Effects of terbium sulfide addition on magnetic properties,microstructure and thermal stability of sintered Nd-Fe--B magnets

To increase coercivity and thermal stability of sintered Nd–Fe–B magnets for high-temperature applications, a novel terbium sulfide powder is added into(Pr_(0.25)Nd_(0.75))_(30.6)Cu_(0.15)Fe_(bal)B_1(wt.%) basic magnets. The effects of the addition of terbium sulfide on magnetic properties, microstructure, and thermal stability of sintered Nd–Fe–B magnets are investigated.The experimental results show that by adding 3 wt.% Tb_2S_3, the coercivity of the magnet is remarkably increased by about 54% without a considerable reduction in remanence and maximum energy product. By means of the electron probe microanalyzer(EPMA) technology, it is observed that Tb is mainly present in the outer region of 2:14:1 matrix grains and forms a well-developed Tb-shell phase, resulting in enhancement of HA, which accounts for the coercivity enhancement.Moreover, compared with Tb_2S_3-free magnets, the reversible temperature coefficients of remanence(α) and coercivity(β) and the irreversible flux loss of magnetic flow(hirr) values of Tb_2S_3-added magnets are improved, indicating that the thermal stability of the magnets is also effectively improved.     

Effects of post-sinter annealing on microstructure and magnetic properties of Nd–Fe–B sintered magnets with Nd–Ga intergranular addition

We investigate the effects of post-sinter annealing on the microstructure and magnetic properties in B-lean Nd–Fe–B sintered magnets with different quantities of Nd–Ga intergranular additions. The magnet with fewer Nd–Ga additions can enhance 0.2 T in coercivity, with its remanences nearly unchanged after annealing. With the further increase of the Nd–Ga addition, the annealing process leads coercivity to increase 0.4 T, accompanied by a slight decrease of remanence. With the Nd–Ga addition further increasing and after annealing, however, the increase of coercivity is basically constant and the change of remanence is reduced. Microstructure observation indicates that the matrix grains are covered by continuous thin grain boundary phase in the magnets with an appropriate Nd–Ga concentration after the annealing process. However, the exceeding Nd–Ga addition brings out notable segregation of grain boundary phase, and prior formation of part RE6 Fe13 Ga phase in the sintered magnet. This prior formation results in a weaker change of remanence after the annealing process.Therefore, the diverse changes of magnetic properties with different Nd–Ga concentrations are based on the respective evolution of grain boundary after the annealing process.     

Abnormal variation of magnetic properties with Ce content in(PrNdCe)_2Fe_(14)B sintered magnets prepared by dual alloy method

Resource-saving(PrNdCe)_2Fe_(14)B sintered magnets with nominal composition(PrNd)_(15-x)Ce_xFe_(77)B_8(x=0–10)were prepared using a dual alloy method by mixing(PrNd)_5Ce_(10)Fe_(77)B_8 with(PrNd)_(15)Fe_(77)B_8 powders. For Ce atomic percent of 1% and 2%, coercivity decreases dramatically. With further increase of Ce atomic percent, the coercivity increases, peaks at 6.38 kOe in(PrNd)_(11)Ce_4Fe_(77)B_8, and then declines gradually. The abnormal dependence of coercivity is likely related to the inhomogeneity of rare earth chemical composition in the intergranular phase, where Pr Nd concentration is strongly dependent on the additive amount of(PrNd)_5Ce_(10)Fe_(77)B_8 powders. In addition, for Ce atomic percent of 8%,7%, and 6% the coercivity is higher than that of magnets prepared by the conventional method, which shows the advantage of the dual alloy method in preparing high abundant rare earth magnets.     

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

MM_(14)Fe_(79.9)B_(6.1)/Nd_(13.5)Fe_(80.5)B_6 magnets were fabricated by dual alloy method(MM, misch metal). Some magnets have two Curie temperatures. Curie temperatures T_(c1)corresponds to the main phase which contains more La Ce, and T_(c1) decreases from 276.5?C to 256.6?C 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.     

Progress in recycling of Nd–Fe–B sintered magnet wastes

Significant efforts have been put into the recycling of bulk Nd–Fe–B sintered magnet wastes around the world in the past decade because bulk Nd–Fe–B sintered magnet wastes are valuable secondary rare-earth resources.There are two major facts behind the efforts.First, the waste magnets contain total rare-earth content as high as more than 30 wt.%, which is higher than most natural rare-earth mines.Second, the waste magnets maintain the physical and chemical properties of the original magnets even with deterioration of the properties on surfaces due to corrosion and contamination.In this review,various techniques for recycling bulk Nd–Fe–B sintered magnet wastes, the overall properties of the recycled Nd–Fe–B sintered magnets, and the mass production of recycled magnets from the wastes are reviewed.     

Magnetic properties of misch-metal partially substituted Nd–Fe–B magnets sintered by dual alloy method

The misch-metal(MM) partially substituted Nd–Fe–B sintered magnets were fabricated by the dual alloy method,and the crystal structure, microstructure, and magnetic properties were analyzed comprehensively. X-ray diffraction(XRD)reveals that the increasing content of the MM has an inconsiderable effect on the crystallographic alignment of the magnets.Grains of the two main phases are uniformly distributed, and slightly deteriorate on the grain boundary. Due to the diffusion between the adjacent grains, the MM substituted Nd–Fe–B magnets contain three types of components with different Ce/La concentrations. Moreover, the first-order reversal curve(FORC) diagram is introduced to analyze the magnetization reversal process, coercivity mechanism, and distribution of reversal field in magnetic samples. The analysis indicates that there are two major reversal components, corresponding to the two different main phases. The domain nucleation and growth are determined to be the leading mechanism in controlling the magnetization reversal processes of the magnets sintered by the dual alloy method.     

Effect of optimized aging processing on properties of the sintered Dy-doped Nd–Fe–B permanent magnet

We investigate the effect of the optimized aging processing on magnetism and mechanical property of the sintered Dydoped Nd–Fe–B permanent magnet. The experimental results show that the magnetism, especially intrinsic coercivity, of the optimized aged Dy-doped Nd–Fe–B magnet is more excellent than that of the sintered one, but the former's strength and hardness are lower than that of the latter. It was observed that the optimized aged Dy-doped Nd–Fe–B magnet have more uniform grain size, thinner(Nd, Dy)-rich boundary phase. By means of the EBSD technology, the number of larger angle grain boundaries in the optimized aged Dy-doped Nd–Fe–B magnet is more than that of the sintered one. The reasons for the increased intrinsic coercivity and decreased mechanical properties of the optimized aged Dy-doped Nd–Fe–B magnet are also discussed.     

Effect of annealing temperature on coercivity of Nd–Fe–B magnets with TbFeAl doping by process of hot-pressing

The Nd–Fe–B magnets are pre-sintered and then processed with hot-pressing, and the resulting magnets are called the hot-pressed pretreated(HPP) magnets. The coercivity of the HPP magnets increases as the annealed temperature increases.When the annealing temperature is 900℃, the coercivity of the magnet is only 17.6 kOe(1Oe = 79.5775 A·m~(-1)), but when the annealing temperature rises up to 1060℃, the coercivity of the magnet reaches 23.53 k Oe, which is remarkably increased by 33.7%. The microstructure analysis indicates that the grain surface of the HPP magnet becomes smoother as the annealed temperature increases. The microstructure factor α is changed according to the intrinsic coercivity model formula. The α of the magnet at 900℃ is only 0.578, but it is 0.825 at 1060℃. Microstructural optimization is due mainly to the increase of coercivity of the HPP magnet.     

Coercivity mechanism of La–Nd–Fe–B films with Y spacer layer

The effect of the Y spacer layer on the phase composition, coercivity, and magnetization reversal processes of La–Nd–Fe–B films has been investigated. The addition of a 10 nm Y spacer layer increases the coercivity of the film to 1.36 T at 300 K and remains 0.938 T at 380 K. As the thickness of the Y spacer layer increases, Y participates in the formation of the main phase in the film, and further regulates the formation of La–B phases. The results of the first-order reversal curve(FORC) and mic...     

Effects of oxidation of DyH_3 in Nd–Fe–B sintered magnets

The effects of oxidation of Dy H3 with respect to dysprosium addition to Nd–Fe–B sintered magnets are examined.Samples sintered with the addition of freshly milled dysprosium hydride, dysprosium hydride exposed to air at room temperature for 15 min and dysprosium hydride exposed to air at 100°C for 3.5 hours are studied from the aspects of magnetic properties, microstructures, and their degradation, respectively. It is found that some oxidized dysprosium is distributed in the Nd-rich phase; hence, the decrease of remanence occurred. The degradation results indicate that preoxidised dysprosium can be a major factor in increasing the corrosion rate. The microstructures and corrosion acceleration test suggested that the oxidation is detrimental to remanence.     

Improvement in coercivity,thermal stability,and corrosion resistance of sintered Nd-Fe-B magnets with Dy_(80)Ga_(20) intergranular addition

To investigate the coercivity,corrosion resistance,and thermal stability of Nd-Fe-B magnets,their properties were investigated at room and high temperature before and after doping with Dy_(80)Ga_(20)(at.%) powder.The coercivity of the magnets increased from the undoped value of 12.72 kOe to a doped value of 21.44 kOe.A micro-structural analysis indicates that a well-developed core-shell structure forms in the magnets doped with Dy_(80)Ga_(20) powder.The improvement in magnetic properties is believed to be related to the refined and uniform matrix grains,continuous grain boundaries,and a hardened(Nd,Dy)_2Fe_(14)B shell surrounding the matrix grains.Additionally,the doped magnets exhibit an obvious improvement in thermal stability.For the magnets with added Dy_(80)Ga_(20) powder,the temperature coefficients of remanence(α) and coercivity(β) increased to-0.106%℃~(-1) and-0.60%℃~(-1) over the range 20-100 ℃,compared to temperature coefficients of-0.117%℃~(-1)(α) and-0.74%℃~(-1)(β) in the regular magnets without Dy_(80)Ga_(20) powder.The irreversible loss of magnetic flux(Hirr) was investigated at different temperatures.After being exposed to 150 ℃ for 2 h,the Hirr of magnets with 4 wt.%Dy_(80)Ga_(20) decreased by ~95%compared to that of the undoped magnets.The enhanced temperature coefficients and Hirr indicate improved thermal stability in the doped Nd-Fe-B magnets.The intergranular addition of Dy_(80)Ga_(20) also improved the corrosion resistance of the magnets because of the enhanced intergranular phase.In a corrosive atmosphere for 96 h,the mass loss of the sintered magnets with 4 wt.%Dy_(80)Ga_(20) was 2.68 mg/cm~2,less than 10%of that suffered by the undoped magnets(28.1 mg/cm~2).     

57Fe Mössbauer spectrometry: A powerful technique to analyze the magnetic and phase characteristics in RE–Fe–B permanent magnets

This review summarizes the recent advances on the application of ⁵⁷Fe M?ssbauer spectrometry to study the magnetic and phase characteristics of Nd–Fe–B-based permanent magnets. First of all, the hyperfine structures of the Ce₂Fe₁₄B,(Ce,Nd)₂Fe₁₄B and MM₂Fe₁₄B phases are well-defined by using the model based on the Wigner-Seitz analysis of the crystal structure. The results show that the isomer shift δ and the quadrupole splitting ?EQ of those 2:14:1 phases show minor changes with the Nd content, while the hyperfine field Bhfincreases monotonically with increasing Nd content and its value is influenced by the element segregation and phase separation in the 2:14:1 phase. Then, the hyperfine structures of the low fraction secondary phases are determined by the ⁵⁷Fe M?ssbauer spectrometry due to its high sensitivity. On this basis,the content, magnetic behavior, and magnetization of the REFe₂ phase, the amorphous grain boundary(GB) phase, and the amorphous worm-like phase, as well as their effects on the magnetic properties, are systematically studied.     

Sm–Co high-temperature permanent magnet materials

Permanent magnets capable of reliably operating at high temperatures up to ~450?C are required in advanced power systems for future aircrafts, vehicles, and ships. Those operating temperatures are far beyond the capability of Nd–Fe–B magnets. Possessing high Curie temperature, Sm–Co based magnets are still very important because of their hightemperature capability, excellent thermal stability, and better corrosion resistance. The extensive research performed around the year 2000 resulted in a new class of Sm_2(Co, Fe, Cu, Zr)_(17)-type magnets capable of operating at high temperatures up to 550?C. This paper gives a systematic review of the development of Sm–Co permanent magnets, from the crystal structures and phase diagrams to the intrinsic magnetic properties. An emphasis is placed on Sm_2(Co, Fe, Cu, Zr)_(17)-type magnets for operation at temperatures from 300?C to 550?C. The thermal stability issues, including instantaneous temperature coefficients of magnetic properties, are discussed in detail. The significance of nanograin structure, nanocrystalline, and nanocomposite Sm–Co magnet materials, and prospects of future rare-earth permanent magnets are also given.     

Phase constitution and microstructure of Ce–Fe–B strip-casting alloy

The strip-casting technique plays an important role in fabricating high coercivity sintered magnet. In this paper, we investigate the phase constitution and the microstructure of rapidly solidified Ce-Fe-B alloy fabricated by strip-casting. We find that the Ce2FelgB phase coexists with Fe, Fe2B, and CeFe2 phases in the Ce-Fe-B strips. The eutectic stucture consisting of Fe and Fe2B is encased in Ce2Fe14B grains, which is blocked by the CeFe2 grains at triple junctions, indicating that the microstructure of Ce-Fe-B strip is characteristic of a peritectic solidification. Thermal analysis indicates that the large supercooling of Ce2Fe14B results in the residual Fe and Fe2B. The microstructural optimization in Ce-Fe-B strips without Fe and Fe2B could be achieved by a heat treatment of 1000 ℃.     

Magnetic Microstructure of Sintered Nd-Fe-B Magnets Made from Casting Strips

The magnetic microstructures of two Dy-AI substituted sintered Nd-Fe-13 magnets with the different nominal compositions of Nd12.2Vy0.6Fe80.4Al0.7B6 (at.%) (composition-A,C-A) and Nd13.7Dy0.6Fe78.8Al0.7B6.2(at.%)(composition-B,C-13) prepared by strip casting technique have been revealed by using a magnetic force microscope. The magnetic properties of sintered C-B magnets are worse than that of C-A sintered magnets. In particular, the value of density products (BH)max for sintered C-A magnets is about 32% higher than that of C-B magnets, which is reflected by their quite different magnetic microstructures. We believe that for the C-B samples, the inappropriate composition and thus the redundant Nd2Fe17(B) phase of the casting strips make its final magnetic microstructures worse than the C-A, and then deteriorates the performance of the C-B magnets.     

Electromagnetic wave absorbing properties and hyperfine interactions of Fe–Cu–Nb–Si–B nanocomposites

The Fe–Cu–Nb–Si–B alloy nanocomposite containing two ferromagnetic phases(amorphous phase and nanophase phase) is obtained by properly annealing the as-prepared alloys. High resolution transmission electron microscopy(HRTEM) images show the coexistence of these two phases. It is found that Fe–Si nanograins are surrounded by the retained amorphous ferromagnetic phase. M¨ossbauer spectroscopy measurements show that the nanophase is the D03-type Fe–Si phase, which is employed to find the atomic fractions of resonant57 Fe atoms in these two phases. The microwave permittivity and permeability spectra of Fe–Cu–Nb–Si–B nanocomposite are measured in the frequency range of 0.5 GHz–10 GHz. Large relative microwave permeability values are obtained. The results show that the absorber containing the nanocomposite flakes with a volume fraction of 28.59% exhibits good microwave absorption properties. The reflection loss of the absorber is less than-10 dB in a frequency band of 1.93 GHz–3.20 GHz.     

Thermal stability,crystallization, and magnetic properties of FeNiBCuNb alloys

Amorphous(Fe_(40)Ni_(40)B_(19)Cu_1)_(100-x)Nb_x(x = 1, 3, 5, 7) ribbons are prepared by using the melt-spinning method. We find that the glass forming ability(GFA) of the as-melt spun ribbons is significantly improved by adding Nb element. In addition, the thermal stability evaluated in steps of ?T = T_(x2)-T_(x1) effectively increases from 16 K to 75 K with Nb content increasing. The as-melt spun(Fe_(40)Ni_(40)B_(19)Cu_1)_(97) Nb_3 ribbon exhibits a lowest coercivity of 2 A/m and relatively large saturation magnetization of 103.7 A·m~2/kg and thus it can be further treated by being annealed at 809 K. The crystallization behavior is confirmed to be determined by two individual crystallization processes corresponding to the precipitation of(Fe,Ni)_(23) B_6 phase and γ-(Fe,Ni) phase. With increasing annealing time, the single(Fe,Ni)_(23)B_6 phase can be transformed into a mixture of(Fe,Ni)_(23)B_6 and γ-(Fe,Ni) phase, and the grain size of γ-(Fe, Ni) phase increases from 5 nm to 80 nm while the grain size of(Fe,Ni)_(23)B_6 remains almost unchanged. Finally, we find that the grain growth in each of(Fe,Ni)_(23)B_6 and γ-(Fe, Ni) deteriorates the overall magnetic properties.     

Mn-based permanent magnets

Mn-based intermetallic compounds have attracted much attention due to their fascinating structural and physical properties, especially their interesting hard magnetic properties. In this paper, we have summarized the magnetic and structural properties of Mn-based intermetallic compounds(Mn X, where X = Al, Bi, and Ga). Various methods for synthesizing single phases of MnAl, MnBi, and Mnx Ga were developed in our lab. A very high saturation magnetization of 125 emu/g,coercivity of 5 kOe, and maximum energy product(BH)max of 3.1 MG·Oe were achieved at room temperature for the pure τ-Mn–Al magnetic phase without carbon doping and the extrusion process. Low temperature phase(LTP) MnBi with a purity above 95 wt.% can be synthesized. An abnormal temperature coefficient of the coercivity was observed for the LTP MnBi magnet. Its coercivity increased with temperature from 100 K to 540 K, reached a maximum of 2.5 T at about540 K, and then decreased slowly to 1.8 T at 610 K. The positive temperature coefficient of the coercivity is related to the evolution of the structure and magnetocrystalline anisotropy field of the LTP MnBi phase with temperature. The LTP MnBi bonded magnets show maximum energy products(BH)max of 8.9 MG·Oe(70 kJ/m~3) and 5.0 MG·Oe(40 k J/m~3) at room temperature and 400 K, respectively. Ferrimagnetic Mnx Ga phases with L10 structures(x 2.0) and D022 structures(x 2.0) were obtained. All of the above structures can be described by a D0_(22) supercell model in which 2 a-Ga and 2 b-Mn are simultaneously substituted. The tetragonal D0_(22) phases of the Mnx Ga show high coercivities ranging from 7.2 kOe for low Mn content x = 1.8 to 18.2 kOe for high Mn content x = 3 at room temperature. The Mn_(1.2) Ga sample exhibits a room temperature magnetization value of 80 emu/g. The hard magnetic properties of coercivity_iH_c = 3.5 kOe, remanence Mr = 43.6 emu/g, and(BH)max = 2.5 MG·Oe were obtained at room temperature. Based on the above studies, we believe that Mn-based magnetic materials could be promising candidates for rare earth free permanent magnets exhibiting a high Curie temperature, high magnetocrystalline anisotropy, and very high coercivity.     

Magnetic and mechanical properties of Ni–Mn–Ga/Fe–Ga ferromagnetic shape memory composite

A ferromagnetic shape memory composite of Ni–Mn–Ga and Fe–Ga was fabricated by using spark plasma sintering method. The magnetic and mechanical properties of the composite were investigated. Compared to the Ni–Mn–Ga alloy,the threshold field for magnetic-field-induced strain in the composite is clearly reduced owing to the assistance of internal stress generated from Fe–Ga. Meanwhile, the ductility has been significantly improved in the composite. A fracture strain of 26% and a compressive strength of 1600 MPa were achieved.