La1-x(La-Ce-Pr-Nd)xFe11Co0.5Si1.5合金的物相分析与磁热效应

采用电弧熔炼法制备了原子配比为La_1-x(La-Ce-Pr-Nd)_xFe₁₁Co_0.5Si_1.5(x=0、0.2、0.4、0.6、0.8、1.0)的合金,其中La-Ce-Pr-Nd为混合稀土。采用X射线衍射、扫描电镜和磁性测试方法研究了合金的物相组成和磁热效应。研究结果表明,当x≤0.4时,合金主要由NaZn₁₃型立方结构主相与少量的α-Fe杂相组成,当x>0.4时,除了NaZn₁₃型立方结构主相与α-Fe杂相,还出现了Th₂Zn₁₇型菱形结构的杂相,且其含量随x的增加而增多。随着混合稀土含量x的增加,NaZn₁₃型主相的晶格常数减小,居里温度降低。居里温度附近的Arrott曲线说明所有合金都发生了二级磁相变,但合金都具有较大的磁热效应,当外磁场变化为2 T时,x=0.6合金的等温熵变最大值为14.2 J·kg^-1·K^-1     

P元素的替代对LaFe_(11.4)Si_(1.6)的磁热效应影响

通过电弧炉熔炼法制备了LaFe11.4Si1.6-x P x(x=0.05,0.1,0.2,0.3)系列合金,XRD分析表明少量P元素替代,LaFe11.4Si1.6-x P x(x=0.05,0.1,0.2和0.3)合金仍然保持NaZn13型结构,但晶格常数减小。在居里温度T c附近磁化曲线表明,该系列合金经历由磁场引起巡游电子由顺磁态到铁磁态变磁转变的一级相变。随着P含量的增加,LaFe11.4Si1.6-x P x(x=0.05,0.1和0.2)的居里温度T c减小,等温磁熵变也减小。在外加磁场变化为0~1.5 T时,等温磁熵变最大值分别为19.3 J/(kg·K),15.3 J/(kg·K)和10.3 J/(kg·K)。     

Si元素的添加对Ni43Mn46Sn11合金磁热效应的影响

通过对合金Ni43Mn46Sn11Six(x=0.0,0.1,0.2,0.3)磁热效应的研究,发现随着Si含量增加,合金的转变温度(TM)从187 K降到160K,合金的磁熵变也略微减小。在外场变化为3 T时,随着x的增加,合金的磁熵变分别为28.7,24.7,26.1和23.3 J.kg-·1K-1。此外,还利用连续和不连续降温两种方法对Ni43Mn46Sn11Six合金的等温磁化曲线进行了测量。发现两种测量方法测量的磁熵变值存在较大的差异,例如,对x=0的样品,在外场变化为3 T时,连续和不连续降温测量方法算得的磁熵变分别为28.74和38.56 J·kg-·1K-1。     

热压La0.8Ce0.2Fe11.45Mn0.25Si1.3H1.8磁工质的性能研究

采用工业纯原料,利用中频感应炉制备La_0.8Ce_0.2Fe_11.45Mn_0.25Si_1.3铸锭,在高纯氩气保护下退火后淬火。铸锭磨成粉末并装入热压炉模具中热压成型,热压温度选取723 K,873 K,1023 K及1173 K,压力30 MPa,保压时间30 min。热压样品切成薄片并饱和渗氢,测试材料结构、微观组织及磁热性能。实验结果表明,块状样品及热压样品均形成NaZn₁₃结构相。与块状样品相比,热压样品的磁热效应均低于块状样品,但随着热压温度的提高,样品的磁热效应逐渐增大。在1.5 T磁场、1173 K温度下,热压样品性能最高,最大磁熵变ΔS_M为10.87 J/(kg·K),体积熵变为66.80 kJ/(m³·K),最大绝热温变ΔT_ad为2.4 K,能够满足室温磁制冷机的应用。     

La_(1.1)Fe_(11.4)Si_(1.55)Ge_(0.05)合金的磁热效应

使用电弧熔炼法制备了La1.1Fe11.4Si1.55Ge0.05合金。研究了用少量的Ge替代Si后,La1.1Fe11.4Si1.55Ge0.05合金的磁性和磁热效应。粉末X射线衍射结果表明:在1273K真空退火处理10d后,合金La1.1Fe11.4Si1.55Ge0.05主相为NaZn13型立方结构,存在微量的α-Fe相。热磁曲线M-T与Arrott曲线表明:在居里温度Tc=205K处发生由铁磁性(TTc)转变为顺磁性(TTc)的二级磁相变。在磁场变化0～1.5T下,根据等温磁化曲线通过Maxwell关系式计算得出最大磁熵变-ΔSmmax=9J.kg-.1K-1。Ge替代Si后该合金在其居里温度Tc处-ΔSm-T曲线半高宽增大,使合金的相对制冷能力RCP(S)有所提高。     

哈斯勒合金Ni-Mn-Sn的磁热效应

采用真空电弧熔炼法和高温淬火法制备了四元哈斯勒合金Ni50-xCuxMn36Sn14(x=0,2,4,6)的化合物。用X射线衍射仪和振动样品磁强计研究了合金的物相与磁热效应。结果表明,部分Cu元素对Ni的替代,并没有改变三元哈斯勒合金Ni-Mn-Sn原有的晶体结构,只是晶格常数开始有减小的趋势,晶胞的体积没有发生太大的变化。M-T曲线的结果表明,该系列哈斯勒合金样品在奥氏体相的铁磁交换作用增强,导致居里温度升高,而结构相变温度降低。此外,通过麦克斯韦方程计算了该系列合金的磁熵变(-ΔSm),在磁场变化为1.5 T的情况下,获得了Ni46Cu4Mn36Sn14合金在330 K附近的最大磁熵变(-ΔSmmax)约为2.0 J·(kg·K)-1。     

钙钛矿La0.67Ca0.33Ti0.01Mn0.99O3的磁致冷性能研究

利用固相烧结的方法制备了La0.67Ca0.33Ti0.01Mn0.99O3磁致冷材料.室温XRD分析表明该材料主要由主相的正交钙钛矿结构锰氧化物和少量La2O3杂相构成.利用VSM测量了样品在磁场下随温度变化的磁化曲线(M-T曲线)和居里温度附近的等温磁化曲线(M-H曲线),通过M-H曲线的一阶导数可得到样品的居里温度Tc(139 K),从不同温度的等温磁化曲线(M-H)计算得到材料在1.5T下的最大磁熵变△SM =0.8 J.(kg·K)-1,由M2-H/M的Arrott曲线表明La0.67Ca0.33 Ti0.01Mn0.99O3相变类型属于二级相变.由于二级相变不伴随晶格体积的变化和潜热的释放,仅是磁性材料磁畴从无序-有序的连续变化,所以二级相变的磁熵变可能较小,但是由于它是个连续的变化过程,发生相变的温区较大,造成的损耗较小.Ti4+离子的掺杂取代的是原有晶格中Mn4+离子(B位)的位置,两者之间不同的离子半径使得晶格发生Jahn-Teller 畸变,同时降低了Mn4+的浓度,使得Mn4+与Mn3+离子之间的双交换作用减弱,铁磁耦合作用减小,导致居里温度降低.该材料体系由于二级相变的温度区间较大,表明材料潜在的致冷能力较强,因此具有较好的应用前景.     

TbNiAl合金磁热效应研究

用真空电弧熔炼法制备了TbNiAl合金。X-射线衍射结果表明,TbNiAl的物相结构为ZrNiAl-型六角结构。磁性研究表明该合金为反铁磁体,奈尔温度为TN=47 K,在47 K以下也有一个小峰,说明反铁磁性为复杂结构,并且具有磁场引起的场致反铁磁到铁磁的转变。转变的临界磁场较小。通过测量不同温度的等温磁化曲线,确定了该转变附近的磁热效应。磁热效应由两部分组成,正磁热效应和反磁热效应。     

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。     

MnP_(1-x)M_x系列合金的磁热效应

研究了1∶1型MnP基系列合金MnP1-xMx(M=Si,Sb,Ge,Zn,Sn)(x=0,0.1)的结构及其磁热效应。室温X射线衍射表明该系列合金的主相结构均为正交MnP结构,空间群为Pnma。在用Ge,Sb,Zn,Sn作为替代元素的合金中存在少量第二相Mn5.64P3。磁性测量表明该系列合金MnP1-xMx(M=Si,Sb,Ge,Zn,Sn)(x=0,0.1)的存在由铁磁-顺磁的二级相变。其居里温度Tc分别为286,295,294,295,295K。通过磁化曲线计算了MnP1-xMx(M=Si,Sb,Ge,Zn,Sn)(x=0,0.1)合金的最大等温磁熵变-ΔSm,均在0.7～1.3J.kg-.1K-1之间。     

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.     

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.     

Glass Forming Ability and Magnetic Property of Fe74Al4Sn2 （PSiB）20 Amorphous Alloy

Amorphous ribbons of Fe74 Al4Sn2 (PSiB)20 alloy have been synthesized by melt spinning and axial design method. The thermal properties of the amorphous ribbons have been measured by differential scanning calorimeter (DSC). The DSC results show that the Fe74 Al4Sn2P12Si4B4 amorphous alloy has relatively wider supercooled liquid region with a temperature interval of 40.38 K (△TX=TX-TR). The alloys with a higher phosphorous content in the metalloid element composition triangle of Fe74Al4Sn2(PSiB)20 have high glass forming ability. The amorphous alloys also show good magnetic properties in which Fe74Al4Sn2P6.67Si6.67B6.67 alloy has a large maximum permeability (μm), Fe78AlSn2P3Si3B10 alloy exhibits a high squareratio (Br/Blo) and FeT~A14Sn2P, Sil2B4 shows a low core loss (P0.5 1.3T). High glass forming ability and good magnetic properties make Fe74Al4Sn2(PSiB)20 amorphous alloys valuable in future research.     

Magnetocaloric Effect of Alloys Gd（Al1-x Cox ）2

The magnetocaloric effect in alloys Gd（Al1-xCox）2 with x = 0, 0.05, and 0.10 were investigated using X-ray diffraction （XRD） and magnetization measurements. It was found that three alloys crystallized in a single phase with MgCu2-type structure. The lattice parameter and Curie temperature decreased with increasing Co content, whereas the magnetic-entropy change increased. With a magnetic-field change of 2 T, the maximum of the magnetic-entropy change reached 4.6 J·kg^-1·K^-1 near Curie temperature at approximately 95 K in the alloy GdAl1.8Co0.2, which appeared to be an alternative candidate for active magnetic refrigerants working in the temperature range centered at 100 K.     

Magnetocaloric effect in ErNi_2 melt-spun ribbons

ErNi2 ribbons were produced by rapid solidification using the melt spinning technique.Their structural,magnetic and magnetocaloric properties in the as-solidified state were studied by X-ray diffraction,scanning electron microscopy,magnetization and specific heat measurements.Samples are single phase with the MgCu_2-type crystal structure,a Curie temperature T_C of 6.8 K and a saturation magnetization at2 K and 5 T of 124.0 A·m~2/kg.For a magnetic field change μ_0△H of 5 T(2 T) ribbons show a maximum magnetic entropy change |△S_M~(peak)| of 24.1(16.9) J/(kg·K),and an adiabatic temperature change △T_(ad)~(max) of8.1(4.4) K;this is similar to the previously reported literature for bulk alloys that were processed through conventional melting techniques followed by prolonged thermal annealing.In addition,the samples also show slightly wider △S_M(T) curves with respect to bulk alloys leading to a larger refrigerant capacity.     

Structure and intrinsic magnetic properties of MM_2Fe_(14)B(MM=La,Ce, Pr,Nd) alloys

MM_(33)Fe_(66)B(MM=La, Ce, Pr, Nd) alloys(mass ratio) were prepared by induction melting and heat-treated at 1353 K for 24 h to produce homogeneous MM_2Fe_(14) B phase. The phase structure and element distribution of the alloys were analyzed by X-ray diffraction(XRD) and scanning electron microscope(SEM). The alloys were applied ball milling to obtain powders with good size distribution and then magnetic aligned in a static magnetic field of 2 T for 4 h, in order to achieve the intrinsic magnetic properties by vibrating sample magnetometer(VSM). XRD results showed that the alloys were composed of the single 2:14:1 main phase and RE-rich phase, which was similar to Nd_2Fe_(14)B structure. Magnetic measurements showed that the saturation magnetization(Ms) and anisotropy field(HA) of the MM_(33)Fe_(66)B alloy were 11.3 k Gs and 48.4 k Oe, respectively, demonstrating its good potential as permanent magnets. The Curie temperature of the MM_(33)Fe_(66)B alloy was determined as 502.9 K by magnetization-temperature curves. Microstructure observation showed that Nd and Pr were mainly in the 2:14:1 ferromagnetic phase, while La and Ce prefered to aggregate in the RE-rich grain boundary phase, which is beneficial to fabricating(Pr, Nd, MM)_2Fe_(14)B magnets with good magnetic properties.     

MnFe1-xTixP0.63Ge0.12Si0.25（x=0,0.01,0.02,0.03）系列化合物的磁热效应

通过X射线衍射分析(XRD)和振动磁强计(VSM)磁性测量,研究了替代元素Ti替代Fe元素含量的MnFe1-xTixP0.63Ge0.12Si0.25(x=0,0.01,0.02,0.03)系列化合物的物相结构与磁热效应的影响。结果表明:该系列化合物的结构为Fe2P型六角晶系结构,空间群为P62m。主相均为(Mn,Fe)2(P,Ge,Si),并含有少量的第二相(Mn,Fe)3Si相。随着Ti原子替代Fe原子的增加化合物的晶格常数a增大,晶格常数c略有减小,晶胞体积V基本保持不变。随着Ti含量增加居里温度(TC)减小,热滞ΔThys的大小改进不太明显。MnFeP0.63Ge0.12Si0.25的TC为305 K,当外磁场变化为0～1.5 T时最大磁熵变的绝对值为14.8 J.(kg.K)-1。     

Collapse of charge ordering in Bi0.5Sr0.5MnO3 by cation disorder： a magnetic and structural investigation

The structure, transport, and magnetic properties of LaxBi0.5.xSr0.5MnO3 （LBSMO） （x=0.1 and 0.4） were studied through X-ray diffraction, magnetization, and electron spin resonance （ESR） measurements. The structural analysis showed that the LBSMO crystallized in an orthorhombic perovskite structure with Pbnm space group for x=-0.1 and Imma space group for x=0.4 and the highly polarizable 6s^2 lone pair of Bi^3＋ was the ttming factor for the structural variations. Magnetic studies revealed that the replacement of Bi ions by La ions resulted in the collapse high temperature charge ordering state of BSMO and it order Ferro Magnetically （FM） with Tc around 355 and 330 K for x=0.1 and 0.4, respectively. Both ESR, temperature and field dependant magnetization suggested that there was a coexistence of FM and the paramagnetic phases well below Tc and the FM and CO-AFM phases below 250 K of LBSMO.     

Fex-C1-x/Si颗粒膜的巨磁电阻效应

利用激光脉冲沉积（PLD）方法制备了沉积于硅基片上的掺杂过渡金属的非晶碳膜结构Fex-C1-x/Si。Fex-C1-x/Si的磁电阻（MR）可正可负，随温度而变化。当温度T〈258K时，Fe0．011-C0.989／Si的MR为负值；当258K〈T〈340K时，该材料的MR为正值，在室温磁场为1T时，该材料的正MR可以大于20％。且在不同的温度范围中，该材料的MR和外加磁场的依存关系呈现出不同的特点：在T=280和300K时，当磁场小于1T时，MR随磁场的增加而快速增加，之后随磁场的继续增加MR增加开始变得缓慢；在T=350K时，MR近似以磁场的B^1.5。的规律变化；而在T=30K时，MR为负值且其大小随磁场的增加而减小。利用双通道模型对该MR效应进行了初步解释。     

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。