巡游电子系化合物La0.8Ce0.2(Fe1-xCox)11.4Si1.6的磁热效应

对制备的化合物La0.8Ce0.2(Fe1-xCox)11.4Si1.6(x=0.02,0.04,0.06)的相组成、巡游电子变磁转变(IEMT)特性和磁热效应(MCE)进行了研究。粉末X射线衍射结果表明,经1373 K真空退火处理7 d后,化合物La0.8Ce0.2(Fe1-xCox)11.4Si1.6(x=0.02,0.04,0.06)均为单相立方NaZn13型晶体结构。随着Co含量由x=0.02增加到x=0.06,样品的居里温度TC由207 K上升到277 K。在0~1.5 T磁场变化下,x=0.02,0.04,0.06时样品的最大磁熵变|ΔSM(T)|分别为40.17,12.60和7.65 J.kg-1.K-1,可见该化合物有巨大的磁熵变,而且随Co含量的增加最大磁熵变迅速减小。该化合物的巨大磁熵变来源于TC处的一级相变,以及在TC以上由磁场诱导IEMT,但由于Co原子对Fe原子的替代能够抑制变磁转变的发生,因此该系化合物最大磁熵变随Co含量的增加迅速减小。     

LaFe11.6Si1.4/10%Co复合材料的磁热效应EI北大核心CSCD

利用SPS(放电等离子烧结)技术制备了La Fe11.6Si1.4/10%Co复合材料,结合XRD,OM和Versa Lab等手段,系统地研究了La Fe11.6Si1.4/10%Co复合材料的相组成、微观结构和磁热性能。不同烧结温度制备的铸态La Fe11.6Si1.4/10%Co复合材料由1∶13相、α-Fe相和Co相组成,烧结温度的提高促进了主相(1∶13相)的分解,恶化复合材料的磁热性能。OM测试结果表明,烧结温度的提高有利于孔隙尺寸的减小,提高铸态La Fe11.6Si1.4/10%Co复合材料的致密度。923 K烧结的铸态La Fe11.6Si1.4/10%Co复合材料的居里温度TC为199.8 K,0～2 T磁场范围的最大等温磁熵变为3.02 J·kg-1·K-1,RC值为40.6 J·kg-1,并表现出二级磁相变的特点,具有良好的磁热性能。     

(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.     

室温以上磁制冷材料La(Fe1-xCox)11.7Al1.3化合物的研究

通过X射线衍射分析和超导量子干涉磁强计（SQUID）磁性测量,研究了Co替代Fe含量对居里温度在室温以上的磁制冷材料La（Fe1-xCox）11.7Al1.3（x=0.072,0.081）磁结构和磁性能的影响。La（Fe1-xCox）11.7Al1.3材料的居里温度随Co的含量增加而增加,La（Fe0.919Co0.081）11.7Al1.3的居里温度为311 K。当外场变化为1.9 T时磁熵变达到3.6 J·kg^-1·K^-1,RCP值为168.6 J·kg^-1,虽然它的磁熵变小于具有巨磁熵变的磁制冷材料,但是它在磁场为1.9 T时的制冷能力与这些材料相当。     

金属间化合物Y（Fe1—xCox）11.3Nb0.7的磁性能机制研究

通过X射线衍射和磁笥测量方法研究了金属间化合物Y（Fe1-xCox)11.3Nb0.7（x=0,0.05,0.10,0.20）的结构与磁性能。粉末样品的X射线衍射和热磁曲线测量表明,所有Y（Fe1-xCox)11.3Nb0.7（x=0,0.05,0.10,0.20）化合物具有ThMn12型结构,具有良好的单相性,Co替代Fe引起居里温度显著提高和晶格常数的单调减小,室温下的饱和磁化强度M。随Co含量的增加在x=0.1-0.2之间呈现极大值,各向异性场Ba随x的增加,先增加而后减小。     

Gd7Pd3-xFex合金磁性及磁热效应的研究

采用电弧熔炼和高温退火的方法制备了Gd7Pd3-xFex(x=0, 0.2, 0.5, 0.8和1)合金材料,并对该系列合金材料的磁特性及磁热效应进行了研究。X射线粉末衍射研究表明,所有的材料均形成Th7Fe3型结构。并且随着x的增大,晶格常数、居里温度、饱和磁化强度和最大磁熵变均有所降低。相比于Gd7Pd3,掺入Fe元素的材料可以获得更接近室温的居里温度和更宽的工作温区,从而导致了7 T磁场下高达1096 J·kg^-1的相对制冷能力(RCP), Gd7Pd3-xFex有望被用于室温附近的磁制冷。     

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。     

四方晶体稀土-铁-硼系金属间化合物的结构和磁性

用磁测量和X射线衍射方法研究了R_(15)B_7Fe_(78)(R=MM,Pr,Nd,Sm,Gd,Y)和Nd_(15)B7(Fe_(1-x)M_x)_(78)(M=Co,Mn,Cr)的结构和内禀磁性。X射线衍射实验表明,这些化合物皆属四方结构。R_(15)B_7Fe_(28)的晶格常数随稀土原子序数的增加而减小,反映了镧系收缩的特点。居里温度随稀土金属原子序数的增加而增高,反映了稀土-铁原子间的间接交换作用的影响,Gd_(15)B_7Fe_(78)具有最高的居里温度。在Nd_(15)B_7(Fe_(1-x)M_z)_(78)中,以Co代Fe时,晶格常数随x的增加而减小;居里温度随x的增加而单调显著上升。以Mn代Fe时,晶格常数随x的增加而增大;居里温度则随x的增加而急剧下降。居里温度的变化,说明R_(15)B_7Fe_(78)的居里温度主要由3d过渡族原子间的直接交换作用所决定的。以Co代Fe,当x=0.2时,Nd_(15)B_7(Fe_(1-x)Co_x)_(78)的饱和磁化强度出现极值。     

过冷度对LaFe10.9 Co0.6 Si1.5合金相的形成及显微组织的影响

采用电磁悬浮熔炼的方法研究了LaFe10.9Co0.6Si1.5合金的凝固行为.应用X射线衍射(XRD)和扫描电镜(SEM)分析了合金组织结构和相组成.结果表明:La(Fe,Si,Co)13相是包晶反应生成的,过冷度变化对合金的凝固行为有很大的影响,当△T≤10 K时,LaFe10.9Co0.6Si1.5合金显微组织由α-(Fe,Si)相和La(Fe,Co)Si相组成,α-(Fe,Si)相为主要相;当△T≥40 K时,LaFe10.9Co0.6Si1.5合金显微组织中出现La(Fe,Si,Co)13相,随过冷度增加La(Fe,Si,Co)13相增多.应用经典形核理论对此进行了解释.     

金属间化合物Ho2Co17-xSix的结构和磁性研究

研究了非磁性原子Si替代Co对Ho2Co17金属间化合物结构和磁性的影响.X射线衍射结果表明, 所有Ho2Co17-xSix(x=0.5,1.0,1.5,2.0,2.5,3.0)化合物都为Th2Ni17型六角结构;化合物的晶格常数和单胞体积都随Si含量的增加而呈线性下降.磁性测量结果表明, Ho2Co17-xSix化合物的饱和磁化强度随Si含量的增加而呈线性下降.从热磁曲线测量观察到, Ho2Co17-xSix化合物在x=0.5时可能呈面各向异性,当0.5≤x≤3.0时出现由易面到易轴的自旋重取向,自旋重取向温度Tsr随Si原子含量的增加先下降,而后又上升,在x=2.5处出现最低点.     

Complex rare-earth tetrelides, RE5(SixGe(1-x))4: new materials for magnetic refrigeration and a superb playground for solid state chemistry

A "giant magnetocaloric effect" discovered in 1997 for Gd5Si2Ge2 near room temperature has triggered optimism that environmentally-friendly, solid-state magnetic refrigeration may be viable to replace gas-compression technology in the near future. Gd5Si2Ge2 is one member of an extensive series of rare-earth compounds, RE5(SixGe(1-x))4. Due to the complexity of their structures and flexibility associated with chemical compositions, this series is an attractive "playground" to study the interrelationships among composition, structure, physical properties and chemical bonding. This tutorial review, which is directed toward students and researchers interested in structure-property relationships in solids, summarizes recent efforts concerning the synthesis, structure, physical properties, chemical bonding and chemical modifications of RE5(SixGe(1-x))4. A brief history of refrigerants, to present certain motivating factors for this research effort, as well as a brief overview of the magnetocaloric effect serves to introduce this review.     

非磁性替代原子对Ce_2Co_(17)居里温度和饱和磁化强度的影响

用真空电弧熔炼法制备了Ce2 Co17-xMx(M =Ga ,Al和Si)化合物。通过X射线衍射和磁性测量手段 ,研究了非磁性替代原子Ga,Al和Si的加入对Ce2 Co17化合物的居里温度和饱和磁化强度的影响 ,其中Si在Ce2 Co17化合物中的固溶度最小 ,并使居里温度和饱和磁化强度下降幅度最大。     

A tale of two metals: new cerium iron borocarbide intermetallics grown from rare-earth/transition metal eutectic fluxes

R(33)Fe(14-x)Al(x+y)B(25-y)C(34) (R = La or Ce; x ≤ 0.9; y ≤ 0.2) and R(33)Fe(13-x)Al(x)B(18)C(34) (R = Ce or Pr; x < 0.1) were synthesized from reactions of iron with boron, carbon, and aluminum in R-T eutectic fluxes (T = Fe, Co, or Ni). These phases crystallize in the cubic space group Im3m (a = 14.617(1) ?, Z = 2, R(1) = 0.0155 for Ce(33)Fe(13.1)Al(1.1)B(24.8)C(34), and a = 14.246(8) ?, Z = 2, R(1) = 0.0142 for Ce(33)Fe(13)B(18)C(34)). Their structures can be described as body-centered cubic arrays of large Fe(13) or Fe(14) clusters which are capped by borocarbide chains and surrounded by rare earth cations. The magnetic behavior of the cerium-containing analogs is complicated by the possibility of two valence states for cerium and possible presence of magnetic moments on the iron sites. Temperature-dependent magnetic susceptibility measurements and M?ssbauer data show that the boron-centered Fe(14) clusters in Ce(33)Fe(14-x)Al(x+y)B(25-y)C(34) are not magnetic. X-ray photoelectron spectroscopy data indicate that the cerium is trivalent at room temperature, but the temperature dependence of the resistivity and the magnetic susceptibility data suggest Ce(3+/4+) valence fluctuation beginning at 120 K. Bond length analysis and XPS studies of Ce(33)Fe(13)B(18)C(34) indicate the cerium in this phase is tetravalent, and the observed magnetic ordering at T(C) = 180 K is due to magnetic moments on the Fe(13) clusters.     

Chemical hydrogenation of La(Fe,Si) family of intermetallic compounds

In the present work, the chemical hydrogenation process of La(Fe,Si)₁₃ compounds has been shown. It was found, that the La(Fe,Si) compound can be easily saturated with hydrogen by performing reaction with 0.6 M hydrochloric acid (HCl) for 2 h. After reaction, the heat treatment process is necessary to make hydrogenated powder homogenous. For the LaFe_11.8Si_1.2 micronized (<50 μm) and hydrogenated powder, the strength of the magnetocaloric effect was estimated by means of magnetocalorimetric measurements on plates consolidated with PVDF thermoplastic polymer. Magnetic entropy change was calculated by use of magnetization data acquired at magnetic fields with induction up to 2T. The adiabatic temperature change is equal to 3 K in magnetic field change 0–1.7T at 335 K, while magnetic entropy change is equal 13 J/kg*K at 2T. The structural homogeneity of initial and hydrogenated powders was validated by powder X-ray diffraction method. The amount of hydrogen in the hydrogenated compounds was evaluated using thermogravimetry method (4 H atoms per formula unit LaFe_11.8Si_1.2).     

不同工艺和原料对Mn_(1.2)Fe_(0.8)P_(0.48)Si_(0.52)化合物磁热效应的影响

用不同的工艺和原料制备了3个名义成分相同的Mn1.2Fe0.8P0.48S i0.52化合物。X射线衍射结果表明,3个化合物均为Fe2P型六角结构(空间群为P-62m),并且存在少量的(Fe,Mn)3S i相。通过磁性测量发现,3个样品的居里温度有所不同,但是都在室温附近(270~290 K)。以Fe2P为原料制备的化合物具有较大的磁熵变,在1.5 T的磁场变化下其最大磁熵变为13.6 J.(kg.K)-1。以行星样品球磨机制备的化合物具有较小的热滞,最小热滞为6.7 K。这些表明不同的制备工艺和原料对化合物的居里温度、热滞和磁熵变都具有一定的影响。同时低成本的原料、简单的制备工艺、较小的热滞和较大的磁熵变使得Mn1.2Fe0.8P0.48S i0.52化合物成为一种理想的室温磁致冷候选材料。     

Spin-glass behavior in LaFe(x)Co(2-x)P2 solid solutions: interplay between magnetic properties and crystal and electronic structures

To explore the evolution of magnetic properties from ferromagnetic LaCo(2)P(2) to paramagnetic LaFe(2)P(2) (both of ThCr(2)Si(2) structure type) a series of mixed composition LaFe(x)Co(2-x)P(2) (x ≤ 0.5) has been comprehensively investigated by means of single-crystal and powder X-ray and neutron diffraction, magnetization and heat capacity measurements, M?ssbauer spectroscopy, and electronic band structure calculations. The Curie temperature decreases from 132 K in LaCo(2)P(2) to 91 K in LaFe(0.05)Co(1.95)P(2). The ferromagnetic ordering is suppressed at higher Fe content. LaFe(0.1)Co(1.9)P(2) and LaFe(0.2)Co(1.8)P(2) demonstrate spin-glass-like behavior, which was also confirmed by the absence of characteristic features of long-range magnetic ordering, namely, a λ-type anomaly in the heat capacity, a hyperfine splitting in the M?ssbauer spectrum, and magnetic reflections in the neutron diffraction pattern. Finally, both LaFe(0.3)Co(1.7)P(2) and LaFe(0.5)Co(1.5)P(2) exhibit paramagnetic behavior down to 1.8 K. The unit cell parameters of the mixed compounds do not follow the Vegard behavior as the increase in the Fe content results in the decrease of average M-M distances (M = Fe, Co). Quantum-chemical calculations and crystal orbital Hamiltonian population analysis reveal that upon aliovalent (nonisoelectronic) substitution of Fe for Co the antibonding character of M-M interactions is reduced while the Fermi level is shifted below the DOS peak in the 3d metal subband. As the result, at higher Fe content the Stoner criterion is not satisfied and no magnetic ordering is observed.     

An application of the "coloring problem": structure-composition-bonding relationships in the magnetocaloric materials LaFe13-xSix

The LaFe(13)-(x)Si(x) (1.0 < or = x < or = 5.0) series is studied experimentally and theoretically to gain possible understanding for the relationships among geometrical structure, chemical composition, magnetic behavior, and physical properties as related to the magnetocaloric effect in these compounds. As the Si concentration increases, LaFe(13)-(x)Si(x) exhibits a structural transformation from the cubic NaZn(13) structure type to a tetragonal derivative due primarily to preferential ordering of Fe and Si atoms. At room temperature, LaFe(13)-(x)Si(x) crystallize in the cubic structure for the range 1 < or = x < or = 2.6 and in the tetragonal for 3.2 < or = x < or = 5. In the range 2.6 < or = x < or = 3.2, it shows a two-phase mixture. Temperature-dependent single-crystal X-ray diffraction experiments near the corresponding Curie temperatures were performed on the room-temperature cubic phases to examine the origin of the large isothermal magnetic entropy changes. A thorough statistical and structural analysis of the data indicates that the noncentrosymmetric F43c space group provides a more adequate atomic arrangement than the centrosymmetric Fm3c space group. This change in space group leads to divergence for specific sets of Fe-Fe distances below the Curie temperature that arises from tilting of Fe-centered [Fe(12)-(x)Si(x)] icosahedra. The noncentrosymmetric space group also agrees with the predominance of icosahedral clusters lacking local inversion symmetry. From extended Hückel and tight-binding linear muffin-tin orbital (TB-LMTO) electronic structure calculations on various model structures, the F43c model is more energetically favorable than the Fm3c model. Extended Hückel calculations on various icosahedral [Fe(12)-(n)Si(n)] (n = 1-5) clusters and TB-LMTO calculations on "LaFe(13)," LaFe(11)Si(2), and LaFe(9)Si(4) have also been carried out to study the effects of a main group element (Si) on stabilizing the cubic NaZn(13)-type structure, influencing the transformation between cubic and tetragonal symmetries, and to study relationships among their chemical bonding and magnetic properties.     

A study of interface-sustained ferromagnetism in 1/2(1-x)Ln2O3-xSrO/1/3Co3O4 nano-composite

The binary oxide composite, consisting of rock salt-type SrO and spinel Co3O4 nano-domains, exhibits soft ferromagnetic properties at ambient temperature. This ferromagnetism is originated from interface-induction, and the magnitude of the magnetic properties can be enhanced when the spinel phase of the composite is doped by a small amount of Ln2O3 (Ln = La, Nd, for instance). In this work, we study the composites of tri-oxide, 1/2(1-x)Ln2O3-xSrO/1/3Co3O4, where 0.01 < or =1-x < or = 0.6, by focusing on three areas: (i) generation of nano-composite dominant by interfacial phase via the pyrolysis of preceramic metallo-organic gel; (ii) influence of post-pyrolysis calcination and Ln2O3 content on the phase composition of the composite; and (iii) elucidation of different magnetic responses caused by the nature of Ln2O3 dissolved in the Co3O4 phase. The Ln(3+)-doped Co3O4 oxide displays only paramagnetic behavior at room temperature, but the ferromagnetic response is attained upon its mixing with SrO in nano-scale. The SrO phase plays the role in assisting Co3O4 phase with aligning unpaired electrons through interfacial induction.