Tuning magnetic properties,thermal stability and microstructure of NdFeB magnets with diffusing Pr-Zn films

Grain boundary diffusion process(GBDP) serves as a promising approach in improving magnetic properties and thermal stability of Nd FeB permanent magnets. Herein, non-heavy rare earth Pr-Zn films deposited on the magnet surface using DC-magnetron sputtering system are reported. The thermal stability and coercivity enhancement mechanism of Pr-Zn GBDP magnets were investigated. Results show that the coercivity of Pr-Zn GBDP magnet increases from 963.96 kA m~(-1) to 1317.14 kA m~(-1) without any remanence reduction. Notably, the demagnetization curve of Pr-Zn GBDP magnet still remains a high squareness ratio. The temperature coefficient of coercivity and anti-demagnetization ability of Pr-Zn GBDP magnet under high temperatures are improved after GBDP treatment. The well-optimized rare earth-rich(RE-rich) grain boundary phases and high effective anisotropy field of(Nd,RE)2 Fe14 B magnetic hardening layers surrounding main grains are the key factors to impact the magnetic properties and thermal stability of Nd FeB permanent magnets via GBDP treatment.     

Properties improvement and structural optimization of sintered NdFeB magnets by non-rare earth compound grain boundary diffusion

Grain boundary diffusion using rare earth (RE)-containing compounds has recently become an effective approach for improving the coercivity and reducing the heavy RE content in sintered NdFeB magnets. Here we report the enhancement of magnetic properties and corrosion resistance of NdFeB magnets by a non-RE compound diffusion process. The Dy-free sintered NdFeB magnets were coated with an MgO layer by magnetron sputtering, followed by solid diffusion heat treatment. With the successful diffusion of MgO into the magnet, the coercivity increasing from 1094 to 1170 kA/m and the maximum energy product increasing from 240 to 261 kJ/m³, together with the enhanced temperature stability and corrosion resistance, have been demonstrated. The underlying mechanisms for these enhancements have been analyzed. Microstructural investigations show that MgO entered mainly into the intergranular regions and modified the composition and structure of the grain boundary phase. The intergranular Nd–O–Fe–Mg phases observed in the MgO diffused magnet contribute to the improved performance. The current non-RE compound grain boundary diffusion process has significance in further minimizing the use of rare earth (RE).     

还原温度对纳米FeCo/Al2O3复合材料结构和磁性的影响

采用溶胶-凝胶法及在氢气中还原的工艺制备了纳米FeCo/Al₂O₃复合材料。利用X射线衍射、透射电镜、振动样品磁强计和Mssbauer谱学对样品微观结构和磁性进行了研究。结果表明：纳米FeCo/Al₂O₃复合材料中的FeCo合金为体心立方结构;随着还原温度的提高,α-FeCo合金晶粒尺寸变大,Al₂O₃的存在有效地抑制了α-FeCo合金晶粒的团聚和生长;随着α-FeCo合金晶粒尺寸的变大,样品的比饱和磁化强度增加,而矫顽力先增大后减小,两者分别在1100℃和1000℃时达到最大值62.41 emu·g-1和208.99Oe,FeCo/Al₂O₃由超顺磁和磁有序的混合状态转变为完全的磁有序状态;矫顽力的变化是由于FeCo合金的磁学结构由单磁畴结构转变为多磁畴结构造成的。     

Role of late transition metals on pitting resistance of Zr-Ti-(Cu,Ni,Co)-Al bulk metallic glasses in 0.6 M NaCl aqueous solution

Four quanternary Zr-based bulk metallic glasses(BMGs)were selected,including the Zr_(46)Ti_2Cu_(45)Al_7,Zr_(61)Ti_2Cu_(25)Al_(12),Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15),due to their robust glass-forming ability and containing a single species of late transition metal(LTM)in compositions.Their pitting resistances in 0.6 M Na Cl aqueous solution were investigated to examine the role of LTM elements in the alloys,with electrochemical measurements,surface morphology observation and x-ray photoelectron spectrometry analysis.It is shown that in comparision with two Cu-bearing BMGs,Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15)BMGs exhibited significantly superior resistance to pitting.Zr_(61)Ti_2Cu_(25)Al_(12),Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15)BMGs manifested distinct passivation behaviour,because of the formation of surface passive film mainly comprising of Zr O_2,Ti O_2and Al_2O_3.However,no significant differences in the electrochemical resistive properties and thicknesses of passive films were found between Zr_(61)Ti_2Cu_(25)Al_(12)and Zr_(55)Ti_4Ni_(22)Al_(19)BMGs.Nevertheless,at the passive film/metal interface,copper enrichment took place in Zr_(61)Ti_2Cu_(25)Al_(12),whereas the nickel was slightly deficient at the interface in Zr_(55)Ti_4Ni_(22)Al_(19).During pitting propagation,selective dissolution of the zirconium,titanium and aluminum over the copper took place in Zr_(61)Ti_2Cu_(25)Al_(12),but it was not the case in Zr_(55)Ti_4Ni_(22)Al_(19).For the two Cu-bearing BMGs,reduction of passive base metal elements in composition resulted in local selective dissolution,even absence of the passivation.     

Development of cost-effective nanocrystalline multi-component(Ce,La,Y)-Fe-B permanent magnetic alloys containing no critical rare earth elements of Dy,Tb,Pr and Nd

Here we first report the fully abundant rare earth(RE)-based nanocrystalline multi-component(Ce,La,Y)-Fe-B alloys containing no critical RE elements of Nd,Pr,Dy,and Tb by melt-spinning technique.The roles of La and Y substitutions for Ce have been fully understood.La plays a positive role on both thermal stability and room-temperature(RT)magnetic properties.The enhanced coercivity Hcj by partial substitution of La is attributed to the increases of anisotropy field HA and the formation of continuously distributed grain boundaries resulting from the suppression of CeFe2 phase.Although Y substitution is not benefit for Hcj,both remanent polarization Jr and thermal stability have been effectively improved since Y2Fe14B shows relatively high saturation magnetization Ms and a positive temperature coefficient of HA over a certain temperature range.In addition,RE element segregation has been confirmed,La prefers to enter into the grain boundaries than Ce and Y prefers to remain in the 2∶14∶1 phase.Based on these understanding,a series of melt-spun(Ce,La,Y)-Fe-B alloys have been designed.A relatively good combination of magnetic properties with maximum energy product(BH)max=7.4 MGOe,Hcj=400 kA/m,and Jr=0.63 T has been obtained in[(Ce0.8La0.2)0.7Y0.3]17Fe78B6 alloy,together with high Curie temperature(Tc=488 K)and low temperature coefficients of remanence(α=-0.255％/K)and coercivity(β=-0.246％/K).     

Coercivity Enhancement of Nd—Fe—B Thin Film Magnets through Dy Surface Diffusion Process

The Dy capping layer was deposited at different temperatures on the Nd-Fe-B thin films to investigate the mechanism of the coercivity enhancement through the Dy surface diffusion. The highest coercivity of 2005 kA/m (25.2 kOe) was obtained at the Dy deposition temperature of 460℃, which was significantly higher than the value of 1297 kA/m (16.3 kOe) without Dy capping layer. By performing the transmission electron microscopy (TEM) analysis, it was found that some of the grain boundaries were enriched with Nd element, which could be partly ascribed to the promotion by the Dy surface diffusion. In comparison to the evolution of the spin reorientation temperature of Nd2Fe14B phase after the deposition of the Dy capping layer, it is concluded that structural modification plays a significant role in the coercivity enhancement due to the Dy surface diffusion.     

Al_2O_(3P)/Al-Cu复合材料的二次加热组织演变

采用原位反应近液相线铸造方法制备Al2O3P/Al-Cu复合材料,对其进行二次加热,研究晶粒的形貌演变和长大规律。用光学显微镜观察组织结构,应用Image Pro Plus软件测量并统计出平均晶粒尺寸及合金液相体积分数,并与理论计算数值进行比较。结果表明,在590℃保温10~60 min后,不含Al2O3颗粒的Al-6.8%Cu基体合金平均晶粒尺寸为89~132μm,液相体积分数为14%~26.8%,而3.6 wt%Al2O3P/Al-6.8%Cu复合材料的平均晶粒尺寸为73~107μm,液相体积分数为11.6%~20.9%。说明Al2O3颗粒在合金的二次加热过程中对晶粒长大行为及液相体积分数的增长均有明显的抑制作用,从而为优化半固态组织提供了一种新思路。     

铝合金表面覆盖SiO2直接氧化生长的反应机理

通过热力学计算和XRD分析,确定了Al-Mg-Si合金熔体与SiO2表面覆盖反应的生成物相为Al2O3,Al,Si和MgAl2O4,直接金属氧化动力学实验表明,SiO2与熔体的接触反应加快了初期的传质过程,使微观传输通道始终处于活性状态,生成的Al2O3构筑了材料的初始骨架,Al2O3/Al复合材料氧化生长的孕育消失。     

Influence of particulate morphology on microstructure and tribological properties of cold sprayed A380/Al_2O_3 composite coatings

In this study, three kinds of A380/Al_2O_3 composite coatings were prepared by cold spray(CS) using spherical, irregular and spherical + irregular shaped Al_2O_3 particulates separately mixed in the original A380 alloy powders. The influence of Al_2O_3 particulates' morphology on the microstructural characteristics(i.e.retention of Al_2O_3 content in coatings, coating/matrix interfacial bonding, pore size distribution and morphology etc.) and wear performance of the coatings was investigated by scanning electron microscopy(SEM), X-ray computed tomography(XCT) and 3-D optical profilometry. Results indicated that the spherical Al_2O_3 shows obvious tamping effect during deposition process. As a result, the interface showed a wavy shape while the matrix and particulates were mechanical interlocked with much improved adhesion. In addition, the porosity of the coating was minimized and the pores exhibited curved spherical structure with reduced dimensions. The irregular Al_2O_3 particles predominantly displayed the embedding effect together with fragmentation of Al_2O_3 particulates. Consequently, poor coating/matrix interfacial bonding, high porosity and the formation of angular-shaped pores were resulted in the coating. Dry sliding wear tests results revealed that the wear resistance of the coating is directly related with the retained content of Al_2O_3 in the coating. The coating containing irregular Al_2O_3 particulates displayed superior wear performance with its wear rate one seventh of that of the pure A380 alloy coating. The coating containing both kinds of Al_2O_3 particulates showed mixed characteristics of above two kinds of Al_2O_3 composite coatings.     

烧结钕铁硼磁体溅射渗镝工艺与磁性能研究

采用直流磁控溅射的方法,在烧结Nd-Fe-B磁体表面制备了Dy薄膜,对比研究了N35烧结态与回火态磁体晶界扩散后组织形貌与性能的变化。N35烧结态与回火态磁体经溅射渗Dy处理后,在剩磁仅降低0.009T和0.03T的情况下,矫顽力大幅度提高,分别提高了708.44kA/m和665.46kA/m,渗Dy处理后磁体中的Dy元素平均质量分数增加不超过0.4%。SEM和EDS能谱的分析结果表明,晶界组织形貌的改善和(Nd,Dy)2Fe14B外延层的形成是矫顽力提升的主要原因。EPMA元素面分布结果显示,Dy主要富集在富Nd相处,三叉型富Nd相处Dy含量最高,而Dy没有扩散到主相晶粒内部,不会导致剩磁大幅度降低,从而有效提高了磁体的综合磁性能。     

含Ti和C的纳米复合Nd2Fe14B／α—Fe磁体研究

研究Ti和C添加对Nd9.4Fe79.6B11合金磁性能的影响规律。结果表明:Ti和C联合添加能够在不降低合金剩磁的情况下显著提高合金的矫顽力,最佳工艺条件下制备出的Nd9.4Fe75.6Ti4B10.5C0.5合金薄带的剩磁Br=0.91T,矫顽力Hcj=975.6kA/m,磁能积(BH)max=135.4kJ/m3。在磁体密度为6.1g/cm3时,黏结Nd9.4Fe75.6Ti4B10.5C0.5磁体剩磁Br=0.68T,内禀矫顽力Hcj=975kA/m,最大磁能积(BH)max=76 kJ/m3,性能和MQ-D磁粉制备的黏结磁体性能相当,具有低价位高性能的特点。     

脉冲电沉积RE-Ni-W-B-PTFE-Al2 O3复合镀层性能的研究

高性能复合镀层具有优良的耐磨、耐蚀性能,能满足工业生产对材料性能的要求.研究了脉冲电沉积RE-Ni-W-B-PTFE-Al2O3复合镀层的成分、形貌及性能.结果表明:脉冲电流及Al2O3固体颗粒能明显提高RE-Ni-W-B-PTFE-Al2O3复合镀层中W和B的含量;与直流电沉积相比,脉冲电沉积RE-Ni-W-B复合镀层的表面裂纹已明显减小,但裂纹仍存在,当Al2O3耐磨颗粒及PTFE减摩微粒嵌入RE-Ni-W-B复合镀层中以后,在SEM 400倍下观察,RE-Ni-W-B-PTFE-Al2O3镀层已不存在裂纹, 而且镀液中Al2O3颗粒含量越多,晶粒就越细;此外,研究表明,镀液中Al2O3颗粒含量增加, RE-Ni-W-B-PTFE-Al2O3复合镀层镀态硬度增加,磨损率降低.     

氧化锆氧化铝复合材料的显微结构

本文研究了在 ZrO_2量为17～78mol%(15～75vol%)的 ZrO_2/Al_2O_3复合材料中 ZrO_2颗粒的分布、晶型以及 Al_2O_3与嵌在 Al_2O_3晶粒内呈球状的 ZrO_2晶界处所形成的反相畴界,并且研究了在该复合材料中形成裂纹时,裂纹两侧和顶端的 ZrO_2颗粒相变后沿相界形成微裂纹的情况。     

铝合金熔体氧化制备Al2O3 / SiC/ Ni/ Al-Si多相模糊界面陶瓷基复合材料

针对Al₂O₃ / Al 复合材料中金属相Al 对其高温性能的不利影响, 本试验在高温下将铝合金熔体氧化渗透到注浆成型的SiC/ Ni 多孔预制体中, 制备了Al₂O₃ / SiC/ Ni/ Al-Si 多相陶瓷基复合材料。借助光学显微镜、电子显微镜(SEM) 、X 射线衍射仪(XRD) 、波谱仪( EDS) 等手段分析了预制体和复合材料的相组成、微观结构及界面特征。结果表明, 复合材料的主晶相为Al₂O₃ 与SiC , 相间存在Al (Si) 复合氧化物、NiAl₂O₄ 及Ni 与Al-Si 合金相, 各相界面处成分呈连续过渡变化趋势, 构筑了具有模糊界面特征的多相复合材料。      

Role of lanthanum in microstructure evolution and enhanced magnetic properties of cerium-containing sintered magnets

In this study, lanthanum was applied to strip cast Ce−Fe−B alloy to improve its phase composition and microstructure. The results reveal that lanthanum doping can significantly enhance the proportion of 2 : 14 : 1 phase and improve the microstructure of Ce−Fe−B alloy. Besides, the influence of the starting alloys structure on the microstructure and magnetic properties of final multi-phases cerium-containing magnets was also systematically investigated. Compared to the multi-phases magnet without lanthanum addition, a pronounced coercivity increment could be distinguished in lanthanum-doping multi-phases magnet, which could be attributed to the finer grain size together with ideal grain boundary. In this work, the superior performance of H_cj = 701.28 kA/m B_r = 1.30 T, and (BH)_max = 313.70 kJ/m³ were obtained by blending Nd−Fe−B alloy with (La_0.35Ce_0.65)-Fe−B alloy to meet 25.0 wt.% lanthanum-cerium utilization content, suggesting that the possibility to develop high abundant rare earth permanent magnetic materials.     

Ta基纳米薄膜扩散阻挡特性的比较研究

采用直流磁控溅射方法在p型(100)Si衬底上制备了Cu/Ta、Cu/Ta-N和Cu/Ta-Al-N复合膜,并对薄膜样品进行了卤钨灯快速热退火.用四探针电阻测试仪(FPP)、AFM、SEM、Alpha-step IQ台阶仪和XRD等分析测试方法对样品的形貌结构与特性进行了分析表征,并对N和Al的掺杂机理进行了讨论.实验结果表明,Ta、Ta-N和Ta-Al-N膜层的Cu扩散阻挡特性逐渐增强,Ta/Si界面上的反应和Cu通过多晶Ta膜扩散到Si底并形成Cu3Si共同导致了Ta阻挡层的失效,而Cu通过Ta-N和Ta-Al-N结晶后产生的晶界扩散到Si底并形成Cu3Si是两者失效的唯一机制.N的掺入促进了非晶薄膜的形成且有利于消除界面反应,而Al的掺入将进一步提高薄膜的结晶温度和热稳定性.     

微量钪在Al-Cu-Li-Zr合金中的存在形式和作用

通过显微组织观察和室温拉伸实验,研究了微量Sc在Al-Cu-Li-Zr合金中的存在形式和对合金微观组织和拉伸性能的影响.结果表明:微量Sc在Al-Cu-Li-Zr合金中主要以初生Al3(Sc,Zr)和次生Al3(Sc,Zr)两种形式存在.初生的Al3(Sc,Zr)是合金凝固过程中形成的,可成为有效的非均质形核中心,显著细化铸态晶粒组织,具有细晶强化和增塑作用;次生Al3(Sc,Zr)是合金在热加工过程中析出的,对位错和亚晶界起钉扎作用,稳定亚结构并有效抑制合金再结晶,具有亚结构强化和直接析出强化作用.因此,加入微量Sc的Al-Cu-Li-Zr合金的强度和塑性大大提高.     

包覆型α-Al_2O_3粉体的制备及表征

以平均粒径为22μm和0.5μm的α-Al2O3粉体为起始原料(以下分别简称Al2O3(C)和Al2O3(F)),分别以聚乙烯亚胺(PEI)和聚甲基丙烯酸铵(APMA)为聚合物电解质,采用非均相凝固法将Al2O3(F)颗粒均匀地包覆在Al2O3(C)粉体表面.重点考察了聚合物电解质的吸附时间、Al2O3(C)/Al2O3(F)的质量比、两种分子量的PEI对包覆型氧化铝粉体制备的影响.当Al2O3(C)/Al2O3(F)的质量比为1∶3,经过分子量约为60 000的PEI处理2 h的Al2O3(C)粉体表面均匀地包覆了Al2O3(F)颗粒(经APMA处理2 h).采用该包覆型粉体制备出片状多孔支撑体,其孔隙率为35.8%,平均孔径为2.9μm,纯水通量为205 m3/(m2.h.MPa).     

Al2(SO4)3反应在制备铝基复合材料中的应用

对传统搅拌铸造法制备铝基复合材料的颗粒加入方式进行改进,采用直接加入Ａｌ２（ＳＯ４）３,由其反应分解产生Ａｌ２Ｏ３原位合成铝基复合材料;由Ａｌ２（ＳＯ４）３分解的ＳＯ３可以对熔体进行精炼、除气;结果表明,Ａｌ２Ｏ３颗粒和基体结合良好,没有发现气孔团聚、集聚、偏析,克服了传统搅拌铸造所带来的铸造缺陷。     

Study on Two-phase Nanocrystalline Nd_(8.5)Fe_(74)Co_5Cu_1Nb_1Zr_3Cr_1B_(6.5)Permanent Magnet

Nd8.5Fe74Co5Cu1Nb1Zr3Cr1B6.5 bonded magnets were prepared by melt-spun and subsequent heat treatment. Magnetic properties of Br=0.68T,JHc=716 kA/m, (BH)max=77kJ/m3 were achieved. The addition of Cr element shows to be significantly advantageous in reducing grain size and increasing the intrinsic coercivity.