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.

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.

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.

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.

Microstructure and magnetic properties of anisotropic Nd-Fe-B magnets prepared by spark plasma sintering and hot deformation

Bulk anisotropic Nd-Fe-B magnets were prepared from hydrogen-disproportionation-desorption-recombination（HDDR） powders via spark plasma sintering（SPS） and subsequent hot deformation. The influence of sintering temperature on the structure and magnetic properties of the spark plasma sintered Nd-Fe-B magnets were studied. The remanence Br, intrinsic coercivity Hcj, and the maximum energy product（BH）max, of sintered Nd-Fe-B magnets first increase and then decrease with the increase of sintering temperature, TSPS, from 650 °C to 900 °C. The optimal magnetic properties can be obtained when TSPS is 800 °C. The Nd-Fe-B magnet sinter treated at 800 °C was subjected to further hot deformation. Compared with the starting HDDR powders or the SPS treated magnets, the hot-deformed magnets present more obvious anisotropy and possess much better magnetic properties due to the good c-axis texture formed in the deformation process. The anisotropic magnet deformed at 800 °C with 50% compression ratio has a microstructure consisting of well aligned and platelet-shaped Nd2Fe14 B grains without abnormal grain growth and exhibits excellent magnetic properties parallel to the pressing axis.

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.

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.

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).

Industrialization of High Performance Sintered NdFeB Magnets

Sintered Nd-Fe-B magnet was manufactured by advanced equipment via a SC (Strip casting) technology.It has integrative performance.

Reduction of Sensitivity to Sintering Temperature for Nd-Fe-B Magnets through Zr and Nb Additions

To reduce the sensitivity of grain growth to sintering temperature for improving property consistency of sintered Nd-Fe-B magnets, combined additions of Zr and Nb were investigated. It was found that when Zr content was increased to 0.07 at. pct, abnormal grain growth was effectively hindered even when the sintering temperature reached 1100℃. With combined additions of 0.07 at. pct Zr and 0.07 at. pct Nb, the sensitivity of grain growth to sintering temperature was greatly reduced consistency than the magnets containing no Zr and also improved. The magnets sintered at 1100℃ showed higher property Nb. In addition, the magnetic properties of magnets were also improved.

Effects and regulation mechanisms of post-sinter annealing treatment on magnetic properties and microstructures of Nd-Fe-B sintered magnets with varying boron contents

In traditional Nd-Fe-B-based sintered magnets,the composition,role of each element and microstruc-tures have been extensively investigated globally since they were invented in 1983.However,the effects of boron(B)content and post-sinter annealing(PSA)on the microstructure and magnetic properties have been least studied so far and the relative mechanisms are not yet clear.In this paper,we investigated the influence of B on the magnetic performance and microstructure of Nd-Fe-B sintered magnets origi-nally containing copper(Cu),gallium(Ga)and titanium(Ti).It is shown that the intrinsic coercivity has a substantial increment of 2.86 kOe and the remanence has a slight reduction of 0.16 kGs when B content is reduced from 0.980 wt.%to 0.900 wt.%.Moreover,there is a coercivity increment of 27.3%and 65.3%for samples with 0.980 wt.%and 0.900 wt.%B content after PSA,respectively.It is shown that the im-pacts of B content and PSA are significant and their regulation mechanisms are worthwhile to be studied systematically.Furthermore,it is revealed by microstructural analysis that high coercivity of the sample with 0.900 wt.%B after PSA results from the uniform distribution of Ga,Cu,Nd,and the formation of RE 6(Fe,M)14(RE=Pr,Nd,M=Cu,Ga)compound in triple junction phases.The dilution of Fe content in grain boundary phases(GB phases)also plays an important role.It is found out that decrease of the re-manence is mainly due to reduction of the matrix phase and c-axis alignment degree.In this study,we explored a new path to develop Nd-Fe-B-based sintered magnets with high comprehensive properties by novel approaches through varying B content,PSA technique and co-adding trace elements.

Temperature stability and microstructure of ultra-high intrinsic coercivity Nd-Fe-B magnets

The variations of intrinsic coercivity and remanence of sintered Nd-Fe-B magnets with ultra-high intrinsic coercivity were investigated. The results showed that the intrinsic coercivity and remanence declined simultaneously with increasing temperature, but the squareness of the magnets has hardly been changed. The temperature coefficients of remanence （α） and coercivity （β） for the magnets were calculated by two different methods, and the variations of the temperature coefficients and the microstructure of sintered Nd-Fe-B magnets were analyzed. The temperature coefficients of remanence （α） and coercivity （β） for the sintered magnets are very small, and the existence of fine microstructure is necessary to obtain sintered Nd-Fe-B magnets with ultra-high intrinsic coercivity.

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.

Effect of yttrium substitution on magnetic properties and service performances of Nd-Fe-B sintered magnets

We successfully fabricated partial Y substituted NdY-Fe-B magnets with nominal compositions of(Nd_(1-x)Y_(x))_(13.80)Fe_(ba1)Al_(0.24)Cu_(0.1)B_(6.04)(at%,x=0,0.1,0.2,0.3,0.4) by powder metallurgy process and the magnetic properties as well as service performances of the magnets were also systematically investigated.The phase constituents of the magnets have no obvious variation within the whole range of Y content,while the main phase grains form in-situ core-shell structure where Y gathers in the core and Nd mainly distributes in the shell.Compared with pure Nd-Fe-B magnets,the magnetic performances of Y substituted magnets slightly decrease on account of the poor intrinsic magnetic properties of Y_(2)Fe_(14)B.Fortunately,the μ_(O)M_(r),μ_(O)H_(cj) and(BH)_(max) of the 20 at% Y magnet still remain at a high level of 1.325 kG,1.173 kOe and 342.884 kj/m^(3),which approaches the performances of commercial N45-grade magnet.The service performances of Y substituted magnets indicate that though the surface corrosion products and Vickers hardness of the NdY-Fe-B magnets increase to a certain extent compared to Nd-Fe-B,the magnets with Y substitution still display relatively good service performances.Therefore,on the basis of sacrificing little partial magnetic and service performances,Y substituted Nd can still prepare NdY-Fe-B medium-grade magnets.By this way,we achieve the balanced utilization of rare earth resources,which has significant meanings for the industry and scientific research.

Short-process recycling of Nd-Fe-B sintered magnet sludge wastes:Challenges and approaches

Nd-Fe-B sintered magnet sludge wastes are one kind of typical commodity of recyclable rare-earth permanent magnet resources,and recycling such kind of wastes with economical and environmentally friendly techniques is crucial to the sustainable rare-earth industry.However,the current multistage wet process recycling technique for the sludge wastes involves high fabrication cost,excessive energy consumption,and heavy environmental burden.Therefore,short-process recycling techniques for Nd-Fe-B sintered magnet wastes have drawn increasing attention in the past decades.In this paper,we review recent efforts into short-process recycling Nd-Fe-B sintered magnet sludge wastes with emphasis on in-situ recycling techniques.

Improvement of microstructure and coercivity for Nd-Fe-B sintered magnets by boundary introducing low melting point alloys

Different from the grain boundary diffusion process(GBDP),which is suitable for modifying thin magnet,a green-pressing agents permeation process(GAPP)that uses low melting point alloys was applied to the Nd-Fe-B green compact with a thickness over 15 mm to reconstruct the boundary microstructure of a sintered Nd-Fe-B magnet.The coercivity increases from 12.3 kOe for the sample free of Pr80Al20 to16.8 kOe for the sample with 2 wt%Pr80Al20.By further increasing the Pr80Al20 content to 3 wt%,the coercivity increases slightly,but the remanence and Hk/Hcj deteriorate obviously.The optimal comprehensive properties of Hcj=16.8 kOe,Br=13.4 kG and Hk/Hcj=0.975 are obtained at 2 wt%Pr80Al20,since matrix phase grains are separated by relatively continuous thin grain boundary layers,which weaken the magnetic coupling between adjacent grains.The coercivities of the samples from the GAPP that use2 wt%Pr80Al20,Pr70Al30 and Pr60Tb20Al20 alloys,respectively,can be enhanced to a large extent.However,the coercivity of the magnet reconstructed with Pr80Al20 is lower than that of the sample with Pr60Tb20Al20 but is higher than that of the sample reconstructed with Pr70Cu30 alloy.Moreover,the coercivity of the sample from the GAPP using 2 wt%Pr80Al20 is much higher than that of the sample from the GBDP,which is due to a nearly uniform boundary microstructure from the surface to the interior of the thick magnet from the GAPP,thus providing new insights into the fabrication of thick and bulky permanent magnets with high coercivity.

Recycled Nd-Fe-B sintered magnets prepared from sludges by calcium reduction-diffusion process

Environmental friendly recycling process for Nd-Fe-B sintered magnet sludges generated in the manufacturing process, which contain large amount of rare earth, including Nd, Pr and Dy, is badly needed so far. In present study, we have developed an effective route to obtain recycled sintered magnets from Nd-Fe-B sintered magnet sludges by calcium reduction-diffusion(RD) process. Compared to conventional recycling process, our research is focused on recovering most of the useful elements, including Nd, Pr, Dy, Co, and Fe together instead of just rare earth elements. To improve the recycling efficiency and reduce pollution, the co-precipitating parameters were simulated and calculated using MATLAB software. Most of useful elements were recovered by a co-precipitation method, and the obtained composite powders were then directly fabricated as recycled Nd-Fe-B powders by a calcium reduction-diffusion(RD) method. The recovery rates are 98%, 99%, 99%, 93%, and 99%, for Nd, Pr, Dy, Co, and Fe, respectively. The amount of useful elements contained in the recovered composite powders is greater than99.71 wt%. The process of RD for synthesizing NdFeB and subsequently removing CaO was thoroughly investigated. Furthermore, the recycled Nd-Fe-B magnet exhibits a remanence of 1.1 T, a coercivity of1053 kA/m, and an energy product of 235.6 kJ/m~3, respectively, indicating that recycled Nd-Fe-B sintered magnet was successfully recovered from the severely contaminated sludges via an effective recycling route.

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.

Effects of Nd-Ga intergranular addition on microstructure and magnetic properties of heavy-rare-earth-free Nd-Fe-B sintered magnets

In this study,we propose an approach of grain boundary modification that can significantly increase the coercivity of the B-lean Nd-Fe-B sintered magnets by intergranular addition of Nd-Ga.The coercivity is substantially enhanced from 1.51 to 2.04 T through optimizing the microstructure and adjusting the phase composition for the grain boundary phase in the annealed magnets.The matrix grains are covered by a continuous thin grain boundary phase accompanying the formation of intermetallic Nd_(6)Fe_(13)Ga phases.The analysis of magnetic behaviors above Curie temperature confirms that the grain boundary phase of annealed Nd-Ga doped magnets appears to be non-ferromagnetic,facilitating the intergrain exchange decoupling.Microstructure observation in grain boundary area indicates that some surface of the matrix grain is dissolved in the formation process of the Nd_(6)Fe_(13)Ga phase.It gives rise to a decrease in the proportion of matrix grains and saturation magnetization of the magnet.The detailed relationship between magnetic properties and microstructure is discussed based on these results.

Extraordinary simultaneous enhancement of the coercivity and remanence of dual alloy HRE-free Nd-Fe-B sintered magnets by post-sinter annealing

Post-sinter annealing process plays an important role in the microstructures and magnetic properties of the Nd-Fe-B sintered magnets.In this paper,systematically investigated are the magnetic properties and microstructures of the as-sintered and post-sinter annealed Nd-Fe-B magnets with Pr-Fe-Ga boundary addition.Two choice consecutive annealing methods are adopted at high and low temperatures,namely the 1 st annealing at 880℃ for 2 h and then the 2^(nd) annealing at 440℃ for 3 h.It is exceptional to find out that both the remanence and coercivity are improved after 2^(nd) annealing process for this type of magnet.The coercivity is hugely increased from 10.09 kOe for the as-sintered sample to 17.19 kOe for the 2^(nd) annealed magnet,with a significant increment of 70.37%in coercivity.The extraordinary magnetic properties of B_(r)=14.44 kGs,H_(cj)=17.19 kOe and(BH)_(max)=51.08 MGOe are obtained for the designated Nd-Fe-B sintered magnets without heavy rare earth(HRE)elements manufactured by dual alloy method.The Curie temperature is monotonically decreased from 634 K to 602 K while the c-axis alignment degree is optimized after annealing.Microstructural observation and analysis indicate that the elemental distribution patterns are altered after the 2^(nd) annealing.The diffusion of the aggregate(Pr,Nd,Cu,Ga)-rich phase from triple junctions into the grain boundary regions is ascribed to the formation of thin and continuous grain boundary layer,which is critical to improve the microstructures and magnetic properties.