Gd5Si1.75Ge1.75Sn0.5的结构、磁相变与磁熵变

采用粉末XRD和振动样品磁强计研究了Gd5Si1.75Ge1.75Sn0.5合金的结构、磁相变和低场变化下的磁熵变。磁性测量结果表明,Gd5Si1.75Ge1.75Sn0.5合金的磁化强度在居里温度附近发生突变,具有一级相变的典型特征,室温具有Gd5Si2Ge2型单斜结构;合金低场磁热效应非常明显,1.8T磁场变化下,在其居里温度272K附近的最大磁熵变为16.7J.kg-1.K-1。用成本低廉的Sn取代Gd5Si2Ge2中部分Si和Ge后,Gd5Si1.75Ge1.75Sn0.5在低磁场变化下的磁熵变比金属Gd大得多并略高于Gd5Si2Ge2。     

(Gd1-xREx)5Si4(RE=Dy, Ho)系列材料磁熵变研究

对 (Gd1-xDyx)5Si4(x=0.1, 0.2, 0.3, 0.35) 和(Gd1-xHox)5Si4(x=0.05, 0.15, 0.25)系列合金的居里温度、磁相变、磁熵变等磁性质进行了研究. 结果发现 该系列合金保持了Gd5Si4的Sm5Ge4正交型晶体结构, 居里温度随着引入的x量的增加而呈近似线性减小趋势;在居里温度附近样品的磁特性符合二级相变规律;通过调节Dy 或Ho的含量调节居里点, 样品中不含贵重元素Ge, 大大降低了成本;在较宽的温度范围和低场下(＜2 T)具有较大的磁熵变值从而使其适合于被制成梯度功能复合材料. 研究表明 (Gd1-xREx)5Si4(RE=Dy, Ho)系列材料有望成为较好的室温低场磁制工质.     

稀土Gd5Ge2(Si2-xAlx)合金系的晶体结构和磁卡效应研究

用磁控电弧炉在氩气气氛下熔炼了Gd5Ge2(Si2-xAlx) (x=0, 0.1, 0.2, 0.5, 1.0)系样品.X射线粉末衍射分析表明, 样品基本为单相结构, 其晶体对称性不会随Al含量的增加而改变.用振动样品磁强计测量了样品的M-T曲线和不同温度下的M-H曲线.居里温度随Al含量x的增加略有减小, 当 x=0.2时Gd5Ge2(Si2-xAlx)有最大-ΔSM值.退火对样品的居里温度和磁卡效应影响不大, 退火前后的居里温度和磁卡效应基本保持一致.     

热处理对Mg-11Gd-2Y-5Sm-0.5Zr合金组织和力学性能的影响

采用光学显微镜、扫描电镜、X射线衍射仪、显微硬度计和万能力学试验机等研究了Mg-11Gd-2Y-5Sm-0.5Zr合金在不同热处理工艺下显微组织和力学性能的变化规律。结果表明:合金的最佳固溶时效热处理工艺为525℃×8 h+225℃×12 h;Mg-11Gd-2Y-5Sm-0.5Zr合金铸态组织主要由α-Mg基体和沿晶界网状分布的Mg_5Gd,Mg_(41)Sm_5相组成,经固溶时效热处理后析出相主要为均匀分布于晶内和晶界的点状或粒状的Mg_5Gd,Mg_(24)Y_5以及Mg_(41)Sm_5相;经该工艺处理后,合金在室温下的硬度和抗拉强度分别为145.6HV和261.4 MPa;固溶时效态合金的主要强化机制为固溶强化和析出相弥散强化。     

钆对La-Mg-Ni系A_2B_7型储氢合金微观结构和电化学性能的影响

用高频感应熔炼方法制备了稀土系A2B7型La0.83-xGdxMg0.17N i3.05Co0.3A l0.15(x=0~0.5)储氢合金,在Ar气氛中和1173 K下对铸态合金进行退火处理,通过X射线衍射(XRD)、电子探针显微分析方法(EPMA)和电化学测试等分析方法系统研究了稀土Gd部分替代La元素对合金微观组织和电化学性能的影响规律。研究结果表明,合金退火组织主要由Ce2N i7型、Gd2Co7型、Pr5Co19型、PuN i3型和CaCu5型相组成,稀土Gd元素能有效减少和抑制退火组织中CaCu5型相的形成,随Gd含量x增加,合金相组成中A2B7型(Ce2N i7和Gd2Co7型)相丰度呈先增加后减小的规律,当x=0.2时其相丰度最大(91.0%)。合金的PCT吸氢平台压随Gd含量的增加而升高,x=0.5时吸氢平台压力接近0.1 MPa,x=0.2时合金的吸氢量达到最大值1.34%。电化学测试分析表明,随Gd含量x的增加,合金电极最大放电容量和容量保持率均呈先增加后减小的规律,适量的Gd元素可明显改善合金的综合电化学性能。当x=0.2时,合金电极放电容量达到最大值392.9 mAh.g-1,经100...     

La_(0.63)Gd_(0.2)Mg_(0.17)Ni_(3.2-x)Co_(0.3)Al_x(x=0～0.4)储氢合金的微观组织和电化学性能

采用真空感应熔炼方法制备了La0.83Mg0.17Ni3.1Co0.3Al0.1和La0.63Gd0.2Mg0.17Ni3.2-xCo0.3Alx(x=0~0.4)贮氢合金,并在氩气气氛900℃进行退火处理。通过X射线衍射(XRD)、显微电子探针(EPMA)分析方法和电化学测试分析研究了Gd和Al元素对合金微观组织和电化学性能的影响。研究结果表明,该系列合金退火组织主要由Ce2Ni7/Gd2Co7型、Pr5Co19型、PuNi3型和CaCu5型相组成;Gd元素的加入使合金中CaCu5型相明显减少,Ce2Ni7型/Gd2Co7型相显著增加,x=0.1时其相丰度达到81.2%;随Al含量x不断增加,合金中CaCu5型相丰度逐渐增多,当x=0.1~0.2时,CaCu5型相丰度为4%~5%,x=0.4时,其相丰度达到66.65%。电化学测试分析表明,Gd和Al元素对合金电极活化性能影响不大,当x=0.1时,含Gd合金电极放电容量达到最大值391 mAh.g-1,随Al含量x进一步增加,合金电极放电容量降低。含Gd和加入适量的Al元素可使合金电极循环稳定性得到明显提高,当Al含量x=0.1,0.2时,经100次充放电循环后其电极容量保持率S100分别为93.7%和90.1%,其中La0.63Gd0.2Mg0.17Ni3.1Co0.3Al0.1合金具有最好的综合电化学性能。     

La-Fe-M(M=Al, Si)化合物磁热性能研究进展

介绍了La-Fe-M(M=AI,Si)化合物在磁热性能研究方面的最新进展。具有NaZn13型晶体结构,含高浓度Fe的La-Fe—M(M=AI,Si)化合物为良好的软磁材料;用少量的Co替代化合物中Si,Al元素可以将化合物的居里温度提高至室温;对La(Fe1-yCoy)xSi13-x化合物,适量的Si,Co组合可使化合物在室温产生可与Gd5Si2Ge2比拟的磁热效应;加入适量的间隙原子H,也可使La(FexSi1-x)13在室温的磁热性能远远大于金属Gd;对含Si量低及含Si量高的La(FexSi1-x)13化合物在相转变点附近由温度和磁场诱导相变的本质做了详细阐述。     

钆对Mg-2Al-1Zn合金高温力学性能的影响

研究了Gd的添加对AZ21基体合金高温（200℃）力学性能和抗蠕变性能的影响。结果表明：AZ21-xGd合金由-αMg和Al2Gd两相组成,中间相Al2Gd使合金高温拉伸性能和抗蠕变性能得到显著提高,但降低了合金的延伸率。在Gd添加量为2%（质量分数）时,200℃下合金的抗拉强度和屈服强度分别达到148和90 MPa,但随着Gd含量的增加,高温拉伸强度有所下降;当Gd添加量为3.5%时,在200℃/50MPa蠕变条件下,合金70 h的蠕变量为1.2%,第二阶段蠕变率比AZ21基体合金下降了1个数量级。晶界上的Al2Gd中间相数量逐渐增多是提高合金的抗蠕变性能的主要原因,但在晶界上过多的Al2Gd中间相不利于提高合金的高温强度。     

热处理对Mg-Gd-Y-Zr合金组织、性能和腐蚀行为的影响EI北大核心CSCD

以铸态、固溶态和时效态Mg-11Gd-2Y-0.5Zr合金为研究对象,采用X射线衍射仪(XRD)、光学显微镜(OM)、带能谱的扫描电子显微镜(SEM)以及电子拉伸试验机分析了热处理对Mg-11Gd-2Y-0.5Zr合金的微观组织、微区成分、物相组成以及力学性能的影响,并通过静态失重实验和电化学测试研究了不同热处理状态合金的耐蚀性能。结果表明:铸态Mg-11Gd-2Y-0.5Zr合金组织主要由α-Mg基体、Mg_(5)Gd和少量的Mg_(24)Y_(5)相组成,固溶处理后组织均匀,部分未熔相(富Y相)以颗粒状形式存在,时效态合金析出相尺寸较小且弥散均匀分布。固溶和时效态合金的抗拉强度有不同幅度提升,分别为191.33和265.73 MPa,均表现为准解理断裂特征,在本研究范围内,Mg-11Gd-2Y-0.5Zr合金耐蚀性主要与热处理工艺、析出相的形貌和尺寸有关,不同状态下的合金在腐蚀过程中化学反应类型相似。     

磁致冷材料钆硅锗系合金中Si和Gd的重量法联测的研究

参考了HClO4脱水重量法测定Si及草酸盐重量法测定Gd的方法,建立了钆硅锗系合金中主成分Si和Gd联合测定的方法,并详细考查了共存元素及杂质元素对测定的影响。合金共存元素Ge在HCl的存在下,绝大部分可以GeCl4的形式被蒸发,达到与被测元素分离的目的。熔样过程引入的杂质元素Ni可与被测元素Gd,用氨水沉淀分离,残留Ni不足以影响Gd的测定。方法回收率在98.5%以上,Si和Gd的测量相对标准偏差分别在2.6%~3.0%和0.4%~0.5%。     

Sc2MgGa2 and Y2MgGa2

Scandium magnesium gallide, Sc₂MgGa₂, and yttrium magnesium gallide, Y₂MgGa₂, were synthesized from the corresponding elements by heating under an argon atmosphere in an induction furnace. These intermetallic compounds crystallize in the tetragonal Mo₂FeB₂‐type structure. All three crystallographically unique atoms occupy special positions and the site symmetries of (Sc/Y, Ga) and Mg are m2m and 4/m, respectively. The coordinations around Sc/Y, Mg and Ga are pentagonal (Sc/Y), tetragonal (Mg) and triangular (Ga) prisms, with four (Mg) or three (Ga) additional capping atoms leading to the coordination numbers [10], [8+4] and [6+3], respectively. The crystal structure of Sc₂MgGa₂ was determined from single‐crystal diffraction intensities and the isostructural Y₂MgGa₂ was identified from powder diffraction data.     

Zur Kenntnis der Dialkalimetalldichalkogenide β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 und Rb2Te2

On Dialkali Metal Dichalcogenides β-Na₂S₂, K₂S₂, α-Rb₂S₂, β-Rb₂S₂, K₂Se₂, Rb₂Se₂, α-K₂Te₂, β-K₂Te₂ and Rb₂Te₂ The first presentation of pure samples of α- and β-Rb₂S₂, α- and β-K₂Te₂, and Rb₂Te₂ is described. Using single crystals of K₂S₂ and K₂Se₂, received by ammonothermal synthesis, the structure of the Na₂O₂ type and by using single crystals of β-Na₂S₂ and β-K₂Te₂ the Li₂O₂ type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na₂O₂ type to the Li₂O₂ type will be explained by means of the examples α-/β-Na₂S₂ and α-/β-K₂Te₂. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb₂S₂ is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.     

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

[(n‐Bu)₂Sn(O₂PPh₂)₂] ( 1 ), and [Ph₂Sn(O₂PPh₂)₂] ( 2 ) have been synthesized by the reactions of R₂SnCl₂ (R=n‐Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

The alkali hypophosphites KH2PO2, RbH2PO2 and CsH2PO2

The structures of the hypophosphites KH₂PO₂ (potassium hypophosphite), RbH₂PO₂ (rubidium hypophosphite) and CsH₂PO₂ (caesium hypophosphite) have been determined by single‐crystal X‐ray diffraction. The structures consist of layers of alkali cations and hypophosphite anions, with the latter bridging four cations within the same layer. The Rb and Cs hypophosphites are isomorphous.     

Syntheses,Spectroscopic Studies,and Crystal Structures of Me2Sn(O2PPh2)2, Ph2Pb(O2PMe2)2, and Ph2Pb(O2PPh2)2

Me₂Sn(O₂PPh₂)₂ ( 1 ), Ph₂Pb(O₂PMe₂)₂ ( 2 ), and Ph₂Pb(O₂PPh₂)₂ ( 3 ) have been synthesized by the reactions of Me₂SnCl₂ or Ph₃PbCl with the corresponding diorganophosphinic acid in methanol. X‐ray diffraction studies show that the diorganophosphinate groups behave as double bridges between the metal atoms leading to polymeric ring‐chain structures with M₂O₄P₂ (M = Pb, Sn) eight‐membered rings. The organic groups bonded to the metal atoms are in trans‐position in the resulting octahedral arrangement around the metal atoms. The IR and the mass spectra were reported and discussed.     

Thermal decomposition of Me3SnO2PCl2, Me2Sn(O2PCl2)2 and Ph3SnO2PCl2

TG and DTA studies on Me₃SnO₂PCl₂, Me₂Sn(O₂PCl₂)₂ and Ph₃SnO₂PCl₂ were carried out under dynamic argon atmosphere. The results show that the decomposition proceeds in different stages leading to the formation of Sn₃(PO₄)₂ as a stable product. This compound was characterized by IR spectroscopy. Decomposition schemes involving reductive elimination reactions were proposed.