高Ce含量RE-Fe-B烧结磁体元素分布与磁性能研究

为了开发具有商业价值的高Ce含量RE-Fe-B磁体,提高高丰度稀土Ce的利用率,对不同Ce替代量RE-Fe-B磁体的磁性能和微观结构进行了研究。实验结果表明,Ce/(Ce+Nd)质量分数达到40%的双主相磁体仍保持着优良的磁性能,剩磁B_r达到1.31 T,最大磁能积(BH)_max达到310.56 kJ/m³。在Ce替代量为40%的单、双主相磁体中,Nd和Ce元素的置换行为存在差异,单、双主相磁体中Nd元素均偏向于进入主相晶粒,Ce元素则趋于聚集在晶界相或主相晶粒表层,且在双主相磁体中形成贫Ce主相和接近名义成分的(Nd_0.6Ce_0.4)_30.5(Fe, M)_balB_0.97主相。通过观察磁畴翻转分析了单、双主相磁体的磁化行为,研究了双主相磁体矫顽力增强机制：贫Ce主相的高各向异性场对富Ce主相的磁矩起到了钉扎作用。Nd和Ce元素扩散行为的研究为制备高Ce含量、高磁性能的商业化RE-Fe-B磁体提供了依据。     

无重稀土烧结Nd-Fe-B磁体的显微结构和磁性能研究

对Ga、Al、Cu和Zr共同掺杂的烧结Nd-Fe-B磁体磁性能和显微结构进行研究，并通过回火工艺对磁体的矫顽力进行调控。结果表明：当一级回火为900℃×150 min,且二级回火为500℃×180 min时，磁体矫顽力H_cj从烧结态的14.33 kOe大幅提高到二级回火态的19.86 kOe,提高了38.6%;方形度H_k/H_cj由0.86增加到0.97;剩磁B_r仅从烧结态13.51 kGs略微下降到二级回火态的13.46 kGs;富稀土相分布更加连续和明显。研究分析表明，矫顽力大幅增加主要是由于含有少量的富Nd相和贫B相的烧结Nd-Fe-B磁体中Ga的掺杂改变了晶界相湿润性，降低了富稀土相中Fe元素的含量。本研究为无重稀土高矫顽力和高剩磁烧结Nd-Fe-B磁体步入产业化夯实了理论基础。     

Nd-Fe-B磁体掺杂Tb-Fe-B制备高性能大块永磁体

应新能源大型设备器件需求,制备兼具高剩磁、高矫顽力的大块永磁材料成为当前研发重点。不同于晶界扩散技术(GBDP),采用双合金工艺(Nd-Fe-B磁体掺杂Tb₁₉Fe₇₅B₆)制备的多主相(Nd, Tb)-Fe-B烧结磁体,不仅可实现高剩磁与高矫顽力而且体型可控,体现出更高的实用价值。微组织分析显示,掺杂Tb₁₉Fe₇₅B₆使得磁体晶界优化并在Nd₂Fe₁₄B晶粒表层形成(Nd, Tb)₂Fe₁₄B壳层,结合Tb₂Fe₁₄B相的存在,矫顽力得以显著提升。而导致多主相(Nd, Tb)-Fe-B磁体同时实现高剩磁与高矫顽力,主要归因于微结构中Tb₂Fe₁₄B单晶与Nd₂Fe₁₄B单晶共存所触发的界面耦合效应。该研究结果为制备高性能大块永磁材料提供...     

Ce取代量对Nd-Fe-B制备工艺及性能的影响

本文研究了不同Ce添加量对烧结Nd Fe B磁体的制备工艺及磁性能的影响,采用阿基米德法对磁体密度进行测量、脉冲磁滞回线测量仪PFM等对磁体性能进行了分析。研究表明,随着Ce的添加量增加,烧结磁体的密度升高,有利于磁体的致密化。含Ce磁体最佳烧结温区960℃~1010℃之间,比传统Nd Fe B烧结温度低50℃~80℃。随着Ce取代量增加,磁体综合性能下降,Ce含量在30%TRE以上时,热处理对性能的提升效用减弱,磁体只需一步烧结即可达到最优性能,从而缩短了制造流程,为低成本稀土磁体的制备提供了基础。     

富稀土合金添加对烧结(MM,PrNd)-Fe-B微观组织和磁性能的影响北大核心

本文采用粉末冶金工艺制备了含有混合稀土的烧结(MM,PrNd)-Fe-B磁体,并研究了富稀土合金添加对磁体微观组织和磁性能的影响。未添加富稀土合金的MM_(7)(PrNd)_(24)Fe_(74.99)B_(1.01)磁体晶界相中存在La、Ce元素聚集现象,添加6%的(PrNd)_(41)Fe_(57.99)B_(1.01)富稀土合金能够部分消除这种聚集现象,同时矫顽力从11.15 kOe提高至11.98 kOe。微观分析表明,添加富稀土合金后,磁体具有双主相结构。晶界中的La、Ce会置换(PrNd)(2)Fe_(14)B主相中Pr、Nd元素,同时Pr、Nd会置换(MM,PrNd)(2)Fe_(14)B主相中La、Ce元素。晶界中La、Ce元素的均匀分布和双主相结构有助于提升磁体的矫顽力。     

烧结温度对Nd24.38Ce0.52Gd6.65Febal.TM1.76B0.95磁体组织与性能的影响

采用双合金法制备Nd24.38Ce0.52Gd6.65Febal.TM1.76B0.95（质量分数,%）永磁体,通过扫描电镜及能谱、AMT-4磁测试仪、电子万能力学试验机等手段研究烧结温度对磁体组织和性能的影响.结果表明：随烧结温度从1060℃升高到1100℃,在烧结温度为1080℃时,晶粒均匀且结合致密,富稀土相分布均匀,能获得较好的组织形态;富稀土相中稀土总含量从84.98%增加到98.04%,烧结过程中铈从主相显著扩散到富稀土相;磁体剩磁Br、矫顽力Hcj、磁能积（BH）max 先升后降,在1080℃烧结时获得较好的磁性能,分别为1.22 T、964 kA/m 和293 kJ/m3,同时磁体抗弯强度也达到最大值为257 MPa.     

高丰度稀土添加对NdFeB微观结构及性能影响

钕铁硼磁体制造过程中速凝铸片微观组织的形态对磁体的性能有重要的影响。本文系统研究了不同Y\La\Ce添加量对烧结NdFeB磁体的铸片微观组织及磁体性能的影响。结果表明Y\La\Ce添加量为10%稀土总量(TRE)时,磁体速凝铸片的微观形貌保持良好的板条状结晶,而随着添加量的增加,速凝铸片的结晶形态变差,磁体性能呈线性下降。不同的取代元素对磁体性能影响程度不同,剩磁衰减量YCeLa,矫顽力衰减量YLaCe,为制备具有良好性能的低成本磁体提供了指导。     

液相扩散对钕铁硼磁体性能和组织结构的影响

用双合金工艺在Nd13.05Dy0.23Fe80.12B6.5铸片主合金中分别添加质量分数为3％～20％的富稀土铸锭辅合金Nd38.2Cc11.8Fe44.88Al4.12B,研究在钕铁硼永磁体中用Ce部分地取代Nd时对永磁体的磁性能的变化规律.实验结果表明,在一定的烧结及热处理工艺条件下,辅合金加入量介于8％ ～ 12％(质量分数)时,磁体的内禀矫顽力和磁能积相对较高,对剩磁的影响不大.显微成分分析表明,采用双合金法,使组织中细小的颗粒状富稀土相增多,形成了更多的对矫顽力有贡献的富稀土相,并且富稀土相分布于晶界上.     

高Dy含量烧结Nd-Fe-B的晶界扩散处理研究

研究了晶界扩散处理对高Dy含量烧结Nd-Fe-B磁体性能和结构的影响。经蒸镀渗Dy晶界扩散处理,高Dy含量Nd-Fe-B磁体的矫顽力从1 713 kA/m提高至2 161 kA/m,而剩磁和最大磁能积基本没有下降,处理后磁体内Dy平均质量分数仅增加0.30%。不同深度片层分析表明,虽然磁体近表面片层比中心片层的Dy含量高,但是片层间矫顽力相差较少,而且所有片层的矫顽力均远高于未处理磁体片层的矫顽力。电子探针Dy元素面分布结果显示,在未处理高Dy含量磁体的晶界与主相中均存在Dy元素富集区且富集浓度较低,而经扩散处理后,晶界富Nd相中的Dy富集区浓度及所占比例明显提高;包括磁体芯部在内,磁体内大部分角隅处富Nd相内Dy含量明显增加,进一步提高了高Dy含量磁体内部各处的矫顽力。     

低氧速凝工艺制备RE(Nd,Pr)-Fe-B稀土永磁母合金的研究

选用Nd-Pr,Fe-B合金,纯铁以及海绵锆为原料,按一定的比例,采用低氧(真空、Ar气)速凝工艺,在1400℃～1450℃,φ600mm×500mm规格铜轮,v=1m/s～2m/s的冷却强度下,制备厚度为0.2mm～0.45mm的(Nd,Pr)-Fe-B稀土永磁母合金薄片,并对产物通过XRD,SEM进行表征.采用一定工艺将合金制备成烧结永磁体,通过对退磁曲线分析,证明可获得性能理想的(Nd,Pr)-Fe-B产品.     

Abnormal corrosion behavior of dual-main phase sintered(Ce,Nd)-Fe-B magnets in different sodium solutions

Sintered(Ce,Nd)-Fe-B magnets with high cost performance were prepared by substituting of Ce for Nd with the dual-main phase method.The corrosion behaviors of dual-main phase sintered(Ce_xNd_(1-x))_(30)Fe_(69)B_1(x=0.15 wt%,0.3 wt%) magnets,which were named as Ce15 and Ce30,were studied in 3.5 wt% NaCl,6.6 wt% Na_2 SO_4 and 3.0 wt% NaOH aqueous solutions,respectively.The galvanic corrosion of Ce30 is stronger than that of Ce15.However,the mass loss value of Ce30 is smaller than Ce15 after free corrosion for 33 d in NaCl solution.In the other two solutions,all the results show that the corrosion resistance of Ce30 is better than that of Ce15.The scanning electron microscope results show that the crack and shedding of the magnetic phase of Ce30 is less than that of Ce15.Combined above,the abnormal corrosion behavior shows that Ce30 magnets perform better corrosion resistance than Ce15,and the degradation degree of magnetic phase mainly affects the corrosion resistance of magnets.     

Effects of grain boundary ternary alloy doping on corrosion resistance of(Ce,Pr,Nd)-Fe-B permanent magnets

To satisfy the application of different environments,grain boundary doping is commonly used in the preparation of sintered magnets to improve the coercivity and the corrosion resistance.In this paper,the alloys were prepared by mixing different ratios of the master alloy(Ce,Pr,Nd)-Fe-B and the sintering aid(Pr,Nd)-Al.The coercivity of sintered(Ce,Pr,Nd)-Fe-B magnet is substantially enhanced by doping 2 wt%of(Pr,Nd)-Al,while the maximum energy product decreases slightly.We systematically investigated the corrosion behavior and micro structure of the sintered magnets in order to determine the mechanism of the degradation.The sintered(Ce,Pr,Nd)-Fe-B magnets with 2 wt% of(Pr,Nd)-Al addition exhibit the decreasing corrosion rate compared with others,due to the distribution of intergranular phases.The electrode potential difference between the main phase and the RE-rich phase is reduced by the addition of Al,improving the potential and stability of RE-rich phase due to the higher electrode potential of Al than that of Nd,Pr or Ce.In addition,the element distribution of the magnets doped by(Pr,Nd)-Al indicates that the Al-rich shell formed at the marginal area of the Ce-rich phase improves its stability.Therefo re,intergranular adding te rnary(Pr,Nd)-Al alloy powders results in both high coe rcivity and good corrosion resistance synchronously.     

Coercivity enhancement of Ce-Fe-B sintered magnets by low-melting point intergranular additive

Ce-Fe-B sintered magnets with enhanced coercivity were prepared by the powder metallurgy method. The mechanism of the coercivity enhancement in Ce-Fe-B sintered magnets with the low-melting point intergranular additive was discussed in details. It was speculated that the low coercivity of Ce-Fe-B sintered magnet was related to the irregular sharps and relatively low magneto-anisotropy field of the matrix phase. After introducing a 20 wt.% Nd-based intergranular additive, the coercivity markedly increased from 108 Oe to 2560 Oe due to the formation of thin and continuous grain boundary layers and the surface modification of the matrix phase grains. Additionally, the formation of the high anisotropy field(Nd,Ce)_2Fe_(14)B shell was beneficial to the increase of the coercivity as well. This work suggested that adding low-melting point intergranular additives was effective to fabricate the practical Ce-Fe-B sintered magnets.     

工业生产高综合性能烧结 Nd-Fe-B永磁关键技术研究

通过优化合金成分设计和改进合金铸锭按需分配技术、磁场取向成型技术以及烧结技术，应用全部国产设备与国内通用的工业生产烧结Nd-Fe-B永磁的原材料，避免使用镓等稀有贵重金属元素，实现了N45H烧结Nd-Fe-B磁体的工业化生产，其典型磁性能为Br=1.386T(13.86kGs),BHc=1059kA/m(13.32kOe),JHc=1418kA/m(17.83kOe),Hk=1357kA/m(17.06kOe),(BH)max=364kJ/m^3(45.8MGOe)。，SEM观察和XRD分析结果表明，制造的N45H烧结Nd-Fe-B磁体具有良好的取向度和晶粒细小而均匀的显微组织。     

Nd-Fe-B永磁制粉技术及特点

对几种重要的Nd-Fe-B稀土永磁粉末的制备技术如盘磨臁磨、机械合金化、熔体快淬、超声气体雾化、带铸以及HDDR（Hydrogenation-Disproportionation—Desorption—Recombination）技术进行了评论。指出制粉技术从物理破碎、快速凝固技术到氢化反应的发展，改变了合金成分及工艺设计，实现了微观结构和磁体性能的改善，促进了Nd-Fe-B稀土永磁材料的应用。     

Influence of dysprosium substitution on magnetic and mechanical properties of high intrinsic coercivity Nd-Fe-B magnets prepared by double-alloy powder mixed method

The double-alloy powder mixed method is very proper for developing new small-mass products by changing the composition of sintered Nd-Fe-B magnets, and there is little research on this aspect. The variation on magnetic and mechanical properties of high intrinsic coercivity Nd-Fe-B magnets prepared by double-alloy powder mixed method was discussed, which is a method blending two-type main phase alloy powders with different components. The results showed that the intrinsic coercivity and density of sintered Nd-Fe-B magnets increased gradually with the increase in Dy content, and the double-alloy powder mixed method could obtain high intrinsic coercivity Nd-Fe-B magnets with good crystallographic alignment and microstructure. The bending strength of sintered Nd-Fe-B magnets declined, and the Rockwell hardness of sintered Nd-Fe-B magnets first declined, and then increased with the increase in Dy content. The microstructure showed that there existed the phenomenon that the Dy element diffused into main phase during sintering process, and the distribution of Dy content in main phase had some variation in homogeneity as a result of incomplete reaction between the double-alloy powder types.     

Dependence of magnetic properties on microstructure and composition of Ce-Fe-B sintered magnets

In this paper,dependence of magnetic properties on microstructure and composition of Ce-Fe-B sintered magnets with Cu-doped Ce-rich alloy addition was investigated.It shows that the maximum energy product(BH)_(max) and coercivity H_(cj) of Ce-Fe-B sintered magnet are improved from 6.76 to 9.13 MGOe by 35.1%,and from 1.44 to 1.67 kOe by 16.0%,respectively,via adding 5 wt% liquid phase alloy of Ce_(35.58)Fe_(57.47)Cu_6 B_(0.95)(at%).Compared with the magnet without Cerich alloy addition,the volume fraction of the grain-boundary phase with low melting point increases in the magnet with Ce-rich alloy additio n,which is be ne ficial to imp roving the microstructure and promoting the coercivity enhancement of the magnet.In the Ce-Fe-B magnet with Ce-rich alloy addition,Cu and Ce enrich in the grain boundaries of the magnet after annealing,therefore the as-annealed magnet has a higher coercivity than the as-sintered magnet.A distinct Fe-rich layer with the average thickness of 60 nm is found in the grain boundaries in the magnet without Ce-rich alloy addition,but it seems that Fe-rich phase disappears in the magnet with Ce-rich alloy addition.The present work suggests that the further improvement of coercivity in the Ce-Fe-B sintered magnets is expectable by designing the composition and structure of added liquid phase alloys.     

烧结钕铁硼永磁材料制备工艺的研究进展

对当前烧结钕铁硼永磁体制备工艺中速凝铸带、氢碎、烧结和热处理以及添加合金元素等工序进行了介绍,并对其研究进展进行综述。同时,对烧结钕铁硼永磁体行业可能的发展方向进行了展望。     

Preparation and Properties of Nd-Fe-B/Fe Nanocomposite Magnets

Nd-Fe-B/α-Fe nanocomposite magnets with high magnetic properties were successfully fabricated through a sonochemical process with carbonyl iron as Fe precursor and subsequently SPS. Experimental results show that α-Fe can increase the remanence of Nd-Fe-B/α-Fe nanocomposite magnets while decrease the coercivity. The demagnetizing curve indicates that the hard and the soft phases did not coupled very well, even though the remanence was improved. The magnetic properties of Br 8.61 kGs, Hcj 8.59 kOe and (BH)_max 12.05 MGOe were obtained for Nd-Fe-B/α-Fe nanocomposite magnets with the nominal Fe content of 5 wt.%. It is noted, the exchange coupling was obviously enhanced by a MA process before SPS, and the magnets properties were increased to Br 9.42 kGs and (BH)_max 14.27 MGOe for Nd-Fe-B/α-Fe nanocomposite magnets with the same Fe content.     

Grain Growth Behavior in Sintered Nd-Fe-B Magnets

The Nd2Fe14B grain growth behavior in sintered Nd-Fe-B magnets was quantitatively described.The effects of sintering temperature and time,and alloy powder size and its distribution on grain growth process were analyzed.Hence,possible grain growth mechanisms in these magnets were qualitatively discussed.The Nd2Fe14B grain growth proceeded at quite a high rate in the initial 0~1 h of sintering and from then onwards the grain growth rate decreased.A large average particle size or a wide particle size distribution of initial alloy powders was found to remarkably accelerate the grain growth process and even result in the occurrence of abnormal grain growth.On the basis of experimental results,two grain growth mechanisms were considered to operate during sintering of Nd-Fe-B magnets,that is,dissolution and re-precipitation of Nd2Fe14B particles,and Nd2Fe14B particle growth by coalescence.It was believed that Nd2Fe14B particle growth by coalescence not only produced a large average grain size and a wide grain size distribution,but also was the fundamental reason for the formation of abnormally large grains in the microstructure of sintered Nd-Fe-B magnets.