La0.67Sr0.33Mn0.9Cr0.1O3的巨磁熵效应

通过测量不同温度下的M-T和M-H曲线，对超大磁阻材料La0．67Sr0．33Mn0．9Cr0．1O3的巨磁熵进行了研究，发现伴随铁磁一顺磁相变有一个大的磁熵变化；在337K左右出现了一个磁熵肩峰，并随磁场的增大而愈加明显。由于磁熵肩峰的出现，磁熵变的峰被拉宽，从而有利于采用ERICSSON循环的磁制冷。这个结果表明La0．67Sr0．33Mn0．9Cr0．1O3可以作为磁制冷技术工作物质。     

铒-钬基高性能低温磁制冷材料的研究

稀土基合金化合物在低温区具有较大的磁有序度变化等物性,在低温磁制冷方面具有重要的研究价值和广阔的应用前景。通过多种磁性和物性测量方法(如直流磁性、交流磁性、比热、粉末中子衍射技术),系统地研究了铒-钬-基合金化合物的磁性和磁热效应。研究发现:随着温度的升高, Ho_(12)Co_7材料呈现出多个磁熵变峰,虽然磁熵变峰值不是特别大,但是0～5 T磁场变化下其磁制冷能力高达554.9 J·kg~(-1),在低温区磁制冷应用中展现出了巨大的优势。进一步分析发现:通过自旋优化以及对材料进行复合的思路,最终获得了磁热效应更加优异的Er-Ho-Co复合磁制冷材料。在对稀土-镍材料体系的系列研究后,成功合成了目前在低温区具有巨大磁熵变的Er_(0.9)Ho_(0.1)Ni化合物, 0～5 T磁场变化下其磁熵变峰值高达34.0 J·kg~(-1)K~(-1),磁熵变峰值和绝热温变峰值较母体材料分别提高了14.9%和21.9%。在交流磁化率以及变温中子衍射实验结果的基础上,对RNi系列材料的磁相变进行了严格论证,探明了上述材料性能得到大幅度提高的物理机制。     

La0.85 Ce0.15Fe11.4Si1.6合金磁热效应的间接测量和直接测量

采用X射线衍射和磁性测量等手段研究了金属间化合物La0.85 Ce0.15Fe11.4Si1.6的结构和磁热效应.结果表明,该化合物在211K附近经历了从铁磁到顺磁的二级相变.当外加磁场从OT增加到1.5T时.磁熵变为4.98J/kg·K.通过直接测量的方法得到了La0.85 Ce0.15Fe11.4Si1.6化合物在211K的1.0T～0T退磁场的绝热温变为1.1K.大的熵变值和绝热温变表明La0.85 Ce0.15Fe11.4Si1.6化合物很有潜力作为相应温区的磁制冷材料.     

磁热效应及磁制冷材料的选择依据

从热力学基本理论出发,解释了磁制冷材料的磁热效应,并推导出等温熵变|ΔSm|和绝热温变ΔTad的基本公式,为选择合适的磁制冷材料提供了理论依据.     

TmGa合金的磁性和磁相图

利用电弧熔炼制备出单相的TmGa化合物,TmGa显示了两个连续的相变:在11.5 K处为反铁磁到反铁磁(AFMΙ-AFMΠ)相变,在15 K处为反铁磁到顺磁(AFMΠ-PM)相变。反铁磁区域存在场诱导的反铁磁到铁磁(AFM-FM)变磁转变。虽然TmGa的基态是反铁磁,但是当在较低磁场(0.02 T)下,在12 K附近诱导出铁磁态,因此在一定磁化强度范围内存在AFMΙ-FM,FM-AFMП和AFMП-PM相变。当磁场为0.2 T时AFMΠ态完全消失,AFM-PM的转变成为FM-PM的转变。低温AFMΙ态随磁场的变化是不可逆的,而AFMΠ态随磁场的变化是可逆的。根据温度和磁场的变化绘制了TmGa的磁相图。TmGa在相变温度附近具有较大的磁熵变(-ΔSM),当磁场变化为5 T时,最大-ΔSM为34.2J·kg-1·K-1。值得注意的是,在磁场变化为1和2 T时,最大-ΔSM分别为12.9和20.7 J·kg-1·K-1。同时通过计算得到在1,2和5 T下的磁制冷能力(RC)分别为69,149和364 J·kg-1。TmGa化合物作为低温磁制冷材料潜在巨大应用前景。     

Gd0.97-xDyxV0.03-Cu复合磁制冷材料的性能研究

对采用真空扩散焊接制备的Gd0.97-xDyxV0.03(x=0.0,0.1,0.2,0.3)-Cu复合磁制冷材料的界面微观特性、磁热性能进行研究。XRD衍射和XPS能谱结果表明所有复合界面基本都是Cu向磁制冷材料内扩散,在Cu基体中基本上没有磁制冷材料元素的扩散;磁制冷材料与Cu之间没有化合物产生,复合扩散层宽度大约为5~8μm,远低于采用传统复合工艺的扩散层宽度(200μm)。在测试温度范围内复合材料相变类型为二级相变特征;复合材料的最大绝热磁熵变为2.83 J/(kg.K),对比复合前虽有所下降,但其绝热磁熵变曲线峰宽显著增加,其半高峰处的温度间距高达110K以上,相对磁制冷能力大于311.3J/kg以上,明显优于复合前;复合材料的最大绝热温变为1.59K,其绝热温变曲线保持较高温变的平台显著拉长,出现较高温变的平台温度有所提高,更趋近于室温。以上结果对磁制冷材料实现商业应用具有意义。     

通过拟合磁化曲线计算钙钛矿锰氧化物La_(1.2-x)Tb_xSr_(1.8)Mn_2O_7(x=0,0.05)的磁熵变

采用传统高温固相反应法制备La_(1.2-x)Tb_xSr_(1.8)Mn_2O_7(x=0,0.05)多晶样品,利用振动样品磁强计(VSM)测量了样品在不同温度下的磁化强度随外场变化曲线(M-H),然后利用正交多项式最小二乘拟合方法对钙钛矿锰氧化物La_(1.2-x)Tb_xSr_(1.8)Mn_2O_7(x=0,0.05)的磁化强度曲线进行拟合,再根据磁熵变的热力学公式计算出样品的磁熵变值。通过计算得到La_(1.2-x)Tb_xSr_(1.8)Mn_2O_7(x=0,0.05)多晶样品的居里温度分别为123 K和75 K,在外加磁场20 k Oe下x=0样品和x=0.05样品的最大磁熵变值分别为2.26 J/(kg·K)和1.6 J/(kg·K),所以x=0样品可作为高温区(77 K以上)磁制冷材料,而x=0.05样品可作为中温区(20 K~77 K)磁制冷材料。计算结果显示,拟合数据和实验数据非常接近,结果比较满意,说明该方法适用于La_(1.2-x)Tb_xSr_(1.8)Mn_2O_7(x=0,0.05)多晶样品的磁熵变计算。     

LaFe11.2Co0.7Si1.1Bx合金在室温区的大磁热效应

从室温磁制冷目的出发,用工业纯原料制备了具有NaZn13型结构的稀土铁基化合物LaFe11.2Co0.7Si1.1Bx(x=0,0.1,0.2,0.25,0.3,0.4,0.5),并对其磁热效应进行了研究.实验结果表明,LaFe11.2Co0.7Si1.1Bx合金在室温区具有大磁热效应,在x＝0.2时,磁熵变|ΔSm|的峰值位于居里温度TC＝270K处,1.5T外磁场下达到7.3J/kg·K,直接测量绝热温变ΔTad达到2.7K;B元素作为置换原子和间隙原子进入NaZn13相,显著提高了合金的磁熵变和居里温度.     

室温磁热效应直接测量仪的研制

简单介绍了室温磁热效应测量仪的工作原理及组成,并且测量了Gd样品的磁热效应T-△Tad曲线,该仪器具有操作简单方便、测量费用低廉等优点,它可以作为室温磁制冷材料研究的重要测量手段,同时也可以解决目前磁制冷材料普遍只研究等温磁熵变的不足的问题.     

Pr2Fe17-xAlx系列化合物的结构与磁熵变

采用熔炼法制备了Pr2Fe17-xAlx系列化合物。利用X射线衍射和MPMSXL-7型磁强计对样品相结构和磁熵变进行了研究。结果表明：Pr2Fe17-xAlx系化合物保持了Th2Zn17型菱方结构，其居里温度可通过成分微调达到室温附近；Pr2Fe17-xAlx系化合物在居里点附近发生的相变属于二级相变，并在较宽温区范围内保持了较大的磁熵变。该化合物在2．0T外场下的最大磁熵变达到纯金属Gd的60％左右，且其化学性质稳定，制冷温区宽，价格低，是一类具有较大应用潜力的新型室温磁制冷工质材料。     

Magnetic Entropy Change of （Gd1-xREx）5Si4（RE = Dy, Ho） Alloys

Magnetic Entropy Change of (Gd_(1-x)RE_x)_5Si_4(RE=Dy, Ho) Alloys     

Mass production of magnetocaloric LaFeMnSiB alloys with hydrogenation

LaFe_(11.39)Mn_(0.35)Si_(1.26)B_(0.1)Hxalloys were prepared by hydrogenation.Samples were annealed at 1343Kfor30-90 hto form the NaZn13 phase.La-rich andα-Fe secondary phases were also detected.Saturated hydrogenation at 553 Kand 0.15 MPa of H_2 pressure for 5hwas employed to improve the Curie temperature of the alloys to 279 K.The maximum magnetic entropy change,relative cooling power,and adiabatic temperature change of LaFe_(11.39)Mn_(0.35)Si_(1.26)B_(0.1)H_x annealed at 1343 Kfor 90hafter hydrogen absorption are 6.38J/(kg·K)(magnetic changesμ0ΔH =1.65T),100.1J/kg(μ0ΔH =1.65T),and 2.2 K(μ0ΔH =1.48T),respectively.Although the maximum magnetic entropy change of the LaFe_(11.39)Mn_(0.35)Si_(1.26)B_(0.1)H_x alloys is lower than those of similar alloys with high purity raw materials,the relative cooling power is nearly the same.The effect of impurities of the raw materials used was also discussed.It is assumed that the impurity of 0.2wt.% Al is responsible for the reduced entropy change of the resulted alloys.The LaFe_(11.39)Mn_(0.35)Si_(1.26)B_(0.1)H_x alloys prepared by this method could be a low cost alternative material for room temperature magnetic cooling applications.     

Thermodynamical Evaluation on Magnetocaloric Effect of Magnetic Refrigerating Materials Near Room Temperature

The relationship between isothermal magnetic entropy change △S and adiabatic temperature change △Tad was deduced according to the principles of thermodynamics. The MCE and the engineering application were discussed for Gd and several new kinds of magnetic refrigerating materials near room temperature, Gd5Si2Ge2, MnFeP0.45As0.55 and LaFe11.2Co0.7Si1.1. Isothermal entropy change is proportional to adiabatic temperature change with a factor of T/C (T is temperature, C is heat capacity). When the comparison of magnetacoloric effect is made for two different materials, we should consider isothermal entropy change as well as adiabatic temperature change.     

Magnetocaloric Properties of （Gd1-x Tbx ）3 Al2 Compounds Near Room Temperature

Recentlytherehasbeenaninterestinmagneticrefrigerationstudiesduetoitspotentialasanenergysavingtechnology[1～ 5] .Theefficiencyofmagneticre frigerationcriticallydependuponmagneticrefriger ants .Forthebestrefrigerantperformance ,verylargeisothermalmagneticentropychangeΔSisrequired ,andthemaximumvalueofΔSmustexistoverawiderrangeoftemperatures[2 ] .Recentdiscoveryofgiantmagnetocaloriceffect(MCE)ΔSinfirst ordertransi tionmaterialsgivesfurtherimpulsetowardsthedevel opmentofbothnewmaterialsandmag…     

Magneto-Caloric Effect of Gd5Si2Ge2Compounds under Different Processing Conditions

The magneto-caloric effect of Gd5 Si2Ge2 compounds produced by various techniques is investigated in terms of their magnetization behaviors in the magnetic field from 0 to 2.0 T.The studied materials include arc-melted, annealed and sintered alloys.The results demonstrate that the Gd5Si2Ge2 alloys obtained under different processing conditions possess distinct magneto-caloric effect due to their various microstructures.Proper annealing treatment can enhance the magneto-caloric effect of the alloy remarkably.While the sintered alloy bears relatively lower value of magnetic entropy change ( △ SM) than arc-melted one.The magnetic entropy change of the annealed Gd5 Si2Ge2 alloy arrives the arrives the maximum value of - △SM = 15.29 J· kg-1· K-1 for magnetic field change under 2.0 T in the present work.     

LaGd_(0.1)Fe_(11.4-x)Co_xSi_(1.6)(x=0.1,0.3,0.5,0.7,0.9)合金的磁热效应

研究了LaGd0.1Fe11.4-xCoxSi1.6(x=0.1,0.3,0.5,0.7,0.9)系列合金的结构以及磁热效应。室温XRD分析表明该系列合金除微量的α-Fe相外,均具有立方NaZn13型立方单相晶体结构,空间群为Fm-3c。晶格常数没有明显变化,分别为1.1458,1.1454,1.1458,1.1459,1.469nm。磁性测量表明该系列合金的Tc随着Co含量的增加而增加,分别为212,231,253,281,302K。在外磁场变化ΔB=1.5T时,最大的磁熵变随着Co含量的增加而减少,由x=0.1的13.8J降为x=0.9J.kg-.1K-1的1.5J.kg-.1K-1。并且随着Co含量的增加存在由一级相变转为二级相变的趋势。     

粉末注射成形在软磁材料中的应用

介绍了粉末注射成形在粘结软磁、烧结软磁生产中的应用、研究开发状况。指出粉末注射成形是能够实现低成本生产新性能、新功能的磁体制造技术，强调利用注射成形技术实现磁性元器件结构功能一体化设计、制造的优势。     

Study of Magnetic Entropy Changes in Gd1-x Tx ( T = Ti, Cr, Fe and Cu) Alloys

Magnetic refrigeration techniques based on the magnetocaloric effect (MCE) were demonstrated as a promising alternative to conventional vapour-cycle refrigeration.Recently, scientists focused their research on room temperature magnetic refrigeration.The rare earth Gd metal is regarded as a prototype for room temperature magnetic refrigerant.Considering the various requirements in application, it is necessary to search for the magnetic refrigerant possessing qualities as good as Gd but having different Tc above or below room temperature.In this article, we report the magnetic entropy changes in Gd1 -xTx(T = Ti, Cr, Fe and Cu) alloys.With a small quantity of T atoms introduced in Gd, the Curie temperature increases.The values of magnetic entropy change in these alloys are almost the same as or a little less than that of Gd.But the refrigerant capacities of these alloys are obviously larger than that of Gd.All these facts suggest that Gd1-xTx(T = Ti, Cr, Fe and Cu) alloys may be good refrigerants for room temperature magnetic refrigeration.     

Effects of manganese doping on magnetocaloric effect in Ge-rich Gd_5Ge_（2.05）Si_（1.95） alloy

The structure, magnetic and magnetocaloric properties of the Ge-rich Gd5Ge2.05-xSi1.95-xMn2x (x=0.01 and 0.03) alloys were investigated by scanning electron microscopy, X-ray powder diffraction, differential scanning calorimeter (DSC) and magnetization measurements. The results of energy dispersive X-ray analysis (EDX) and X-ray diffraction analyses showed that the composition and crystal structure of the alloys were desired. DSC measurements were performed to determine the transformation temperatures for each alloy. Both alloys exhibited the first order phase transition around room temperature. The alloys showed an anti-ferromagnetic transition around 60 K. The isothermal magnetic entropy changes of the alloys were determined from the isothermal magnetization measurements by using the Maxwell relation. The maximum values of isothermal magnetic entropy change of the Gd5Ge2.05-xSi1.95-xMn2x alloy with x=0.01 was found to be -12.1 and -19.8 J/(kg·K) using Maxwell equation around 268 K in applied fields of 2 and 5 T, respectively.