Magnetic properties and microstructure of nanocrystalline bulk Nd-Fe-B with Ce-Co addition

The influence of Ce-Co alloy addition and sintering holding time on permanent magnetic properties and micro structure of nanocrystalline Nd-Fe-B bulk alloy were investigated.The coercivity of Nd-Fe-B bulk alloy can be enhanced greatly by more than 100% after adding Ce-Co powders.However,when the concentration of Ce-Co is up to 30 wt%,the density of the magnet can reach the maximum value of 7.58 g/cm~3,but the coercivity does not increase significantly.On the other hand,with the increase of holding time to 10 min,the density and coercivity of magnets increase gradually,reaching up to 7.55 g/cm~3 and 1134.3 kA/m,respectively.After the addition of Ce-Co alloy,Ce-Co may easily diffuse into the Nd-Fe-B matrix during hot-pressing and under the high pressure and temperature,thus increasing the content of grain boundary phase and the pinning effect of grain boundary,which leads to the increase of coercivity.The extension of the hot-pressing holding time may be more conducive to the diffusion of CeCo into the Nd-Fe-B matrix.In addition,the effect of Ce-Co addition on the magnetic properties of Nd-FeB with different content of rare earth was also studied.The addition of Ce-Co can effectively increase the coercivity of nanocomposite Nd_2 Fe_(14)B/α-Fe magnets.The addition of Nb to the parent alloy can further improve the coercivity.For Nd_(11)Fe_(81.5)Nb_1 Ga_(0.5)B_6 alloy with 10 wt% Ce-Co addition,the coercivity can increase from 740.28 to 1098.48 kA/m.     

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.     

Effect of heterogeneous microstructure on magnetization reversal mechanism of hot-deformed Nd-Fe-B magnets

The hot-deformed(HD) Nd-Fe-B magnets show heterogeneous microstructure composed of coarse and fine grain regions. It is significant to fully understand the influence of this complex microstructure on the magnetization reversal process which can give the guidance for the enhancement of the magnetic properties. In this paper, the heterogeneous microstructure of the(HD) Nd-Fe-B magnets were characterized from the morphology, size, macro-texture and micro-structure. In addition, the magnetization reversal process of the HD Nd-Fe-B magnets was systematically analyzed by magnetic measurement, insitu domain evolution observation and micromagnetic simulation. The results indicate that the HD NdFe-B magnets mainly consist of fine grain regions(FGRs) and coarse grain regions(CGRs). The FGRs show plate-like grains with fine grain size and strong c-axis texture, while the CGRs show equiaxial grains with large grain size and weak c-axis texture. In particular, it is worth noting that the texture in homogeneity exists not only between FGRs and CGRs, but also inside both the FGRs and CGRs. The dominant coercivity mechanism of the HD Nd-Fe-B magnets is domain wall pinning. Also, the experimental analysis shows that the reverse domain is formed and expanded in the CGRs at low reverse applied field, while the reverse domain occurs in the FGRs at higher reverse applied field. The micromagnetic simulation results also confirm the above magnetization reversal process. In addition, micromagnetic simulation results also show that the orientation of the grains also affects the pinning strength, besides the grain size.     

High coercivity Nd-Ce-Fe-B nanostructured ribbons prepared from melt spinning technique

The Ce-substituted(Nd_(1-x)Ce_x)_(12.2) Fe_(81.6) B_(6.2)(x=0.0, 0.2, 0.4, 0.6) nanocrystalline ribbons were prepared by annealing amorphous ribbons from melt spinning. It is found that all ribbons are in a multiphase state consisting of a-Fe phase, Nd(Ce)-rich phases and RE_2 Fe_(14) B(RE = Nd, Ce) phases. However, the coercivity of all annealed ribbons can reach a considerably high value without doping any heavy rare earth or other coercivity enhanced elements. A strong intergranular exchange coupling appears in these nanocrystalline ribbons. The Nd_(12.2) Fe_(81.6) B_(6.2) ribbons with multiphase have a coercivity of about 11.3 k Oe, and the coercivity decreases slightly with increasing Ce content. A coercivity of 7.5 kOe can be obtained when60 at% of Nd is replaced by Ce(x = 0.6) due to the grain refinement and the strong intergranular exchange coupling. This provides a practical approach of fabricating high coercivity Ce-substituted Nd-Fe-B materials.     

Improved corrosion resistance and thermal stability of sintered Nd-Fe-B magnets with holmium substitution

The effects of Ho substitution for Nd on the microstructure, corrosion resistance and thermal stability of the Nd-Fe-B magnets were investigated. The(Nd,Ho)-O phase was formed with increasing Ho substitution. The results of potentiodynamic polarization and highly accelerated stress test show improved corrosion resistance with increasing Ho substitution. The optimum mass loss 0.29 mg/cm~2 is achieved.Moreover, the average temperature coefficients for remanence and coercivity in the range of 25-150℃are both closer to zero, indicating improved thermal stability. The mechanisms for the improved corrosion resistance and thermal stability are discussed in relation to the microstructure featuring the(Nd,Ho)-O phase.     

Sandwiched structure of hot-deformed Nd-Fe-B permanent magnets processed by Nd-Cu eutectic alloys diffusion

A series of sandwiched structures with different near-surface mass fractions x(x=3 wt%,4 wt%,5 wt%)was employed to develop high-coercivity hot-deformed Nd-Fe-B magnets by the addition of 2 wt%Nd-Cu eutectic alloys via adjusting the middle thickness and near-surface thickness.The designed magnet with a pronounced composite structure shows a 23% increase in coercivity with a 6% loss of remanence by adjusting the sandwiched structure at 4 wt% Nd-Cu eutectic alloys in the near-surface regions.The results indicate that the near-surface Nd-Cu-rich "shell" structure can effectively suppress the magnetization reversal of overall magnets,enhancing the coercivity.With the help of loading stress,Nd-Cu liquid enriched at the near-surface regions of the sample is infiltrated into the Nd-Cu-lean middle region,resulting in a concentration gradient.Microstructure characterizations further demonstrate that the infiltrated Nd-Cu eutectic plays a critical role in inhibiting grain growth and intergranular magnetic interaction.The optimized microstructure features suppress the reversed magnetization process,which makes a positive contribution to coercivity.     

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 Br=～0.75 T, Hcj=～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 Br=～0.66 T, Hcj=～0.92 mA·m-1, and(BH)max=～70 kJ·m-3, which are approximately comparable to the commercially available MQPB boned one(Br=～0.73 T, Hcj=～0.79 mA·m-1, and(BH)max=～86 kJ·m-3).     

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.     

工业生产高综合性能烧结 Nd-Fe-B永磁关键技术研究

通过优化合金成分设计和改进合金铸锭按需分配技术、磁场取向成型技术以及烧结技术，应用全部国产设备与国内通用的工业生产烧结Nd-Fe-B永磁的原材料，避免使用镓等稀有贵重金属元素，实现了N45H烧结Nd-Fe-B磁体的工业化生产，其典型磁性能为Br=1.386T(13.86kGs),BHc=1059kA/m(13.32kOe),JHc=1418kA/m(17.83kOe),Hk=1357kA/m(17.06kOe),(BH)max=364kJ/m^3(45.8MGOe)。，SEM观察和XRD分析结果表明，制造的N45H烧结Nd-Fe-B磁体具有良好的取向度和晶粒细小而均匀的显微组织。     

Coercivity enhancement mechanism of grain boundary diffused Nd-Fe-B sintered magnets by magnetic domain evolution observation

The grain boundary diffusion(GBD) technology was used to prepare high performance Nd-Fe-B sintered magnets by NdH_3 and TbH_3 nanoparticle diffusion.The factors affecting the coercivity of GBD magnets include distribution of rare earth rich grain boundary phase and substitution of the heavy rare earth.In order to distinguish the influence of various factors on the coercivity,the microstructure and magnetic domain evolution of the original,reference,Nd-diffused,and Tb-diffused magnets were analyzed.The core-shell structure formed by heavy rare earth substitution is the main factor of coercivity enhancement,and it can transform the magnetic domain reversal mode from easy-nucleation(EN) to difficultnucleation(DN).With increasing the diffusion depth,the shell of the core-shell structure gradually becomes thinner,DN grains gradually decrease while the EN grains gradually increase,indicating that the magnetic domain reversal mode is directly related to the core-shell structure.     

Enhanced magnetic properties in chemically inhomogeneous Nd-Dy-Fe-B sintered magnets by multi-main-phase process

Homogeneous substitution of Dy for Nd in the hard magnetic 2:14:1 phase can effectively enhance coercivity to ensure the high temperature operation,however,inevitably deteriorate remanence at expense.In this work,we performed a comparative investigation of the two magnets prepared by multimain-phase(co-sintering Nd_2 Fe_(14)B and(Nd,Dy)_2 Fe_(14)B powders) and single-main-phase(sintering(Nd,Dy)_2 Fe_(14)B powders) approaches.The comparative investigation reveals that at the same Dy substitution level(2.16 wt%),such chemically inhomogeneous multi-main-phase magnet possesses better roomtemperature magnetic properties as well as thermal stability than those of the single-main-phase one with homogenous Dy distribution in the matrix grains.Room-temperature magnetic properties H_(Cj)=1664 kA/m,B_r=1.33 T and(BH)_(max)=350.4 kJ/m~3 for the multi-main-phase magnet are all better than those for the single-main-phase magnet with H_(Cj)=1536 kA/m,B_r=1.29 T and(BH)_(max)=318.4 kj/m3.In addition,over the temperature range from 295 to 423 K,both the temperature coefficients of coercivity and remanence for the multi-main-phase magnet are also lower than that for the single-main-phase magnet.Such superior magnetic performance is attributed to the short-range magnetic interactions inside individual 2:14:1 phase grains and the long-range magnetostatic interactions between adjacent grains with inhomogeneous Dy distribution.Our work provides a feasible approach of enhancing coercivity and retaining energy product simultaneously in the Nd-Dy-Fe-B permanent magnets.     

Effect of fluxes on synthesis and luminescence properties of BaSi2O2N2:Eu2+ oxynitride phosphors

Eu²⁺ activated BaSi₂O₂N₂ oxynitride bluish-green phosphor was synthesized adopting conventional high-temperature solid-state reaction method, in which BaF₂, Na₂CO₃ and NH₄Cl were used as the fluxes. The phase formation, size distribution and microscopic morphology were characterized to investigate the influence of adding fluxes on photoluminescence properties. The results indicate that with the addition of BaF₂ flux, the particle morphology becomes regular and size distribution narrows and the phase purity of BaSi₂O₂N₂:Eu²⁺ phosphor can be improved effectively. The photoluminescence intensity of BaSi₂O₂N₂:Eu²⁺ phosphor with BaF₂ as flux gets enhanced obviously, which is much higher than that of Na₂CO₃, NH₄Cl and without flux. The optimum content of BaF₂ flux is 4 wt%, and the maximum photoluminescence intensity of the BaSi₂O₂N₂:Eu²⁺ phosphor prepared with BaF₂ flux rises to 141%, meanwhile, the phosphors with BaF₂ flux exhibits low thermal quenching. The results indicate that the BaSi₂O₂N₂:Eu²⁺ is sort of promising bluish-green phosphor for application in full-spectra LED.