Simultaneous enhancement in coercivity and remanence of Nd2Fe14B permanent magnet by grain boundary diffusion process using NdHx

We have successfully developed a Dy-free grain boundary diffusion process with neodymium hydride (NdH_x) alloy to the permanent magnet Nd₂Fe₁₄B powders using hydrogenation – disproportionation – desorption – recombination (HDDR) method. All the diffusion treatments were performed at 700–800 °C for various annealing time under the high vacuum with rotating diffusion method that effectively control the abnormal grain growth. The coercivities of Dy-treated Nd₂Fe₁₄B powders were varied from 9.5 kOe to 13.2 kOe but the remanence was decreased to 8.1 kG (10% reduction) depending on dysprosium hydride (DyH_x) content and diffusion treated time. However, the coercivity and remanence of Dy-free diffusion treated powder have been increased to 12.2 kOe (28.5% enhancement) and 11.1 kG (22% enhancement) at the optimal diffusion treatment (800 °C for 3 h), respectively. This unique simultaneous enhancement is to isolate the magnetic coupling between Nd₂Fe₁₄B grains by creating non-magnetic Nd grain boundaries and enhance the alignment of the Nd₂Fe₁4B hard magnetic phase, fabricated by optimal diffusion conditions.     

Coercivity enhancement of anisotropic Dy-free Nd–Fe–B powders by conventional HDDR process

Coercivity enhancement of Dy-free Nd–Fe–Co–B–Ga–Zr powders was studied using the conventional hydrogenation–decomposition–desorption–recombination (HDDR) process. It was found that the addition of Al together with the proper Nd content and the slow hydrogen desorption of the HDDR treatment can induce high coercivity in the powder. For example, the 14.0 at% Nd–2.0 at% Al powder exhibits H_cJ of 1560 kA/m, B_r of 1.22 T, and (BH)_max of 257 kJ/m³. The high coercivity inducement of the powder is thought to be attributed to the formation of Nd-rich phase, which continuously surrounds fine Nd₂Fe₁₄B grains.     

Origin of anisotropy for the HDDR Nd13.5Fe79.5B7 magnetic powders

For the HDDR Nd_13.5Fe_79.5B₇ magnetic powders, effects of disproportionation time and hydrogen pressure on the anisotropy were studied during the slow desorption stage. Studies showed that shorter disproportionation times caused the magnetic powders displaying higher anisotropy. With increasing disproportionation times, the degree of crystallographic alignment decreased. This in turn caused a drop in remanence and anisotropic character. Longer disporportionation times have also been correlated to a change in disproportionated microstructure from lamella to columnar. XRD (X-Ray Diffraction) studies showed that except NdH₂,α-Fe and Fe₂B, no other phases were included in the disproportionation mixture. This elucidated that the strong anisotropy is only related to a lamella disproportionation microstructure, which corresponds to a short disproportionation times. The lamella disproportionation microstructure may remain or inherit the alignment of original Nd₂Fe₁₄B grain, and may also be related to the alignment of the newly formed Nd₂Fe₁₄B grain. Thus, the anisotropic formation mechanism of ternary magnetic powders accords with “anisotropy-mediating phase” model. If the disproportionation mixture were carried out an optimum hydrogen pressure treatment during the HDDR process, the degree of crystallographic alignment can be further enhanced.     

TEM studies of the effects of Zr additions on some HDDR-processed, high boron, NdFeB-type powders and hot-pressed magnets

The transmission electron microscope has been used to study the physical and magnetic microstructures of two HDDR-processed NdFeB-type alloys, one without Zr and the other containing 1.1 at% Zr. Studies were made of the as-produced powders and the solids produced following hot-pressing at 900°C. In the HDDR powders, the principal effects of adding Zr were to reduce the average grain size by and made the grain size distribution more uniform. In the hot-pressed samples, the effect of Zr was more dramatic in that grain growth was very significantly reduced. Zr-containing phases were identified and a simple model, due to Zener, used to provide a plausible explanation of how the small amount of Zr present could stabilise the grain size to ≈0.5 μm. The microstructural results correlated well with measured magnetic properties.     

Effects of the conventional HDDR process and the additions of Co and Zr on anisotropy of HDDR Pr-Fe-B-type magnetic materials

Effects of the conventional hydrogenation disproportionation desorption recombination (HDDR) process and the additions of Co and Zr on anisotropy of HDDR PrFeB-type magnetic materials are investigated. The results show that the degree of anisotropy in conventional HDDR Pr₁₃Fe₈₀B₇ materials decreases monotonically with the prolonged disproportionation time, and short disproportionation time is helpful for preparing highly anisotropic Pr₁₃Fe₈₀B₇ material. However, it is notable that the degree of anisotropy in conventional HDDR Pr₁₃Fe₈₀B₇ materials is significantly smaller than that in solid-HDDR Pr₁₃Fe₈₀B₇ materials with the same disproportionation time. At the same time, it is found that the addition of Co and Zr may make HDDR Pr-Fe-B materials that have higher anisotropy compared with HDDR pure ternary Pr₁₃Fe₈₀B₇ materials under the same HDDR process, but their degree of anisotropy will also decrease monotonically with the prolonged disproportionation time, and will be close to zero when the disproportionation time is greater than 20 h. Based on this, the origin of anisotropy is discussed by X-ray diffraction (XRD) investigations for the disproportionated products of the above alloys. The results show that the origin of anisotropy in HDDR Pr-Fe-B materials with the addition of Co or Zr may differ from that in HDDR pure Pr₁₃Fe₈₀B₇ materials, and the former maybe from the residual “Pr₂(Fe,Co,Zr)₁₄B” nucleus while the latter is not. Finally, it is also found that HDDR Pr-Fe-B materials with Co or Zr can obtain high-magnetic properties even if the high-desorption temperature is used, and this shows the addition of Co and Zr may make HDDR Pr-Fe-B materials that have a larger process temperature range.     

锰、铝、锆对NdFeCoB合金HDDR磁粉性能的影响

采用HDDR技术制备NdFeCoB合金磁各向异性磁粉,研究了添加元素Mn,Al和Zr对NdFeCoB合金HDDR磁粉磁性能及磁各向异性的影响. 结果发现:在NdFeCoB合金中加入2%Mn,可提高合金HDDR磁粉的磁各向异性和剩磁,但磁粉的矫顽力和最大磁能积降低;在NdFeCoB合金中,分别加入0.8%Al,0.1%Zr时,可使合金的HDDR磁粉的磁各向异性DOA值从0.23增加到0.5和0.41,但此时磁粉的矫顽力和最大磁能积较低;加入2%Mn,0.8%Al和0.1%Zr,没有改变NdFeCoB合金的相组成;添加Mn,Al,Zr使NdFeCoB合金HDDR磁粉磁各向异性增加,与这些元素的加入提高了硬磁相Nd2Fe14B在氢气中的稳定性有关.     

钴在HDDR各向异性NdFeB中的作用

研究了钴对HDDR各向异性NdFeB的磁性能和各向异性的影响,发现钴有利于得到高矫顽力的各向异性NdFeB磁粉,组织分析表明钴掺优进入合金初始组织的富钕相,其次进入Nd2Fe14B相,改变了它们在氢气中的稳定性,影响了HDDR相变的动力学过程,使得材料既具有较高的矫顽力,又有利于各向异性的形成。     

Magnetic properties and microstructure of HDDR isotropic Nd-Dy-Fe-Co-B bonded magnets with high coercivity

The effect of small amount of Co and Dy addition on the magnetic properties of HDDR isotropic Nd-Dy-Fe-Co-B bonded magnets was investigated. The experimental results show that the intrinsic coercivity H_cj and the reversible temperature coefficient of remanence of (Nd_0.65 Dy_0.35)_12.5-(Fe_0.9Co_0.1)₈₁B_6.5 magnet were 1.53 MA·m^-1(19.3 kOe) and -0.059%/°C (25–155°C), respectively. The high coercivity and low temperature coefficient of the magnet are due to the enhanced anisotropy field, increased Curie temperature and improved microstructure by Dy and Co addition.     

Dy与Co对HDDR粘结磁体的温度稳定性与磁性能的影响

添加微量元素Dy和Co后可使HDDR工艺制备的各向同性NdDyFeCoB粘结磁体的温度特性、磁性能以及微晶结构显著改善,从而得到一种具有实用价值的低温度系数、高内禀矫顽力粘结磁体.结果表明:添加适量的Dy和Co可使25—80℃时的磁通可逆温度系数α在-0043%℃左右,25—155℃时的磁通可逆温度系数α=-0056%℃;经155℃老化处理12h不可逆损失hirr为35%;最高内禀矫顽力Hci>1600kAm-1时,最大磁能积(BH)max仍可获得一个较好值. 关键词： HDDR工艺 温度特性 微结构 内禀矫顽力     

Texture in a ternary Nd16.2Fe78.2B5.6 powder using a modified hydrogenation–disproportionation–desorption–recombination process

A modified hydrogenation–disproportionation desorption-recombination (HDDR) process consisting of (i) solid disproportionation and (ii) slow recombination under partial hydrogen pressure has been applied to a Nd_16.2Fe_78.2B_5.6 alloy. Scanning electron microscopy shows that an initially fine rod-like structure of NdH_2±x and Fe observed after 15 min of hydrogenation at 900°C is transformed into a granular morphology with prolonged annealing. Simultaneously, finely dispersed tetragonal Fe₃B particles of 10–50 nm diameter exist. XRD studies show that this metastable Fe₃B phase is transformed to Fe₂B and Fe on further annealing. Short solid-disproportionation times result in a higher degree of anisotropy after recombination, whereas long annealing times and conventional processing lead to isotropic material. It is concluded that the formation of the intermediate tetragonal Fe₃B phase after solid disproportionation is pivotal for the inducement of texture in HDDR processed ternary NdFeB-type alloys.