Enhancement of terbium efficiency by gallium and copper co-doping in (Pr,Nd)-Fe-B sintered magnets

It is well known that Tb substitution for (Pr, Nd) in (Pr, Nd)-Fe-B based sintered magnetic materials is an effective way to increase intrinsic coercivity, but it is not quite clear whether the increment depends on the different matrix phases with various doping ingredient or not, which is essential to develop high quality magnets with high coercivity more efficiently and effectively with economic consumption of expensive Tb and other costly heavy rare earths. In this paper, we investigated the efficiency of Tb substitution for magnetic property in (Pr, Nd)-Fe-B sintered permanent magnets by co-doping Ga and Cu elements. It is shown that Ga and Cu co-doping can effectively improve the efficiency of Tb substitution to increase the thermal stability and the coercivity. The intrinsic coercivity increases up to 549 and 987 kA/m respectively by 1.5 wt% and 3.0 wt% Tb substitution in Ga and Cu co-doped magnets while the intrinsic coercivity increases up to only 334 and 613 kA/m respectively by the same amounts of Tb substitution in non-Ga and low-Cu magnets. In other words, it demonstrates that there is about 329–366 kA/m linear equivalent enhancement of intrinsic coercivity by 1.0 wt% Tb substitution for (Pr, Nd) in Ga and Cu co-doped magnets. The temperature coefficients of both intrinsic coercivity β and remanence α at 20–150 °C by 3.0 wt% Tb substitution for the magnets with Ga and Cu co-doping are −0.47%/K and −0.109%/K respectively, and in contrast those values are −0.52%/K and −0.116%/K respectively for the non-Ga and low-Cu magnets. It is the principal reason for more efficient enhancement of magnetic property by Tb substitution in the Ga and Cu co-doped magnets in which Tb atoms are expelled from triple junction phases (TJPs) to penetrate into the grain boundary phases (GB phases) and thus modify the grain boundary. It is prospected that the efficiency of Tb substitution would rely on different matrix phases with various doping constituents.     

Effect of roasting activation of rare earth molten salt slag on extraction of rare earth,lithium and fluorine

A new process was proposed to extract rare earth elements(REEs),Li and F from electrolytic slag of rare earth molten salt by synergistic roasting and acid leaching.Firstly,the thermodynamic analysis of roasting reaction was carried out,then the effects of roasting factors on leaching REEs,Li and F in slag were investigated.In additions,the mineral phase and morphology of molten salt slag,roasting slag and acid leaching slag were characterized,and the migration mechanism of REES,Li and F minerals...     

Recovery of neodymium,dysprosium,and cobalt from NdFeB magnet leachate using an unsymmetrical dialkylphosphinic acid extractant,INET-3

Rare earths (REs) and Co are critical strategic resources.Their recovery is crucial for ensuring that their supplies are adequate and for reducing environmental pollution.End-of-life NdFeB magnets are important secondary RE sources.The separation of Dy,Nd,and Co from NdFeB leachate using a relatively new extractant (2,3-dimethylbutyl)(2,4,4'-trimethylpentyl)phosphinic acid (INET-3),was investigated in this study.The separation parameters,such as equilibrium pH,phase ratio,INET-3 concentration,and number of counter-current extraction stages,were optimised.The results show that INET-3 can separate Dy,Nd,and Co efficiently.For the preferential extraction of Dy from synthetic iron-free NdFeB leachate,the optimum equilibrium pH is 2.60.Under this condition,separation of Dy from the leachate requires four counter-current extraction stages at A/O (volume ratio of aqueous to organic)=1:2.This is demonstrated by a simulated four-stage counter-current extraction process.At equilibrium pH=2.52and A/O=1:2,98%of Dy is recovered with 95%purity.As to the subsequent separation of Nd from the leachate,nearly 100%is recovered with 99%purity through a simulated three-stage counter-current extraction process at equilibrium pH=5.33 and A/O=1:1.Approximately 95%of Co remains in the raffinate with 99.98%purity.     

Corrosion resistance and mechanical properties of (Ho,Nd)FeB magnets

(Ho,Nd)FeB magnets with different Ho contents were prepared by Ho substitution for part of Nd during the casting process. Effects of Ho contents on the corrosion resistance and mechanical properties of (Ho,Nd)FeB magnets were analyzed by a highly accelerated aging tester, an electrochemical workstation, a microhardness tester, a bending tester, a scanning electron microscope and an X-ray diffractometer. Results show that the addition of Ho can change the main phase structure, optimize the distribution of rare-earth rich (RE-rich) phases in grain boundary, and improve the corrosion resistance and mechanical properties of NdFeB magnets. When the content of Ho increases from 0 to 21.0 wt%, the weight loss of magnets decreases from 2.672 to 0.933 mg/cm², and the microhardness and bending strength increase from 528.74 HV and 374.92 MPa to 633.84 HV and 459.80 MPa, respectively.     

Magnetic properties and magnetization mechanism of anisotropic NdFeB/SmFeN hybrid bonded magnets prepared with different coercivity NdFeB powders

Anisotropic NdFeB/SmFeN hybrid bonded magnets were prepared by warm compaction process under an orientation magnetic field of 22 kOe,mixing with anisotropic SmFeN powders in different addition and HDDR-NdFeB powders in different coercivity.With the addition of 20 wt% SmFeN,the density and remanence of hybrid magnets increase from 5.58 g/cm³,8.4 kGs to 6.02 g/cm³,9.0 kGs,respectively.And as the addition amount of SmFeN powders varies from 20 wt% to 40 wt%,the maximum energy ...     

Coordination-reduction leaching process of ion-adsorption type rare earth ore with ascorbic acid

The magnesium sulfate(MgSO₄)-ascorbic acid(Vc) compound leaching technique can extract rare earth elements(REEs) existing in ion-exchangeable phase and colloidal phase from ion-adso rption type rare earth ore through the synergy effect of coordination and reduction,but its reaction process and mechanism remain unclear.In this paper,the coordination-reduction leaching mechanism was analyzed from the perspectives of leaching thermodynamics and kinetics,which provide theoretical guidance...     

液相扩散对钕铁硼磁体性能和组织结构的影响

用双合金工艺在Nd13.05Dy0.23Fe80.12B6.5铸片主合金中分别添加质量分数为3％～20％的富稀土铸锭辅合金Nd38.2Cc11.8Fe44.88Al4.12B,研究在钕铁硼永磁体中用Ce部分地取代Nd时对永磁体的磁性能的变化规律.实验结果表明,在一定的烧结及热处理工艺条件下,辅合金加入量介于8％ ～ 12％(质量分数)时,磁体的内禀矫顽力和磁能积相对较高,对剩磁的影响不大.显微成分分析表明,采用双合金法,使组织中细小的颗粒状富稀土相增多,形成了更多的对矫顽力有贡献的富稀土相,并且富稀土相分布于晶界上.     

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.     

Tailoring the mechanical anisotropy of sintered NdFeB magnets by PrCu grain boundary reconstruction

Pr_(83)Cu_(17)(wt%) grain boundary reconstruction was applied to prepare sintered NdFeB magnets. The effects of addition amount and annealing on the bending strength were investigated. The results show that Pr_(83)Cu_(17) can not only effectively enhance the bending strength, but also change the mechanical anisotropy in two directions parallel and perpendicular to c-axis. The bending strength perpendicular to c-axis reaches 404 MPa in 10 wt% addition magnet, higher than 348 MPa along parallel direction. This change is attributed to the preferred distribution of boundary phases, i.e., ductile(Nd,Pr)-Fe-Cu phase along perpendicular direction to c-axis and(Nd,Pr)-Fe phase along parallel direction. Moreover, the Cu migration during 480 ℃ annealing is found to be related to this boundary phase distribution.     

Calcium hydride reduced high-quality Nd–Fe–B powder from Nd–Fe–B sintered magnet sludge

The structural and magnetic properties were studied for recycling Nd–Fe–B powders from Nd–Fe–B sintered magnets sludge via reduction diffusion (RD) with calcium hydride (CaH₂) particles. For comparison, traditional reducing agent calcium granules were applied to prepare recycled Nd–Fe–B powders. Finer particle size and better size distribution as well as lower impurity content are achieved by using CaH₂ instead of Ca. In detail, the average particle size of the recycled Nd–Fe–B powder is reduced from 4.66 to 3.43 μm, and the bimodal distribution disappears. Moreover, the residual calcium content and oxygen content are reduced to about 0.080 wt% and 0.32 wt%. As a consequence, the room-temperature magnetization of the CaH₂-recycled Nd–Fe–B powder is increased to 146.30 emu/g, 6.8% and 33%, respectively, higher than that of Ca-reduced powder and the initial sludge. Further analysis indicates that CaH₂ is able to reduce the sludge at lower temperature to fabricate well-dispersed, uniform recycled powder with high magnetization arising from a combination factors of its low melting point, low thermodynamic behavior, and the release of hydrogen during the reaction.     

Effect of Annealing of a Pr–Dy–Fe–Co–B Alloy on Its Phase Composition and the Properties of Related Sintered Magnets

The effect of annealing of a (Pr_0.41Ce_0.12Dy_0.47)_13.46(Fe_0.64Co_0.36)_80.3B_6.24 alloy at 1000°C on its microstructure and the properties of sintered magnets made of it has been studied. In the annealed state, the composition of the main magnetic phase (Pr,Dy)₂(Fe,Co)₁₄B changes sharply (dysprosium content changes), the residual induction of the sintered magnets made of the annealed alloy increases by 6%, and the coercive force determined from magnetization increases by 8.5%. The volume content of the main magnetic phase R₂(Fe,Co)₁₄B in sintered magnets (Nb,Dy)–(Fe,Co)–B and (Pr,Dy)–(Fe,Co)–B is found. The content of this phase in neodymium-based magnets is approximately half as much.     

Adsorption of rare earth elements on organic matter in coal

The occurrence modes of rare earth elements(lanthanide and yttrium,abbreviated as REY) in coal are impo rtant both for coal geochemistry studies and the application potential of REY as a by-product of coalbased resources.In this study,the adsorption behaviors of REY on organic matter in coal were investigated by leaching tests using REY solution and ultra-low ash coal samples.On this basis,the adsorption mechanism of REY on organic matter in coal was also studied by molecular simulation calculat...     

Leaching recovery of rare earth elements from the calcination product of a coal coarse refuse using organic acids

Due to the increasing criticality of rare earth elements(REEs),it has become essential to recover REEs from alternative resources.In this study,systematic REEs leaching tests were performed on the calcination product of a coal coarse refuse using hydrochloric acid and different types of organic acid as lixiviants.Experimental results show that the recovery of REEs,especially heavy REEs(HREEs)and scandium(Sc),is improved by using selected organic acids.Citric acid and DL-malic acid afford the best leaching performances;whereas,malonic acid,oxalic acid,and DL-tartaric acid are inferior to hydrochloric acid.Results of zeta potential measurements and solution chemical equilibrium calculations show that malonic acid is more likely adsorbed on the surface of the calcined material compared with citric acid and DL-malic acid.The adsorption may reduce the effective concentration of malonic species in solution and/or increase the amount of REEs adsorbed on the surface,thereby impairing the leaching recovery.Compared with light REEs(LREEs),a stronger adsorption of the HREEs on the surface is observed from electro-kinetic test results.This finding explains why organic acids impose a more positive impact on the leaching recovery of HREEs,By complexing with the HREEs,organic acids can keep the metal ions in solution and improve the leaching recovery.The adsorption of Sc³⁺on the surface is the lowest compared with other REEs.Therefore,rather than complexing,the organic anionic species likely play a function of solubilizing Sc from the solid,which is similar to that of hydrogen ions.     

Fractionation and fixation of rare earth elements in soils: Effect of spiking with lanthanum,cerium, and neodymium chlorides

Industrial and agricultural activities lead to the release of rare earth elements(REEs)in wastewater and aquatic ecosystems,and their accumulation in soils.However,the behavior of REEs in soils remains somewhat unclear.In the present work the fractionation and fixation of REEs in soddy-podzolic and chernozem soils spiked with La,Ce,and Nd chlorides were studied using dynamic(continuous flow)extraction,which allows natural conditions to be mimicked and artefacts to be minimised.The eluents applied are aimed to dissolve exchangeable,specifically sorbed,bound to Mn oxides,bound to metal-organic complexes,and bound to amorphous and poorly ordered Fe/Al oxides fractions extractable by 0.05 mol/L Ca(NO₃)2,0.43 mol/L CH₃COOH,0.1 mol/L NH₂OH·HCl,0.1 mol/L K₄P₂O₇ at pH 11,and 0.1 mol/L(NH4)₂C₂O₄ at pH 3.2,respectively.It is found that the fixations of added La,Ce,and Nd in the form of metal-organic complexes is predominant for both types of soils:35%-38%in soddy-podzolic soil and 50%-79%in chernozem.The fixation of added elements in the first three fractions(exchangeable,specifically sorbed,and bound to Mn oxides)is significant for soddy-podzolic soil(5%-25%).For chernozem,the relative contents of added Ce and Nd in these fractions are nearly negligible.Only the content of exchangeable La is notable,about 5%.Adding any of three elements(La,Ce,or Nd)at the level of100 mg/kg to an initial sample results in changing the fractionation and bioaccessibility of other REEs present in soil.Their contents increase in the first three fractions and decrease in fifth(oxalate extractable)fraction for both soddy-podzolic soil and chernozem.The main difference is the behavior of REEs in pyrophosphate extractable fraction.For soddy-podzolic soil,adding La,Ce,or Nd results in decreasing the contents of other REEs associated with organic matter.For chernozem,on the contrary,the contents of REEs in the form of metal-organic complexes slightly increase.These processes may be attributed to competitive binding of elements and soil properties;they must be taken into account when assessing the environmental risks of soil pollution with REEs.     

Selective Leaching Process for Neodymium Recovery from Scrap Nd-Fe-B Magnet

Neodymium-iron-boron (Nd-Fe-B) magnets were most widely applied to permanent magnetic products in the world due to their high magnetic force. The increasing growth of scrap Nd-Fe-B magnets resulted in disposal problems and the reduction of neodymium (Nd) valuable resources. In this study, we developed a simple hydrometallurgical precipitation process with pH adjustment to separate and recover Nd 100 pct recovery from scrap Nd-Fe-B magnets. Several physical and chemical methods such as demagnetization, grinding, screening, and leaching processes were also adopted to investigate the recovery of Nd and other metals from scrap Nd-Fe-B magnets. The leaching process was carried out with four leaching reagents such as NaOH, HCl, HNO₃, and H₂SO₄. Batch studies were also conducted to optimize the leaching operating conditions with respect to leaching time, concentration of leaching reagent, temperature, and solid/liquid ratio for both HCl and H₂SO₄ leaching reagents. Nd was successfully separated and recovered with 75.41 wt pct from optimized H₂SO₄ leaching solution through precipitation. Further, the purity and weight percentage of the obtained Nd product was analyzed using scanning electron microscopy–energy-dispersive spectroscopy (SEM-EDS) analysis. An X-ray diffraction (XRD) study confirmed the obtained product of Nd was in the form of NdOOH and Nd(OH)₃.     

Anti-corrosion performance of Si-surface-alloying NdFeB magnets obtained with magnetron sputtering and thermal diffusion

Si alloying in the surface layer of NdFeB magnets was realized by thermal diffusion combined with magnetron sputtering. The surface composition, phase structure and morphology of NdFeB(S–Si) specimens were characterized by an X-ray diffractometer, an X-ray photoelectron spectrometer and a field emission scanning electron microscope, respectively. The corrosion resistance of bare NdFeB(S–Si) was analyzed by static full immersion corrosion test and electrochemical experiments. Effects of sputtering and thermal diffusion on the microstructure and corrosion resistance of the surface layer were studied. Results show that surface alloying layer can effectively improve the corrosion resistance of bare NdFeB with the optimized static total immersion corrosion test time in NdFeB(1S–Si)-800 of 36 h, which is much longer than that of the pristine NdFeB (less than 0.5 h). The E_corr of NdFeB(1S–Si)-800 positively shifts from −1.05 to −0.92 V, indicating that the corrosion tendency is obviously lower. The J_corr is 1.45 × 10⁻⁶ A/cm² which is 2 orders of magnitude lower than that of the pristine NdFeB (5.25× 10⁻⁴ A/cm²). The intergranular composite oxides existing in Nd-rich phase contribute to the enhancement of corrosion resistance of Si-surface-alloying NdFeB.     

Superior corrosion resistance and corrosion mechanism of dual-main-phase (Ce15Nd85)30FebalB1M magnets in different solutions

The electrochemical corrosion behavior of both(Ce₁₅Nd₈₅)₃₀Fe_balB₁ M sintered magnets prepared with dual-main-phase method and N45-type magnets was studied in 3.5 wt% NaCl,1.1 wt% NaH₂ PO₄,and2.5 wt% NaOH solutions,respectively.The(Ce₁₅Nd₈₅)₃₀Fe_balB₁ M sintered magnets perform superior corrosion resistance than N45-type magnets in the tested solutions.In general,two ...     

Oxidative Roasting–Selective Pressure Leaching Process for Rare Earth Recovery from NdFeB Magnet Scrap

To recover rare earths (RE) with low acid consumption and low environmental pollution, selective pressure leaching with hydrochloric acid from roasted NdFeB scrap was explored. The phase evolution of NdFeB scrap during roasting at 800 °C as a function of time was confirmed, and after complete oxidation, its phase components consisted of Fe2O3, NdFeO3, and NdBO3. In the selective pressure leaching procedure, the optimal leaching was achieved at 110 °C for 30 min, in which the leaching rate of rare earth was 96.27% along with 13.33% of Fe. Subsequently, the effects of the hydrochloric acid dosage, the hydrochloric acid concentration and the particle size of the roasted NdFeB powder on the leaching rate of rare earth were investigated. For leaching at 110 °C for 30 min, the leaching of 13.33% Fe2O3 was derived from the Fe2O3 and NdFeO3 phases in the fully oxidized NdFeB scrap. This phenomenon was verified by the leaching of Fe from Fe2O3 of analytical purity and synthetic NdFeO3. Moreover, the leaching of Nd and Fe from the NdFeO3 phase was found to occur simultaneously. The advantages of the selective pressure leaching process using hydrochloric acid for the oxidized NdFeB scrap were comprehensively evaluated.     

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.     

晶界扩散中Tb对烧结NdFeB磁体微观组织和磁性能的影响

通过晶界扩散技术提升烧结钕铁硼(NdFeB)磁体矫顽力的方法已获得广泛应用,为了研究重稀土磁粉对磁体综合磁性能的影响,本文采用喷涂扩散的方法将重稀土Tb含量为6.0%(质量分数)的磁粉作为复合扩散源的一部分进行晶界扩散并制备了高性能烧结NdFeB磁体。结果表明,当主扩散源占比为60%(质量分数)时,Nd₄₀Tb₆₀对应扩散磁体的矫顽力最高达到21.52 kOe,矫顽力增幅明显。经过微观组织结构和XRD表征分析,重稀土元素Tb沿晶界相扩散进入磁体内部的同时发生了晶格取代反应,可在晶粒表层生成磁晶各向异性场更强的(Nd,Dy/Tb)₂Fe₁₄B硬磁相,显著增强了磁体矫顽力。当主扩散源占比为20%、40%和80%(质量分数)时,Nd₈₀Tb₂₀,Nd₆₀Tb₄₀和Nd₂₀Tb₈₀对应扩散磁体的矫顽力增幅较小,其中Nd₈₀Tb₂₀扩散...