Effects of Pr-Cu-Ti intergranular addition on microstructure and magnetic properties of heavy-rare-earth-free Nd-Fe-B sintered magnets

By intergranular addition of Pr-Cu-Ti alloy powders in the Nd-Fe-B sintered magnets with the normal B component, we propose an approach to the optimization of grain boundary and local Nd-Fe-B composition system. The coercivity is enhanced from 1.42 to 1.86 T, while further addition leads to a reduction in remanence and coercivity. The analyses of phase composition reveal that Ti mainly exists in the form of metallic Ti alloy, and part of Ti combines with B to form the TiB₂ phase after the liquid phase sintering process. This process results in a consumption of B in the local Nd-Fe-B composition system and a change of the grain boundary component, which contributes to the formation process of the RE₆(Fe,M)₁₄ phase after the annealing process. Therefore, with the modification of grain boundary and composition system, the intergranular addition of Pr-Cu-Ti induces the generation of continuous thin grain boundary phases. It promotes the intergrain exchange decoupling, increasing the coercivity in the annealed magnet. While the excess addition results in the segregation of TiB₂, as well as the precipitation of TiB₂ into the Nd-Fe-B phase, which leads to structural defects. Thus, the further effort for the addition alloy with Ti to reduce the deterioration of the microstructure will lead to further improvement in magnetic properties.     

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.     

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.     

Improvement of microstructure and coercivity for Nd-Fe-B sintered magnets by boundary introducing low melting point alloys

Different from the grain boundary diffusion process(GBDP),which is suitable for modifying thin magnet,a green-pressing agents permeation process(GAPP) that uses low melting point alloys was applied to the Nd-Fe-B green compact with a thickness over 15 mm to reconstruct the boundary microstructure of a sintered Nd-Fe-B magnet.The coercivity increases from 12.3 kOe for the sample free of Pr_(80)Al_(20) to16.8 kOe for the sample with 2 wt% Pr_(80)Al_(20).By further increasing the Pr_(80)Al_(20) content to 3 wt%,the coercivity increases slightly,but the remanence and H_k/H_(cj) deteriorate obviously.The optimal comprehensive properties of H_(cj)=16.8 kOe,B_r=13.4 kG and H_k/H_(cj)=0.975 are obtained at 2 wt% Pr_(80)Al_(20),since matrix phase grains are separated by relatively continuous thin grain boundary layers,which weaken the magnetic coupling between adjacent grains.The coercivities of the samples from the GAPP that use2 wt% Pr_(80)Al_(20),Pr_(70)Al_(30) and Pr_(60)Tb_(20)Al_(20) alloys,respectively,can be enhanced to a large extent.However,the coercivity of the magnet reconstructed with Pr_(80)Al_(20) is lower than that of the sample with Pr_(60)Tb_(20)Al_(20) but is higher than that of the sample reconstructed with Pr_(70)Cu_(30) alloy.Moreover,the coercivity of the sample from the GAPP using 2 wt% Pr_(80)Al_(20) is much higher than that of the sample from the GBDP,which is due to a nearly uniform boundary microstructure from the surface to the interior of the thick magnet from the GAPP,thus providing new insights into the fabrication of thick and bulky permanent magnets with high coercivity.     

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.     

Influence of Pr-Al-Co alloy diffusion source on magnetic properties and microstructure of sintered Nd-Fe-B magnets processed by grain boundary diffusion

In this study, the influence of the content of Al and Co in the diffusion source on the magnetic performance and microstructure of the diffused magnet was studied by grain boundary diffusion treatment with Pr₇₀Al_30–xCo_x (x = 0 at%, 10 at%, 15 at%, 20 at%, 30 at%) alloys. When the Co content in the diffusion source increases from 0 at% to 10 at%, the coercivity enhancement in the Pr₇₀Al₂₀Co₁₀ diffused magnet is the highest, increased from 1.62 to 2.24 T, higher than 2.01 T of the Pr₇₀Al₃₀ diffused magnet. With further increase of Co content in the diffused source, the coercivity of the diffused magnet decreases gradually, the coercivity of Pr₇₀Al₁₅Co₁₅, Pr₇₀Al₂₀Co₁₀ and Pr₇₀Co₃₀ diffused magnet is 2.15, 1.99 and 1.81 T, respectively. Microstructural analysis shows that plenty of continuous grain boundary phases (CGBPs) can be formed in the Pr₇₀Al₂₀Co₁₀ diffused magnet under the synergistic effect of Al and Co, which leads to the enhancement of magnetic isolation between more adjacent grains. However, the amount of CGBP in the diffused magnets gradually decreases with the further increase of Co content in the diffusion source.     

Improvement of coercivity and corrosion resistance of Nd-Fe-B sintered magnets by doping aluminium nano-particles

Nd-Fe-B permanent magnets with a small amount of Al nano-particles doping were prepared by conventional sintered method. Effect of Al content on magnetic property, corrosion resistance and oxidation properties of the magnets were studied. Investigation showed that the coercivity rose gradually, while the remanence decreased simultaneously with increase of Al doping amount. Further investigation revealed that most Al element diffused into the main phase and some Al element diffused into the Nd-rich phase. The autoclave test results showed that the corrosion rate of the magnets decreased with Al content increasing. After oxidation, the maximum energy product losses of the magnets with 0.0 wt.% and 0.2 wt.% Al nano-particles doping were 6.13% and 3.99%, respectively. Therefore, Al nano-particles doping was a promising way to enhance the coercivity and corrosion resistance of sintered Nd-Fe-B magnet.     

Effect of niobium on thermal stability and impact toughness of Nd-Fe-B magnets with ultra-high intrinsic coercivity

The effects of Nb on the thermal stability and impact toughness of ultra-high intrinsic coercivity of Nd-Fe-B magnets were investigated.The results showed that the addition of Nb could improve the thermal stability,and obviously increased the impact toughness of sintered Nd-Fe-B magnets.The optimum thermal stability of sintered Nd-Fe-B magnets was obtained when the content of Nb was 1.0 at.%.The maximum impact toughness of sintered Nd-Fe-B magnets was obtained when the content of Nb was 1.5 at.%,but the magnetic properties of sintered Nd-Fe-B magnets drastically deteriorated when the content of Nb increased from 1.0 at.% to 1.5 at.%.The microstructure showed that overfull Nb addition made many ultra-fine grains get together,which led to the density of sintered Nd-Fe-B magnets decline and drastically deteriorated the magnetic properties of sintered Nd-Fe-B magnets.     

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.     

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.     

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...     

Optimization of core-shell structure distribution in sintered Nd-Fe-B magnets by titanium addition

In view of the uneven distribution of the core-shell structure of sintered Nd-Fe-B magnets after grain boundary diffusion,this study proposes to use high-melting-point and reactive element titanium(Ti) as an additive to increase the diffusion channels and to enhance the diffusion of heavy rare earth elements along the grain boundary phase.By adding Ti element,the diffusion depth and hence the intrinsic coercivity of magnets are increased significantly.The addition of Ti increases the coercivity ...     

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.     

Effect of aluminum on microstructure and magnetic properties of sintered Nd-Fe-B magnets processed by grain boundary diffusion of Tb-Al

The grain boundary diffusion process(GBDP) of Tb can improve the coercivity of sintered Nd-Fe-B magnets.In this study,the effect of AI on the diffusion of Tb in the GBDP was investigated.The content of diffused Tb-Al was precisely controlled by adjusting the magnetron sputtering process.The Tb equivalent of Al was also studied.Results show that AI promotes the diffusion of Tb deeper into the magnet,reducing the thickness of the shell in the core-shell structure.This study is helpful for further ...     

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.     

Coercivity enhancement of nanocrystalline hot-deformed Nd-Fe-B magnets by low-melting eutectic MM-Cu(MM=La,Ce,Pr,Nd) alloys addition

MM_(85)Cu_(15)(MM = La,Ce,Pr,Nd) eutectic alloys were added into the hot-deformed Nd-Fe-B magnets to enhance the coercivity.It is found that three endothermic peaks occur on the differential scanning calorimetry curve of the MM-Cu melt-spun ribbons at 432.2,451.1 and 516.5℃.The peaks substantially correspond to three types of MM-Cu low-melting eutectic phase.The coercivity of magnets increases when the MM-Cu content is lower than 4 wt%,and then keeps almost no change with the content further increasing to 5 wt%.The coercivity of the hot-deformed magnets with 4 wt% and without MM-Cu addition is 948 and 683 kA/m,respectively.Nearly all the platelet-shaped grains are isolated by the thickened intergranular phase after MM-Cu addition.Moreover,the average grain size of the magnets with MM-Cu addition decreases compared with that of the magnet without MM-Cu addition.Scanning electron microscopy images show that the areal fraction of the RE-rich grain boundary phase increases from 8.6% to 15.1% after MM-Cu addition.The La,Ce together with Cu and Ga aggregate at the grain boundary regions separating neighboring grains and smoothing the grain boundaries.Therefore,both the thickened grain boundary and decreased mean grain size result in the enhancement of coercivity after MM-Cu eutectic alloy addition.     

Recycling of waste Nd-Fe-B sintered magnets by doping with dysprosium hydride nanoparticles

Recycling of waste sintered Nd-Fe-B permanent magnets by doping DyH3 nanoparticles was investigated. The effect of the DyH3 nanoparticles on the microstructure and magnetic properties of the recycled m...     

Simultaneous increase in remanence and coercivity during grain refining of Nd-Fe-B deformed magnets

To explore the feasibility of deep grain-size refinement in overcoming the problem of traditional B_r-H_ci trade-off in bulk permanent magnets, the effect of deformation temperature on the texture strength, grain refining, and magnetic properties of slow-deformed Nd-Fe-B magnets was systematically studied. As a result, strong textures with gradual grain refining from conventionally large size of D_L = 650 nm to small nanoscale size of D_L = 53 nm (D_L denotes the lateral size of the aligned plate-like grains) are observed as the temperature reduces from T_d = 650 °C to T_d = 450 °C. Moreover, magnetic observations show a simultaneous increase in remanence and coercivity as the grain refines from D_L = 650 nm to D_L = 127 nm. The increase in coercivity results from the grain size refinement as well as the smaller aspect ratio of the plate-like grains, and the increase in remanence results from the improved texture homogeneity. As compared with the D_L = 650 nm magnets, the simultaneous increase in remanence and coercivity leads to optimum enhancements of 57% in coercivity, 10% in remanence, and 25% in energy product, which demonstrate the feasibility of near-nanoscale grain refinement in overcoming the traditional B_r-H_ci trade-off for improved (BH)_max values. The failure of higher coercivities in the D_L ≤ 80 nm magnets is closely related with the defect effects of the grain boundaries. Mechanisms explaining the grain refining and texture changing behavior were also discussed.     

Effect of Terbium addition on the coercivity of the sintered NdFeB magnets

The effects of Tb addition on the microstructure and magnetic properties of the NdFeB magnets prepared by HD method were investigated by X-ray diffraction(XRD) and BH magnetometers.The results of the microstructure showed that both the Tb-doped and undoped permanent magnets were composed mostly of Tetragonal phase Nd2Fe14B(space group P42/mnm) and a trace amount of Nd-rich phase.Accordingly,addition of Tb led to a decrease of the pole density factor of(004),(006) and(008) crystal plane of the Nd2Fe14B phase calculated by Horta formula,but the coercivity of the magnets increased from 2038 kA/m up to 2302 kA/m as a consequence of Tb addition.The study of the Hc(T)/Ms(T) versus/Ms(T) behavior showed that the nucleation was the dominating mechanism for the magnetization reversal in both sintered magnets,and the microstructural parameters of αk and Neff were obtained also.The Kronmüller-plot showed an increase of the αk responsible for an increase of the coercivity.     

Microstructure improvement related coercivity enhancement for sintered NdFeB magnets after optimized additional heat treatment

The microstructure, especially the Nd-rich phase and the grain boundary, in sintered NdFeB magnets plays an important role in magnetic reversal and coercivity mechanism. To better understand the effects of the microstructure on the coercivity, we investigated the microstructure and properties improvements of a commercial sintered NdFeB magnet after optimized additional heat treatment. The coercivity is enhanced from 1399 to 1560 kA/m. This enhancement has been explained in terms of the evolution of the grain boundary structure, and the formation of continuous thin layers of Nd-rich phase is important for high coercivity. The micromagnetic simulation together with the numerical analysis based on the nucleation model suggest that the reversed magnetic domains nucleate mainly at the interface of multi-junctions of Nd₂Fe₁₄B grains with high stray fields during the demagnetization process. Both improved anisotropy fields at grain boundaries and reduced stray fields at multi-junction Nd-rich phases contribute to the coercivity enhancement. This work has importance in understanding the crucial microstructure parameters and enhancing the obtainable properties for sintered NdFeB magnets.