Effect of adding non-ferromagnetic nanoparticles to grain boundary on coercivity of sintered Nd-Fe-B magnet

In this work, we investigated the influence of additional compounds of Nd-Cu-Al, Dy-Nb-Al, Dy-Zr-Al and Nb-Cu-Al on coercivity of sintered Nd-Fe-B magnets. The additional nanoparticles with size in the range of 40–80 nm was mixed with the micrometer Nd-Fe-B powder before sintering process. The results show that the coercivity of the sintered Nd-Fe-B magnets can be improved by introducing additional nanoparticles to their grain boundaries. The improvement of the coercivity of the magnets is clearly dependent on composition and fraction of the additional compounds. While the Dy-Nb-Al, Dy-Zr-Al and Nb-Cu-Al compounds degrade the coercivity of the sintered Nd-Fe-B magnets, the Nd-Cu-Al nanoparticles considerably improve this quantity. The coercivity the sintered Nd_16.5Fe₇₇B_6.5 magnets has been enhanced about 40% by adding 3 wt% of the Dy-free compound of Nd₄₀Cu₃₀Al₃₀.     

相分布和晶粒尺寸对Nd2Fe14B/ɑ-Fe纳米复合永磁材料矫顽力的影响

本文采用统计平均方法研究了软、硬磁性晶粒尺寸及相分布对Nd2Fe14B/α-Fe纳米复合永磁材料矫顽力的影响。计算结果表明：对于单相纳米硬磁材料，磁体矫顽力随着硬磁性晶粒尺寸的减小而降低；对于软、硬两磁性相组成的Nd2Fe14B/a-Fe纳米复合永磁材料，两相的随机分布将导致磁体矫顽力随硬磁性晶粒尺寸的减小呈现极大值。本文的计算结果还表明当硬磁性晶粒尺寸大于软磁性晶粒的最佳尺寸时(15nm)，具有多层膜结构的Nd2Fe14B/a-Fe纳米复合永磁材料将比两相随机分布时具有更大的矫顽力。     

Nano-sized disorders in hard magnetic grains and their influence on magnetization reversal at artificial Nd/Nd2Fe14B interfaces

We have investigated the effect of lattice disorders near the surface of hard magnetic Nd₂Fe₁₄B grains on coercivity using artificial interfaces created by sputter depositing Nd on polished surface of Nd-Fe-B sintered magnets. The interfacial structure was manipulated by annealing the coated samples at 550 °C in vacuum with and without Ta cap. Nano-beam electron diffraction revealed a few nm thick disordered layer within the Nd₂Fe₁₄B phase at the Nd/Nd₂Fe₁₄B interface of a low coercivity sample, while a high coercivity sample showed a well-defined crystal structure of Nd₂Fe₁₄B near the NdO_x/Nd₂Fe₁₄B interface.     

High coercivity FePt-C bulk magnet processed by spark plasma sintering and hot deformation

A high coercivity of 11 kOe has been obtained in spark plasma sintered and hot-deformed Fe₅₃Pt₄₄C₃ bulk magnets. The origin for the high coercivity has been investigated using X-ray diffraction and transmission electron microscopy. The average grain size of the ordered phase was ∼100 nm, which is less than the single domain size of the L1₀-FePt phase. Fe₃C particles were found surrounding the L1₀-FePt grains, which suppress the grain growth. The L1₀ ordering is also found to increase in hot-deformed sample by annealing in a magnetic field of 10 T at 600 °C.     

Effect of the intergrain interactions on the coercivity and its angular dependence for Nd(FeCo)B sintered magnets

Effects of interactions between grains with different alignment degrees on the coercivity and its angular dependence for Nd₁₆(Fe_0.8Co_0.2)₇₈B₆ sintered magnets have been studied. The experiments show that the intrinsic coercivity _jH_c decreases with enhancing grain alignment (decreasing alignment coefficient σ), the coercivity _jH_c(θ) increases with increasing angle θ between the applied field and the texture axis of the magnets and the variation ratio is larger for the magnets with better grain alignment. The coercivity of the magnets should be determined by the critical field making the moment of individual grains reverse and the interactions between the grains. For the sintered magnets composed of the grains with μm size, the magnetostatic interaction between the grains is stronger than the exchange coupling interaction and it makes the coercivity of magnet increase with increasing alignment coefficient σ. Taking into account the intergrain interactions, the starting field theory of coercivity is in good agreement with the experimental results for Nd₁₆(Fe_0.8Co_0.2)₇₈B₆ sintered magnets.     

Microstructure of sintered ND-Fe-Ga-B magnets with Mo and MoS2 addition

The effect of Mo and MoS₂ additions on the magnetic and microstructure properties has been investigated in Nd-Fe-Ga-B sintered magnets. Coercivity can be increased by both the additions, but the MoS₂ addition provides the larger increase per Mo atom for up to 0.6 at.% Mo. Microstructure investigation reveals a new amorphous intergranular Ga rich phase. This phase forms a thin layer in the grain boundaries and leads to a wetting behavior of the grain boundary phase, therefore increasing the coercivity. Molybdenum addition in the form of MoS₂ is found to modify the Nd₂Fe₁₄B phase, rather than form new minority phases, and the coercivity enhancement of the magnet is due to the increased anisotropy field of the hard magnetic phase.     

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.     

Microstructural behavior on particle surfaces and interfaces in Sm2Fe17N3 powder compacts during low-temperature sintering

Sm₂Fe₁₇N₃ sintered compacts were prepared below 450 °C by a high-pressure current sintering technique. The coercivity of the sintered compacts decreased linearly as the sintering temperature increased. Transmission electron microscopic analyses indicated that thin Fe-rich layers containing α-Fe phases were formed just inside the initial oxide layer on the particle surfaces and interfaces in the sintered samples. The generation of α-Fe phases was supposed to cause the coercivity decrease. In addition, X-ray photoelectron spectroscopy analysis revealed that Fe₂O₃ and FeO contained in the oxide layer of the raw powder disappeared subsequent to heat treatment. These results suggested that the α-Fe phases were generated by the oxidation–reduction reaction between the initial iron oxides and the primary Sm₂Fe₁₇N₃ phase but not by thermal decomposition or exogenous oxidation during sintering. This mechanism was supported by the fact that extending the sintering time did not result in any further decrease in the coercivity.     

The magnetic properties,thermal stability and microstructure of Nd–Fe–B/Ga sintered magnets prepared by blending method

The effect of gallium added by blending method on the magnetic properties, thermal stability and microstructure of Nd_16.5Dy_16.0Fe_53.45Co_13.0B_1.05 (wt%) sintered magnets was investigated. The experimental results show that an appropriate Ga addition can markedly increase the coercivity, reduce the irreversible loss and slightly enhance the remanence. For instance, by adding 0.5 wt% Ga, the coercivity is increased from 1232 to 1819 kA/m; the irreversible loss after being exposed at 200°C for 0.5 h is reduced from above 33% to below 5%. Microstructure analyses show that the grain boundaries of the magnets with and without Ga addition are substantially different. The grain boundaries of the Ga-free magnet are meandrous. On the other hand, most of the boundaries of Ga-containing magnets are straight and smooth. These characteristics can be explained by the appearance of new phases during sintering process.     

The effects of annealing at 1000 °C for 24 h on the extrinsic properties of Pr-Fe-B and Nd-Fe-B-type sintered magnets

Recent studies have shown the effects of a post sintering heat treatment at 1000 °C for 24 h on the microstructure and magnetic properties of Pr-Fe-B/Nd-Fe-B magnets based on Nd₁₆Fe₇₆B₈ and Pr₁₆Fe₇₆B₈. In an attempt to understand the influence of environmental factors, an investigation into the effects of annealing under different degrees of vacuum for both types of sintered magnets has been carried out. The effect of annealing the Pr-Fe-B magnets at 1000 °C for 24 h resulted in a general increase in the magnetic properties, especially the intrinsic coercivity, although the degree of improvement appeared to be dependent on the initial annealing conditions (ambient pressure). Oxygen analysis of sintered and annealed magnets indicates a change in the nature of the grain boundary phases after the annealing treatment. The effect of annealing the Nd-Fe-B magnets at 1000 °C for 24 h resulted in a general decrease in the magnetic properties, especially the intrinsic coercivity.     

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.     

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.     

Magnetization reversal mechanism of anisotropic HDDR Nd2Fe14B-based magnet powder

The coercivity mechanism of anisotropic Nd₂Fe₁₄B-based magnetic powders prepared by hydrogenation–decomposition–esorption–recombination process was studied. Polarization and corresponding differential susceptibility curves of the powders in its thermally demagnetized state were measured. Microstructure and constituents of the powders were investigated by means of transmission electron microscope and scanning electron microscope with energy dispersive X-ray detector. In addition, theoretical calculation of the intrinsic coercive force of the magnetic powders was performed. It is concluded that the magnetic hardening mechanism of the powders is the pinning of domain walls at grain boundaries of the Nd₂Fe₁₄B main phase and Nd-rich phase that distributes homogeneously around some conglomerations composed of fine Nd₂Fe₁₄B grains. The coercive force of the powders is mainly determined by the pinning of domain walls by Nd-rich boundary phase.     

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.     

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.     

Effects of sintering temperature on grain growth and the complex permeability of Co0.2Ni0.3Zn0.5Fe2O4 material prepared using mechanically alloyed nanoparticles

Nanoparticle-sized Co_0.2Ni_0.3Zn_0.5Fe₂O₄ was prepared using mechanical alloying and sintering. The starting raw materials were milled in air and subsequently sintered at various temperatures from 600 to 1300 °C. The effects of sintering temperature on physical, magnetic and electrical characteristics were studied. The complex permittivity and permeability were investigated in the frequency range 10 MHz to 1.0 GHz. The results show that single phase Co_0.2Ni_0.3Zn_0.5Fe₂O₄ could not be formed during milling alone and therefore requires sintering. The crystallization of the ferrite sample increases with increasing sintering temperature; which decrease the porosity and increase the density, crystallite size and the shrinkage of the material. The maximum magnetization value of 83.1 emu/g was obtained for a sample sintered at 1200 °C, while both the retentivity and the coercivity decrease with increasing the sintering temperature. The permeability values vary with both the sintering temperature and the frequency and the absolute value of the permeability decreased after the natural resonance frequency. The real part of the permittivity was constant within the measured frequency, while the loss tangent values decreased gradually with increasing frequency.     

Effect of sintering temperature and the particle size on the structural and magnetic properties of nanocrystalline Li0.5Fe2.5O4

Sintering temperature and particle size dependent structural and magnetic properties of lithium ferrite (Li_0.5Fe_2.5O₄) were synthesized and sintered at four different temperatures ranging from 875 to 1475 K in the step of 200 K. The sample sintered at 875 K was also treated for four different sintering times ranging from 4 to 16 h. Samples sintered at 1475 K have the cubic spinel structure with a small amount of α-Fe₂O₃ (hematite) and γ-Fe₂O₃ (maghemite). The samples sintered at≤1275 K do not show hematite and maghemite phases and the crystals form the single phase spinel structure with the cation ordering on octahedral sites. Particle size of lithium ferrite is in the range of 13-45 nm, and is depend on the sintering temperature and sintering time. The saturation magnetization increased from 45 to 76 emu/g and coercivity decreases from 151 to 139 Oe with an increase in particle size. Magnetization temperature curve recorded in ZFC and FC modes in an external magnetic field of 100 Oe. Typical blocking effects are observed below about 244 K. The dielectric constant increases with an increase in sintering temperature and particle size.     

Re-exchange of Fe and Cu at the interface in sintered Nd–Fe–B magnets: A method to eliminate Fe precipitation at grain boundaries

According to the decoupling hypothesis for magnetic grains, the coercivity in sintered Nd–Fe–B magnets is increased after Cu doping, which is due to the formation of non-magnetic grain boundaries. However, this method partially fails, and ferromagnetic Fe-segregation occurs at the grain boundary. We discovered both experimentally and through calculation that the Fe content at the grain boundaries can be tuned across a wide range by introducing another element of Ag. Segregated Fe at high temperature at the grain boundary re-dissolves into Nd₂Fe₁₄B grains during annealing at low temperature. Both configurable and magnetic entropies contribute a large driving force for the formation of nonmagnetic grain boundaries. Almost zero Fe content could be achieved at the grain boundaries of sintered Nd–Fe–B magnet.     

Consolidation of hydrogenation–disproportionation–desorption–recombination processed Nd–Fe–B magnets by spark plasma sintering

We have successfully consolidated hydrogenation–disproportionation–desorption–recombination (HDDR) processed Nd–Fe–Co–Zr–B–Ga powder by spark plasma sintering (SPS). The field compacted samples were sintered at different temperatures (T_S) from 550 to 600 °C with compressive pressure of 80 MPa for 20 min. Microstructural investigations by transmission electron microscopy indicated that the sintered specimen exhibits Nd₂Fe₁₄B grains of ~300 nm with Nd-rich grain boundary phase. The optimum magnetic properties of B_r: 1.22 T, H_c: 928 kA/m, _BH_c: 600 kA/m, (BH)_max: 210 kJ/m³ were obtained in the sample sintered at 550 °C. The strategy for further improving the coercivity and remanence is discussed based on the microstructure-property relationships.     

NdFeB纳米复合永磁材料的交换耦合相互作用和有效各向异性

以Nd₂Fe₁₄B/αFe为例，采用立方体晶粒结构模型，研究了纳米复合永磁材料中不同磁性晶粒间的交换耦合相互作用和有效各向异性.纳米复合永磁材料的有效各向异性Keff等于软、硬磁性相各向异性的统计平均值，每个晶粒的各向异性由晶粒表面交换耦合部分和晶粒内部未交换耦合部分的各向异性共同确定.计算结果表明，软、硬磁性相晶粒尺寸分布显著地影响有效各向异性Keff的值.当软、硬磁性晶粒尺寸D相同时，Keff随晶粒尺寸和硬磁性相体积分数的降低而减小, 当D<20nm 时，K 关键词： 纳米复合永磁材料 交换耦合相互作用 有效各向异性 晶粒尺寸