Effect of TbF_(3)diffusion on the demagnetization behavior and domain evolution of sintered Nd-Fe-B magnets by electrophoretic deposition

We studied the magnetic properties and domain evolution of annealed and TbF3-diffused sintered Nd-Fe-B magnets using the electrophoretic deposition method.After TbF_(3)diffusion,the coercivity increased significantly by 9.9 kOe and microstructural analysis suggested that Tb favored the formation of the(Nd,Tb)_(2)Fe_(14)B shell phase in the outer region of the matrix grains.The first magnetization reversal and the dynamic successive domain propagation process were detected with a magneto-optical Kerr microscope.For the TbF_(3)-diffused magnet,the magnetization reversal appeared at a larger applied field and the degree of simultaneous magnetization reversal decreased compared with an annealed magnet.During demagnetization after full magnetization,the occurrence of domain wall motion(DWM)in the reproduced multi-domain regions was observed by the step method.The maximum polarization change resulting from the reproduced DWM was inversely related to the coercivity.The increased coercivity for the diffused magnet was mainly attributed to the more difficult nucleation of the magnetic reversed region owing to the improved magneto-crystalline anisotropy field as a result of Tb diffusion.

MAGNETIZATION BEHAVIOR IN SINTERED Nd-Fe-B MAGNETS

Magnetization and demagnetization curves and hysteresis loops applied different magnetizing.fields in sintered Nd-Fe-B and Nd-Dy-Fe-B magnets from thermally demagnetized and dc field-demagnetized states were investigated at temperatures of up to 150℃.The first-quadrant remagnetization curves and the curves of coercive forces _MH_C versus rernagnetizing fietds H_m from dc field-demagnetized state at room temperature show a step around magnetizing field as absolute value of the maximum intrinsic coercivity.The steps of _MH_C-H_m curves shifted to lower remagnetizing fields and the shapes of magnetization curves changed from step type to precipitous type when temperature went up to 100～150℃ or after the specimen was thermally demagnetized at a temperature higher than the Curie temperature.The steep rise of knee coereivity with increasing magnetizing field is behind that of _MH_C.Note that the magnetic hardening in sintered Nd-Fe-B magnets is controlled by pinning of domain walls.

Grain Growth Behavior in Sintered Nd-Fe-B Magnets

The Nd2Fe14B grain growth behavior in sintered Nd-Fe-B magnets was quantitatively described.The effects of sintering temperature and time,and alloy powder size and its distribution on grain growth process were analyzed.Hence,possible grain growth mechanisms in these magnets were qualitatively discussed.The Nd2Fe14B grain growth proceeded at quite a high rate in the initial 0~1 h of sintering and from then onwards the grain growth rate decreased.A large average particle size or a wide particle size distribution of initial alloy powders was found to remarkably accelerate the grain growth process and even result in the occurrence of abnormal grain growth.On the basis of experimental results,two grain growth mechanisms were considered to operate during sintering of Nd-Fe-B magnets,that is,dissolution and re-precipitation of Nd2Fe14B particles,and Nd2Fe14B particle growth by coalescence.It was believed that Nd2Fe14B particle growth by coalescence not only produced a large average grain size and a wide grain size distribution,but also was the fundamental reason for the formation of abnormally large grains in the microstructure of sintered Nd-Fe-B magnets.

Effect of annealing temperature on magnetic properties of a sintered Nd-Fe-B magnet after grain boundary diffusion with Dy_(70)Cu_(30) alloy

Grain boundary diffusion process(GBDP)has been developed as an effective approach to increase the coercivity of sintered Nd-Fe-B magnets by regulating the compositions and phase distributions near grain boundaries.This work aims to explore how to select the optimum annealing temperature after GBDP.In this work GBDP was performed on a sintered Nd-Fe-B magnet using Dy_(70)Cu_(30) alloy.After GBDP the low eutectic temperature of the grain boundary phases decreases from the initial 492 to 451℃.The magnetic property dependent on different annealing temperatures near the low eutectic temperature was studied.The magnetic properties,especially the squareness factor of demagnetization curve show a strong dependence on the annealing temperature.After GBDP the optimal magnetic properties can be obtained after annealing just above the low eutectic temperature of the grain boundary phases.The mechanism is discussed based on the microstructure analysis.

Optimization of core-shell structure distribution in sintered Nd-Fe-B magnets by titanium addition

In view of the uneven distribution of the core-shell structure of sintered Nd-Fe-B magnets after grain boundary diffusion,this study proposes to use high-melting-point and reactive element titanium(Ti)as an additive to increase the diffusion channels and to enhance the diffusion of heavy rare earth elements along the grain boundary phase.By adding Ti element,the diffusion depth and hence the intrinsic coercivity of magnets are increased significantly.The addition of Ti increases the coercivity at two stages:initially from 16.07 to 16.29 kOe by addition effect,and then from 16.29 to 25.16 kOe by facilitating the diffusion of Tb element.The formation of TiB_(2) phase improves the periodic arrangement of the crystal structure in the surroundings of the grain boundary phase and enhances its activity.The improved grain boundary diffusion and better core-shell structure distribution provide a theoretical guidance fo r solving the problem of diffusion depth in bulk magnets.

Magnetic properties and microstructures of terbium coated and grain boundary diffusion treated sintered Nd-Fe-B magnets by magnetron sputtering

Tb coating on the surface of commercial sintered Nd-Fe-B magnet was prepared by DC magnetron sputtering.The secondary heat treatment was used to regulate the microstructure for the enhancement of coercivity,namely diffusion treatment and annealing treatment.The coercivity increases significantly from 18.3 to 28.0 kOe,the remanence decreases slightly from 14.1 to 14.0 kGs,and the comprehensive magnetic properties are higher than 75(Hcj+(BH)_(max)=76.7).SEM results indicate that,on the one hand,950℃is the optimal diffusion temperature.Lower diffusion temperature results in insufficient diffusion of Tb element.Higher diffusion temperature can lead to the main phase grain growth,the decrease of Nd-rich phase,and forming holes in the magnet.On the other hand,500℃is the optimal annealing temperature.Lower annealing temperature can result in the reduction of Nd-rich phase.Higher annealing temperature can generate the non-defined Nd-rich thin layer between grains.

Toward understanding the microstructure characteristics,phase selection and magnetic properties of laser additive manufactured Nd-Fe-B permanent magnets

Nd-Fe-B permanent magnets play a crucial role in energy conversion and electronic devices.The essential magnetic properties of Nd-Fe-B magnets,particularly coercivity and remanent magnetization,are significantly infuenced by the phase characteristics and microstructure.In this work,Nd-Fe-B magnets were manufactured using vacuum induction melting(VIM),laser directed energy deposition(LDED)and laser powder bed fusion(LPBF)technologies.Themicrostructure evolution and phase selection of Nd-Fe-B magnets were then clarified in detail.The results indicated that the solidification velocity(V)and cooling rate(R)are key factors in the phase selection.In terms of the VIM-casting Nd-Fe-B magnet,a large volume fraction of theα-Fe soft magnetic phase(39.7 vol.%)and Nd2Fe17Bxmetastable phase(34.7 vol.%)areformed due to the low R(2.3×10-1?C s-1),whereas only a minor fraction of the Nd2Fe14B hard magnetic phase(5.15 vol.%)is presented.For the LDED-processed Nd-Fe-B deposit,although the Nd2Fe14B hard magnetic phase also had a low value(3.4 vol.%)as the values of V(<10-2m s-1)and R(5.06×103?C s-1)increased,part of theα-Fe soft magnetic phase(31.7vol.%)is suppressed,and a higher volume of Nd2Fe17Bxmetastable phases(47.5 vol.%)areformed.As a result,both the VIM-casting and LDED-processed Nd-Fe-B deposits exhibited poor magnetic properties.In contrast,employing the high values of V(>10-2m s-1)and R(1.45×106?C s-1)in the LPBF process resulted in the substantial formation of the Nd2Fe14B hard magnetic phase(55.8 vol.%)directly from the liquid,while theα-Fe soft magnetic phase and Nd2Fe17Bxmetastable phase precipitation are suppressed in the LPBF-processed Nd-Fe-B magnet.Additionally,crystallographic texture analysis reveals that the LPBF-processedNd-Fe-B magnets exhibit isotropic magnetic characteristics.Consequently,the LPBF-processed Nd-Fe-B deposit,exhibiting a coercivity of 656 k A m-1,remanence of 0.79 T and maximum energy product of 71.5 k J m-3,achieved an acceptable magnetic performance,comparable to other additive manufacturing processed Nd-Fe-B magnets from MQP(Nd-lean)Nd-Fe-Bpowder.

Statistical model of magnetization reversal in Nd-Fe-B sintered magnets

Statistical model of magnetization reversal was used to simulate the magnetization reversal behavior in the sintered Nd-Fe-B magnets with double grain-size distributions due to the abnormal grain growth (AGG). The magnetic properties and mechanical properties due to the formation of AGG grains in Nd-Fe-B sintered magnets were tested. The results show that the magnetic properties, especially the rectangularity were severely deteriorated after the formation of the AGG grains and a step was shown on the demagnetization curve, and the occurrence of AGG may account for the poor rectangularity and existence of the step on demagnetization curve according to the statistical model of magnetization reversal. The fracture toughness and bending strength are lowered because of the stress concentration in the AGG grains. The SEM images show that the formation of AGG grains is caused by the solid sintering due to the absence of RE-rich phase. Statistical model of magnetization reversal can qualitative by explain the dependence of the magnetization reversal behavior on the grain size in the Nd-Fe-B sintered magnets.

Thermal expansion behavior of sintered Nd–Fe–B magnets with different Co contents and orientations

The thermal expansion behavior of sintered Nd–Fe–B magnets is a crucial parameter for production and application.However, this aspect has not been thoroughly investigated. In this study, three different sintered Nd–Fe–B magnets with varying Co content(Co = 0, 6, 12 wt%) were prepared using the conventional powder metallurgy method, and four magnets oriented under different magnetic fields were prepared to compare. The thermal expansion behavior for the magnets was investigated using a linear thermal dilatometry in the temperature range of 20℃–500℃. It was found that, the coefficient of thermal expansion(CTE) increases with the increase of Co contents, while the anisotropy of thermal expansion decreases.The introduction of Co leads to continuous changes from negative to positive thermal expansion in the vertically oriented direction, which is important for the development of zero thermal expansion magnets. The thermal expansion of nonoriented magnets was found to be isotropic. Additionally, the anisotropy of thermal expansion increases with the increase of orientation degree. These results have important implications for the development of sintered Nd–Fe–B with controllable CTE.

Optimization of the grain boundary diffusion process by doping gallium and zirconium in Nd–Fe–B sintered magnets

As the channel for grain boundary diffusion(GBD)in Nd–Fe–B magnets,grain boundary(GB)phases have a very important effect on GBD.As doping elements that are commonly used to regulate the GB phases in Nd–Fe–B sintered magnets,the influences of Ga and Zr on GBD were investigated in this work.The results show that the Zr-doped magnet has the highest coercivity increment(7.97 kOe)by GBD,which is almost twice that of the Ga-doped magnet(4.32 kOe)and the magnet without Ga and Zr(3.24 kOe).Microstructure analysis shows that ZrB_(2)formed in the Zr-doped magnet plays a key role in increasing the diffusion depth.A continuous diffusion channel in the magnet can form because of the presence of ZrB_(2).ZrB_(2)can also increase the defect concentration in GB phases,which can facilitate GBD.Although Ga can also improve the diffusion depth,its effect is not very obvious.The micromagnetic simulation based on the experimental results also proves that the distribution of Tb in the Zr-doped magnet after GBD is beneficial to coercivity.This study reveals that the doping elements Ga and Zr in Nd–Fe–B play an important role in GBD,and could provide a new perspective for researchers to improve the effects of GBD.

Electrochemical Corrosion Behavior of Nd-Fe-B Sintered Magnets in Different Acid Solutions

Electrochemical corrosion behavior of Nd-Fe-B sintered magnets in nitric acid, hydrochloric acid, sulfuric acid, phosphate acid and in oxalic acid was studied. Potentiodynamic polarization curves and immersion time dependence of corrosion rates of Nd-Fe-B sintered magnets in different acid solutions were tested. Microstructures of corroded Nd-Fe-B sintered magnets were investigated by means of SEM and AFM. The results indicate that in strong acid solutions of similar hydrogen ion concentration, the corrosion current increases in the order of HCl 〉 H3SO4 〉 HNO3 solution and Nd-Fe-B sintered magnets are passivated in phosphate acid and oxalic acid. Within 25 min, the corrosion rates of Nd-Fe-B sintered magnets in H2SO4 and H3PO4 solutions show a declining trend with immersion time, while in HNO3 and HCl solutions the corrosion rates are rising. And in H2C2O4 solution, weight of the magnets increases. The brim of Nd-Fe-B sintered magnets is corroded rather seriously and the size of the magnets changed greatly in nitric acid. The surfaces of the corroded magnets in the above mentioned acid solutions are all coarse.

Recycle for Sludge Scrap of Nd-Fe-B Sintered Magnet as Isotropic Bonded Magnet

The reduction diffusion method was performed for the sludge scrap of Nd-Fe-B sintered magnets with adding Ca metal to recover the oxidized Nd-Fe-B phase. After washing the resultant powders to remove Ca metal component, the powders obtained were recycled as an isotropic magnetic powder by the melt spinning method. The magnetic properties of powders as recycled were inferior, especially for the coercivity value, due to the deletion of rare earth metals during the washing process. The adjustment of metal composition, i.e., the addition of Nd metal, at the melt spinning process improved the magnetic properties to be B r=～0.75 T, H cj=～0.93 mA·m -1, and (BH) max=～91 kJ·m -3. The magnetic properties of the bonded magnets prepared from the composition-adjusted powders were B r=～0.66 T, H cj=～0.92 mA·m -1, and (BH) max=～70 kJ·m -3, which are approximately comparable to the commercially available MQPB boned one (B r=～0.73 T, H cj=～0.79 mA·m -1, and (BH) max=～86 kJ·m -3).

Microstructural investigation of Nd-rich phase in sintered Nd-Fe-B magnets through electron microscopy

The distribution, morphologies and structures of intergranular Nd-rich phase in sintered Nd-Fe-B magnets were studied through electron microscopy. Backscattered electron （BSE） imaging revealed that Nd-rich particles with various morphologies and sizes were randomly distributed at the grain boundaries and the triple junctions of the tetragonal Nd2FelnB matrix. Through selected area electron diffraction （SAED） analysis under a systematic tilting condition, most intergranular Nd-rich phase particles, with sizes ranging from hundreds of nanometres to several micrometres, were identified as face-centred cubic （FCC） structure. Such particles possessed several approximate orientation relationships with their adjacent Nd2FelaB matrix grains, such as （002）Nd2Fe14B/ （200）FCC_Nd-rieh [120] Nd2Fe14B//[001]FCC Nd-fich, （002）Nd2Fe14B//（220）FCC_Nd-rich [110] Nd2Fe14B//[l12]FCC_Nd-rich, as well as （011）Nd2Fe14B// （13 1 ）rcc Nd-rich [111 ] Nd2Fe14B//[ 114]FCC Nd_rich, which could be attributed to minimising interracial energy. The combination of high- resolution electron microscopy with energy-dispersive X-ray spectroscopy revealed the internal inhomogeneous nature of Nd-rich phases. The large lattice distortion and nanoscale-ordered structures within a single Nd2rich grain were observed.

Microstructure and magnetic properties of sintered Nd-Fe-B magnets with Ce substitution for Nd by intergranular-alloy method

Aiming at the comprehensive utilization of the rare-earth resources and the preparation of the high-performance low-cost Nd-Fe-B magnets,sintered magnets with different Ce substitution amounts of 17.2 wt%,24.8 wt%and 31.8 wt%were prepared by intergranularalloy method.The influence of substitution of Ce for Nd on their microstructure and magnetic properties in this work was detailedly investigated.The results indicated that the remanence(Br)and the maximum energy product((BH)max)of the sintered magnets decreased monotonic ally with the increase in Ce substitution.However,the obvious enhancement of coercivity(Hcj)was also observed,which was mainly due to the improvement of microstructure and the smooth,continuous grain boundary(GB).It can be found that a reasonable Ce substitution of 24.8 wt%for the sintered magnets could promote the refinement of microstructure,leading to the realization of superior magnetic properties.It is expected that the investigations could be beneficial to offer a feasible method for preparing the high-performance low-cost Ce-doped magnets.

Regeneration of waste sintered Nd-Fe-B magnets to fabricate anisotropic bonded magnets

The waste sintered Nd-Fe-B magnets were regenerated as magnetic powders via manually crushing （MC） or hydrogen decrepitation （HD） to fabricate anisotropic bonded magnets. Effect of size distribution on the magnetic properties of the regenerated magnetic MC and HD powders was investigated. For the MC powders, as the particle size decreased, the remanence （Br） increased first, and then decreased again, while the coercivity （Hci） dropped monotonically. The powders with particle size in the range of 200-450μm possessed the best magnetic properties ofBr of 1.22 T and Hci of 875.6 kAJm. The corresponding bonded magnet exhibited magnetic properties ofBr of 0.838 T, Hci of 940.9 kA/m, and （BH）max of 91.4 kJ/m^3, respectively. On the other hand, the liD powders with particle size range of 200-450 μm bore the best magnetic properties Of Br of 1.24 T and Hci of 860.4 kA/m. Compared with magnetic properties of the waste magnet, the powders retained 93.9% of Br and 70.0% of Hci, respectively. The bonded magnet produced from HD powders possessed Br of 0.9 T, Hci of 841.4 kA/m, and （BH）max of 111.6 kJ/m^3, indicating its good potential in practical applications.

An Efficient Process for Recycling Nd-Fe-B Sludge as High-Performance Sintered Magnets

Given the increasing concern regarding the global decline in rare earth reserves and the environmental burden from current wet-process recycling techniques,it is urgent to develop an efficient recycling technique for leftover sludge from the manufacturing process of neodymium-iron-boron(Nd-Fe-B)sintered magnets.In the present study,centerless grinding sludge from the Nd-Fe-B sintered magnet machining process was selected as the starting material.The sludge was subjected to a reduction-diffusion(RD)process in order to synthesize recycled neodymium magnet(Nd2Fe14B)powder;during this process,most of the valuable elements,including neodymium(Nd),praseodymium(Pr),gadolinium(Gd),dysprosium(Dy),holmium(Ho),and cobalt(Co),were recovered simultaneously.Calcium chloride(CaCl2)powder with a lower melting point was introduced into the RD process to reduce recycling cost and improve recycling efficiency.The mechanism of the reactions was investigated systematically by adjusting the reaction temperature and calcium/sludge weight ratio.It was found that single-phase Nd2Fe14B particles with good crystallinity were obtained when the calcium weight ratio(calcium/sludge)and reaction temperature were 40 wt% and 1050℃,respectively.The recovered Nd2Fe14B particles were blended with 37.7 wt% Nd4Fe14B powder to fabricate Nd-Fe-B sintered magnets with a remanence of 12.1 kG(1 G=1×10^-4T),and a coercivity of 14.6 kOe(1 Oe=79.6A·m^-1),resulting in an energy product of 34.5 MGOe.This recycling route promises a great advantage in recycling efficiency as well as in cost.

Corrosion prevention of sintered Nd-Fe-B magnet by a phosphate chemical conversion treatment

The corrosion-resistant coating formed on the surface of sintered Nd-Fe-B magnet by a phosphate chemical conversion(PCC)treatment was studied.The morphology,phase composition and thickness of the coating were investigated by field emission scanning electron microscopy(FE-SEM),energy-dispersive spectrometer(EDS),Fourier transform infrared(FTIR)spectrometer and coating thickness gauge.The corrosion behaviour of the phosphated magnet was evaluated by copper sulphate spot test,neutral salt spray test and electrochemical potentiodynamic polarization experiment.The magnetic properties of the phosphated magnet were also tested.The experimental results show that the phosphate coating has such characteristics as dense granular growth,uniform distribution and thickness range of 10-18μm.The corrosion resistance of the magnet is significantly improved by phosphate coating without losing magnetic properties.Therefore,this highly efficient PCC was a good way for increasing the corrosion resistance of the sintered Nd-Fe-B magnets.

Effect of optimal aging treatment on magnetic performance and mechanical properties of sintered Nd-Fe-B permanent magnets

The magnetic performance and mechanical properties including hardness, brittleness, fracture toughness and strength characteristics of the as-sintered and the optimal aged Nd-Fe-B magnets were examined in this work. A new method of Vickers hardness indentation combined with acoustic emission was used to test the brittleness of the magnets.The results show that the magnetic properties of the magnets could be improved through aging treatment, especially the intrinsic coercive force. But it is accompanied by a decrease of strength and fracture toughness. Theoretical calculation confirms that acoustic emission energy accumulated count value could be used to characterize the material brittleness. The bending fracture morphologies of the as-sintered and the optimal aged Nd Fe B magnets were investigated with the emphasis on the relationship between mechanical properties and microstructure using a field emission scanning electron microscopy(FE-SEM). The research results indicate that the intergranular fracture is the primary fracture mechanism for both as-sintered and optimal aged Nd Fe B magnets. Aging treatment changes the morphology and distribution of the Nd-rich phases, reducing the sliding resistance between Nd_2Fe_(14)B main crystal grains and lowers the grain boundary strength, which is the main reason for the strength and fracture toughness decrease of the aged Nd-Fe-B magnets.

Magnetic Properties and Thermal Stability of Sintered Nd-Fe-B Magnet with Dy-Ni Additive

A sintered（Nd_（0.8）Pr_（0.2））_（30.7）FebalB_（0.98）Cu_（0.2） magnet with 3% intergranular Dy_（85）Ni_（15） additive is prepared to study the magnetic properties and thermal stability of the Nd-Fe-B magnet. The results show that the magnet with or without additive obtains its optimum comprehensive magnetic properties at the sintering temperature of 1 030 ℃ and 1 040 ℃, respectively. The maximum coercivity of the magnet with additive reaches 15.16 k Oe, while that of the magnet without additive is just 11.88 k Oe. Further investigation on microstructure indicates that the grains of the magnet with additive form a modified ＂core shell＂ structure. Adding Dy_（85）Ni_（15） can significantly enhance the coercivity of Nd-Fe-B magnet and thus decrease its coercivity temperature coefficient.

Homogeneity of H_(cj) in Sintered Bulk Nd-Fe-B Magnets

High performance magnets not only have high magnetic properties, but also have good homogeneity. The homogeneous of Nd14.2DyxAl0.8Cu0.1B6.2Febal. bulk magnets was studied. The sizes of the samples produced by conventional sintering process were 53×50.5×25.3/40.2/50.4/61.0 mm. The magnetic character and microstructure of the samples were determined by NIM-10000H hysteresigraph, optical metaloscope, and SEM respectively. The results show that the Hcj reduces with increasing C content at the same process parameters. And the Hcj shows dependence not only on the ageing processing but also on the size of the bulk and loading capacity etc. The Hcj increases with prolonging ageing time and the ageing time should be different with different size of the bulk. With the increase of the loading capacity, the Hcj reduces promptly and is very inhomogeneous. The microstructure of the samples shows that the grain of the hard magnetic phase is finer and the neodymium-rich boundary is distributed homogeneously with prolonging ageing time. And so is the sample in a small amount of the bulks.