Improvement in coercivity,thermal stability,and corrosion resistance of sintered Nd-Fe-B magnets with Dy_(80)Ga_(20) intergranular addition

To investigate the coercivity,corrosion resistance,and thermal stability of Nd-Fe-B magnets,their properties were investigated at room and high temperature before and after doping with Dy_(80)Ga_(20)(at.%) powder.The coercivity of the magnets increased from the undoped value of 12.72 kOe to a doped value of 21.44 kOe.A micro-structural analysis indicates that a well-developed core-shell structure forms in the magnets doped with Dy_(80)Ga_(20) powder.The improvement in magnetic properties is believed to be related to the refined and uniform matrix grains,continuous grain boundaries,and a hardened(Nd,Dy)_2Fe_(14)B shell surrounding the matrix grains.Additionally,the doped magnets exhibit an obvious improvement in thermal stability.For the magnets with added Dy_(80)Ga_(20) powder,the temperature coefficients of remanence(α) and coercivity(β) increased to-0.106%℃~(-1) and-0.60%℃~(-1) over the range 20-100 ℃,compared to temperature coefficients of-0.117%℃~(-1)(α) and-0.74%℃~(-1)(β) in the regular magnets without Dy_(80)Ga_(20) powder.The irreversible loss of magnetic flux(Hirr) was investigated at different temperatures.After being exposed to 150 ℃ for 2 h,the Hirr of magnets with 4 wt.%Dy_(80)Ga_(20) decreased by ~95%compared to that of the undoped magnets.The enhanced temperature coefficients and Hirr indicate improved thermal stability in the doped Nd-Fe-B magnets.The intergranular addition of Dy_(80)Ga_(20) also improved the corrosion resistance of the magnets because of the enhanced intergranular phase.In a corrosive atmosphere for 96 h,the mass loss of the sintered magnets with 4 wt.%Dy_(80)Ga_(20) was 2.68 mg/cm~2,less than 10%of that suffered by the undoped magnets(28.1 mg/cm~2).     

Coercivity enhancement of sintered Nd-Fe-B magnets by grain boundary diffusion with Pr80-xAlxCu20 alloys

A grain boundary diffusion (GBD) process with Pr_80-xAl_xCu₂₀ (x = 0, 10, 15, 20) low melting point alloys was applied to commercial 42M sintered Nd-Fe-B magnets. The best coercivity enhancement of a diffused magnet was for the Pr₆₅Al₁₅Cu₂₀ GBD magnet, from 16.38 kOe to 22.38 kOe. Microstructural investigations indicated that increase in the Al content in the diffusion source can form a continuous grain boundary (GB) phase, optimizing the microstructure to enhance the coercivity. The coercivity enhancement is mainly due to the formation of a continuous GB phase to separate the main phase grains. Exchange decoupling between the adjacent main phase grains is enhanced after the GBD process. Meanwhile, the introduction of Al can effectively promote the infiltration of Pr into the magnet, which increases the diffusion rate of rare-earth elements within a certain range. This work provides a feasible method to enhance coercivity and reduce the use of rare-earth resources by partial replacement of rare-earth elements with non-rare-earth elements in the diffusion source.     

Effects of post-sinter annealing on microstructure and magnetic properties of Nd–Fe–B sintered magnets with Nd–Ga intergranular addition

We investigate the effects of post-sinter annealing on the microstructure and magnetic properties in B-lean Nd–Fe–B sintered magnets with different quantities of Nd–Ga intergranular additions. The magnet with fewer Nd–Ga additions can enhance 0.2 T in coercivity, with its remanences nearly unchanged after annealing. With the further increase of the Nd–Ga addition, the annealing process leads coercivity to increase 0.4 T, accompanied by a slight decrease of remanence. With the Nd–Ga addition further increasing and after annealing, however, the increase of coercivity is basically constant and the change of remanence is reduced. Microstructure observation indicates that the matrix grains are covered by continuous thin grain boundary phase in the magnets with an appropriate Nd–Ga concentration after the annealing process. However, the exceeding Nd–Ga addition brings out notable segregation of grain boundary phase, and prior formation of part RE6 Fe13 Ga phase in the sintered magnet. This prior formation results in a weaker change of remanence after the annealing process.Therefore, the diverse changes of magnetic properties with different Nd–Ga concentrations are based on the respective evolution of grain boundary after the annealing process.     

不同易轴取向下对Nd_2Fe_(14)B/Fe_(65)Co_(35)磁性双层膜的微磁学模拟

运用三维数值模拟计算方法,计算了膜面外不同易轴取向下Nd2Fe14B/Fe65Co35磁性双层膜的磁滞回线、角度分布、成核场、矫顽力和磁能积等,并与实验结果进行了细致比较.计算结果表明:只有当易轴与外场之间的夹角β=0?时,才有明显的成核现象,其成核场和矫顽力均随着软磁相厚度Ls的增加而降低;随着易轴偏角β的增大,剩磁逐渐减小,磁滞回线的方形度降低,从而磁能积减小,在Ls=1 nm,β=0?时磁能积(561.61 kJ/m3)最大.理论计算所得的磁滞回线与实验磁滞回线符合得很好,剩磁和矫顽力的理论值与实验值相差很小.     

利用Pr_(70)Cu_(30)晶界扩散改善烧结钕铁硼废料矫顽力的研究

钕铁硼磁体制备过程中出现的部分块体废料由于矫顽力较低,性能难以满足使用要求.本文主要通过晶界扩散技术来提高废料磁体的矫顽力.采用Pr_(70)Cu_(30)合金作为扩散介质,对烧结钕铁硼废料磁体进行了晶界扩散处理,研究了扩散温度、扩散时间和回火时间对扩散后的磁体性能的影响.结果显示,800℃下扩散3 h,磁体的矫顽力从原来的7.88 kOe(1 Oe=79.5775 A/m)提升至11.55 kOe,提升幅度为46.6%,同时剩磁没有明显降低.扩散后回火对矫顽力的提升有一定的作用.800℃下扩散4h后的磁体在500℃回火3h后,最高矫顽力可达11.97 kOe,比原磁体废料提高了51.9%,接近成品磁体的水平.显微组织分析证实了晶界扩散的作用.扩散处理后的磁体中,主相晶粒间形成了连续晶间相,起到有效的磁隔离作用,有利于矫顽力的提高.研究还发现,Pr_(70)Cu_(30)晶界扩散虽然可以使磁体腐蚀电位上升,但也会增加腐蚀电流密度,不利于磁体抗腐蚀性的改善.本文工作对于提高材料的成品率具有重要意义.     

Effect of adding non-ferromagnetic nanoparticles to grain boundary on coercivity of sintered Nd-Fe-B magnet

In this work, we investigated the influence of additional compounds of Nd-Cu-Al, Dy-Nb-Al, Dy-Zr-Al and Nb-Cu-Al on coercivity of sintered Nd-Fe-B magnets. The additional nanoparticles with size in the range of 40–80 nm was mixed with the micrometer Nd-Fe-B powder before sintering process. The results show that the coercivity of the sintered Nd-Fe-B magnets can be improved by introducing additional nanoparticles to their grain boundaries. The improvement of the coercivity of the magnets is clearly dependent on composition and fraction of the additional compounds. While the Dy-Nb-Al, Dy-Zr-Al and Nb-Cu-Al compounds degrade the coercivity of the sintered Nd-Fe-B magnets, the Nd-Cu-Al nanoparticles considerably improve this quantity. The coercivity the sintered Nd_16.5Fe₇₇B_6.5 magnets has been enhanced about 40% by adding 3 wt% of the Dy-free compound of Nd₄₀Cu₃₀Al₃₀.     

Magnetization reversal of Nd-Fe-B sintered magnets at low temperatures

Barkhausen-like magnetization jumps at temperatures T < 9.5 K and the behaviour of the coercive field at low temperatures are studied in sintered Nd-Fe-B magnets with different chemical and phase compositions. The nonlinear temperature dependence of the coercive field H_c is well described in the thermal activation model at T > 10 K. The low temperature anomalies of H_c are discussed in terms of the quantum tunneling of the domain wall through the intergrain boundaries.     

Effect of Co on the thermal stability and impact toughness of sintered Nd–Fe–B magnets

The effect of Co on the thermal stability and impact toughness of sintered Nd–Fe–B magnets has been investigated. The results showed that the addition of Co decreased the intrinsic coercivity and the temperature coefficient of remanence (α), and increased the temperature coefficient of coercivity (β) for sintered Nd–Fe–B magnets. The impact toughness of sintered Nd–Fe–B magnets with the addition of Co first decreases, reaches a minimum, and then starts to increase. The possible reasons for increasing the temperature coefficients of coercivity (β) for sintered Nd–Fe–B magnets were analyzed, and the relations between the microstructure and impact toughness of sintered Nd–Fe–B magnets were studied.     

Abnormal variation of magnetic properties with Ce content in(PrNdCe)_2Fe_(14)B sintered magnets prepared by dual alloy method

Resource-saving(PrNdCe)_2Fe_(14)B sintered magnets with nominal composition(PrNd)_(15-x)Ce_xFe_(77)B_8(x=0–10)were prepared using a dual alloy method by mixing(PrNd)_5Ce_(10)Fe_(77)B_8 with(PrNd)_(15)Fe_(77)B_8 powders. For Ce atomic percent of 1% and 2%, coercivity decreases dramatically. With further increase of Ce atomic percent, the coercivity increases, peaks at 6.38 kOe in(PrNd)_(11)Ce_4Fe_(77)B_8, and then declines gradually. The abnormal dependence of coercivity is likely related to the inhomogeneity of rare earth chemical composition in the intergranular phase, where Pr Nd concentration is strongly dependent on the additive amount of(PrNd)_5Ce_(10)Fe_(77)B_8 powders. In addition, for Ce atomic percent of 8%,7%, and 6% the coercivity is higher than that of magnets prepared by the conventional method, which shows the advantage of the dual alloy method in preparing high abundant rare earth magnets.     

Magnetic anisotropy induced in Nd16Fe76B8 by Hf additions

Remanence, coercivity and maximum energy product (BH)_max of Nd₁₆Fe_76−xHf_xB₈ (x=0, 0.1, 0.2) magnets processed under different hydrogenation-disproportionation-desorption-recombination (HDDR) conditions, were studied. Vibrating sample magnetometry results showed that Hf-doped materials develop an important degree of anisotropy, especially for the case of solid-HDDR treatments at 800°C and 850°C, with the largest effect at 850°C. Maximum values of remanence and coercivity were observed for Hf-added samples S-HD at 850°C, and 900°C, respectively. The highest (BH)_max value was also observed in S-HD 900°C Hf-added samples. These results are discussed in terms of the expected microstructure of the intermediate HD and final HDDR processed powders.     

Annealing dependence of magnetic properties in nanostructured Sm0.5Y0.5Co5

Nanocrystalline Sm_0.5Y_0.5Co₅ powders with high coercivity H_C and enhanced remanence M_r were prepared by mechanical milling and subsequent annealing. Annealing temperatures T ranging from 973 to 1173 K, and times t ranging from 1 to 5 min were used. X-ray diffraction (XRD) and DC-magnetization measurements were carried out to study the microstructure and magnetic properties of these samples. XRD patterns demonstrate that the average grain size D of the nanocrystalline powders depends on the annealing temperature T and time t: D ranges from 11 nm (for T=973 K and t=1 min) to 93 nm (for T=1173 K and t=5 min). Magnetic measurements performed at room temperature indicate high coercivity values (H_C>955 kA/m), and enhanced remanence (M_r/M_max>0.5) for all samples. A strong annealing-induced grain size dependence of these magnetic properties was found.     

Effect of Tb on the intrinsic coercivity and impact toughness of sintered Nd–Dy–Fe–B magnets

The effect of Tb on the coercivity and impact toughness of sintered Nd–Dy–Fe–B magnets has been investigated. The results showed that the addition of Tb enhanced the intrinsic coercivity, reduced the remanence and improved the impact toughness of sintered magnets. The optimum impact toughness of sintered magnets was achieved when 1.0 at% Tb was incorporated. The possible reasons for increasing the intrinsic coercivity and improving impact toughness of sintered magnets were analyzed, and the relations between the microstructure and impact toughness of sintered magnets were studied.     

镁基合金自由枝晶生长的相场模拟研究

利用定量相场模型, 以Mg-0.5 wt.%Al合金为例模拟了基面((0001)面)内镁基合金的等温自由枝晶生长过程. 通过研究该合金体系数值模拟的收敛性, 获得了最优化值耦合参数λ = 5.5及网格宽度Δx/W₀ = 0.4, 并在该参数下系统研究了各向异性强度和过饱和度对枝晶尖端生长速度、尖端曲率半径、Péclet数及稳定性常数σ^* 的影响. 结果表明, 由微观可解性理论得到的稳定性系数σ^* 与ε₆ 拟合值σ^*≅ ε₆ ^1.81905, 更接近理想值σ ^* (ε₆) ≅ε₆ ^1.75. 此外, 当过饱和度Ω < 0.6时, 稳定性系数σ ^* 不随ε₆ 的变化而变化, 而当Ω > 0.6时, 稳定性系数σ ^* 随着ε₆ 的增加而减小. 这反映了枝晶的生长由扩散控制向动力学控制的转变. 随着过饱和度的增加, 枝晶形貌由雪花状枝晶向圆状枝晶转变.     

Magnetic properties of YCo5 (70%wt)+Y2Co17 (30%wt) nanocomposite powders at low temperatures

Nanostructured YCo₅ (70%wt)+Y₂Co₁₇ (30%wt) composite powders were prepared by mechanical milling and subsequent annealing at 1073 K for 1.5 min. The average grain size D of the YCo₅ and Y₂Co₁₇ phases, obtained from XRD data, was 14 and 12 nm, respectively. The temperature dependence of the magnetic properties was studied by DC magnetization measurements at temperatures T ranging from 3 to 300 K. Hysteresis loops (H_max=70 kOe) show that both the coercivity H_C and the squareness σ_r/σ_max are temperature-dependent. The coercivity increases from 12 kOe at room temperature to 18 kOe at T=3 K. The observed enhanced remanence (σ_r/σ_max>0.5) indicates that a strong exchange coupling is present at all temperatures used in this study. The maximum magnetization σ_max changes little with temperature and has a value of about 70% of the effective saturation magnetization of the title compound.     

非等电子Sb替换Cu和Te后黄铜矿结构半导体Cu_3Ga_5Te_9的热电性能

热电材料是一类能够实现热与电相互转换的功能材料,在制冷和发电领域极具应用潜力.本文采用金属Sb元素非等电子替换Cu3Ga5Te9化学式中的Cu和Te,观察到材料Seebeck系数和电导率提升的现象.这些电学性能的改善与载流子浓度和有效质量的增大及迁移率基本维持不变有关.载流子浓度的提高是由于Sb原子占位在Te晶格位置后费米能级进入到价带所产生的空穴掺杂效应所致,同时也与Cu含量减少后铜空位(V-1Cu)浓度增大相关联.另外,非等电子替换后,阴离子(Te2-)移位导致了晶格结构缺陷参数u和η的改变,其改变量fiu和fiη与材料晶格热导率(κL)的变化密切相关.在766 K时,适量的Sb替换量使材料的最大热电优值(ZT)达到0.6,比Cu3Ga5Te9提高了近25%.因此,通过选择替换元素、被替换元素及替换量有效地调控了材料的电学及热学性能,在黄铜矿结构半导体中实现了非等电子元素替换改善热电性能的思想.     

Determination of the crystallographic texture of sintered PrFeB magnets based on X-ray diffraction patterns

An alternative method for determining the degree of crystallographic alignment (cos Θ) of the magnetic Pr₂Fe₁₄B phase (Φ) is proposed. The method is based on the relative X-ray diffracted intensities of the Φ planes of sintered magnets with and without texture. The degree of crystallographic alignment is also determined by X-ray pole figures using the (0 0 4) reflection and considered as a standard reference for comparison. The method is applied to Pr₁₆Fe₇₆B₈ magnets with 0.51cos Θ0.97. The difference between the crystallographic alignments determined by these two methods is 3% within the experimental error. The advantages and limitations of using X-ray diffraction patterns to quantitatively evaluate the texture of sintered magnets are also discussed.     

Ge-Sb-Se硫系玻璃的折射率和热光系数

Ge-Sb-Se硫系玻璃被认为是极佳的红外传输材料和有潜力的非线性光学材料.在光学设计中,玻璃的线性折射率(n)及其热光系数(ζ)是关键技术参数.以预测和调控Ge-Sb-Se玻璃的n和ζ为目的,考察了玻璃的n,ζ,密度(d)和体积膨胀系数(β)与化学参数dSe和拓扑网络结构参数r的内在联系.研究发现,玻璃的n随d的增加而增大;ζ随β的增大而近似线性减小;β随dSe的减小或r的增大而减小;当Ge含量固定时, d随dSe的减小或r的增大而增大,当Sb含量固定时, d在dSe=0时具有最小值.基于实测d和n,拟合获得了Ge, Sb和Se元素在2—12μm波段的摩尔折射度(R_i),分别为R_(Ge)=10.16—10.50 cm~3/mol,RSb=16.71—17.08 cm~3/mol和RSe=11.15—11.21 cm~3/mol,根据d和R_i计算得到的n与实测值的偏差小于1%.基于实测ζ和β,拟合得到了Ge, Sb和Se元素在2—12μm波段的摩尔折射度温度系数(φ_i),分别为φ_(Ge)=21.1—22.6 ppm/K,φ_(Sb)=7.2—8.4 ppm/K和φ_(Se)=90.2—94.2 ppm/K,根据β和φ_i计算得到的ζ与实测值的偏差小于6 ppm/K.     

20GeS2·80Sb2S3硫系玻璃的析晶行为及动力学机理研究

实现玻璃微晶化过程控制的基础是要充分认识其析晶行为及动力学机理. 利用示差扫描量热法和析晶热处理等手段, 研究发现 20GeS₂·80Sb₂S₃硫系玻璃属于表面析晶, 在268℃(T_g+30℃)下热处理60 h, 可以获得表面约40 μm的Sb₂S₃晶层复合玻璃陶瓷样品. 在此基础上, 利用非等温法从理论上分析该玻璃的析晶动力学机理. 计算得到其析晶活化能E_c为(223.6±24.1)kJ·mol^-1, 在热处理温度(268℃)下的析晶速率常数K为1.23×10^-4 s^-1, 属于较难析晶的玻璃组成; 玻璃的晶体生长指数m和晶体生长维数n均为2, 表明其Sb₂S₃相的析晶行为是二维生长过程, 与析晶实验结果完全相符. 由此可知, 对于Sb₂S₃晶体复合的硫系玻璃陶瓷样品可通过玻璃粉末压片烧结、带铸法或丝网印刷法制备获得, 为今后功能硫系玻璃的开发提供实验依据和理论指导. 关键词： 硫系玻璃 微晶化 析晶动力学 析晶行为     

Anti-function solution of uniaxial anisotropic Stoner-Wohlfarth model

The anti-trigonometric function is used to strictly solve the uniaxial anisotropic Stoner-Wohlfarth (SW) model, which can obtain the relation of the angle α (θ) between the magnetization (the anisotropy field) and the applied magnetic field. Using this analytic solution, the hysteresis loops of uniaxial anisotropic SW particles magnetized in typical directions could be numerically calculated. Then, the hysteresis loops are obtained in randomly distributed SW particle ensembles while ignoring the dipole interaction among them with the analytic solution. Finally, the correctness of the analytic solution is verified by the exact solutions of remanence, switching field, and coercivity from the SW model. The analytic solution provides an important reference for understanding the magnetizing and magnetization reversal processes of magnetic materials.     

Production for high thermal stability NdFeB magnets

To improve sintered NdFeB magnets’ thermal stability and magnetic properties, combined addition of elements Cu and Gd was investigated. It was found that with Gd addition increase to 1.0%, the temperature coefficient α improved from −0.15 to −0.05%/°C (maximum working temperature 120 °C), but the remanence and the maximum energy product linearly decreased. With addition of Cu in Gd-containing magnets the intrinsic coercivity increased greatly, and the remanence increased also because of their density improvement, and optimum Cu content was achieved at 0.2%. Microstructure analysis showed that most of the Cu distributed at grain boundaries and led to clear and smooth morphologies. Magnets with high thermal stability α=−0.05%/°C and magnetic properties were obtained with addition of Gd=0.8% and Cu=0.2%.