Enhanced alignment and magnetic properties of die-upset nano-crystal Nd2Fe14B magnets with Nb addition

It is difficult to obtain the crystallographic alignment for stoichiometric Nd₂Fe₁₄B alloys by applying the melt-spun and subsequent hot-pressing and hot-deformation techniques. However, the enhanced alignment and magnetic properties of die-upset nano-crystal Nd₂Fe₁₄B magnets have been obtained by Nb addition in the present paper. The magnetic properties studies show that Nb addition leads to the remarkable increase of remanence B_r and intrinsic coercivity H_ci, which is due to the improvement of c-axis texture and refinement of microstructure. Microstructure studies using transmission electron microscopy (TEM) and X-ray diffraction (XRD) reveal that Nb atoms are enriched at grain boundary and the NbFeB phase is observed with increasing Nb content. Since some Fe atoms in the Nd₂Fe₁₄B phase participate in the formation of NbFeB phase, the excessive Nd atoms may be enriched at grain boundary, which may improve the physical property of grain boundary and provide a mass transport pass for preferential growth of oriented Nd₂Fe₁₄B grains, thus leading to the enhanced alignment and magnetic properties.     

Mössbauer study of intergranular phase in Nd 8 Fe86 − x Nb x B6(x = 0, 1, 2, 3) nanocomposite magnet

Nd₈Fe_86???x Nb _x B₆ (x = 0, 1, 2, 3) nanocomposite magnet has been studied by Mössbauer spectroscopy and nanostructure observation. It was found that intergranular phase formed between α-Fe and Nd₂Fe₁₄B phase in NdFeNbB alloys plays a significant role on the magnetic properties. By the addition of Nb into Nd₈Fe₈₆B₆ composition, coercivity was found to increase by 25% due to the grain refinement of both the soft and hard magnetic phases which was decreased from 50 nm of virgin Nd₈Fe₈₆B₆ to 25 nm in Nd₈Fe₈₅Nb₁B₆ alloys. The role of Nb addition was confirmed to stabilize the Nd₂Fe₁₄B lattice preventing from thermal vibration of the corresponding sites at where Fe atoms are substituted by Nb in the Nd₂Fe₁₄B lattice. The enhanced coercivity was originated from the exchange hardening of soft and amorphous phases surrounding the hard magnetic Nd₂Fe₁₄B crystal.     

热处理对非晶态合金Nd4Fe96-xBx磁性的影响

本文研究了用单辊急冷方法制备的非晶态合金Nd₄Fe_96-xB_x的晶化,以及热处理对其硬磁性和相组成的影响,发现非晶态合金Nd₄Fe_96-xB_x的晶化温度比相同B含量的非晶态合金Fe_100-xB_x高120—190K,X射线衍射和热磁测量表明,15≤x≤25的样品晶化相是由Nd₂Fe₁₄B(T 关键词：     

Magnetic properties and phase compositions of rapidly quenched Nd4Fe96−x B x after crystallization

Permanent magnets, composition Nd₄Fe_96?x B _x (x=10–21), were made by rapid quenching followed by crystallization. The effects of B concentration and annealing time on the magnetic properties and phase compositions were studied by Mössbauer spectroscopy and magnetic measurements. The stripping method was adopted to obtain the subspectral area of each Fe phase. Optimum magnetic properties are obtained for the composition Nd₄Fe₇₇B₁₉ annealed at 670°C for 3 minutes. Then the remanence is 12.0 kGs, the intrinsic coercivity 3.2 kOe, and the maximum energy product 12.6 MGOe. The crystalline phases are Fe₃B, Nd₂Fe₁₄B and α-Fe with volume percentages of 60%, 36%, and 4%, respectively.     

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.     

Nd-Fe(Co,Nb)-B交换耦合磁体的磁性

用熔体快淬法结合热处理制备了高性能纳米复合永磁合金Nd₉Fe_85.5-xCo_xNb₁B_4.5(0≤x≤16).最佳磁性能对应的成分为Nd₉Fe_81.5Nb₁B_4.5,其永磁性能如下：最大磁能积(BH)_max＝156kJ/m³,剩磁J_r＝1.11T 关键词：     

Complete suppression of metastable phase and significant enhancement of magnetic properties of B-rich PrFeB nanocomposites prepared by devitrifying amorphous ribbons

The effect of refractory element addition on phase transformation, crystallization behavior and magnetic properties of Pr_8.5Fe_81.5B₁₀ (addition-free) and Pr_8.5Fe_81.5M₂B₁₀ (M=V, Cr, Nb, Zr, Ti) ribbons has been investigated. The annealed addition-free ribbon as well as the samples with V or Cr additions are mainly composed of the metastable Pr₂Fe₂₃B₃ phase, whereas annealed ribbons with Nb, Zr or Ti additions primarily consist of Pr₂Fe₁₄B and a minor amount of Fe₃B/boride. The complete suppression of the metastable Pr₂Fe₂₃B₃ phase due to Nb, Zr or Ti additions leads to a significant enhancement of the magnetic properties. For example, the remanence, the coercivity and the energy product are remarkably increased from 2.5 kG, 0.4 kOe and 0.2 MG Oe for the addition-free material to 9.2 kG, 4.7 kOe and 7.6 MG Oe for the specimens with Nb addition. The successful elimination of the metastable Pr₂Fe₂₃B₃ phase is believed to profit from two factors: (a) Nb, Zr or Ti atoms substitute the Pr site, comparatively increase the Pr content, and thus inhibit the nucleation of Pr-lean Pr₂Fe₂₃B₃ phases, and (b) the formation of Nb, Zr, or Ti borides consumes some part of B, which hinders the generation of the B-rich Pr₂Fe₂₃B₃ phase.     

The Mössbauer study of Nd−Fe−Co−B permanent magnetic alloys

Sintered Nd₁₇ (Fe_1?x Co_x)₇₅B₈ permanent magnetic alloys have been studied by Mössbauer effect, X-ray diffraction and electron probe micro-analysis, The results show that the alloys are composed of the tetragonal phase Nd₂(Fe,Co)₁₄B, the B-rich phase Nd₁₁₁(Fe,Co)₄B₄ and the Nd-rich phase Nd₈₀(Fe,Co)₁₉B. In the tetragonal phase, Co atoms occupy preferentially the k₂ and j₂ sites, and Fe atoms occupy randomly the k₁ site and preferentially the j₁ site while the e and c sites seem to be completely occupied by Fe atoms.     

Magnetic and structural properties of the Nd2(Fe100−x Nb x )14B system prepared by arc melting

In this work the magnetic and structural properties are investigated by Mössbauer spectrometry, Vibrating Sample Magnetometry and X-ray diffraction of Nd₂(Fe_100?x Nb _x )₁₄B powdered alloys with x?=?0, 2 and 4 prepared by arc melting. The Mössbauer spectra of the samples were fitted with several contributions from: Nd₂Fe₁₄B, α-Fe and a paramagnetic phase associated with Nd_1.1Fe₄B₄ for x?=?0 and additionally from NbFeB and Nd₂Fe₁₇ for x?=?2 and x?=?4. The relative fractions of α-Fe and Nd₂Fe₁₄B are smaller for x?=?4 than for x?=?0, indicating that the amount of these two phases is reduced with increasing Nb content, while the relative fraction of Nd₂Fe₁₇ increases. The α-Fe grain size slightly decreases while that of the Nd₂Fe₁₄B phase is increasing, when the Nb content increases. The hysteresis loops indicate that these samples behave as hard ferromagnets, with a coercive field which decreases when the Nb content increases, but with rather low remanent magnetization.     

Nd1.9M0.1Fe12Co2B,M = Ti or Hf as a material for permanent magnets

Magnetic properties (saturation magnetizations, anisotropy fields and Curie temperatures) of the alloys of the composition Nd_1.9M_0.1Fe₁₂Co₂B, with M = Ti and Hf are presented. All of the compounds crystallize in the tetragonal Nd₂Fe₁₄B structure. With substitution of Nd by Ti or Hf, the saturation moment and Curie temperature decrease, but the anisotropy fields, H_A, are found to increase significantly. Theoretical energy products are reduced from 65 to 63 MGOe when Nd is replaced by Ti or Hf to the extent of x = 0.1.     

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.     

Effect of niobium on microstructure and magnetic properties of bulk anisotropic NdFeB/α-Fe nanocomposites

Bulk anisotropic NdFeB/α-Fe nano-composites were obtained directly from alloys of Nd₁₁Dy_0.5Fe_82.4−xNb_xB_6.1 (x=0,0.5,1.0,1.5). High resolution transmission electron microscopy images showed the existence of Nb-rich amorphous grain boundary phase in the alloys with Nb doped. Field emission scanning electron microscope morphologies and X-ray diffraction patterns revealed the grain size and grain alignment of hot pressed and hot deformed nanocomposites. It was found that Nb could refine the grain size and grain texture in hot worked ribbons. Vibrating sample magnetometer results showed that the magnetic properties of the anisotropic nanocomposites were improved with increased Nb doping. The remanence, coercivity and maximum energy product of the bulk anisotropic Nd₁₁Dy_0.5Fe_80.4Nb₂B_6.1 nanocomposites were 1.04 T, 563 kA/m and 146 kJ/m³, respectively.     

Si对Nd2Fe14B四方相结构和磁性的影响

本文对Si加入Nd₂Fe₁₄B四方相后所形成的合金相的结构和磁性进行了研究。结果表明,Si加入Nd₂Fe₁₄B四方相后并不破坏它的结构(Si的含量可达B的两倍),而形成Nd₂(Fe,Si)₁₄B赝三元金属间化合物。随着Si含量的增加,晶格常数和饱和磁化强度随之减小,但居里温度则随之增加。Si的加入,并不改变Nd₂Fe₁₄B的室温各向 关键词：     

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.     

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.     

Research on the magnetic properties and crystal lattice aberrance of melt-spun Nd9Fe85−xMnxB6 (x=0–1)

Magnetic properties and crystal lattice aberrance of melt-spun Nd₉Fe_85−xMn_xB₆ (x=0,0.5,1) nanocomposite materials were investigated by DTA, XRD, EXAFS and VSM. It was found that a certain amount of manganese added to Nd₉Fe₈₅B₆ magnets can promote crystal and enhances the hard magnetic properties. The coercivity and remanence ratio increases from 4.3 kOe and 0.70 to 5.0 kOe and 0.72, respectively. The remain magnetization has not distinct reduce under the optimum annealing method. M–T shows Mn doping decreases the Curie temperature of the Nd₂Fe₁₄B phase and raises that of α-Fe phase. The origin for the enhancement of magnetic properties is not only related to the reduction of grain size which enhances the exchange coupling between grains but also to the precise crystal structure.     

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.     

Pr2Fe14(C,B)/α-(Fe,Co)型纳米晶复合磁体的结构与磁性

研究了Pr_xFe_82-x-yTi_yCo₁₀B₄C₄ (x=9—10.5;y=0, 2)纳米晶薄带的结构与磁性. 结果表明,所有薄带皆主要由2∶14∶1, 2∶17和α-(Fe, Co)三相组成. 对于y=0的合金,其内禀矫顽力随Pr含量x的增加而增加,剩磁随Pr含量x的增加而减小. 以Ti置换部分Fe (y=2),合金的磁性能得到显著提高,表现为:添加Ti后,合金的剩磁B_r基本不降低,x=10.5时合金的B_r值甚至有较明显的提高;同时添加Ti后,合金的内禀矫顽力及退磁曲线的方形度都明显改善. 当x=10.5,y=2时,合金薄带的磁性能达到最佳值为: B_r=9.6 kGs(1 Gs=10^-4 T),_iH_c =10.2 kOe(1 Oe=79.5775 A/m)和(BH)_max＝17.4 MGOe. 随着Pr含量的提高,合金中的硬磁相2 ∶14 ∶1的含量相对增加,内禀矫顽力提高;而Ti置换Fe抑制了软磁相α-(Fe, Co)在快淬和热处理过程中的优先长大,使合金中软磁相和硬磁相的晶粒尺寸及比例趋向最佳组合,交换耦合作用明显增强. 关键词： 纳米晶永磁材料 2Fe₁₄(C')" href="#">Pr₂Fe₁₄(C B) Ti添加 交换耦合     

Exchange-coupled nanoscale SmCo/NdFeB hybrid magnets

Nanoscale hybrid magnets containing SmCo₅ and Nd₂Fe₁₄B hard magnetic phases have been produced via a novel “in-one-pot” processing route. The grain size of the processed bulk composite materials is controlled below 20 nm. The refinement of the nanoscale morphology leads to effective inter-phase exchange coupling that results in single-phase like magnetic properties. Energy product of 14 MGOe was obtained in the isotropic nanocomposite magnets at room temperature. At elevated temperatures, the hybrid magnets have greatly improved thermal stability compared to the Nd₂Fe₁₄B single-phase counterpart and have substantially increased magnetization and energy products compared to the single-phase SmCo₅ counterpart.     

Fe65B22Nd9Mo4 bulk nanocomposite permanent magnets produced by crystallizing amorphous precursors

The Fe₆₅B₂₂Nd₉Mo₄ nanocomposite permanent magnets in the form of a rectangular cross sectioned rod have been prepared by annealing the amorphous precursors. The thermal behavior, structure and magnetic properties of the magnets have been investigated by differential scanning calorimetry, X-ray diffractometry, electron microscopy and magnetometry techniques. The as-cast Fe₆₅B₂₂Nd₉Mo₄ alloy showed soft magnetic properties, which changed into magnetically hard after annealing. Results provoke that the magnetic properties of the alloy are sensitive to thermal processing conditions. The optimum hard magnetic properties with a remanence (B_r) of 0.56 T, coercivity (_iH_c) of 920.7 kA/m and maximum energy product (BH)_max of 50.15 kJ/m³ were achieved after annealing the alloy at 983 K for 10 min. The good magnetic properties of Fe₆₅B₂₂Nd₉Mo₄ magnets are ascribed to the exchange coupling between the nano-scaled soft α-Fe, Fe₃B and hard Nd₂Fe₁₄B magnetic grains.