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).     

La2Fe14B和Ce2Fe14B合金在快淬和热处理过程中相析出行为的比较

研究了溶体快淬三元La_2Fe_(14)B和Ce_2Fe_(14)B合金的相析出行为和磁性能,对不同快淬速度(10~50 m/s)和不同热处理温度下制备的样品进行了系统分析。结果表明,通过直接快淬,La_2Fe_(14)B合金中不能形成2∶14∶1硬磁相,而Ce_2Fe_(14)B合金可以获得2∶14∶1相。La_2Fe_(14)B合金在10m/s快淬时主要由La和α-Fe相组成,而Ce_2Fe_(14)B合金中2∶14∶1硬磁相在10m/s和20m/s快淬时析出。随着辊速的增加,非晶相逐渐增多并成为主相。在热处理过程中,La_2Fe_(14)B合金析出相以α-Fe和La相为主,并且高温下液态的富La相和α-Fe相可以共存;而Ce_2Fe_(14)B合金中先析出α-Fe,后析出2∶14∶1硬磁相,随后析出相长大。结果还表明,La_2Fe_(14)B比Ce_2Fe_(14)B有更高的非晶居里温度和更低的α-Fe相析出温度。由于硬磁相的析出,Ce_2Fe_(14)B合金可以获得较好的硬磁性能,包括一定的矫顽力。此研究对含La、Ce稀土永磁材料的生产具有一定的指导作用。     

New kind of NdFeB magnet prepared by spark plasma sintering

We have produced an anisotropic Nd/sub 15.5/Dy/sub 1.0/Fe/sub 72.7/Co/sub 3.0/B/sub 6.8/Al/sub 1.0/ magnet by the spark plasma sintering (SPS) technique and compared it with a magnet of the same composition processed by the conventional sintering method. We investigated magnetic properties, microstructure, and constituents by a B-H loop-line instrument, a scanning electron microscope, and an energy-dispersive X-ray detector, and studied the effects of processing conditions on the magnetic properties, dimensional precision, and density. We also examined the magnet's electrochemical properties in electrolytes and its corrosion behavior in oxidizing environments. We found that the microstructure of the SPS NdFeB magnet is different from that of the conventional one. In the SPS-processed magnet, the grain size is fine and uniform while the distribution of the Nd-rich phase is heterogeneous. The SPS NdFeB magnet has a maximum energy product of 240 kJ/m/sup 3/ and a coercive force of 1260 kA/m. The density of the magnet reaches 7.58 g/cm/sup 3/, and its dimensional precision is about 20 /spl mu/m. The electrochemical properties and the corrosion resistance of the SPS NdFeB magnet are better than those of the conventional one. The SPS process is a promising method for the production of NdFeB magnets with ideal overall performance.     

用人工神经网络研究合金元素对NdFeB永磁体磁性能的影响

为了系统研究合金元素对Nd-Fe-Co-Zr-B系永磁合金磁性能的影响，采用均匀设计方法设计了Nd、Co、Zr和B的4因素6水平U18（6^4）试验方案，根据试验结果，建立了合金成分与磁性能之间的人工神经网络（ANN）预测模型。利用该预测模型获得的成分-性能的二维曲线、三维曲面及等高线图，研究了单个合金元素以及多元素间的交互作用对NdFeB磁体磁性能的影响规律。结果表明：预测结果与实测结果吻合良好，预测精度高；Nd、Zr为提高矫顽力Hcj而降低剩磁Br的元素；Co、B则对提高Br有利而对提高Hcj不利；合金元素对Hcj与Br的影响呈相反的趋势；元素间交互作用对磁性能影响显著。     

磁场热处理对NdFeB非晶快淬粉末的晶化与磁性的影响

研究了外中磁场对非晶Ｎｄ５．５Ｆｅ６６Ｂ１８．５Ｃｒ５Ｃｏ５，Ｎｄ４．５Ｆ３７７Ｂ１８．５和Ｎｄ１０．５Ｆｅｎ７０Ｂ７．０Ｚｒ２．５Ｃｏ１０粉末的晶化与磁性的影响，发现在热处理过程中加磁场可促进淬非晶粉末的晶化，使相转变在较低的温度下进行，讨论了各向异性复合纳米永磁材料可能的制备方法。     

Research and development of Ce-containing Nd_2Fe_(14)B-type alloys and permanent magnetic materials

Much demanded and overused are the critical rare-earth elements such as Pr, Nd, Dy, and Tb with increasing need of Nd Fe B-type rare-earth permanent magnets in the enlarging application areas, developing new high-tech industries, and emerging cutting-age frontiers. The balance and efficient use of rare-earth resources comes into being the national strategy, national defense, and border safety for many major countries and regions in the world.(Nd,Ce)Fe B-based permanent magnetic materials, which can not only reduce cost but also offer a feasible way for integrated and effective utilization of rare earth resources,have received much attention in recent years. The existence of CeFe_2 and the mixed valence state of Ce in Ce Fe B compound, the different metallurgy behavior and the particular processing as well as potential various magnetic-hardening mechanisms, however, make it quite different from Nd-based alloys.For instance, the coercivity of Ce-containing magnets in some certain composition range, is even higher than that of the counterpart pure Nd-based magnets though the Ce-containing magnets possess inferior intrinsic properties. Consequently, it is very important to design proper composition and structure, optimize processing, and analyze the mechanisms in depth for this kind of magnet. High performance and cost-effective magnets can be fabricated if we can make full use of the composition's inhomogeneous and abnormal coercivity variation of the Ce-containing permanent magnets. In this paper, we have summarized the phase structures, magnetic properties and microstructures of(Nd,Ce)Fe B-based permanent magnetic materials to shed light on further research and development of this type of so-called "gap magnet".     

Structural and Magnetic Properties of Nanocomposite Nd–Fe–B Prepared by Rapid Thermal Processing

Nanoscale permanent magnetic materials, which possess excellent magnetic and mechanical properties, thermal stability, and corrosion resistance, have become a research hotspot for permanent magnets. In reality, however, the obtained maximum energy product, (BH)_max, is not satisfactory in comparison with the theory limit, especially for exchange-coupled nanocomposite magnets. The construction of an ideal microstructure still remains a challenge in the synthesis and preparation of nanoscale permanent magnets. This work reported the impact of rapid thermal process (RTP) with electron-beam heating on the microstructures of Nd_12.5-xFe_80.8+xB_6.2Nb_0.2Ga_0.3 (x = 0, 2.5) nanocomposites. It was found that the crystallization time was greatly reduced, from 15 min under the conventional annealing conditions to 0.1 s under the RTP. For Nd₂Fe₁₄B single-phase materials, the crystallization temperature of the RTP ribbons decreased by about 248 °C compared with that of the ribbons produced by the conventional annealing method. A synergetic crystallization of the Nd₂Fe₁₄B and α-Fe phases was observed under the RTP, which restrained not only the shape, size distribution, and compositions of the hard and the soft phases, but also the interface between them. This modification effect became more obvious as the fraction of Fe increased. Due to the improvement in the uniformity of the Nd₂Fe₁₄B and α-Fe phases, and their grain size distribution, better magnetic properties were achieved using RTP in comparison with the conventional annealing method.     

Surface modification of spherical NdFeB magnetic powders by a fluid-bed nickel electrodeposition

The spherical NdFeB magnetic powders were coated with Ni using a fluid-bed electrodeposition device. The oxidations of rich Nd phase or Fe phase were restrained after Ni coating. After annealing at 300 °C for 30 min, the magnetic properties of both coated and uncoated magnets were decreased. However, the Ni-coated powders showed better magnetic properties than the uncoated powders after the annealing. The compressive strength of bonded magnets improved after annealing due to enhancement of the adhesion between the adhesive and the surface of the magnetic powders.     

放电等离子烧结NdFeB磁体的氧化和腐蚀行为

采用放电等离子烧结技术制备了新型NdFeB磁体,研究了NdFeB磁体在湿热环境下的氧化行为和在电解质溶液中的电化学特性.在扫描电子显微镜下分析了磁体的显微组织结构和成分.结果表明,与传统烧结NdFeB磁体相比,新型磁体的显微组织特征为:主相Nd2Fe14B晶粒细小、均匀,富钕相在主相晶粒边界上分布较少,主要集中在三角晶界处.这种组织结构有效抑制了磁体沿富钕相发生的晶间腐蚀的过程,使磁体具有良好的耐腐蚀性能.     

Direct-write 3D printing of NdFeB bonded magnets

We report a method to fabricate Nd–Fe–B (NdFeB) bonded magnets of complex shape via extrusion-based additive manufacturing (AM), also known as 3D-printing. We have successfully formulated a 3D-printable epoxy-based ink for direct-write AM with anisotropic MQA NdFeB magnet particles that can be deposited at room temperature. The new feedstocks contain up to 40 vol.% MQA anisotropic NdFeB magnet particles, and they are shown to remain uniformly dispersed in the thermoset matrix throughout the deposition process. Ring, bar, and horseshoe-type 3D magnet structures were printed and cured in air at 100°C without degrading the magnetic properties. This study provides a new pathway for fabricating NdFeB bonded magnets with complex geometry at low temperature, and presents new opportunities for fabricating multifunctional hybrid structures and devices.     

Microstructure and thermal stability of melt-spun Al-Nd and Al-Ce alloy ribbons

Alloys of compositions Al-6Nd, Al-9Ce, Al-16Nd and Al-22Ce (wt%) were prepared by chill-block melt-spinning at a surface speed of 29 m s^–1 into ribbons of thickness between 20 and 70 m. The melt-spun ribbons were heat treated for 2 h at 200, 300, 400 and 500 °C. The as-spun and heat-treated ribbons were tested for microhardness and investigated by optical and transmission electron microscopy and X-ray diffraction. Age hardening was not observed for any of the alloys, indicating only a limited amount of extended solid solubility as a result of the melt-spinning conditions used. Al-9Ce and Al-6Nd were found to be relatively stable at a hardness of 90 HK0.01 and 75–80 HK0.01, respectively, unaffected by heat treatment at up to 300 °C for 2 h, but heat treatment for 2 h at 400 or 500 °C caused softening. Al-6Nd and Al-9Ce as-solidified ribbons comprised a cellular Zone B structure with Al cells (of size 0.5 m) and intercellular orthorhombic Al₁₁(Nd, Ce)₃. The hardness of Al-16Nd as-spun was measured as 330±20 HK0.01 unchanged by heat treatment at 200 °C for 2 h, while heat treatment for 2 h at higher temperatures caused softening. As-spun Al-16Nd consisted of Zone A only comprising Al solid solution and orthorhombic or tetragonal Al₁₁Nd₃ partly coherent with the matrix. Al-22Ce had a hardness of 330±20 HK0.01 as-spun but softened on treatment for 2 h at 200 °C. As-spun Al-22Ce consisted partly of Zone A structure extending from the wheel side of the ribbon through half of the thickness. The remaining part of the ribbon consisted of cellular Zone B (cell size 0.2 m) with intercellular Al/Al₁₁Ce₃ lamellar eutectic together with areas that were 100% lamellar eutectic (interlamellar spacing 0.09±0.02 m). All the as-spun microstructures showed coarsening upon heat treatment at sufficiently high temperature. The resulting microstructure after treatment at 500 °C for 2 h consisted of a bimodal distribution of Al₁₁ (Nd, Ce)₃ which formed as large particles on the grain boundaries and smaller ones in the grain interiors. The corresponding microstructure was less coarse for Al-16Nd and Al-22Ce.     

Magnetic Properties and Structure of Nanocrystalline Nd4.5Fe76Co1B18.5 Alloys

In this paper, the technology, structures and magnetic properties of Nd4.5Fe76Co1B18.5 nanocomposite magnets were investigated. The effect of crystallizing treatment temperature and time on structures and magnetic properties of Nd4.5Fe76Co1B18.5 amorphous ribbons was studied. The results show that Nd4.5Fe76Co1B18.5 containing more analogue metals is easy to form a morphous. The magnetic properties of 16 m/s quenched ribbon for 710 degrees Cx900 s crystallizing treatment reach H-i(c)=242.1 kA/m, B-r=0.9410 T and (BH)(max)=59.64 kJ/m(3). The even grain size is about D-Fe3B=34 nm and D-Nd2Fe14B=23 nm.     

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。     

Crystallization behaviour and mechanical properties of rapidly solidified Al<Subscript>87.5</Subscript>Ni<Subscript>7</Subscript>Mm<Subscript>5</Subscript>Fe<Subscript>0.5</Subscript> amorphous alloy

The crystallization behaviour and the mechanical properties of rapidly solidified Al_87.5Ni₇Mm₅Fe_0.5 alloy ribbons have been examined in both as-melt-spun and heat-treated condition using differential scanning calorimetry, X-ray diffractometry (XRD), transmission electron microscopy (TEM), tensile testing and Vicker’s microhardness machine. XRD and TEM studies revealed that the as-melt-spun ribbons are fully amorphous. The amorphous ribbon undergoes three-stage crystallization process upon heating. Primary crystallization resulted in the formation of fine nanocrystalline fcc-Al particles embedded in the amorphous matrix. The second and third crystallization stages correspond to the precipitation of Al₁₁(La,Ce)₃ and Al₃Ni phases, respectively. Microhardness and tensile strength of the ribbons were examined with the variation of temperature and subsequently correlated with the evolved structure. Initially, the microhardness of the ribbon increases with temperature followed by a sharp drop in hardness owing to the decomposition of amorphous matrix that leads to formation of intermetallic compounds     

High Coercive NdFeB Thin Film Obtained by Diffusion Annealing

1. IntroductionSince the discovery of the high performance NdFeB permanent magnetll'2] ) there has been much interest in the magnetic properties and its applications.In most of the applications, bulk NdFeB magnetsare used. Due to the dependence of magnetic properties on ndcrostructure, the systematical change ofthe length scales and illtergranular phase, such asin thin films, have been illterested to optimize theirmagnetic properties. The film magnets are made bysputteringl3], MBEI4] and l…     

Structure and Magnetic Properties of Nd-Fe-B/a-Fe Nanocomposite Magnets by Co, Nb, Dy Substitutions

Structure and magnetic properties of the nanocomposite magnets prepared by mechanical alloying procedure with composition 55 wt pct Nd (Fe0.92B0.08)5.5+45 wt pct a-Fe, 55 wt pct Nd(Fe0.8-xCo0.12Nbx B0.08)5.5+45 wt pct a-Fe (x=0.00, 0.01, 0.03) and 55 wt pct (Nd0.9Dy0.1) (Fe0.77Co0.12Nb0.03B0.08)5.5+45 wt pct a-Fe were studied. It was found that substitution of Co for Fe could significantly improve the permanent magnetic properties of the nanocomposite magnets and typically, the maximum magnetic energy product was increased from 104.8 kJ/m3 (13.1 MGOe) to 141.6 kJ/m3 (17.7 MGOe). In contrast to the case of conventional nominally single-phase magnets, the addition of Nb results in promoting the growth of a-Fe grain and is thus unfavorable for the improvement of permanent magnetic properties of the nanocomposites. Although the addition of Dy can increase the coercivity of the magnets, the increase of magnetic anisotropy of hard phase leads to decrease of the critical grain size of soft phase. Additionally it causes the difficulty of preparing the nanocomposites because it is more difficult to control the grain size of soft phase to meet the requirement of appropriate exchange coupling between hard and soft grains.     

Hard magnets

Abstract

The properties and production of hard magnets are described by particular reference to NdFeB magnets. Thus, both the intrinsic properties (e.g. saturation magnetisation) and extrinsic properties (e.g. coercivity H_c) are discussed and it is shown how these properties are exploited in sintered magnets.

MST/1320     

Book review

Abstract

Magnesium based Mg–9Al–1Zn–5RE (RE=Y, La, Nd, Ce, or Pr) alloys with or without an addition of 1%Si were rapidly solidified by chill block melt spinning and splat quenching. The base alloy AZ91 (Mg–9Al–1Zn) was also rapidly solidified. Isochronal heat treatment for 1 h at 100–400°C showed that the microhardness of the ribbon maintained a similar level to that of the as spun alloy up to 300°C but decreased when heat treated at 400°C. Isothermal heat treatment for up to 24 h at 250–350°C showed that there were aging responses for the sample treated at 250°C while above this temperature, the microhardness decreased as the treatment time increased. The addition of 5% of RE elements to AZ91 displaced the Mg₁₇Al₁₂ phase in AZ91 with fine dispersoids of Al₂RE (RE=Y or Nd) or Al₁₁RE₃ (RE=La, Nd, Ce, or Pr) in Mg–9Al–1Zn–5RE alloys. These Al–RE intermetallics remained fine and precipitated at the grain boundaries so restraining grain growth during heat treatment at up to 400°C. Although Mg₂Si precipitates were found to be present in the silicon containing alloys after heat treatment at 400°C, their size was greater than those of Al–RE intermetallics, indicating that Mg₂Si has a lower thermal stability than these Al–RE intermetallics. The relationship between microhardness and grain size is discussed.

MST/3400     

Effect of the Ce Content on the Magnetic Properties and Microstructure of CeCo<Subscript>5</Subscript>-based Sintered Bulk Magnets

CeCo₅-based magnets have recently attracted much attention due to their moderate magnetic performance and low cost. Nevertheless, there have been few studies on the effects of Ce content on the magnetic properties and microstructures of CeCo₅-based magnets. In response to this, the magnetic properties of sintered bulk magnets with nominal compositions of Ce(Co_0.73Cu_0.135Fe_0.135) _z (z =?4.95, 5.15, 5.35, and 5.55), prepared by the conventional powder metallurgy method, were investigated here. Based on experimental findings, it was shown that Ce(Co_0.73Cu_0.135Fe_0.135)_5.15 sintered bulk magnets had comprehensive magnetic properties—maximum energy product of 80 kJ m^??3 (10 MGOe) and intrinsic coercivity (H _cj) of 452 kA m^??1 (5.69 kOe)—superior to those previously reported by us. For z =?5.35 and 5.55, due to the presence of the minor Ce₂Co₁₇ phase (which has a Curie temperature (T _c ) <?20 °C), magnets had low H _cj values. Based on x-ray diffraction and scanning electron microscopy observations, it was suggested that the volume fraction of the 1:5 matrix phase was the main factor determining the H _cj of CeCo₅-based sintered bulk magnets obtained with different Ce contents. Furthermore, the importance of the dispersion characteristics of the Ce₂O₃ phase within the matrix was emphasized. Uniform dispersion of the Ce₂O₃ phase can significantly improve the overall magnetic performance of CeCo₅-based magnets.     

Fabrication of bulk amorphous Fe67Co9.5Nd3Dy0.5B20 alloy by hot extrusion of ribbon and study of the magnetic properties

We report on the preparation of bulk amorphous Fe₆₇Co_9.5Nd₃Dy_0.5B₂₀ by hot extrusion of melt-spun ribbons. X-ray diffraction studies were performed to check the structure of the as-spun ribbons and the consolidated bulk specimens. Differential scanning calorimetry (DSC) analysis of the amorphous ribbons revealed that crystallization proceeds in two stages. The first crystallization step leads to the formation of soft magnetic α-(FeCo) and (FeCo)₃B and the second crystallization step corresponds to the formation of the hard magnetic (NdDy)₂(FeCo)₁₄B phase. The hysteresis loop of the as-spun ribbon reveals soft magnetic properties which change to hard magnetic behavior with enhanced remanence after annealing at 973 K for 7 min. X-ray diffraction analysis proves the presence of both soft and hard magnetic phases in the annealed sample. The viscosity of the powder obtained from crushed ribbons was investigated by parallel plate rheometry, showing a distinct viscosity drop in the supercooled liquid region that allows for easy consolidation of the crushed ribbons. The hot extruded sample that was subsequently annealed at 973 K for 7 min exhibits good hard magnetic properties with coercivity H_c = 218 kA/m, saturation magnetization J_s = 1.36 T, maximum energy product (BH)_max = 91.3 kJ/m³ and remanence B_r = 1.18 T (after demagnetization field correction), respectively.