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.

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.

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.

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.

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.

Multilayer ceramic coating for impeding corrosion of sintered NdFeB magnets

Sintered NdFeB magnets have complex microstructure that makes them susceptible to corrosion in active environments.The current paper evaluated the anticorrosion characteristics of multilayer titanium nitride ceramic coating applied through cathodic arc physical vapour deposition(CAPVD) for protection of sintered NdFeB permanent magnets.The performance of ceramic coating was compared to the electrodeposited nickel coating having a copper interlayer.Electrochemical impedance spectroscopy(EIS) and cyclic polar...

Influence of Solidiflcation Rate on Microstructures of Cast Strips and Corresponding Sintered NdFeB Magnets

The influences of solidification rate on the microstructures of cast strips and corresponding sintered NdFeB magnets were investigated. The experimental results show that the volume fraction and size of columnar grains vary with the wheel speed V, and the fraction is highest to more than 90% with 3.5μm in average width at V = 2m·s-1. The reasons for the improved magnetic performance were discussed based on the micromagnetic theory and microstructure analyses of the strips and sintered magnets. The magnetic properties of sintered NdFeB magnets made from the (Nd,Dy)13.0(Fe,Ga, Al)80.5B6.5 cast strip which was obtained at V = 2 m·s-1 are as follows: Br = 1.15 T( 11.25 kG), iHc = 2799 kA·m-1 (35.2 kOe) and (BH)max = 242 kJ·m-3(30.35 MGOe).

High Energy and High Coercivity Sintered NdFeB Magnets by Low Oxygen Process

Using ball milling and single direction pressing, we can produce high performance NdFeB sintered magnets. The oxygen content of sintered magnets can be controlled under 1500xl0^-6 and the magnetic performance can be improved by using low oxygen processing. The high preformance NdFeB sintered magnets with Br=(1.4 ± 0.2)T, iHc>796 kA/m and (BH)max=(390± 16) kJ/m^3, have been batch produced.

Hydrogen absorption of NdDyFeCoNbCuB sintered magnets

Hydrogen absorption and desorption characteristics for high coercivity NdDyFeCoNbCuB sintered bulk magnets were studied, by differential scanning calorimetry （DSC） measurement and hydrogenation kinetics measurement. The DSC measurements showed that hydrogenation of Nd-rich phase occurred in the temperature range of 40-185 ℃, hydrogenation of the tetragonal （Ф） phase in the temperature range of 185-220 ℃, as well as the disproportionation of the Ф phase that occurred in a broad temperature range from around 500 to 800 ℃. The hydrogenation kinetics measurements indicated that hydrogen absorption of the bulk magnets at 50 ℃ absorbed more hydrogen than at 150 ℃, although this procedure was slower at 50 ℃ than at 150℃. This phenomenon was discussed by means of pressure-concentration-temperature （p-c-T） diagrams.

Study on Key Techniques for Producing High Performance NdFeB Sintered Permanent Magnets

High energy products (BH) max of 365 and 310 kJ·m -3 with intrinsic coercivity iH c of 1640 kA·m -1 of NdFeB sintered magnets were produced. Some new techniques were applied, such as thin NdFeB ingot technique, narrow particle distribution on jet mill, low oxygen content control and high aligned magnetic field press. It is necessary to produce thin NdFeB ingot with fine flake crystal, narrow particle distribution, the average size of NdFeB powders less than 4.0 μm, uniform microstructure, high oriented Nd 2Fe 14B small grains, and finally high performance NdFeB sintered magnets were prepared.

Influence of misch metal content on microstructure and magnetic properties of R–Fe–B magnets sintered by dual alloy method

MM14Fe79.9B6.1/Nd13.5Fe80.5B6 magnets were fabricated by dual alloy method（MM, misch metal）. Some magnets have two Curie temperatures. Curie temperatures Tc1corresponds to the main phase which contains more La Ce, and Tc1 decreases from 276.5℃ to 256.6℃ with the content of MM increasing from 30.3 at.% to 50.6 at.%. The variation of Br with the increase of MM indicates the existence of inter-grain exchange coupling in the magnets. When MM/R ≤ 30.3 at.%,the magnetic properties can reach the level of the intrinsic coercivity Hcj≥ 7.11 kOe and the maximum energy product（BH）max≥ 41 MGOe. Compared with Nd, La and Ce are easier to diffuse to the grain boundaries in the sintering process,and this will cause the decrease of H（cj） Due to the diffusion between the grains, the atomic ratio of La, Ce, Pr, and Nd in each grain is different and the percentage of Nd in all grains is higher than that in misch metal.

Research and Develop ment of Rare Earth Per manent Magnets in China

The research and development of RE magnets in China were briefly reviewed. The research achievements of RE magnets reach international level. The intermetallic nitrides with ThMn12-type structure of RFe series which possess Chinese proprietary were prepared. The output of RE magnets has ranked second in the world. The production of RE magnets will be steadily expanding with the expiration of NdFeB patent in 2003. Some related data were also presented.

1∶7 Type Nanocrystalline SmCo_6Fe Sintered Magnet Prepared by Spark Plasma Sintering

Bulk nanocrystalline SmCo6Fe sintered magnet was prepared by Spark Plasma Sintering technique (SPS). XRD patterns show that the magnet exhibits a stable TbCu7 structure. TEM observation indicates that the microstructure of the magnet is composed of SmCo6Fe single phase grains with an average grain size of 30 nm. Magnetic measurement shows that under 9 T magnetic field, the coercivity of the magnet reaches 1.12 T; the saturation magnetization and the remanence are 1.13 and 0.67 T, respectively. The magnet has a (BH)max of 75.6 kJ·cm-3.

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.

Influence of Mean Particle Size on Magnetic Properties of Sm （ Co0.72Fe0. 15 Cu0. 1Zr0. 03 ）7.5 Sintered Magnets

The influence of mean particle size on magnetic properties ofSm （ Co0.72Fe0. 15 Cu0. 1Zr0. 03 ） 7.5 sintered magnets, prepared by the conventional powder metallurgy method, was studied. With increasing ballmilling time, mean particle size decreases, specific surface increases, and sintering temperature decreases. The optimum sintering temperature of powders fabricated by baH-milling for 5, 7, 9 and 11 h are 1225, 1225, 1215 and 1215℃ respectively. The optimum value of Br, （BH）max, Hob and Hci of Sm （ Co0.72Fe0. 15 Cu0. 1Zr0. 03 ） 7.5 sintered magnets with powders ball-milling for 9 h and sintering at 1215 ℃ can reach 0.94 T, 708.4 kA·m^-1, 171.9 kJ·m^-3 and 2276.6 kA·m^-1 respectively, and the irreversible flux loss is less than 5 % after the sample ageing at 550 ℃ for 2 h, so the temperature stability improves and the magnets may be expected to be applied in the circumstances of 550 ℃.

HD Processes in the Production of SmCo_5 Permanent Magnets

The application of ‘extreme’ hydrogen-decrepitation (HD) process using high-pressure disproportionation was extended to Sm-Co5-type-alloy. The alloy with nominal composition of Sm36Co64 was treated under 1.0～2.0 MPa H2 pressure for several hours at room temperature for decrepitation. After disproportionation were high hydrogen pressures, the bulk alloys were disproportionated into particles with a size of 200. Investigations by powder X-ray diffractometer (XRD) showed, the after HD sample crystallized in the hexagonal CaCu5-type structure. The temperature dependence of pressure analysis (TPA) curve of the SmCo5 alloy showed that the hydrogen absorption temperature was about 150 ℃. Cylindrical sintered magnets of composition Sm36Co64 were prepared using HD ball milled, isostatic pressing, vacuum sintering and subsequent heat treatment. The demagnetization curves showed that the HD processes could improve the magnetic properties and squareness factor of the SmCo5 sintered magnet.

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.

Magnetic Properties of Ga Doped Nd-Fe-B Sintered Magnets

The magnetic properties of Nd_(16)Fe_(77)B_7 and Nd_(16)Fe_((61-x))Co_(16)Ga_xB_7(x=0,1,2,4,7)have been measured.It is found that the remanent magnetization(Br),maximum energy product(BH)_(max)and the Curie temperature (T_c)decrease with the increase of Ga content.The coercive force(He)increases with the increase of Ga content when x is less than 2,but decreases when x>2.At x=2,the coercive force reaches its maximum value.It is also found in all the samples investigated that there is a linear relationship between H_c^(1/2)and T^(2/3),which can not be explained by Gaunt's wall barrier model.The temperature dependence of the calculated values of H_v and(4bf) has been discussed.

Effect of Sintering on the Magnetism and Magnetoresistance of La_(1/3)Nd_(1/3)Ca_(1/3) MnO_3

Perovskite-like bulk La_1/3Nd_1/3Ca_1/3MnO_3 is prepared by solid phase reaction method. The temperature dependence of the magnetization and the relationship between CMR effect and sintering have been studied. The CMR is up to 673.9% under 1 T applied magnetic field and 100 K temperature, and that also reaches 93.5% in 0.2 T and 100 K.