)3

Spherical Li₃V₂(PO₄)₃ was synthesized by using N₂H₄ as reducer. The products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that single-phase, spherical and well-dispersed Li₃V₂(PO₄)₃ has been successfully synthesized in our experimental process. Electrochemical behaviors have been characterized by charge/discharge measurements. The initial discharge capacities of Li₃V₂(PO₄)₃ were 123 mAh g⁻¹ in the voltage range of 3.0–4.3 V and 132 mAh g⁻¹ in the voltage range of 3.0–4.8 V.     

Structural and thermal studies on Na2U(MoO4)3 and Na4U(MoO4)4

In Na–U(IV)–Mo–O system, two quaternary compounds Na₂U(MoO₄)₃ and Na₄U(MoO₄)₄ were prepared by solid state reactions of Na₂MoO₄, UMoO₅ and MoO₃ in the required stoichiometric ratio at 500 °C in evacuated sealed quartz ampoules. The crystal structure of both the compounds were derived from X-ray powder diffraction data in the tetragonal system by Rietveld profile method. Na₂U(MoO₄)₃ has scheelite structure, whereas Na₄U(MoO₄)₄ has scheelite superlattice structure.

TG curves of Na₂U(MoO₄)₃ and Na₄U(MoO₄)₄ did not show any significant weight change up to 750 °C in an inert atmosphere. During the heating cycle in an inert atmosphere, DTA curves of Na₂U(MoO₄)₃ and Na₄U(MoO₄)₄ showed endothermic peaks due to the melting of the compounds at 740 °C and 730 °C, respectively. Na₂U(MoO₄)₃ and Na₄U(MoO₄)₄, when heated in air atmosphere at 1200 °C, decomposed to form Na₂U₂O₇ which was confirmed by weight loss calculation and XRD.     

氧化铝掺杂对Ba0.6Sr0.4(Zr0.2Ti0.8)O3陶瓷介电性能的影响

Zr4+取代Ti4+的Ba0.6Sr0.4(Zr0.2Ti0.8)O3固溶体在降低介电常数的同时,保持了BST固溶体优异的可调性。为降低BST材料的介电损耗和介电常数,以氧化铝为改性剂对Ba0.6Sr0.4(Zr0.2Ti0.8)O3材料(BSZT材料)进行了掺杂。随着氧化铝掺杂质量分数从1%到10%增加,BSZT材料的介电常数从5000降低到了1550(100kHz),介电损耗降低到0.001(100kHz)以下,而材料的介电可调性保持在35%左右(1.5kV/mm)。X射线衍射图谱表明,烧结后得到的BSZT材料具有典型的钙钛矿结构。扫描电子显微镜观察表明,氧化铝的掺杂使得陶瓷致密度较高,晶粒均匀。     

Crystal structure of Nax(MoO)5(P2O7)4 studied by synchrotron X-ray diffraction

The crystal structure of sodium pentamolybdyl tetradiphosphate Na_x(MoO)₅(P₂O₇)₄ has been determined from synchrotron diffraction data collected at 293 K on two microcrystals. The compound crystallizes in a monoclinic space group I 1 1 2/a (no. 15, setting 11), with unit cell parameters a = 22.905(3), b = 23.069(2), c = 4.8537(2) Å, γ = 90.641(9)° and a = 22.898(3), b = 23.056(2), c = 4.8551(2) Å, γ = 90.82(1)°, for crystals I and II, respectively. The structure is pseudo-tetragonal, and the crystals are pseudo-merohedrally twinned by 90° rotation around the c-axis. The structure closely resembles the previously reported Li-deintercalated Mo_1.3OP₂O₇ [V.V. Lisnyak, N.V. Stus, P. Popovich, D.A. Stratiychuk, Ya. Filinchuk, V.M. Davydov, J. Alloys Compd. 360 (2003) 81–84]. Comparison of the two structures led us to conclude that the Mo₂ and Mo₃ clusters were erroneously identified in Mo_1.3OP₂O₇. A revised structure of Mo_1.3OP₂O₇ contains a fully occupied oxygen site instead of the 16% occupied Mo(2) site, thus the revised formulae for the Li-deintercalated compound is (MoO)₅(P₂O₇)₄. In both structures, the (MoO)₅(P₂O₇)₄ framework strongly resembles the one in the earlier reported Ag(MoO)₅(P₂O₇)₄, while the location of Na and Ag atoms differ.     

Mechanical relaxations of a (Zr77.5Ti22.5)55(Ni48Cu52)21.25Be23.75 amorphous alloy studied using dynamic mechanical analysis

The dynamic mechanical properties of a (Zr_77.5Ti_22.5)₅₅(Ni₄₈Cu₅₂)_21.25Be_23.75 amorphous alloy were investigated by frequency-dependent elastic moduli and isothermal multi-frequency measurements. The frequency-dependent loss modulus showed a relaxation behavior resulting from a glass transition, and the variation of the peak frequency was related to the Arrhenius equation. Isothermal multi-frequency measurement data were used to construct the master curves of the elastic moduli and tan δ by applying the time-temperature superposition principle. The temperature dependence of the shift factor was found to follow the Arrhenius relationship, and the activation energies for the low temperature relaxation and glass transition were approximately 156.6kJ/mol and 554kJ/mol, respectively. The glass transition temperature (T _g) was manifested by the crossover region of the shift factor dependence, and from the relationship between the shift factors and the temperature aboveT _g), the fragility index of this alloy was estimated.     

Phase equilibria in the AlVO4-Al2(MoO4)3 system

The phase equilibria established in the AlVO₄-Al₂(MoO₄)₃ system over the whole component concentration range up to 1000 °C have been investigated. A phase diagram has been constructed using the results of DTA and XRD methods. The AlVO₄-Al₂(MoO₄)₃ system is not a true two-component system, even in the subsolidus area.