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.     

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 ...     

Recent progress of grain boundary diffusion process for hot-deformed Nd-Fe-B magnets

Grain boundary diffusion process(GBDP) was first proposed for sintered Nd-Fe-B magnets to achieve the high utilization efficiency of heavy rare earth elements.Recent success of fabricating high performance nanocomposite magnets by GBDP indicates that this method also exerts huge applicable potential on hot-deformed Nd-Fe-B magnets.In this review,the development and magnetic property enhancement mechanisms of different diffusion methods proposed on hot-deformed magnets were thoroughly elucidated....     

Effect of MgCl2 on electrophoretic deposition of TbF3 powders on Nd-Fe-B sintered magnet

Using electrophoretic deposition(EPD) method,the TbF₃ powders were deposited on the surface of sintered Nd-Fe-B magnets,and the effects of MgCl₂ on electrophoretic deposition and grain boundary diffusion were investigated.The results show that addition of 5 wt% MgCl₂ can significantly improve the EPD efficiency and improve the adhesion of the coating by releasing local stress through the formation of special gully morphology.Combining with Biesheuvel equation,the...     

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...     

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.     

Correlation of mechanical anisotropy with fine grain strengthening for Sm2Co17-type sintered permanent magnets

The as-solution-treated Sm₂Co₁₇-type magnets exhibiting a single 1:7H phase with different average grain sizes (D) were designed. Anisotropy of bending strength (R_bb) and compressive strength (R_mc) of the magnets were investigated. Moreover, the R_bb increases from 86 to 173 MPa with D decreasing from ～52 to ～18 μm for group c//h samples. The Hall–Petch correlation was employed to reveal the effect of grain size on mechanical properties of the magnets, giving deep understanding of the mechanical anisotropy characteristics. The relatively high Hall–Petch coefficient K^Rbb (0.79 MPa?m^1/2) gives rise to the largest R_bb (173 MPa) for group c//h samples. The mechanical anisotropy of the samples is well explained based on crystal structure and grain size features (grain boundaries). Grain refinement is an effective way to enhance the mechanical properties of Sm₂Co₁₇-type sintered magnets.     

Coercivity enhancement of Ce-containing hot-deformed magnets by grain boundary diffusion of DyF3

The samples with full density were prepared by hot pressing the the melt-spun powders mixed with DyF₃powders of different mass fractions followed by hot-deformation process.The magnetic properties and temperature dependence of coercivity were obtained by BH tracer and VSM,respectively.The microstructure were analyzed by scanning electron microscopy(SEM)and transmission electron microscopy(TEM).The coercivity of Ce-containing hot-deformed magnets is increased from 1.41 to 1.95 T by grain boundary diffusion of 3 wt%DyF₃,and is further enhanced to 2.05 T after annealing treatment.The thermal stability of coercivity and remanence is improved.The annealing condition in this work crucially plays a role in thickening the grain boundary phase.Microstructure analysis reveals that the continuous and thick grain boundary phase formed after DyF₃diffusion can weaken the magnetic coupling between grains,and suppress the platelet shaped grain size and the aspect ratio.The Dycontaining shell structure formed by the partial diffusion of Dy into the main phase can increase the magnetic anisotropy field,which is the main reason for the coercivity improvement.After optimizing the structure by DyF₃diffusion,the"dendritic-like"reverse domain is transformed into the"dot scatteredlike"reverse domain.     

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.     

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.     

Effect of Pr-Ga dual-alloys diffusion on magnetic properties and thermal stability of hot-deformed PrNd-Fe-B magnets

To investigate the influence of the addition of Pr-Ga alloys on magnetic properties and morphology of materials,the hot-deformed PrNd-Fe-B magnets were prepared...     

Magnetovisual method for monitoring thermal demagnetization of permanent magnets used in magnetostrictive actuators

The design and measuring potential of the latest generation of the magnetic scanner called Magscanner-Maglab System （MMS） was presented. It enabled the fast acquisition of 3D signals from magnetic sensors and their visualization as digitalized mag- netic images. This system was used for monitoring of a thermal demagnetization process of permanent magnets. The original method and measurement devices were capable for examination of magnetic, mechanical and thermal defects in cylindrical rods made of NdFeB and non-rare earth components. Effectiveness of the method and device was tested for the reference demagnetized magnet dedicated for magnetostrictive actuators.     

Magnetic properties enhancement of hot-deformed NdFeB magnets by two different methods of CeNdCu diffusion

Two different ways were used to control the distribution of cerium for the enhancement of coercivity. One was by coating CeNdCu in the prepared magnet and annealing to make CeNdCu diffuse into the grain boundary to increase the coercivity, the other was by mixing CeNdCu with initial magnetic powders and then preparing the hot-deformed magnet. The SEM-EDS result indicates that cerium diffuses more easily into the main phase by the mixing way, while cerium is mainly distributed in the grain boundary via the coating way. The heat-treatment process may be one of the dominant influencing factors for the distribution of Ce. Multi-steps heat treatment in the mixing way, consisting of hot-pressing, hot-deforming and post heat process, easily introduces Ce into the main phase Nd₂Fe₁₄B, which forms the Ce₂Fe₁₄B shell resulting in the decrease of H_A. But the coating way can ensure uniform dispersion of Ce in the grain boundary, which leads to the high coercivity.     

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.     

Magnetic properties and microstructures of terbium coated and grain boundary diffusion treated sintered Nd-Fe-B magnets by magnetron sputtering

Tb coating on the surface of commercial sintered Nd-Fe-B magnet was prepared by DC magnetron sputtering.The secondary heat treatment was used to regulate the microstructure for the enhancement of coercivity,namely diffusion treatment and annealing treatment.The coercivity increases significantly from 18.3 to 28.0 kOe,the remanence decreases slightly from 14.1 to 14.0 kGs,and the comprehensive magnetic properties are higher than 75(Hcj+(BH)_max=76.7).SEM results indicate that,on the one hand,950℃is the optimal diffusion temperature.Lower diffusion temperature results in insufficient diffusion of Tb element.Higher diffusion temperature can lead to the main phase grain growth,the decrease of Nd-rich phase,and forming holes in the magnet.On the other hand,500℃is the optimal annealing temperature.Lower annealing temperature can result in the reduction of Nd-rich phase.Higher annealing temperature can generate the non-defined Nd-rich thin layer between grains.     

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 ...     

Effect of Na~+ on catalytic performance of CoCe/ZSM-5 catalysts for oxidation of toluene

A CoCe/ZSM-5 catalyst was prepared by ultrasonic-assisted impregnation for the catalytic combustion of toluene.To study the effect of Na+on catalytic performance of CoCe/ZSM-5 catalysts,a series of different Si/Al ZSM-5 zeolites and catalysts doped with Na were synthesized.The experimental results show that 0.71 wt%Na+can inhibit active growth,generate more active small crystal grains,and promote improvement of the catalytic activity by the grain boundary segregation block mechanism,and the catalyst with 0.71 wt%of Na shows toluene conversion of 90 vol%at 250℃.Over 0.71 wt%of Na+content will neutralize the acid centre of the catalyst,lowering the specific surface area of the catalyst and resulting in a gradual decrease in the catalytic activity.     

Investigation on mechanism of magnetization reversal for nanocrystalline Pr-Fe-B permanent magnets by micromagnetic finite element methods

Magnetization configurations were calculated under various magnetic fields for nanocrystalline Pr-Fe-B permanent magnets by micromagnetic finite element method. According to the configurations during demagnetization process, the mechanism of magnetization reversal was analyzed. For the Pr2Fe14B with 10 nm grains or its composite with 10vol.% α-Fe, the coercivity was determined by nucleation of reversed domain that took place at grain boundaries. However, for Pr2Fe14B with 30 nm grains, coercivity was controlled by pinning of the nucleated domain. For Pr2Fe14B/α-Fe with 30vol.% α-Fe, the demagnetization behavior was characterized by continuous reversal of α-Fe moment.     

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.