A comparative study of NdY-Fe-B magnet and NdCe-Fe-B magnet

Low cost and high abundance rare earth elements Y and Ce have attracted tremendous interests of the industrial and scientific societies for fabricating the highly cost-performance efficient rare earth permanent magnets. However, the effect of separate replacement of Nd by Y or Ce on the performances of NdFeB-type magnet under the same atomic ratio and preparation conditions is still unclear. In this work, we systematically investigated the magnetic properties, thermal stabilities and service performances of (Nd_0.8Y_0.2)_13.80Fe_balAl_0.24Cu_0.1B_6.04 (atomic fraction, denoted as 20Y) and (Nd_0.8Ce_0.2)_13.80Fe_balAl_0.24Cu_0.1B_6.04 (atomic fraction, denoted as 20Ce) magnets. The results demonstrate that the μ₀M_r, μ₀H_c and (BH)_max of 20Y magnet are respectively 1.325 T, 1.173 T and 343.467 kJ/m³, which are comprehensively higher than those of 20Ce magnet (μ₀M_r = 1.310 T, μ₀H_c = 0.948 T, (BH)_max = 321.105 kJ/m³). Moreover, the 20Y magnet has higher thermal stability compared with 20Ce magnet which is favorable for the magnetic performances at elevated temperatures. The investigation of microstructure and elemental distribution indicates that the excellent magnetic performances of NdY-Fe-B magnet can be attributed not only to the preferable intrinsic properties 4πM_s, H_a and T_c of Y₂Fe₁₄B, but also to the in-situ core–shell structure of the 2:14:1 matrix phase grain with Y-rich core and Nd-rich shell, along with the thicker grain boundary layer between the adjacent matrix phase grains in NdY-Fe-B magnet. Furthermore, the 20Y magnet exhibits better mechanical property and higher corrosion resistance than 20Ce magnet, which are helpful for prolonging the service life of the magnet in practical application.     

Anisotropic corrosion behavior of sintered (Ce0.15Nd0.85)30FebalB permanent magnets

In this work, the corrosion behavior of the surface parallel to the oriented c-axis(c‖) and perpendicular to c-axis(c⊥)in the(Ce_(0.15)Nd_(0.85))_(30)Fe_(bal)B dual main phase magnet was studied. With the addition of Ce,the volume fraction of RE-rich phase shown in the backscattered electron(BSE) images is basically approximate on the two surfaces. The free corrosion potential(E_(corr)) of the c‖ surface is more negative,which shows the worse corrosion resistance from the perspective of thermodynamics. While the reaction kinetics parameters with the smaller free corrosion current(i_(corr)) and the larger transfer resistance(R_(ct)) react the opposite conclusion in 3.5 wt% NaCl solution. Moreover, the c‖ surface performs smaller ions concentration of corrosion product and less damaged corrosion morphology compared to c⊥ surface after the free corrosion. The inconformity is not affected by the RE-rich phase, but by the anisotropy of the grains that the c‖ surface has larger density of the atoms and the lower ratio of(Nd, Ce)/Fe.     

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-xY_x)_13.80Fe_ba1Al_0.24Cu_0.1B_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 grain...     

Abnormal corrosion behavior of dual-main phase sintered(Ce,Nd)-Fe-B magnets in different sodium solutions

Sintered(Ce,Nd)-Fe-B magnets with high cost performance were prepared by substituting of Ce for Nd with the dual-main phase method.The corrosion behaviors of dual-main phase sintered(Ce_xNd_(1-x))_(30)Fe_(69)B_1(x=0.15 wt%,0.3 wt%) magnets,which were named as Ce15 and Ce30,were studied in 3.5 wt% NaCl,6.6 wt% Na_2 SO_4 and 3.0 wt% NaOH aqueous solutions,respectively.The galvanic corrosion of Ce30 is stronger than that of Ce15.However,the mass loss value of Ce30 is smaller than Ce15 after free corrosion for 33 d in NaCl solution.In the other two solutions,all the results show that the corrosion resistance of Ce30 is better than that of Ce15.The scanning electron microscope results show that the crack and shedding of the magnetic phase of Ce30 is less than that of Ce15.Combined above,the abnormal corrosion behavior shows that Ce30 magnets perform better corrosion resistance than Ce15,and the degradation degree of magnetic phase mainly affects the corrosion resistance of magnets.     

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 Nd₆Fe₁₃Ga 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 Nd₆Fe₁₃Ga 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.     

The microstructure and magnetization reversal behavior of melt-spun (Nd1−xCex)-Fe-B ribbons

In this study,the alloy ingots with nominal compositions of(Nd_(1-x)Ce_x)_(31)Fe_(bal)Co_(0.2)Ga_(0.1)B(x=0, 0.1 wt%,0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%) were prepared and then melt-spun to form nanocrystalline ribbons at the wheel speed of 20 m/s. XRD results show that all melt-spun ribbons exhibit the tetragonal structure(Nd,Ce)_2 Fe_(14)B phase with the space group P42/mmm. The Curie temperature and lattice constant decrease with the increase of Ce content. The Curie temperature decreases gradually from 306 to 247 ℃with the increase of Ce content. Those results indicate that Ce element has been incorporated into Nd_2 Fe_(14)B main crystalline phase and formed(Ce,Nd)-Fe-B hard magnetic phase. It is also found that the remanence ratio(M_r/M_s) decreases from 0.693 to 0.663 and the coercivity(H_c) decreases from 18.7 to14.2 kOe with the increase of Ce content. However, a relatively high coercivity of 18.3 kOe for(Nd_(1-x)Ce_x)_(31)Fe_(bal)Co_(0.2)Ga_(0.1)B(x = 0.2) melt-spun ribbon is achieved. The coercivity is sensitive to microstructure. The AFM patterns show the sample(x = 0.2) has the most uniform and finest microstructure. The magnetization reversal behavior(δM plots) is discussed in detail. The positive δM value is observed in every sample, which confirms the existence of exchange coupling interaction. Evidently, theδM maximum value reaches 0.9 in the sample(x = 0.2). It is indicated that the intergranular exchange coupling effect is the strongest, which is consistent with coercivity enhancing.     

Effects of grain boundary ternary alloy doping on corrosion resistance of(Ce,Pr,Nd)-Fe-B permanent magnets

To satisfy the application of different environments,grain boundary doping is commonly used in the preparation of sintered magnets to improve the coercivity and the corrosion resistance.In this paper,the alloys were prepared by mixing different ratios of the master alloy(Ce,Pr,Nd)-Fe-B and the sintering aid(Pr,Nd)-Al.The coercivity of sintered(Ce,Pr,Nd)-Fe-B magnet is substantially enhanced by doping 2 wt%of(Pr,Nd)-Al,while the maximum energy product decreases slightly.We systematically investigated the corrosion behavior and micro structure of the sintered magnets in order to determine the mechanism of the degradation.The sintered(Ce,Pr,Nd)-Fe-B magnets with 2 wt% of(Pr,Nd)-Al addition exhibit the decreasing corrosion rate compared with others,due to the distribution of intergranular phases.The electrode potential difference between the main phase and the RE-rich phase is reduced by the addition of Al,improving the potential and stability of RE-rich phase due to the higher electrode potential of Al than that of Nd,Pr or Ce.In addition,the element distribution of the magnets doped by(Pr,Nd)-Al indicates that the Al-rich shell formed at the marginal area of the Ce-rich phase improves its stability.Therefo re,intergranular adding te rnary(Pr,Nd)-Al alloy powders results in both high coe rcivity and good corrosion resistance synchronously.     

Improvement of coercivity and thermal stability of Nd-Fe-B sintered magnets by intergranular addition of Tb80Fe20 alloy

To improve the coercivity and temperature stability of Nd-Fe-B sintered magnets for high-temperature applications, the eutectic Tb₈₀Fe₂₀ (wt%) alloy powders were added into the Nd-Fe-B sintered magnets by intergranular method to enhance the coercivity (H_cj) and thermal stability. The microstructure, magnetic properties and thermal stability of the Nd-Fe-B magnets with different Tb₈₀Fe₂₀ contents were studied. The experimental results demonstrate that the coercivity (H_cj) of the sintered Nd-Fe-B magnet is significantly enhanced from 14.12 to 27.78 kOe, and the remanence (B_r) decreases not obviously by introducing 4 wt% Tb₈₀Fe₂₀ alloy. Meanwhile, the reversible temperature coefficients of coercivity (β) and remanence (α) of the Nd-Fe-B magnets are increased from ?0.5634%/℃ to ?0.4506%/℃ and ?0.1276%/℃ to ?0.1199%/℃ at 20–170 ℃, respectively. The Curie temperature (T_C) of the Nd-Fe-B magnet is slightly enhanced with the increase of Tb₈₀Fe₂₀ content. Moreover, the irreversible flux magnetic loss (h_irr) is obviously reduced as Tb₈₀Fe₂₀ addition increases. Further analysis of the microstructure reveals that a modified microstructure, i.e. clear and continuous RE-rich grain boundary layer, is acquired in the sintered magnets by introducing Tb₈₀Fe₂₀ alloy. The associated mechanisms on improved coercivity and thermal stability were comprehensively researched.     

Toughness of Sintered NdFeB Magnets

The failure mechanism of sintered NdFeB magnets was studied from the view of fracture model and fracture mechanism, and the effect of alloying on strength and toughness of the magnets was researched too. The results showed that intercrystalline fracture was the main fracture model and cracks elongated along the interface between 2–14–1 phase and Nd-rich phase. Generally, the methods for improving toughness include enhancing bond strength of the interface between the two phases mentioned just, refining grains of 2–14–1 phase and increasing the amount of particles of Nd-rich phase localized at grain boundary. The fracture model of the Nd_15.5Fe_76.5Al₁Ti_0.5B_6.5 magnets was transcrystalline cleavage fracture, whose value of fracture toughness increased about 30% compared to that of the Nd_15.5Fe₇₈B_6.5 magnets. Otherwise, the value of fracture toughness of the magnets with a proper amount of addition of Ag increased about 70% compared to that of the Nd_15.5Fe₇₈B_6.5 magnets. Moreover, the two sorts of modified magnet mentioned just could be drilled successfully. In addition, development of the research about increasing the strength and toughness of sintered NdFeB magnets is reviewed in this article.     

Effect of La–Y co-substitution on magnetic properties and microstructure of NdFeB alloy ribbons

Committed to obtaining cost-effective NdFeB based permanent magnets, Nd_27–xLa₃Y_xFe_balAl_0.1Cu_0.1B₁ (x = 0–3) alloys were fabricated to detect the magnetic properties and microstructure. When x = 1.8, coercivity of 1004 kA/m and the magnetic remanence of 0.75 T are obtained, which are close to those of the original Nd₃₀Fe_balAl_0.1Cu_0.1B₁ alloy ribbons. The temperature coefficient of coercivity (β) and the temperature coefficient of remanence (α) of the LaY-substituted alloys are better than those of the original alloys. The research results manifest that La is mainly distributed in the grain boundary phases and plays the role of refining the main grains, optimizing the grain boundary phases and improving the wettability between the main phases and the grain boundary phases, while Y tends to enrich in the main phases and enhances the short-range exchange coupling.     

Improvement in magnetic properties,corrosion resistance and microstructure of Nd–Fe–B sintered magnets through intergranular addition of Tb68Ni32

New energy vehicles and offshore wind power industries have a high demand for sintered Nd–Fe–B magnets with high intrinsic coercivity and high corrosion resistance. In this study, the magnetic properties, anticorrosion properties, and microstructure of Nd–Fe–B sintered magnets with the intergranular addition of low-melting-point eutectic Tb₆₈Ni₃₂ alloy powders were investigated. The aim is to determine if the addition of Tb₆₈Ni₃₂ can improve these properties. A low melting-point eutectic alloy Tb₆₈Ni₃₂ powders was prepared as a grain boundary additive and blended with the master alloy powders prior to sintering. The coercivity of the resultant magnets gradually increases from 1468 to 2151 kA/m by adding increasing amounts of Tb₆₈Ni₃₂. At the same time, the remanence first increases and then slightly decreases. After studying the microstructure and elemental composition of the Tb₆₈Ni₃₂ added magnets, it is found that the significant increase in coercivity and the negligible reduction in remanence is due to densification, improved grain orientation, a uniform and continuous boundary phase distribution, as well as the generation of a (Nd,Pr,Tb)₂Fe₁₄B “core–shell” structure surrounding the main-phase grain. Moreover, the corrosion resistance of the magnet is greatly improved owing to the enhancement of electrochemical stability, as well as the optimization of the distribution and morphology of the intergranular phase.     

Nd取代对Pr-Nd-Fe-B烧结磁体耐腐蚀性的影响

以HAST加速寿命试验后磁体失重,以及在不同腐蚀介质中磁体动电位极化曲线为表征,研究稀土元素Nd取代Pr对烧结Pr-Nd-Fe-B磁体耐腐蚀性的影响.结果表明:用Nd完全取代Pr后,磁体失重减小,室温下在0.1 mol/L HCl溶液、3.0 % NaOH溶液、3.5 % NaCl溶液中腐蚀电位不同程度地正移,表明磁体耐腐蚀性得到改善.通过场发射扫描电子显微镜观察HAST试验后磁体的微观组织形貌发现,Nd取代Pr后,晶界分布变得更加连续、清晰,且晶界交隅处的富稀土相含量减少,从而延缓了晶界腐蚀速率,使磁体的总体耐腐蚀性得到提升.      

Evaluating organic acids as alternative leaching reagents for rare earth elements recovery from NdFeB magnets

This study proposes an advanced leaching method using organic acids to recover rare earth elements (REEs) from NdFeB permanent magnets from end-of-life computers hard disk drives (HDDs). The end-of-life HDDs were first dismantled in order to recover NdFeB magnets, which were then thermally demagnetized at 350 °C during 30 min before crushing in a ball mill under inert atmosphere. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) analyses performed on the NdFeB magnets show the heterogeneous structure containing the major matric phase Nd₂Fe₁₄B and the REEs-rich phase containing Nd and Pr oxides. Additionally, X-ray diffraction (XRD) and Mössbauer spectroscopy (MS) analyses on the ground NdFeB magnet show that grinding NdFeB magnets under inert atmosphere helps to minimize its oxidation. Chemical analysis shows that the composition of the ground sample is Nd: 22.8 wt%, Pr: 3.3 wt%, Dy: 1.2 wt%, Fe: 62.6 wt%, Co: 1.5 wt%, B: 0.9 wt%, Ni: 0.6 wt%. Diagrams of speciation and equilibrium phases (E_h vs. pH) were calculated to determine the predominance of the formed species in the REEs–organic acids systems. The influence of the organic acid type (acetic acid, formic acid, citric acid and tartaric acid), the acid concentration (10 vol%, up to saturation), and the solid/liquid (S/L) ratio (0.5%–10%) on NdFeB magnets leaching was investigated employing an optimal experimental design conceived by the statistical software JMP. Acetic acid (CH₃COOH) shows the highest leaching performance of REEs, allowing leaching yields over 90% for Nd, Dy and Pr in the acid concentration range of 1.6–10 mol/L and the S/L ratio range of 0.5%–5% at a temperature of 60 °C. The results presented in this investigation suggest that REEs can be recovered from magnets of end-of-life HDDs using an eco-friendly method assisted by organic acids.     

Origin mechanism of pitting corrosion induced by cerium inclusions

In this paper, the origin mechanism of pitting corrosion induced by Ce₂O₃, Ce₂O₂S, and CeAlO₃ inclusions in a microalloyed steel was investigated by field emission scanning electron microscopy with energy dispersive spectroscopy and electron backscattered diffraction, conductivity atomic force microscopy, immersion test, and first-principles calculation. The results show that the Ce₂O₃, Ce₂O₂S, and CeAlO₃ inclusions are non-conductive, which are impossible to form corrosion couples with the steel matrix. There are no obvious lattice distortion zones in the steel matrix around the Ce₂O₃, Ce₂O₂S, and CeAlO₃ inclusions, so it is difficult to form micro-galvanic corrosion near the Ce inclusion. The order of work functions of the Ce inclusions and the steel matrix from small to large is Ce₂O₂S < Ce₂O₃<CeAlO₃<steel matrix, which is consistent with their dissolution sequence in the immersion test in 3.5 wt% NaCl solution. Consequently, it is effective and reliable to use work function to predict or judge the dissolution behaviors of the Ce inclusions or steel matrix in corrosive solution. The Ce₂O₃, Ce₂O₂S, and CeAlO₃ inclusions have the tendency of self-dissolution and dissolve preferentially to the steel matrix in the solution by the salt effect, which lead to pitting corrosion of Ce-containing microalloyed steel.     

Magnetic Alignment Study of Hybrid Magnet Consisting of R-Rich and R-Lean Nd-Fe-B Alloys

A hybrid magnet was prepared by the hot-pressing and die-upsetting of the mixture of the R-rich Nd_xFe_93.5–xGa_0.5B₆ (x= 13.5 and 11.8) alloy and the R-lean Nd_xFe_93–xNb₁B₆ (x = 6, 9) alloy melt-spun ribbons. The microstructure and magnetic properties of the hybrid magnet were investigated. In the hot-pressed or die-upset hybrid magnet the R-rich and R-lean alloy regions existed independently without alloying between them. The two alloy regions in the die-upset hybrid magnet were coupled effectively via a magnetostatic interaction. A texture was developed only in the R-rich Nd₂Fe₁₄B single phase alloy region in the die-upset hybrid magnet, and this led to an anisotropic nature in die-upset hybrid magnet. The die-upset hybrid magnets containing higher Nd-content (13.5 at%) host alloy shows consistently a better magnetic alignment with respect to the magnets with lower Nd-content (11.8 at%) host alloy.     

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 than 99.71 wt%. The process of RD for synthesizing Nd₂Fe₁₄B and subsequently removing CaO was thoroughly investigated. Furthermore, the recycled Nd-Fe-B magnet exhibits a remanence of 1.1 T, a coercivity of 1053 kA/m, and an energy product of 235.6 kJ/m³, respectively, indicating that recycled Nd-Fe-B sintered magnet was successfully recovered from the severely contaminated sludges via an effective recycling route.     

Spark Plasma Sintering Nd-Fe-B Permanent Magnets With Good All-Around Property

In present study, sintered Nd-Fe-B permanent magnets with different compositions were fabricated by using both Spark Plasma Sintering (SPS) technique and conventional sintering technique. Microstructure and compositions of both magnets are observed by scanning electron microscope with energy dispersive X-ray detector. Magnetic properties, mechanical properties, and chemical stabilities of both Nd-Fe-B magnets are investigated. Compared with the conventional sintered magnets, SPS Nd-Fe-B magnets possess comparable magnetic properties, better corrosion resistance and mechanical properties. Further investigation shows that the good all-around properties of the SPS magnets result from their unique microstructure. In detail, the grain size of Nd₂Fe₁₄B main phase is fine and uniform, only a few Nd-rich phase forms along the grain boundaries of Nd₂Fe₁₄B, while most of them agglomerates into the triple junctions. As a result, SPS process is expected to be a promising method for the production of new Nd-Fe-B magnets with good all-around properties.     

Effects of grain boundary diffusion process on magnetic properties enhancement and microstructure evolution of hot-deformed Nd-Fe-B magnets

Grain boundary diffusion(GBD) process is an important approach for producing Nd-Fe-B magnets with high coercivity and high thermal stability.The GBD for hot-deformed Nd-Fe-B magnets with nanocrystalline micro structure is more complicated compared to sintered magnets.Here,we investigated the effects of different GBD methods,i.e.,intergranular addition(in-situ GBD 1#),in-situ GBD from magnet surface during hot pressing and hot deformation(in-situ GBD 2#),and conventional GBD,on the magnetic prope...     

Effect of Rare Earth Substitution on Machinability of R-Fe-B Sintered Magnets

The machinability of sintered Nd-Fe-B magnets with nominal compositions of (Nd_1–xDy_x)₁₆Fe₇₈B₆ (x = 0, 0.05, 0.10, 0.15) and (Nd_1–yPr_y)₁₆Fe₇₈B₆ (y = 0, 0.33, 0.67, 1), has been investigated. The bending strength, fracture toughness and the Vickers Hardness were measured. It shows that the Dy substituted magnets shows higher Vickers Hardness than the Pr substituted magnets. The brittle index for investigated magnets improves monotonously with increasing Dy content, reduces with increasing Pr content, respectively, which seems to relate closely to the change of the lattice parameters.     

Constitution of melt-spun NdFeB-magnets studied by analytical field ion microscopy

An analytical field ion microscope was applied to melt-spun NdFeB magnets with various cobalt substitutions. The microstructure of melt-spun NdFeB magnets consists of three phases. Whereas the Nd₂Fe₁₄B- and the metastable Nd₇Fe₃-phase determine the magnetic properties of optimally quenched specimens the Nd_1.1Fe₄B₄-phase additionally influences the magnetic behaviour of overquenched and annealed material. With Co substitution the Nd-rich phase transforms via the metastable Nd₂₃(Fe_1−xCo_x)₇₅B₂ intermediate stage of optimally quenched specimens to the stable Nd(Fe_1−xCo_x)₂-phase in over-quenched and annealed ribbons. From our experimental data we conclude that a nucleation model of coercivity is consistent with the magnetic measurements.