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。     

Dy(Co1-xMx)2(M=Al, Si)系列合金的磁熵变研究

利用电弧熔炼的方法制备Dy(Co1-xMx)2(M=Al，si)系列合金；发现用少量的Al或Si替代Co后所形成的系列合金的居里温度都有显著的提高。且随着替代量的增大，样品的相变类型从一级转为二级。文中着重研究了Dy(Co1-xMx)2系列合金的在较低磁场下(1T)的磁熵变，并且讨论了该系列合金具有较大磁熵变的原因以及用少量Al或Si替代Co后对磁熵变的影响，同时对它们的应用前景也进行了探讨分析。     

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.     

Gd0．6DY0．4Co2-xAlx系合金磁热性能的研究

用量子磁强仪对Cd0.6Dy0.4Co2-xAlx(x=0,0.1)系合金的居里温度、磁相变、磁熵变等磁性质进行了研究.结果表明:该系合金居里温度随着X量的引入而增加;热处理后,X=0,0.1合金由双相晶体结构基本变为单相晶体结构,磁熵变比铸态合金分别提高53.2%和33.1%,居里温度基本不变.铝元素的加入并没有改变合金的相变类型,合金仍保持二级相变.     

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。     

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。     

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。     

一级相变磁制冷材料LaFe_(11.6)Si_(1.4)合金的磁相变特性系统分析

以La Fe11.6Si1.4合金为研究对象,系统分析了该一级相变材料的居里温度(TC)、磁场诱导磁相变的临界磁场(HC)、磁化率(χ)、磁滞、磁熵变(ΔS)、制冷能力(RCP)等磁性特性。结果表明:温度诱导磁相变的居里温度和磁场诱导磁相变的临界磁场均随磁场呈线性增加,ΔTC和ΔH随磁场和温度的变化率的值分别为4.1 K·T-1和0.2 T·K-1。当合金处于纯铁磁态和顺磁态时熵变磁熵变几乎为零,但磁场诱导的磁相变,会导致某一定温度下合金磁熵变有一个突变。但合金最大熵变并不是随磁场的增加而线性增加,当磁场达到一定值后随磁场增加其值基本没有变化。不同模型计算的制冷能力均随磁场的增加而呈线性增加。在两相共存态中,同一温度下两种不同铁磁的磁化率存在差异,即因磁场诱导的铁磁态相与合金中本身的铁磁态相的磁化率存在差异,且前者小于后者,这种物理现象对深入研究温度诱导和磁场诱导磁相变的差异有一定的参考价值。     

镝掺杂钙钛矿锰氧化物Gd0.67Ca0.33MnO3的磁性和磁卡效应EI北大核心CSCD

借助传统的固相反应法制备了多晶系列样品Gd0.67-xDyxCa0.33Mn O3(x=0,0.05,0.15),探究了Dy掺杂后对该系列样品磁性和磁卡效应的影响。研究结果表明：该系列样品呈现良好的单相性,均是立方钙钛矿结构,空间群为Pbnm;3个样品的铁磁性减弱、反铁磁性增强,并且Dy掺杂后系统内长程铁磁有序增强,形成了AFM团簇;通过该系列样品的临界行为分析,表明该系列样品均与平均场模型拟合较好;通过Arrott曲线和重标定曲线,发现母相和掺杂样品x=0.05,0.15均经历了一级相变到二级相变的过渡阶段;3个样品外加磁场为5 T的最大磁熵变值分别为1.53,1.44,1.40 J·kg-1·K-1。     

Gd_(1-x)Ho_xTiGe的物相结构和磁性及磁热效应

用真空电弧熔炼和热处理法制备了Gd_(1-x)Ho_xTiGe (x=0, 0.2, 0.4)合金。X射线衍射分析表明:Gd_(1-x)Ho_xTiGe为GdTiGe型四方结构,空间群为I4/mmm,随着Ho含量的增加衍射峰总体上偏向高角度移动,晶胞参数a,c收缩,体积变小。Ho含量的增大对衍射峰的强度几乎没影响。通过磁性测量研究了磁性及磁热效应。利用Maxwell关系导出0～1 T, 0～2 T, 0～3 T的等温磁熵变。随着Ho的增加居里温度降低,使其成为室温区磁制冷材料。     

Lanthanoid Single-Ion Magnets Based on Polyoxometalates with a 5-fold Symmetry: The Series [LnP(5)W(30)O(110)](12-) (Ln(3+) = Tb, Dy, Ho, Er, Tm, and Yb)

A robust, stable and processable family of mononuclear lanthanoid complexes based on polyoxometalates (POMs) that exhibit single-molecule magnetic behavior is described here. Preyssler polyanions of general formula [LnP(5)W(30)O(110)](12-) (Ln(3+) = Tb, Dy, Ho, Er, Tm, and Yb) have been characterized with static and dynamic magnetic measurements and heat capacity experiments. For the Dy and Ho derivatives, slow relaxation of the magnetization has been found. A simple interpretation of these properties is achieved by using crystal field theory.     

纳米块体金属钆和镝的磁性相变分析

对纳米晶钆(Gd)和镝(Dy)块体材料的磁性进行了研究.与多晶比较,通常纳米晶的磁化强度减小,居里温度TC降低,但平均粒径为10 nm的纳米晶Dy的居里温度TC反而升高到100 K,平均粒径为10 nm的纳米晶Gd中还存在明显的反铁磁相.通过RKKY交换作用的计算知道,晶面晶界处原子的交换积分会发生正负号的变化,能量最低的稳定状态对应三种有序相:铁磁相、反铁磁相和扇相,晶粒中在一定条件下出现三相共存.对于平均粒径为10 nm的纳米晶,晶面晶界处原子所占比例很大,三相叠加的结果,对于Gd,即是在相变点附近出现磁化强度尖峰;对于Dy,则是磁化强度随温度升高下降缓慢,表现为居里温度TC比多晶升高.     

Structural,electrical, and magnetic properties of a series of molecular conductors based on BDT-TTP and lanthanoid nitrate complex anions (BDT-TTP = 2,5-Bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene)

The platelike crystals of a series of novel molecular conductors, which are based on the pi-donor molecules BDT-TTP (2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene) with a tetrathiapentalene skeleton and lanthanide nitrate complex anions [Ln(NO3)x](3-x)(Ln = La, Ce, (Pr), Tb, Dy, Ho, Er, Tm, Yb, Lu) with localized 4f magnetic moments, were synthesized. Except for the Ce complex, the salts were composed of (BDT-TTP)(5)[Ln(NO(3))(5)] and were isostructural. Even though the Ce crystal had a different composition, (BDT-TTP)(6)[Ce(NO(3))(6)](C(2)H(5)OH)(x)() (x approximately 3), the crystals all had the space group P(-)1. Although the X-ray examination of the Pr salts was insufficient, the existence of two modifications was suggested in these systems by preliminary X-ray examination. Previously, we reported the crystal structures and unique magnetic properties of (BDT-TTP)(5)[Ln(NO(3))(5)] (Ln = Sm, Eu, Nd, Gd). Thus, by combining the results of this work with previous one, we for the first time succeeded in obtaining a complete set of organic conductors composed of the identical pi-donors (BDT-TTP in this case) and all the lanthanide nitrate complex anions (except the complex with Pm(3+)). The crystals were all metallic down to 2 K. Electronic band structure calculations resulted in two-dimensional Fermi surfaces, which was consistent with their stable metallic states. Except for the Lu complex, which lacked paramagnetic moments, the magnetic susceptibilities were measured on the six heavy lanthanide ion complex salts by a SQUID magnetometer (Ln = Tb, Dy, Ho, Er, Tm, Yb). The large paramagnetic susceptibilities, which were caused by the paramagnetic moments of the rare-earth ions, were obtained. The Curie-Weiss law fairly accurately reproduced the temperature dependence of the magnetic susceptibilities of (BDT-TTP)(5)[Ho(NO(3))(5)] in the experimental temperature range (2-300 K) and a comparatively large Weiss temperature (|THETAV;|) was obtained (THETAV;(Ho) = -15 K). A Weiss temperature (THETAV;(Tm) = -8 K) was also obtained for Tm. The |THETAV;| values of other (BDT-TTP)(5)[Ln(NO(3))(5)] salts and (BDT-TTP)(6)[Ce(NO(3))(6)](C(2)H(5)OH)x(x approximately 3) were as follows: |THETAV;|/K = 4 (Er), < or =2 (Ce, Tb, Dy, Yb). The comparatively strong intermolecular magnetic interaction between Ho(3+) ions, which was suggested by the |THETAV;| value, is inconsistent with the traditional image of strongly localized 4f orbitals shielded by the electrons in the outer 5s and 5p orbitals. The dipole interactions between Ln(3+) ions causing the Curie-Weiss behavior and the comparatively large THETAV; value of (BDT-TTP)(5)[Ho(NO(3))(5)] is inconsistent with the data, since the complexes exhibit isostructural properties and there is not a clear relationship between the magnitudes of THETAV; values and those of magnetic moments. Therefore, it is possible that the 4f orbitals of Ho atom are sensitive to the ligand field, which will have an effect on the orbital moment of the Ho(3+) ion and/or produce a small amount of mixing between 4f and ligand orbitals to give rise to "real" intermolecular antiferromagnetic interaction through intermolecular overlapping between pi (BDT-TTP) and ligand orbitals of lanthanide nitrate complex anions.     

A binuclear Fe(III)Dy(III) single molecule magnet. Quantum effects and models

The binuclear [FeIII(bpca)(mu-bpca)Dy(NO3)4], having Single Molecule Magnet (SMM) properties, belonging to a series of isostructural FeIIILnIII complexes (Ln = Eu, Gd, Tb, Dy, Ho) and closely related FeIILnIII chain structures, was characterized in concise experimental and theoretical respects. The low temperature magnetization data showed hysteresis and tunneling. The anomalous temperature dependence of M?ssbauer spectra is related to the onset of magnetic order, consistent with the magnetization relaxation time scale resulting from AC susceptibility measurements. The advanced ab initio calculations (CASSCF and spin-orbit) revealed the interplay of ligand field, spin-orbit, and exchange effects and probed the effective Ising nature of the lowest states, involved in the SMM and tunneling effects.     

氯冉酸阴离子桥联的Nd(III)-Nd(III), Dy(III)-Dy(III)和 Ho(III)-Ho(III)双 核配合物的合成与磁性

本文合成了三个以氯冉酸阴离子为桥基的稀土双核配合物,Ln~2(Phen)~4(CA)(NCS)~4(Ln=Nd,Dy,Ho;Phen=菲咯啉;CA=氯冉酸二价阴离子)。通过元素分析,红外光谱,电导,电子吸收光谱及变温(4-300K)磁化率表征了配合物,并由变温磁化率观察到的数据和理论方程通过最小二乘法拟合,得出分子内稀土离子间的相互作用参数:Z'J'=-0.79(Nd),-0.67(Dy),-0.63cm^-^1(Ho);表明稀土离子间存在极弱的反铁磁性交换相互作用。零场分裂参数Δ=-0.16(Nd),-0.76(Dy),-2.55cm^-^1(Ho);g=0.618(Nd),1.739(Dy),1.601(Ho),拟合因子≈10^-^4。     

Structure, magnetism and theory of a family of nonanuclear Cu(II)5Ln(III)4-triethanolamine clusters displaying single-molecule magnet behaviour

Synthesis, crystal structures and magnetic studies are reported for four new heterometallic Cu(II)-Ln(III) clusters. The reaction of Cu(NO(3))(2)·3H(2)O with triethanolamine (teaH(3)), pivalic acid, triethylamine and Ln(NO(3))(3)·6H(2)O (Ln=Gd, Tb, Dy and Ho) results in the formation of four isostructural nonanuclear complexes of general formula [Cu(II)(5)Ln(III)(4)O(2)(teaH)(4){O(2)CC(CH(3))(3)}(2)(NO(3))(4)(OMe)(4)]·2MeOH·2Et(2)O [Ln=Gd (1), Tb (2), Dy (3) and Ho (4)]. The metal core of each cluster is made up of four face- and vertex-sharing tetrahedral units. Solid-state DC magnetic susceptibility studies reveal competing anti- and ferromagnetic interactions within each cluster leading to large-spin ground states for 1-4. Solid-state AC magnetic susceptibility studies show frequency-dependent out-of-phase (χ'(M)) signals for 2-4 below 4 K, suggestive of single-molecule magnet behaviour. Ab initio calculations on one of the anisotropic examples (3) provided a rare set of J values for Dy-Cu and Cu-Cu exchange interactions (Dy-Dy zero), some ferro- and some antiferromagnetic in character, that explain its magnetic behaviour.     

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。     

Synthesis and magnetism of rare earth (Nd,Gd,Dy,Ho,Er,Y) pentafluoropropionate binuclear complexes with 2-(4''''-methoxy-phenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide

Six compounds of the general formula [Ln(pfpr)3]2(NITPhOMe).nH2O, where Ln=Nd, Gd, Dy, Ho, Er, Y, pfpr=pentafluoropropionate, NITPhOMe=2-(4'-methoxyphenyl)-4,4,5, 5-tetra-methylimidazoline-1-oxyl-3-oxide, and n=4 (for Nd, Dy, Er); 3 (for Gd); 6 (for Ho); 5 (for Y), have been synthesized. These complexes were characterized by elemental analyses, IR, electronic spectra and molar conductances. The variable temperature (4-300 K) magnetic susceptibility of the complex [Gd(pfpr)3]2(NITPhOMe).3H2O was determined. The observed susceptibility data were fit to those from theoretical magnetic equation by least-squares method. The exchange integral, J, was found to be equal to 2.14 cm-1. This indicates a weak ferromagnetic spin-exchange interaction between the radical and the gadolinium(III) ion.