Observation of hydrogen induced intermediate borides in PrFeB based alloys by Mössbauer effect spectroscopy

In the present work, a quantitative analysis of the phase compositions by Mössbauer effect spectroscopy of solid and conventional hydrogen disproportionated Pr_13.7Fe_80.3B_6.0 and Pr_13.7Fe_63.5Co_16.7Zr_0.1B_6.0 alloys was carried out. Significant amounts of intermediate borides t-Fe₃B and Pr(Fe, Co)₁₂B₆ were detected after solid hydrogen disproportionation treatment in Pr_13.7Fe_80.3B_6.0 and Pr_13.7Fe_63.5Co_16.7Zr_0.1B_6.0 alloys, respectively. After conventional hydrogenation–disproportionation–desorption–recombination treatment these phases were not detected and in no case residual Pr₂Fe₁₄B-phase was found. It was observed that the amount of intermediate borides after disproportionation can be correlated with the degree of texture after recombination at various temperatures.     

Sm2Fe17合金的氢化-歧化过程演化

通过X射线衍射(XRD)、扫描电镜(SEM)和能谱分析(EDX)等手段重点研究了Sm2Fe17合金在氢化-歧化过程中的相组成、相的变化以及微观结构的演化规律。研究表明：在0．1MPa的H2气氛下，Sm2Fe17合金首先吸氢；400℃时合金出现部分脱氢现象；在T≥500℃逐渐开始歧化为SmHx和α—Fe，同时生成了大量的微晶或非晶组织；随着温度的升高，合金中的微晶非晶逐渐晶化，750℃时晶化完全，晶粒长大至20～100nm。通过对Sm2Fe17合金的氢化一歧化过程研究，建立了该过程的微观结构变化规律的物理模型。     

HDDR过程中三元和多元Nd-Fe-B合金磁畴结构的MFM研究

用磁力显微镜研究了三元Nd-Fe-B合金在HDDR过程的不同阶段(铸态、不充分吸氢歧化、充分吸氢歧化和脱氢再复合)的破畴结构。在铸态样品表面清楚地观察到了易磁化轴互相垂直的柱状晶表面的两类磁畴图型。当样品不充分吸氢歧化和充分吸氢歧化时，破畴结构明显发生变化，反映了Nd-Fe-B的分解产物NdH2，α-Fe和Fe2B及其微晶结构的变化。脱氢再复合后形成的微晶的磁畴结构则表明样品保留了铸态样品柱状晶的构型。此外，还对比研究了多元Nd-Fe-B合金在HDDR过程中的磁畴结构，并根据微磁结构分析，指出过量的Ga元素添加可抑制Nd2(Fe，M)14B相的吸氢歧化，从而导致相应HDDR粘结磁体性能降低。     

Effect of microstructure on the coercivity of HDDR Nd-Fe-B permanent magnetic alloy

The effect of the grain boundary microstructure on the anisotropy and coercivity was investigated in an HDDR Nd-Fe-B permanent magnetic alloy. Considering the special microstructure of its magnetic powder grain, an anisotropic theoretical model influenced simultaneously by the structure defect at the grain boundary and the exchange coupling interaction was put forward. The variations of the structure defect factors based on the nucleation and pinning mechanism with 2r ₀/lex (where r ₀ and lex are the defect thickness and the length of exchange coupling, respectively) were calculated. The results show that the coercivity mechanism of an HDDR Nd-Fe-B permanent magnetic alloy is greatly related to its microstructure defect at the grain boundary. For a fixed lex, when 2r ₀/lex < 1.67, the coercivity is controlled by the pinning mechanism; when 2r ₀/lex > 1.67, it is determined by the nucleation mechanism. The coercivity reaches the maximum when 2r ₀/lex = 1.67. The calculation result is consistent well with the experimental result given by Morimoto et al. Supported by the National Natural Science Foundation of China (Grant No. 50671055)     

纯三元及含Zr, Ga元素磁粉的各向异性

未经均匀化热处理的纯三元及含Zr, Ga元素的SC合金铸片经优化的HDDR工艺处理都可以制备各向异性NdFeB磁粉。这表明：元素的添加及SC铸片是否进行了均匀化热处理都不是HDDR磁粉各向异性形成的必要条件。磁粉各向异性形成的关键因素在于HDDR工艺的调节,即适当地加快歧化反应过程,减缓脱氢再结合过程以及控制脱氢再结合时的合适氢气压强均有利于磁粉各向异性的形成。本文将为制备低成本高各向异性磁粉提供重要的指导。     

Ultra-fine grained Nd–Fe–B by high pressure reactive milling and desorption

This paper reports on the grain refinement in dynamic hydrogenation disproportionation desorption and recombination (d-HDDR) processed Nd-rich Nd₂Fe₁₄B and stoichiometric Nd₂Fe₁₄B powders using high pressure reactive milling (HPRM) followed by a subsequent desorption and recombination. In contrast to the dynamic-HDDR processed anisotropic powder with a grain size of the Nd₂Fe₁₄B phase of 300 nm, the new approach yields a further reduction of the Nd₂Fe₁₄B₁ grain size to less than 70 nm. Nd-rich Nd₂Fe₁₄B powder produced by HPRM and subsequent desorption exhibits a coercivity μ_0iH_c=1.35 T and a remanence of 0.80 T. In the stoichiometric material, the reduction of the Nd-content leads to an increase in remanence to 0.85 T. Additionally, it is demonstrated that highly anisotropic powders can also be obtained by dynamic-HDDR processing of stoichiometric Nd₂Fe₁₄B powders.     

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.     

Domain structures of Nd13Fe80B7 magnets during HDDR process

The domain structures of Nd13Fe80B7 alloy at different stages of the HDDR process have been revealed using a magnetic force microscope. In the as-cast samples, the columnar crystals with easy axis perpendicular to one another are clearly characterized by their different domain structures. For the insufficient and sufficient HD treatment, an obvious change of domain structure occurs, which is related to the variation of composition and crystalline microstructure during the HD process. And for the samples after sufficient DR processing, it is confirmed that the configuration of the columnar crystals is retained by the detected domain structures.     

Effects of additives on hydrogen absorption and desorption characteristics of Nd(Fe,Mo)12 alloys

Effects of such additives as Co, Zr, Nb or Ga on hydrogen absorption and desorption characteristics of Nd(Fe,Mo)₁₂ alloys are investigated. It is found that Zr or Nb addition increases the disproportionation temperature of Nd(Fe,Mo)₁₂ alloys, and Co or Ga addition decreases the recombined temperature of its disproportionated products. This shows that Zr or Nb addition retards the disproportionation, while Co or Ga addition is effective for improving the recombination, which is similar to the effects of the additives on the hydrogen absorption and desorption characteristics of Nd₂Fe₁₄B alloys. However, according to X-ray diffraction (XRD) investigations for the magnetic-oriented samples, the final hydrogenation disproportiontation desorption recombination (HDDR) NdFe_10.5−XM_XMo_1.5 (M=Co, Zr, Nb or Ga) products are isotropic. The effects of additives on hydrogen absorption and desorption characteristics of Nd₂Fe₁₄B and Nd(Fe,Mo)₁₂ alloys are very similar, but the magnetic anisotropy of the final two HDDR products are different. In order to investigate this, similarities and differences of the two alloy systems and their corresponding HDDR phenomena are further studied. The results show that the formation of anisotropic powders may be related to the disproportionated products and crystal growth direction of the Nd₂Fe₁₄B and Nd(Fe,Mo)₁₂ system.     

Preparation,microstructure, and magnetic properties of a nanocrystalline Nd12Fe82B6 alloy by HDDR combined with mechanical milling

Nanocrystalline Nd₁₂Fe₈₂B₆ (atomic ratio) alloy powders with Nd₂Fe₁₄B/α-Fe two-phase structure were prepared by HDDR combined with mechanical milling. The as-cast Nd₁₂Fe₈₂B₆ alloy was disproportionated via ball milling in hydrogen, and desorption–recombination was then performed. The phase and structural change due to both the milling in hydrogen and the subsequent desorption–recombination treatment was characterized by X-ray diffraction (XRD). The desorption–recombination behavior of the as-disproportionated alloy was investigated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The morphology and microstructure of the final alloy powders subject to desorption–recombination treatment were observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. The results showed that, by milling in hydrogen for 20 h, the matrix Nd₂Fe₁₄B phase of the alloy was fully disproportionated into a nano-structured mixture of Nd₂H₅, Fe₂B, and α-Fe phases with average size of about 8 nm, and that a subsequent desorption–recombination treatment at 760 °C for 30 min led to the formation of Nd₂Fe₁₄B/α-Fe two-phase nanocomposite powders with average crystallite size of 30 nm. The remanence B_r, coercivity H_c, and maximum energy product (BH)_max of such nanocrystalline Nd₁₂Fe₈₂B₆ alloy powders achieved 0.73 T, 610 kA/m, and 110.8 kJ/m³, respectively.