Magnetic properties of melt-spun ribbons(Sm_(1-x)Zr_x)(Fe_(0.92)Ti_(0.08))_(10) with ThMn_(12) structure and their hydrides

The structure and magnetic hysteresis properties of the cast Sm_(1-x)Zr_x(Fe_(0.92)Ti_(0.08))_(10)(x = 0-0.3)alloys and melt-spun ribbons prepared from them were studied.In the cast alloy with x0.2, a considerable amount of the eutectic phase is found in the SEM micrographs.Analysis of the temperature dependences of the magnetic susceptibility and XRD patterns allows amorphous state in the as-spun ribbons with x0.2 to be determined.The specific magnetization measured in a field of 17 kOe and remanence decrease with increasing annealing temperature from 800 to 900 ℃ and weakly depend on Zr concentration.The maximal value of coercivity Hc = 4.7 kOe is obtained on the ribbons with x = 0.2 after annealing at 850℃ for 10 min.After additional hydrogenation of the ribbons,both the coercivity and remanence increase by 54% and 7%,respectively.     

Effect of wheel speed on phase formation and magnetic properties of (Nd0.4La0.6)-Fe-B melt-spun ribbons

The effect of wheel speed on phase formation and magnetic properties of (Nd_0.4La_0.6)₁₅Fe_77.5B_7.5 and (Nd_0.4La_0.6)_13.4Fe_79.9B_6.7 ribbons prepared by melt-spinning method was investigated experimentally. Based on X-ray diffraction results, all melt-spun ribbons consist of the main phase with the tetragonal 2:14:1 type structure and the minor α-Fe phase. Magnetic measurements show the maximum magnetic energy product ((BH)_max) and the remanence (M_r) increases firstly and then decreases with the increase of wheel speed, while the coercivity (H_ci) increases, resulting from the variation of the average volume fraction of the α-Fe phase and the average grain size in the melt-spun ribbons. Using Henkel plots, the interaction between the 2:14:1 phase and the α-Fe phase in the melt-spun ribbons was analyzed and the intergranular exchange coupling is manifested. Optimal magnetic properties of H_ci = 7.27 kOe, M_r = 90.94 emu/g and (BH)_max = 12.10 MGOe are achieved in the (Nd_0.4La_0.6)₁₅Fe_77.5B_7.5 ribbon with the wheel speed of 26 m/s. It indicates that magnetic properties of Nd-Fe-B melt-spun ribbons with highly abundant rare earth element La can be improved by optimizing alloy composition and preparation process.     

Large magnetic entropy change and adiabatic temperature rise of a ternary Gd_(34)Ni_(33)Al_(33) metallic glass

A low cost Gd_(34)Ni_(33)Al_(33) metallic glass with excellent magnetocaloric properties was successfully prepared in the present work.The magnetic properties of the ribbons were measured by constructing the relationship of magnetic entropy change(-ΔS_m) on temperature as well as magnetic field.The amorphous alloy shows typical magnetocaloric behaviors,large maximum-ΔS_m(11.06 J/(kg·K) under 5 T)and adiabatic temperature rise(4.3 K under 5 T) near 40 K,indicating that the low cost Gd_(34)Ni_(33)Al_(33)metallic glass is a good candidate material for low temperature magnetic refrigeration.     

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。     

Evolution of crystallographic alignment in Tb-Fe-B melt-spun ribbons

Ternary Tb-Fe-B ribbons were prepared via melt-spun technique under different wheel speeds of 5-25 m/s.Effect of wheel speed on the crystal structure and microstructure of the ribbons was investigated.All the ribbons quenched under different wheel speeds crystallized in single Tb2Fe14B phase with tetragon structure.Different crystallographic alignment evolutions were observed in the free side surface and wheel side surface of the ribbons.On the free-side surface,an in-plane c-axis crystal texture of Tb2Fe14B phase was found in the ribbons quenched at 5 m/s.However,with the increase in the wheel speed,the direction of the c-axis texture turns to perpendicular to the ribbon surface.On the wheel-side surface,a strong c-axis texture perpendicular to the ribbon surface was observed in the ribbons quenched at 5 m/s,and then weakened gradually with the increase in the wheel speed.Further investigation showed that the competition of the two types of temperature gradients during the quench process was responsible for the crystallographic alignment evolution in the ribbons.     

Gd含量对Gd5Si2Ge2晶体结构和磁性能的影响

用非自耗电弧炉熔炼了Gd5 xSi2Ge2系列样品。用X射线粉末衍射(XRD)和Rietveld方法研究了Gd5 xSi2Ge2系列样品的晶体结构。用自制的仪器测量了样品的居里温度,用振动样品磁强计研究了样品的磁卡效应。对样品的晶体结构分析结果表明:Gd的含量x的变化对Gd5Si2Ge2化合物的晶体结构有较大的影响,当x>0时,样品中含有Gd5(Si,Ge)4和Gd5(Si,Ge)3两个相,并且随着x的增加Gd5(Si,Ge)4相会减少,Gd5(Si,Ge)3相会增加;当x<0时,样品会形成Gd5(Si,Ge)4和Gd(Si,Ge)两相,并且随着x的减少Gd5(Si,Ge)4相会减少,Gd(Si,Ge)相会增多。对样品的磁性能分析结果表明:Gd的含量x>0和x<0时都会降低样品的磁卡效应,样品的居里温度会随着x的增加而增加。     

The microstructure and magnetization reversal behavior of melt-spun (Nd1−xCex)-Fe-B ribbons

In this study,the alloy ingots with nominal compositions of(Nd_(1-x)Ce_x)_(31)Fe_(bal)Co_(0.2)Ga_(0.1)B(x=0, 0.1 wt%,0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%) were prepared and then melt-spun to form nanocrystalline ribbons at the wheel speed of 20 m/s. XRD results show that all melt-spun ribbons exhibit the tetragonal structure(Nd,Ce)_2 Fe_(14)B phase with the space group P42/mmm. The Curie temperature and lattice constant decrease with the increase of Ce content. The Curie temperature decreases gradually from 306 to 247 ℃with the increase of Ce content. Those results indicate that Ce element has been incorporated into Nd_2 Fe_(14)B main crystalline phase and formed(Ce,Nd)-Fe-B hard magnetic phase. It is also found that the remanence ratio(M_r/M_s) decreases from 0.693 to 0.663 and the coercivity(H_c) decreases from 18.7 to14.2 kOe with the increase of Ce content. However, a relatively high coercivity of 18.3 kOe for(Nd_(1-x)Ce_x)_(31)Fe_(bal)Co_(0.2)Ga_(0.1)B(x = 0.2) melt-spun ribbon is achieved. The coercivity is sensitive to microstructure. The AFM patterns show the sample(x = 0.2) has the most uniform and finest microstructure. The magnetization reversal behavior(δM plots) is discussed in detail. The positive δM value is observed in every sample, which confirms the existence of exchange coupling interaction. Evidently, theδM maximum value reaches 0.9 in the sample(x = 0.2). It is indicated that the intergranular exchange coupling effect is the strongest, which is consistent with coercivity enhancing.     

GdDyFe和GdTbFe合金的磁热效应研究

研究了 Gd0 .5Tb0 .5- x Fex 及 Gd0 .5Dy0 .5- y Fey(x=0 .2 ,0 .3,y=0 .2 ,0 .3)系列稀土合金在 2 6 0～ 2 90 K温区范围的磁熵变 ,发现这二种系列合金均具有较大的磁熵变△ SM,适合作为低磁场下 (～ 1.5 T)的室温磁制冷材料。     

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。     

Structure,magnetism and magnetic thermal properties of heavy rare earth Tb_(1-x)Tm_xFeO_3(x=0.00,0.15,0.25) polycrystalline samples

Tb_(1-x)Tm_xFeO_3(x = 0.00,0.15,0.25) polycrystalline series were synthesized using a solid-state reaction.Our results show that all three prepared samples are in a distorted orthogonal structure and their space group is pbnm.When the Tm~(3+)doping amount increases,the characteristics of the spin-flip of the sample decreases following an initial increase at the beginning;the antiferromagnetic property almost reaches zero;the magnetization decreases at the beginning but increases later on.The maximum magnetic entropy change and magnetic refrigeration effect RCP are reduced at varying degrees.Under a 7 T magnetic field,the maximum magnetic entropy change,△S_(max),for the three samples of Tb_(1-x)Tm_xFeO_3 with x=0.00,0.15,0.25 is 13.78,-9.28,and 10.69 J/(K·kg),respectively;the magnetic refrigeration capacity(RCP) is 316.85,175.2,and 297.60 J/kg,respectively.In summary,doping with the element Tm reduces △S_(max) and RCP of the sample.Since the maximum magnetic entropy change and the cooling capacity for the three samples are relatively large,they can be used as an alternative for magnetic refrigerants.     

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.     

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…     

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。     

Magnetic properties and large magnetocaloric effects of GdPd intermetallic compound

With the intention to explore excellent magnetocaloric materials, the intermetallic compound GdPd was synthesized by arc melting and heat treatment. The microstructure, magnetic and magnetocaloric properties of the intermetallic compound of GdPd were investigated by X-ray diffraction(XRD), scanning electron microscopy(SEM) and the physical property measurement system(PPMS). A large reversible magnetocaloric effect is observed in GdPd accompanied by a second order magnetic phase transition from paramagnetism to ferromagnetism at ～39 K. The paramagnetic Curie temperature(θp) and the effective magnetic moment(μ_(eff))are determined to be 34.7 K and 8.12 μ_B/Gd,respectively. The maximum entropy change(|△S_M~(Max)|) and the relative cooling power(RCP) under a field change of 5 T are estimated to be 20.14 J/(kg·K) and 433 J/kg, respectively. The giant reversible magnetocaloric effects(both the large△S_M and the high RCP) together with the absence of thermal and field hysteresis make the GdPd compound an attractive candidate for low-temperature magnetic refrigeration.     

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。     

Effects of different introduction methods of Ce4+ and Zr4+ on denitration performance and anti-K poisoning performance of V2O5-WO3/TiO2 catalyst

The purpose of this work is to explore the effects of the introduction methods of Ce⁴⁺ and Zr⁴⁺ on the physicochemical properties, activity, and K tolerance of V₂O₅-WO₃/TiO₂ catalyst for the selective catalytic reduction of NO_x by NH₃. Four different methods, namely pre-impregnation, post-impregnation, co-impregnation, and co-precipitation, were used to synthesize a series of V₂O₅-WO₃-TiO₂-CeO₂-ZrO₂ catalysts. The catalysts were characterized by XRD, BET, NH₃-TPD, XPS, and H₂-TPR techniques. Moreover, the activity and anti-K poisoning performance were tested by an NH₃-SCR model reaction. The results show that the introduction of Ce⁴⁺ and Zr⁴⁺ can improve the catalytic performance of V₂O₅-WO₃/TiO₂ catalyst, but the impregnation method cannot enhance the anti-K poisoning performance. Ce⁴⁺ and Zr⁴⁺ introduced by co-precipitation method can effectively improve the tolerance of K, which is mainly due to the incorporation of Ce⁴⁺ and Zr⁴⁺ into TiO₂ lattice to form a uniform TiO₂-CeO₂-ZrO₂ solid solution, resulting in the optimal surface acidity and redox performance, and reducing the decreases caused by K-poisoning. Furthermore, based on the best introduction method, we further optimized the molar ratio of Ce⁴⁺/Zr⁴⁺. It is found that the catalyst exhibits the best anti-K poisoning performance when the molar ratio of Ce⁴⁺/Zr⁴⁺ is 2:1.     

Effect of cobalt substitution on structure and magnetic properties of Nd_(0.4)Zr_(0.6)Fe_(10-x)Co_xSi_2(x =0-3) alloys and their ribbons

This study reports the stabilization of the RFe_(12)-type based compounds where part of R and Fe are substituted with Zr and Co and Si, respectively, in order to examine whether these rare-earth-lean materials are suitable for applications as permanent magnets. Structural and magnetic characterization of the family of alloys with the general formula Nd_(0.4) Zr_(0.6) Fe_(10-x)Co_xS_i2(x = 0 -3) and their melt-spun ribbons were carried out using X-ray diffraction and M€ossbauer spectroscopy. The ThMn_(12)-type structure is obtained for all samples as the majority phase with a minority a-Fe(CoSi) phase(less than 5 wt%) as it was estimated by XRD for x = 1 and 2. The Curie temperature increases linearly with Co substitution from 561 K for x = 0 to 712 K for x = 3. The saturation magnetization decreases slightly from 130.5(x =1)to 129.1 A·m~2/kg(x=3), while the anisotropy field is following the same trend.     

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.     

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

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