新型的氧化物磁制冷工质与隧道磁电阻材料--2004年度国家自然科学二等奖获奖项目介绍

文章介绍了2004年度国家自然科学二等奖获奖成果[21].类钙钛矿型材料是一类物理内涵极其丰富的化合物,它是著名的高温超导材料、铁电材料、压电材料,又是庞磁电阻效应材料,目前又显示出具有大磁熵变效应与隧道磁电阻效应.文章作者系统地研究了锰钙钛矿磁性化合物的磁熵变与组成、微结构以及颗粒尺寸的关系,研究结果表明,磁性钙钛矿化合物具有显著的磁熵变,居里温度易调,并且化学稳定性佳,从而成为一类新型的磁制冷工质候选材料.此外,文章作者还研究了钙钛矿化合物纳米颗粒体系的磁电阻效应,发现除人们发现的居里温度附近的本征的庞磁电阻效应外,在很宽的低温区,存在与温度不甚敏感的隧道磁电阻效应.     

钆硅锗确有巨磁热效应

室温磁制冷在近几年取得重要进展,尤其是造出了高性能的样机和发现了巨磁热材料,但近来因为巨磁熵变发生在一级相变点,在磁熵变的计算上国际诸研究小组出现了分歧,本文对此进行了详细的讨论,给出了统一的处理方法,结果表明钆硅锗的确具有巨磁热效应。     

新型MnFe基复合磁热材料及其在回热制冷循环中的性能特性

基于三种MnFe基磁热材料的热容及等温磁熵变随温度变化的实验数据,本文应用热力学理论设计一种新型MnFe基复合磁热材料,获得三种组分磁热材料与复合材料的优化摩尔质量比,进一步以该复合磁热材料为工质构建回热式Ericsson和Brayton制冷循环,基于热力学分析和数值计算,比较这两种制冷循环的非平衡回热量、净制冷量及性能系数等重要热力学参量,同时将复合材料的相关结果与单组分磁热材料的加以对比,结果表明:复合材料的大磁熵变温区要比任何一种组分材料的宽得多,而以复合材料为工质的制冷循环的净制冷量在近15 K温区内都较大,所得结果能为室温磁制冷机的参数优化设计提供有益的参考。     

在室温磁制冷中铁磁体作为工作物质的可能性

在室温磁制冷中铁磁体是合适的工作物质．铁磁体内部存在的交换相互作用，使我们能够以较低的外场达到排出磁熵的目的．同时，铁磁体磁热过程本身的可逆性，使我们有可能用它构成高效的磁制冷机．本文从铁磁体磁热效应的基本实验事实出发，讨论磁制冷机工作物质选择的判据，强调真实磁化过程在制冷应用中的意义，利用分子场近似给出对材料选取有用的公式，通过对比指出，Ｆｅ基合金具有很好的应用前景．     

La2/3Ca1/3MnO3的巨磁熵效应

本文对超大磁阻材料Ｌａ２／３Ｃａ１／３ＭｎＯ３的巨磁熵效应进行了研究,通过测量不同磁场下的磁化－温度曲线,发现伴随铁磁－顺磁相变有一个大的磁熵变化,这个结果表明钙钛矿锰氧化物可以作为磁致冷技术中的工作物质。     

铁氧体磁卡效应的研究

对磁铅石型铁氧体，尖晶石型铁氧体，石榴石型铁氧体以及正铁氧体部分样品的磁卡效应进行了实验研究，研究了非磁性离子的代换对居里温度以及磁熵变的影响。 关键词：     

一级相变磁制冷材料的基础问题探究

由于一级相变磁制冷材料发生磁相变时有晶胞体积的突变,相变过程中有相变潜热存在,其磁化过程中有许多磁学问题有待于进一步探究.本文以LaFe13-xSix合金为研究对象,在现有对磁一级相变基础问题的分析基础上,对一级相变材料中系统熵变、等温熵变、绝热温变、热滞、磁滞、铁磁与顺磁态两相共存的温度区间和磁场区间、制冷能力的计算等磁学基础问题进行了较为细致的探究.分析表明,在忽略完全铁磁态和顺磁态对磁热效应的贡献时,Maxwell方程和Clausius-Clapeyron方程计算熵变的值具有等效性.等温磁化过程中升温和降温曲线包围的面积SABCE(磁滞的大小),实际上是升温过程和降温过程中磁场做的净功,等于相变潜热之差.磁滞和热滞的大小与磁化过程数据测量的时间有关,测量时间越长则滞后越小,当相变是平衡相变则滞后为零.另外,对温度和磁场诱导磁相变过程进行了分析,提出了一级相变磁制冷材料制冷能力的不同计算模型.本文对一级相变磁制冷材料的磁学基础问题研究有一定的参考价值.     

TbDyFe薄膜对三明治膜巨磁阻抗效应的影响

将600℃退火后的超磁致伸缩材料(Tb0.27Dy_0.73)_0.3Fe_0.7薄膜作为Ni_80.2Fe_14.1Si_0.2Mn_0.4Mo_5.1三明治膜的基底，制备出四层膜.结果表明：附加的磁致伸缩并没有减小材料的巨磁阻抗(GMI)效应，而由于磁场下磁致伸缩材料的应力效应影响了三明治膜中的各向异性场，使三明治膜的GMI效应增大了4倍.再将制备态的四层膜在280℃下真空退火，退火态四层膜也增大了三明治膜的GMI效应，但可能由于磁致伸缩向磁性层中的扩散，其GMI效应相对于制备态四层膜则有所降低. 关键词： 巨磁阻抗(GMI)效应 三明治膜 TbDyFe薄膜 各向异性场     

有限输入阻抗下压电/磁伸层叠材料磁电效应理论及实验

将磁致伸缩材料及压电材料本构方程与运动方程结合,考虑压电材料具有的高输出阻抗的特点及测试设备的有限输入阻抗和传输信号引线电容对磁电效应输出电压的影响,推出了Terfenol-D巨磁伸材料与横向极化Pb(Zr_1-xTi_x)O₃压电材料的磁电效应理论,研制了由一维磁伸材料构成的三明治结构元件并对其性能进行了测试,采用考虑了测试系统有限输入阻抗后建立的磁电效应理论结果与实验结果更符合.理论结果表明磁电元件在有限输入阻抗 关键词： 磁电效应 有限输入阻抗 压电/磁伸复合 一维磁伸材料     

FeCuCrVSiB单层和多层膜的横向巨磁阻抗效应

用射频溅射法制备了Fe_71.5Cu₁Cr_2.5V₄Si₁₂B₉单层膜和结构为(F/S)₃/M/(F/S)₃的多层膜，在制备过程中加72kA/m的纵向磁场.研究表明在制备过程中加磁场明显改善了材料的软磁性能，降低了材料的矫顽力.将样品经不同温度退火热处理后，发现经230℃退火1.5h的单层膜和多层膜具有最佳的软磁性能和最大的磁阻抗效应，单层膜最大横向磁阻抗比为37.5%，多层膜最大横向磁阻抗比高达277%.通过比较单层和多层膜磁阻抗效应随频率和磁场的变化，发现多层膜具有较低的磁阻抗效应的临界频率和峰值特征频率，和较大的磁阻抗变化率，而且有较低的横向磁阻抗效应的饱和场. 关键词： 铁基合金 多层膜 巨磁阻抗效应     

Crystallography,magnetic properties and magnetocaloric effect in Gd4(BixSb1−x)3 alloys

A study of magnetic and thermal properties has been carried out on the alloys from the Gd₄(Bi_xSb_1−x)₃ series with x=0, 0.25, 0.5, 0.75, and 1. All of the alloys are ferromagnetic below their respective Curie temperatures which vary from 266 K for x=0 to 332 K for x=1.0. The magnetocaloric effect calculated from the temperature and magnetic field dependencies of the magnetization and heat capacity is moderate when compared to that of other materials, which order in the same temperature range. Both the magnetic ordering and the magnetocaloric effect peak temperatures increase nearly linearly with the increasing Bi content. Experimental magnetocaloric effect data obtained from two different measurement techniques are in excellent agreement.     

The magnetic and magnetocaloric effect of (Mn0.5Co0.5)65Ge35 alloy in low magnetic field

The crystal structure and magnetocaloric effect (MCE) of water-quenched and annealed (Mn_0.5Co_0.5)₆₅Ge₃₅ alloys were studied in this paper. A CoMnGe-single phase was formed in the water-quenched alloy, and mixture phases of CoMnGe and Mn+2O in the annealed alloy. The annealed alloy has a smaller crystal parameter than the water-quenched alloy. The Curie temperature is 275 and 298 K for the water-quenched and annealed alloys, respectively, which means that the magnetic-transition temperature in this material can be controlled by anneal. In addition, the same magnetic entropy change was found in these two alloys, even though their Curie temperatures have a significant difference.     

Structure,magnetic properties and magnetocaloric effects of Fe50Mn15−x Co x Ni35 alloys

Fe50Mn15-xCoxNi35(x=0,1,3,5,7)alloys were prepared by arc melting under purified argon atmosphere.The ingots were homogenized at 930°C for 90h followed by water quenching.The crystal structure,magnetic properties and magnetocaloric effects of the alloys were studied by X-ray diffraction(XRD)and MPMS-7-type SQUID.The results show that all samples still maintained a single-(Fe,Ni)-type phase structure.With the increase of the content of Co,the Curie temperatures of these alloys increased and exhibited a second-order magnetic transition from ferromagnetic(FM)to paramagnetic(PM)state near Curie temperature.The maximum magnetic entropy change and the relative cooling power of Fe50Mn10Co5Ni35alloy was 2.55 J/kg·K and 181 J/kg,respectively,for an external field change of 5T.Compared with rare earth metal Gd,Fe50Mn15-xCoxNi35 series of alloys have obvious advantage in resource price;their Curie temperatures can be tuned to near room temperature,maintain a relatively large magnetic entropy change at the same time and they are a type of potential magnetic refrigeration materials near room temperature.     

Magnetocaloric effect in the intermetallic compound DyNi

Magnetic and heat capacity measurements have been carried out on the polycrystalline sample of DyNi, which crystallizes in the orthorhombic FeB structure (space group Pnma). This compound is ferromagnetic with a Curie temperature of 59 K. Magnetization-field isotherms at low temperatures show a multi-step behavior characteristic of metamagnetic transitions. The magnetocaloric effect has been measured both in terms of isothermal magnetic entropy change and adiabatic temperature change for various applied magnetic fields. The maximum values of the entropy change and the temperature change are found to be 19 J kg⁻¹ K⁻¹ and 4.5 K, respectively, for a field of 60 kOe. The large magnetocaloric effect is attributed to the field-induced spin-flop metamagnetism occurring in this compound, which has a noncollinear magnetic structure at low fields.     

Magnetic and magnetocaloric properties of martensitic Ni2Mn1.4Sn0.6 Heusler alloy

The evolutions of magnetic properties at low temperatures and the influence of magnetic field on the temperature dependence of specific heat in martensitic Ni₂Mn_1.4Sn_0.6 Heusler alloy are studied. The frequency-dependent blocking temperature and considerable exchange bias below it are measured in the martensitic phase. From the analysis of the specific heat curves under magnetic field, a large inverse magnetocaloric effect manifested as the magnetic field induced rise of isothermal magnetic entropy and/or magnetic field induced adiabatic temperature decrease in the vicinity of the reverse magnetostructural transformation and a significant value of the conventional magnetocaloric effect at the Curie temperature are obtained. The Debye temperature and electronic coefficient equal to Θ_D=310±2 K and γ= 16.6±0.3 mJ/K²mol, respectively, do not depend on the magnetic field.     

The magnetic entropy change in La0.8Ce0.2Fe11.4Si1.6Bx compounds prepared by copper-mold casting

The magnetocaloric effect (MCE) of La_0.8Ce_0.2Fe_11.4Si_1.6B_x (x=0.0-0.5) compounds, prepared by a copper-mold casting (CMC) method, has been investigated. Comparing with the conventional arc-melting (CAM) method, the relatively homogenous composition and microstructure were achieved in the precursor alloys prepared by the CMC method. As a result, the annealing time is dramatically shortened from several weeks for CAM alloys to 2 h for CMC alloys, suggesting that CMC method is a time-saving and energy-saving method for fabrication of MCE alloys. On the other hand, it is revealed that B addition gives rise to an enhancement of Curie temperature (T_C), a reduction of thermal lag and magnetic hysteresis and a broadening of working temperature span as well. Although the peak value of magnetic entropy change decreases with B content, various B-contained compounds hold close refrigerant capacities. Comprehensively considering magnetocaloric properties of the B-contained La_0.8Ce_0.2Fe_11.4Si_1.6B_x compounds, it can be concluded that the B-contained compounds prepared by CMC method are promising candidates of magnetocaloric materials in practical application.     

The influence of a minority magnetic phase on the field dependence of the magnetocaloric effect

The field dependence of the magnetic entropy change can be used to detect the existence of a minority magnetic phase without experimentally reaching its Curie temperature. In this work, we present results that could suggest a breakdown of the recently proposed universal behaviour of the magnetocaloric effect in materials with a second-order magnetic phase transition in some La-containing samples. The behaviour of the outlier La-containing materials is an evidence of the existence of minority phases, preventing the construction of the universal curve with a single reference temperature. However, the use of two reference temperatures avoids this difficulty and allows applying the universal curve for practical purposes even with the presence of the minority phase.     

The influence of Al substitution on the phase transitions and magnetocaloric effect in Ni43Mn46Sn11−xAlx alloys

The effects of Al substitution on the phase transitions and magnetocaloric effect of Ni₄₃Mn₄₆Sn_11−xAl_x (x=0-2) ferromagnetic shape memory alloys were investigated by X-ray diffraction and magnetization measurements. With the increase of Al content, the cell volume decreases due to the smaller radius of Al, and the martensitic transformation temperature increases rapidly, while the Curie temperature of austenitic phase shows a small increase. A large positive and a negative magnetic entropy change were observed near the first-order martensitic transition and the second-order magnetic transition, respectively. The magnetic entropy changes, hysteresis behavior, and refrigerant capacity near the two transitions are compared.     

Magnetic and magnetocaloric properties of the high-temperature modification of TbTiGe

The high-temperature form (HT) of the ternary germanide TbTiGe was prepared by melting. The investigation of HT-TbTiGe by x-ray and neutron powder diffractions shows that the compound crystallizes in the tetragonal CeScSi-type structure (space group I4/mmm; a?=?404.84(5) and c?=?1530.10(9)?pm as unit cell parameters). Magnetization and specific heat measurements as well as neutron powder diffraction performed on HT-TbTiGe reveal a ferromagnet having T(C)?=?300(1)?K as the Curie temperature; the Tb-moments are aligned along the c-axis. This magnetic ordering is associated with a modest magnetocaloric effect around room temperature. The isothermal magnetic entropy change ΔS(m) was determined from the magnetization data; ΔS(m) reaches, respectively, a maximum value of -?4.3 and -?2.0?J?K(-1)?kg(-1) for a magnetic field change of 5 and 2?T.     

Magnetocaloric properties and Griffiths phase of ferrimagnetic cobaltite CaBaCo4O7

We present a study on the magnetocaloric properties of a CaBaCo$_{4}$O$_{7}$ polycrystalline cobaltite along with research on the nature of magnetic phase transition. The magnetization as a function of temperature identifies the ferrimagnetic to paramagnetic transition at a Curie temperature of 60 K. Moreover, a Griffiths-like phase is confirmed in a temperature range above $T_{\rm C}$. The compound undergoes a crossover from the first to second-order ferrimagnetic transformation, as evidenced by the Arrott plots, scaling of the universal entropy curve, and field-dependent magnetic entropy change. The maximum of entropy change is 3 J/kg$\cdot$K for $\Delta H = 7$ T at ${T}_{\rm C}$, and a broadening of the entropy peak with increasing magnetic field indicates a field-induced transition above $T_{\rm C}$. The analysis of the magnetic entropy change using the Landau theory reveals the second-order phase transition and indicates that the magnetocaloric properties of CaBaCo$_{4}$O$_{7}$ are dominated by the magnetoelastic coupling and electron interaction. The corresponding values of refrigerant capacity and relative cooling power are estimated to be 33 J/kg and 42 J/kg, respectively.