LaFe_(13-x)Si_x合金中不同铁磁态磁化率与磁场诱导磁相变的临界磁场实验研究

通过对采用不同方法制备或热处理的LaFe_(13-x)Si_x合金中处于不同磁状态的1∶13相磁化过程的观察和分析,实验研究了该系合金中各种铁磁态的最大磁化率,以及磁场诱导顺磁态到铁磁态的巡游电子变磁相变临界磁场与温度的关系。结果表明,在居里温度以下合金中铁磁态的最大磁化率,高于居里温度以上因磁场诱导由顺磁态相变而来的铁磁态的最大磁化率。居里温度附近两相共存态中的顺磁态,由磁场诱导转变为铁磁态的临界磁场,小于居里温度以上合金处于完全顺磁态时由磁场诱导转变为铁磁态的临界磁场随温度变化的线性关系外推值。且在两相共存态中,因磁场诱导的铁磁态的最大磁化率也小于合金中本身存在的铁磁态的最大磁化率。另外,当合金中1∶13相处于顺磁态和铁磁态两相共存时,经励磁-退磁至零场后转变为铁磁态,两相共存现象消失。     

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。     

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.     

Dy_3NiSi_2合金磁相变与磁热性能研究

通过对Dy_3NiSi_2合金样品的X射线粉末衍射谱、等温变磁磁化曲线、等磁场变温磁化曲线分析,主要研究了合金的相结构和晶格参数、磁相变属性和磁热性能。X射线衍射谱表明Dy_3NiSi_2样品几乎为Gd_3NiSi_2型正交结构(空间群:Pnma, No.62)的单相合金,其晶格常数分别为a=1.1242(3) nm,b=0.41073(3) nm,c=1.1223(9) nm。在45～300 K温度范围内, Dy_3NiSi_2合金仅展现出铁磁-顺磁相变, 0.01 T磁场下的dM/dT和0～2 T磁场下的Arrott图表明, Dy_3NiSi_2合金的磁相变为居里温度T_c=54 K的铁磁-顺磁二级磁相变。在0～2 T磁场范围内, Dy_3NiSi_2合金居里温度处的最大磁熵变为3.65 J·(kg·K)~(-1),相对制冷量为167.9 J·kg~(-1)。     

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。     

(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.     

钙钛矿锰氧化物La_(0.875)Eu_(0.025)Sr_(0.1)MnO_3的磁性和磁卡效应研究

多晶样品La_(0.875)Eu_(0.025)Sr_(0.1)MnO_3用传统固相反应法制备得到。X射线衍射仪(XRD)表明样品为纯相。通过测量磁化强度随温度的变化曲线(M-T)、不同温度下磁化强度随磁场的变化曲线(M-H)研究了该多晶样品的磁性及磁卡效应。研究发现:样品在低温部分表现出团簇自旋玻璃的特征,在15～125 K温度范围内表现为铁磁特征;在125～350 K温度范围内表现出预成型团簇相的特征;在350 K以上表现出纯顺磁特征。在居里温度T_C≈119 K附近,系统发生了二级相变而且出现较大的磁熵变值,样品在7 T外加磁场下的最大磁熵变绝对值为2.83J·K~(-1)·kg~(-1),磁制冷效率为427.53 J·kg~(-1)。因此,该样品具有在高温区实现磁制冷的潜能。     

Tb(Co_(1-x)Sn_x)_2合金的结构和磁热效应

通过X射线衍射和磁性测量研究了Tb(Co1-xSnx)2(x=0,0.025,0.050,0.075,0.100)合金的相结构和磁热性能。经分析可知Sn在TbCo2中的替代是有限的,X粉末衍射分析确定TbCo2具有MgCu2结构,其他样品由TbCo2,TbCo3和Tb5Sn3三相组成,TbCo2为主要相。随着Sn成分的增加,杂质相TbCo3和Tb5Sn3的含量增加,所有样品保持第二序磁相变。Sn的替代使磁相变的温度稍微有所提高,样品TbCo2的TC值为230 K,样品Tb(Co0.950Sn0.050)2的TC值为233 K,但Sn的成分继续增加,样品的TC值有所下降。在外加磁场2 T的作用下,样品Tb(Co1-xSnx)2(x=0,0.025,0.050,0.075)最大磁熵变值分别为3.44,2.29,1.64,1.16 J.kg-1.K-1。     

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。     

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.     

La-Fe基NaZn13型化合物的磁场诱导熵变研究

围绕具有一级磁性相变的La-Fe基NaZn13型化合物的磁场诱导熵变研究,从室温磁制冷目的出发讨论了材料研究和熵变机制。La-Fe-Si在190K附近5T磁场下的熵变值可达29J.kg-1.K-1。用少量Co替代Fe,可以获得室温附近5T磁场下熵变为15J.kg-1.K-1的大熵变材料。这类材料中的熵变主要由磁有序熵变和晶格熵变组成。分析了一级磁性相变体系中磁有序熵变和晶格熵变对总熵变的贡献,并发现大的熵变来源于被晶格贡献抵消后的磁有序熵变。     

Irreversible Structural Phase Transition in [(9-triptycylammonium) ([18]crown-6)][Ni(dmit)2]: Origin and Effects on Electrical and Magnetic Properties

Materials exhibiting irreversible phase transitions, leading to changes in their properties, have a potential for novel application in electronic components such as a non-rewritable high-security memory. Here, we focused on the two salts, [(9-triptycylammonium)([18]crown-6)][Ni(dmit)₂] ( 1 ) and [(9-triptycylammonium)([15]crown-5)][Ni(dmit)₂] ( 2 ), which featured 2D sheet structures with alternately stacked cation and anion layers. Both salts exhibit similar cation arrangements, however, their anion arrangements differ significantly. The temperature-dependent magnetic susceptibilities of 1 and 2 were well reproduced by the alternating chain model (J_AC1/k_B=−306(8), J_AC2/k_B=−239(3) K) and the Curie-Weiss model (θ=−3.9(1) K), respectively. 1 experience a reversible phase transition around 40–60 K, causing anomalies in magnetic behavior. Moreover, an irreversible single-crystal-to-single-crystal phase transition to 1′ undergo at ~381 K, inducing a rearrangement of [Ni(dmit)₂]⁻ anions and a resistivity decrease from 6.5×10⁶ to 6.5×10² Ω cm. The susceptibility curve of 1′ was reproduced by a combination of the Curie-Weiss and dimer models (J_dimer/k_B=−407(5), θ=−26.7(5) K). The irreversible transition of 1 is the first example for such supramolecule and [Ni(dmit)₂]⁻ system to our knowledge, in opening potential new-type materials.     

Virtual isotropic‐nematic transitions in alkyl cyanobiphenyls

Pretransitional fluctuations in the isotropic phase of liquid crystalline and non‐liquid crystalline alkyl cyanobiphenyls have been investigated using light scattering and magnetic birefringence measurements. We find evidence for a virtual isotropic‐nematic phase transition in short‐chain alkyl cyanobiphenyls with no observable nematic phase. The measured temperature dependence of fluctuations is well‐described by mean‐field theory. Virtual phase transition temperatures extrapolated from separate light scattering and magnetic birefringence experiments are in good agreement. Landau–de Gennes model parameters for the compounds investigated are calculated from the experimental results.     

Low Temperature Specific Heat Capacity of 3d Transition Metal Chlorine Boracites (T3B7O13Cl; T=Cr,Mn, Fe,Co, Ni,Cu, Zn or Mg)

The heat capacities of eight chlorine boracites T₃B₇O₁₃Cl (T=Cr, Mn, Fe, Co, Ni, Cu, Zn or Mg) have been measured in the temperature range 2 to 100 K. Magnetic phase transitions occur below 20 K in the compounds studied except in the two non-magnetic substances Zn₃B₇O₁₃Cl and Mg₃B₇O₁₃Cl. The magnetic specific heat capacities give information on magnetic ground state of the transition metals and the entropy related to the phase transitions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Magnetic phase transition of Li0.75CoO2 compared with LiCoO2 and Li0.5CoO2

Magnetic and thermodynamic properties of the LiCoO₂ positive-electrode material used in lithium-ion battery were first examined. Partially deintercalated LiCoO₂ that is Li_0.75CoO₂, showed definite anomaly in the magnetic susceptibility at T=ca. 175 K probably related to magnetic phase transition which was supported by observation of a weak anomaly in heat capacity. On the other hand, LiCoO₂ did not show such magnetic phase transition as expected, whereas Li_0.5CoO₂ a weak one in the similar temperature range. These behaviors are discussed in association with the mixing of Co³⁺ and Co⁴⁺ electronic structures.     

Preparation and Performance of Dual-functional Magnetic Phase-change Microcapsules

The fabrication of desired anti-magnetic materials for irradiation shielding remains a challenge to date. In this work, a new type of dual-functional magnetic shielding phase change microcapsules with paraffin as the core, melamine-formaldehyde (MF) resin as the shell and doped with magnetic particles in the shell were successfully prepared by in situ polymerization. The magnetic particles were dispersed in the shell layer by coating a hydrophilic emulsifier on the surface. These microcapsules were specifically applied to the field of magnetic shielding by the screen printing method. The effect of magnetic particles on the performance of phase-change microcapsules was examined by differential scanning calorimetry and thermogravimetric analyses. The magnetic type and magnetic strength of the microcapsules were studied by the vibrating sample magnetometer. Moreover, the effects of different magnetic particles (Fe₃O₄, CrO₂) on the performance of phase change microcapsules and the magnetic strength of microcapsules were compared. The results showed that these two kinds of magnetic particles can greatly improve the phase change latent heat, thermal stability, and thermal conductivity of the microcapsules. Finally, the great magnetic shielding role of these microcapsules was demonstrated in both static and pulsed magnetic fields through the screen printing of magnetic shielding ink on wallpaper. Incorporating 0.5 g Fe₃O₄ inside of microcapsules, specifically, the magnetic intensity was effectively reduced by ∼250 Oe within a short distance in the static field. We expect that these magnetic microcapsules hold great potential for the shielding of irradiations via the screen printing on various substrates.     

D-和L-丙氨酸的低温磁相变——磁场变化下的比热和直流磁化率(英文)

为了解D-和L-丙氨酸单晶晶格在极低温下是否存在磁手性相变,在2-20 K下改变磁场强度(0,1,3,5T)测定其比热.实验结果表明比热和温度之间的函数关系很好地符合C(T)=aT3+b/T2方程,其中aT3项为晶格声子的贡献,可由公式CV=(12/5)π4R(T/ΘD)3来描述(ΘD为德拜温度),b/T2项为磁场对比热的贡献.实验发现,在2-20 K范围内D-和L-丙氨酸单晶在不同磁场强度下均存在Boson峰(在Cp/T3-T曲线中表现为一个最大值).磁的贡献导致D-和L-丙氨酸单晶的四条Cp/T3-T曲线在2-12 K时不重合,且在12-20 K时消失,此即Schottky反常.零磁场下,D-和L-丙氨酸的Boson峰分别为9.44和10.86 K;德拜温度分别为151.5和152.7 K.结合磁场强度1 T下的直流磁化率测定,发现在温度低于5 K时,D-和L-丙氨酸单晶有相反的磁化率行为,反映了核自旋和电子自旋弱相互作用的手性表现.     

新型过渡金属配合物合成,磁性和生物活性

报道９种新的过渡金属［Ｃｒ（Ⅲ）、Ｍｎ（Ⅱ）、Ｆｅ（Ⅲ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ）］五苯并咪唑甲基二乙三胺双核配合物的研究。变温磁化率分析结果表明，双核离子间存在反铁磁相互作用。对于二价过渡金属离子，磁交换作用大小为．对配合物进行了体外抗癌活性和农药活性测定，发现部分配合物具有生物活性。     

Magnetic phase transitions and specific heat of single crystalline cupric oxide

The antiferromagnetic phase transitions in a CuO single crystal are studied by specific heat in magnetic fields up to 6T. The magnetic field dependence of the incommensurate-to-commensurate-antiferromagnetic transition atT _L is found to be highly anisotropic.T _L is observed to increase nonlinearly for B_a c-axis, whereas, a linear reduction is observed forB _a b-axis. The magnetic field dependence ofT _L and the jumps in magnetic susceptibility atT _L are explained thermodynamically using the Clausius-Clapeyron equation.We thank Dr. T. Chattopadhyay for providing the CuO crystal. We thank K. Ripka and the Röntgen service of the institute for technical assistance.