直接测量(Nd1-xCex)2Fe17化合物的磁热效应

用真空高频悬浮炉在氩气保护下熔炼了(Nd1-xCex)2Fe17系材料(x=0.32,0.41,0.60).通过x射线衍射对退火前后的样品进行相结构分析.在磁场H=1.5T条件下,用永磁式室温磁热效应测量仪和VSM直接测量了三个样品的绝热温变 ΔTad及测量并计算了Nd1.18Ce0.82Fe17样品的ΔSm.随着Nd含量的增加,(Nd1-xCex)2Fe17系合金的磁相变温度显著提高,同时,绝热温变ΔTad略有增加,有望成为具有实用价值的室温磁制冷材料.     

Gd4(BixSb1-x)3系列合金在低磁场下的磁热效应

用高频悬浮炉熔炼了Gd4(BixSb1-x)3系列合金,利用X光粉末衍射技术确定其结构。在1.3T的磁场下,利用自制的△Tad-T曲线测量仪直接测量了该系列合金的磁热效应。发现Gd4(BixSb1-x)3系列合金在低磁场下具有较大的磁热效应,通过改变Bi的含量,其居里温度在267K～332K温度之间增加,从而在一个较宽的温度范围内能获得较大的绝热温变。在对退火前后的样品进行△Tad-T测量后,发现其热稳定性很好。实验结果说明Gd4(BixSb1-x)3系列合金是一种性能良好的磁致冷材料。     

水热合成La0.65Ca0.18Sr0.17MnO3及其磁热效应的研究

为了合成居里温度在室温附近的钙钛矿磁致冷材料,用简单的无机原料,采用水热合成法合成了La0.65Ca0.18Sr0.17MnO3钙钛矿材料.用粉末X射线衍射表征材料的相组成,用扫描电镜(SEM)观测样品形貌,用直接法测量材料的绝热温变.通过研究水热合成条件如碱度、水热温度、水热时间等对其样品磁热效应的影响,确定水热合成的最佳条件为碱度4 mol·L-1、水热温度240 ℃、水热时间80 h.该条件下合成的样品为单一钙钛矿相,由能谱图知不同形貌的晶体具有相同的成分.此材料的居里温度为323 K,最大绝热磁温变为0.29 K.     

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.     

知识窗

磁致冷是指以磁性材料为工质的一种全新的制冷技术 ,其基本原理是借助磁致冷材料的磁热效应(ＭｅｇｎｅｔｏｃａｌｏｒｉｃＥｆｆｅｃｔ ,ＭＣＥ) ,即磁致冷材料等温磁化时向外界放出热量 ,而绝热退磁时 ,从外界吸取热量 ,达到制冷的目的。也就是磁热效应ＭＣＥ是在绝热条件下由于顺磁性或铁磁性材料磁化时自旋有序度增加 ,原子磁矩的磁熵降低而产生的。在强磁场下 ,能量降低 ,使材料的温度升高 ,去除磁场后 ,自旋有序度降低 ,能量增加 ,材料温度降低。磁致冷材料的磁致冷性能主要由居里点Ｔｃ、外加磁场Ｈ、磁热效应ＭＣＥ和磁比热ＣＨ 等…     

粉末冶金法制备La(Fe11.05Co0.85Si1.1)B0.25化合物的磁热效应

用非自耗电弧炉熔炼制备了La(Fe<,11.05>Co<,0.85>Si<,1.1>)B<,0.25>铸锭,并将该铸锭在氩气保护中球磨制粉,采用SPS(放电等离子烧结技术SparkPlasma Sintering)将该粉制成La(Fe<,11.05>Co<,0.85>Si<,1.1>)B<,0.25>合金,在高温(1070℃)下对其进行20 h热处理;空冷之后用XRD及SEM检测了铸锭热处理样品、SPS烧结样品及SPS热处理后样品的相及组织结构,利用VSM和磁热效应直接测量仪测量了这3种状态下合金的等温磁熵变和绝热温变.结果表明,铸锭合金的基相组织结构中晶粒大小规则较均匀,晶界清晰明显,在0～1.5 T的变化磁场下测得其等温磁熵变达到-5.22 J·(kg·K)<'-1>-,绝热温变也达到2.3 K,而采用SPS技术制得的样品的基相组织结构中没有明显晶界且夹杂较多,其等温磁熵变为-3.90 J·(kg·K)<'-1>,绝热温变为1.9 K(0～1.5 T);经过热处理的SPS样品基相组织结构中,有少量晶界形成,但晶粒大小不规则,测得其等温磁熵变为-3.72 J·(kg·K)<'-1>,绝热温变为1.5 K(0～1.5 T);与铸锭相比较,SPS技术制得的合金样品和经过高温热处理之后的SPS样品的绝热温变值和等温熵磁变值均降低,同比之下这两种样品较铸锭样品的居里点和半峰宽却发生了改变,均显著提高;可以看出采用SPS技术制备的室温磁制冷材料La(Fe<,11.05>Co<,0.85>Si<,1.1>)B<,0.25>能够在较宽的温度范围内制冷,但其磁热效应却相对降低.     

热处理工艺对( Mn,Fe)2(P,Si)系列化合物磁性的影响

用机械合金化方法成功制备了Mn1.35Fe0.65 P1-x Six(x=0.56和0.57)化合物,分别采用了两种不同的工艺对化合物进行热处理.用X射线衍射仪、振动样品磁强计和绝热温变测量仪分别对样品的结构、等温磁熵变和绝热温变进行了测量.实验结果表明,经过两种不同热处理工艺处理的化合物都形成了Fe2P型六角结构,空间群为P62m,在经过淬火处理的Mn1..Fe0 eP0..Si0.56化合物中存在少量的(Mn,Fe) 5Si3第二相,空间群为P63/mcm.样品的居里温度都在室温附近,在278 ～296 K之间变化,不同热处理工艺对化合物的居里温度具有一定的影响.经过淬火处理的化合物存在较小的热滞和较大的等温磁熵变,两种化合物的热滞都由自然冷却处理时的5K降低到淬火处理时的3K.当Si的含量分别为0.56和0.57时,与经过自然冷却处理的化合物相比,经过淬火处理的化合物的最大磁熵变分别提升了33％和20％.在经过淬火处理的Mn1.35Fe0.65P0.44Si0.56化合物磁熵变最大,磁熵变的最大值为4.3J·kg-1·K-1.经过自然冷却处理的Mn1.35 Fe0.65P0.44 Si0.56化合物的最大绝热温变为1.2K.低成本的原料、较小的热滞、理想的制冷温区和较大的磁热效应使得Mn1.35 Fe0.65P1-xSix这一系列化合物在室温磁致冷方面有应用前景.     

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.     

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.     

NaZn13型LaFe基室温磁致冷材料研究进展

介绍了LaFe基室温磁致冷材料在磁热效应和制备方面的研究进展.指出具有NaZn13型结构且Fe含量高的LaFe基化合物是良好的软磁材料,其居里温度可通过Co取代Fe或添加非金属元素H、C、B等来提高;采用甩带和添加其他稀土元素取代La可缩短材料获得NaZn13型结构的退火时间.通过调整LaFe基化合物的元素配比,将有可能制备出具有巨磁热效应的室温磁致冷材料.     

Research Advance on Magnetocaloric Effect of La-Fe-M(Al, Si) Compounds

Inviewofenergysavingandenvironmentalpro tection ,magneticrefrigerationnearroomtemperaturehasastrongimpactonconventionalgascompressiontechnology .However ,coolingefficiencyofthesystemformagneticrefrigerationismainlydecidedbythemagnitudeofmagnetocaloriceffectformagneticrefrig eratingmaterialsinthesystemunderacertainmagnet icfieldchange .Therefore ,developmentofnewrefrig eratingmaterialswithgreatmagnetocaloriceffectnearroomtemperatureisespeciallyimportant .Therearetwoparameterswhichareusedtochara…     

Gd3-xMnxAl2系合金的晶体结构和磁熵研究

采用真空高频磁悬浮炉制备出一系列的Gd3-xMnxAl2(x=0,0.1,0.2,0.3)合金。通过Mn对Gd的部分替代,研究了Mn元素微量替代对Gd3Al2合金结构和磁熵的影响。实验结果表明,Gd3-xMnxAl2系合金的结构与Gd3Al2相同;随着Mn含量的增加,Gd3-xMnxAl2系合金的居里温度和磁熵发生了变化。说明Mn对Gd的部分替代改变了Gd3Al2合金的磁热效应。     

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 effect in Gd5(Si,Ge)4 based alloys and composites

The research on magnetocaloric materials for applications concentrates, among other, on two parameters: the ordering temperature and the value of the magnetocaloric effect (MCE). The optimization consists in tuning the former without significant drop in the latter. These studies report on the magnetic susceptibility, magnetization curves, heat capacity and magnetocaloric effect measurements for compositionally and structurally modified Gd₅Si₄ compound. The modifications are based on the doping of the parent compound with an excess Gd atoms and substitution of Si with B as well as on the dimensional effect studied by mechanical milling. Moreover, composite samples of the type Gd:Gd₅Si₂Ge₂ were investigated revealing the influence of the intergranular interactions on the magnetocaloric properties. It appears that these interventions enable a controllable steering of the ordering temperature shifting it towards the room temperature with, in some cases, minor reduction of the parameters characterizing MCE.     

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.     

Study on Gd-Si-Ge Alloys Using Domestic Gd

To evaluate the possibility of using Gd-Si-Ge alloys in magnetic refrigerators, samples of Gd-Si-Ge alloys were made of domestic Gd. The magnetocaloric effect of samples was estimated by magnetic entropy change (-△ASm) calculated from M-H curves according to Maxwell relation. The first order phase transformation was destroyed due to the impuritiesin the commercial Gd, so that no giant magnetocaloric effect was found. The samples made of purified Gd exhibit first order phase transformation, and the -△Sm is basically consistent with the published data of Ames laboratory, USA. This work proves that Gd-Si-Ge alloys made of domestic Gd can be utilized in magnetic refrigerators.     

室温磁热效应直接测量仪的误差分析

简单介绍了室温磁热效应测量仪的组成、工作原理及其优点;用金属G d作为标准样品,用两个不同尺寸的温度传感器,测量了两个大小不同的样品。结果表明,相同条件下测量的数据重复性很好,而不同条件下测量的数据有一些差别,对此进行了分析,发现测量样品时特别是样品较小时,温度传感器的热容以及绝热条件等因素是引起误差的主要原因。     

Low-field magnetic entropy changes in （Gd1-xYx）3Al2 alloys

The effects of Y substitution on the magnetic properties and magnetocaloric effect of(Gd1-xYx)3Al2(x=0-0.3) alloys were investigated by X-ray diffraction and magnetization measurements.All samples crystallized in single phase with Zr3Al2-type tetragonal structure.The lattice parameters and magnetic transition temperature decreased obviously with increasing Y content.The magnetic entropy change and refrigerant capacity of these alloys were calculated.The adjustable transition temperature and favorable proper...     

Magnetocaloric Effect of Ni56Mn18.8Ga24.5 Gd0.7 Alloy

Inrecent years materials with high magnetocaloriceffect (MCE) have attracted considerable attention ow-ingto its potential application as a magnetic refriger-ant .Many material systemsthat underwentthefirst-or-der magnetic transition have been found to exhibit agiant MCE. Their typical representatives areGd5(SixGe1 -x)4[1 ,2]and La (FexSi1 -x)13[3 ,4]alloys .Ni MnGa is aferromagnetic shaped memory alloy whichundergoes a reversible first-order structural phase tran-sition (SPT) with the …     

Magnetocaloric Effect in Colossal Magnetoresistance Material（ La0.6 Dy0.1 ） Sr0.3 MnO3

The magnetocaloric effect was discovered in 1881by Warburg[1]. When a magnetic field is applied to amagnetic material, the unpaired spins are aligned par allel to the magnetic field, which lowers the magneticentropy and causes the sample to heat up. I…