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 w...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 developing the process,reducing the consumption of heavy rare earth elements(Tb),and improving the coercivity of sintered Nd-Fe-B magnets.展开更多
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 nanocomposit...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.Moreover,the improve room for further property enhancement and the accompanying problems of GBDP on hot-deformed magnets are also discussed in this article.展开更多
The rare earth-iron-boron magnets based on high abundance rare earths(REs)show potential for costeffective permanent magnets but their hard magnetic properties have to be greatly improved.The grain boundary diffusion ...The rare earth-iron-boron magnets based on high abundance rare earths(REs)show potential for costeffective permanent magnets but their hard magnetic properties have to be greatly improved.The grain boundary diffusion process(GBDP)is known as an effective way to improve the coercivity of Nd-Fe-B magnets,however,the conventional diffusion method faces a challenge for Ce-based magnets since there is no enough continuous GB layer as the diffusion channel.Here,a two-step(Nd-Cu doping followed by Nd-Cu diffusion)GBDP was introduced for hot deformed(Ce,La,Y)-Fe-B magnet,and the excellent magnetic properties ofμ0Hc=0.63 T,μ0Mr=0.68 T,and(BH)max=72.4 kJ/m^(3)were achieved.The Nd-Cu doping helps the formation of RE-rich GB layer,and then it acts as the diffusion channel for increasing the ef-ficiency of the subsequent Nd-Cu diffusion and results in the increased volume fraction of continuously distributed GB phase,whose paramagnetism was verified by 57Fe Mössbauer spectrometry.Those paramagnetic GB phases help to form the discontinuous domain walls,as observed by Lorentz transmission electron microscopy,and break the magnetic exchange coupling of RE2Fe14B grains.It thus contributes to the coercivity enhancement of the hot deformed magnet with two-step diffusion,which is further proved by micromagnetic simulation.This study proposes a potential technique to prepare anisotropic hot deformed(Ce,La,Y)-Fe-B magnet with high cost-performance.展开更多
The influence of aluminum and copper content in the starting Nd-Fe-B magnet on grain boundary diffusion process(GBDP) was studied by observing the phase transformation behaviors of the magnets in-situ at high temperat...The influence of aluminum and copper content in the starting Nd-Fe-B magnet on grain boundary diffusion process(GBDP) was studied by observing the phase transformation behaviors of the magnets in-situ at high temperature. A higher coercivity increment is discovered in the sample with higher AI/Cu despite the fact that its Dy diffusion amount is the same as the other. DSC analysis shows an evident melting behavior in the higher Al/Cu sample. Laser scanning confocal microscopy(LSCM) in-situ characterization shows a large amount of melted intergranular phase spills out to the surface simultaneously at around 600 ℃ in the high Al/Cu sample, while the phase spills out gradually one after another in the range between 623 and680 ℃ in the other sample, which indicates that the intergranular phase can be more easily melted in the sample containing more AI/Cu. The area fraction of matrix phase remarkably shrinks while that of intergranular phase enlarges after LSCM heating, which demonstrates the outer region of the Nd_2 Fe_(14)B grains melt at the temperature of 900 ℃. Electron probe microanalyzer result(EPMA) shows that the Nd and Dy concentrate in edge regions and subsequently mix into the intergranular phase with the melting of the grain edge, while a large amount of AI and Cu in the intergranular phase spill out. Nevertheless, the sample with higher starting AI/Cu still remains higher residual contents after LSCM experiments, and that could probably be the main reason why the high AI/Cu magnet shows smaller coercivity decrement after LSCM experiment. Overall, the increase of AI/Cu in the starting magnet optimizes the Dy distribution and the wettability of intergranular phase, enhancing coercivity increment effect further.展开更多
The magnetic performance of Nd-Fe-B magnets depends on their grain boundary structure.Intergranular addition and grain boundary diffusion(GBD)process are effective approaches for enhancing coercivity with low material...The magnetic performance of Nd-Fe-B magnets depends on their grain boundary structure.Intergranular addition and grain boundary diffusion(GBD)process are effective approaches for enhancing coercivity with low material cost.This review summarizes the development of grain boundary modification techniques with emphasis on our recent work using cost-effective non-rare earth(non-RE)sources for GBD.Up to now,heavy rare earth(HRE)based compounds,metals and light rare earth(LRE)based alloys have been successfully employed as the diffusion sources for coercivity enhancement.Inspired from the previous investigations on the intergranular addition of non-RE compounds and alloys for Nd-Fe-B magnets,in 2015,we firstly proposed a novel GBD process based on diffusion source of Mg O.After that,various non-RE diffusion sources have been developed.The fundamentals of non-RE additives and non-RE diffusion sources for hard magnetic properties enhancement of Nd-Fe-B magnets are summarized here based on both the experimental and computational results.In particular,the properties-microstructure relationships of non-RE GBD modified magnets are discussed.The non-RE alloys or compounds modify the composition and structure of the grain boundary by diffusing into the intergranular regions,resulting in enhanced coercivity and corrosion resistance.Recently,we used Al-Cr coatings for both coercivity enhancement and surface protection,which shortens the production process and makes non-RE diffusion sources more competitive.The opportunity and future directions for non-RE GBD are also discussed in this review.展开更多
High-performance Nd2Fei4B magnets have been widely required in various fields recently due to the lightweight and miniaturization of devices.In this work,we synthesize Nd2Fei4B nanostructures with tunable magnetic pro...High-performance Nd2Fei4B magnets have been widely required in various fields recently due to the lightweight and miniaturization of devices.In this work,we synthesize Nd2Fei4B nanostructures with tunable magnetic properties through surfactant-assisted high energy ball milling(SAHEBM)process,achieving prominently enhanced coercivity by forming non-magnetic layers as grain boundary phase.When the reduction annealing process was carried out as pellet with Ca,the coercivity increased from 0.8 kOe to over 3 kOe as Nd2Fei4B powder,which is proved to be the contribution of the chemical diffusion of Nd elements and the formation of Nd-rich layer as magnetic insulating medium.In addition,two-dimensional graphene oxide(GO)was employed to build extra grain boundary,by which the coercivity of the core@dual-shell structure can achieve up to 8 kOe,tenfold of the original sample.The intrinsic mechanism indicated that the Nd-diffusion induced Nd-rich phase along with the reduced GO in the system could form non-magnetic layer as grain boundary and magnetically isolate the adjacent grains,significantly enhancing the exchange coupling effect.This work markedly opens up an effective approach for the chemical preparation of high-performance Nd2Fe14B nanostructured magnets,especially after post treatment,and gives an insight on the interactions at nanoscale.展开更多
基金supported by the National Key R&D Program of China(2021YFB3502902)Ningbo Major Special Projects of Science and Technology Innovation 2025 Plan(2020Z045)Key Research and Development Program of Zhejiang Province(2020C05013)。
文摘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 developing the process,reducing the consumption of heavy rare earth elements(Tb),and improving the coercivity of sintered Nd-Fe-B magnets.
基金Project supported by the Pioneer and Leading Goose R&D Program of Zhejiang(2020C01190)the Science and Technology Innovation 2025Major Project of Ningbo(2020Z064)+1 种基金the Zhejiang Province Postdoctoral Science Foundation(ZJ2021080)the Inner Mongolia Major Technology Project(2021ZD0035)。
文摘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.Moreover,the improve room for further property enhancement and the accompanying problems of GBDP on hot-deformed magnets are also discussed in this article.
基金the National Key Research and Development Program of China(Nos.2022YFB3505004,2022YFB3503400 and 2022YFB3503401)the National Natural Science Foundation of China(Nos.52071143,52171175,U21A2052,and U1908220)+3 种基金the Key R&D project of Zhejiang Province(Nos.2023C01077 and 2021C01023)the Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515010431 and 2022A1515011453)the GDAS Project of Science and Technology Development(Nos.2019GDASYL-0103067,2022GDASZH-2022010104,and 2022GDASZH-2022030604-04)the China Postdoctoral Science Foundation funded project(2022M720845).
文摘The rare earth-iron-boron magnets based on high abundance rare earths(REs)show potential for costeffective permanent magnets but their hard magnetic properties have to be greatly improved.The grain boundary diffusion process(GBDP)is known as an effective way to improve the coercivity of Nd-Fe-B magnets,however,the conventional diffusion method faces a challenge for Ce-based magnets since there is no enough continuous GB layer as the diffusion channel.Here,a two-step(Nd-Cu doping followed by Nd-Cu diffusion)GBDP was introduced for hot deformed(Ce,La,Y)-Fe-B magnet,and the excellent magnetic properties ofμ0Hc=0.63 T,μ0Mr=0.68 T,and(BH)max=72.4 kJ/m^(3)were achieved.The Nd-Cu doping helps the formation of RE-rich GB layer,and then it acts as the diffusion channel for increasing the ef-ficiency of the subsequent Nd-Cu diffusion and results in the increased volume fraction of continuously distributed GB phase,whose paramagnetism was verified by 57Fe Mössbauer spectrometry.Those paramagnetic GB phases help to form the discontinuous domain walls,as observed by Lorentz transmission electron microscopy,and break the magnetic exchange coupling of RE2Fe14B grains.It thus contributes to the coercivity enhancement of the hot deformed magnet with two-step diffusion,which is further proved by micromagnetic simulation.This study proposes a potential technique to prepare anisotropic hot deformed(Ce,La,Y)-Fe-B magnet with high cost-performance.
文摘The influence of aluminum and copper content in the starting Nd-Fe-B magnet on grain boundary diffusion process(GBDP) was studied by observing the phase transformation behaviors of the magnets in-situ at high temperature. A higher coercivity increment is discovered in the sample with higher AI/Cu despite the fact that its Dy diffusion amount is the same as the other. DSC analysis shows an evident melting behavior in the higher Al/Cu sample. Laser scanning confocal microscopy(LSCM) in-situ characterization shows a large amount of melted intergranular phase spills out to the surface simultaneously at around 600 ℃ in the high Al/Cu sample, while the phase spills out gradually one after another in the range between 623 and680 ℃ in the other sample, which indicates that the intergranular phase can be more easily melted in the sample containing more AI/Cu. The area fraction of matrix phase remarkably shrinks while that of intergranular phase enlarges after LSCM heating, which demonstrates the outer region of the Nd_2 Fe_(14)B grains melt at the temperature of 900 ℃. Electron probe microanalyzer result(EPMA) shows that the Nd and Dy concentrate in edge regions and subsequently mix into the intergranular phase with the melting of the grain edge, while a large amount of AI and Cu in the intergranular phase spill out. Nevertheless, the sample with higher starting AI/Cu still remains higher residual contents after LSCM experiments, and that could probably be the main reason why the high AI/Cu magnet shows smaller coercivity decrement after LSCM experiment. Overall, the increase of AI/Cu in the starting magnet optimizes the Dy distribution and the wettability of intergranular phase, enhancing coercivity increment effect further.
基金supported by the National Natural Science Foundation of China(Nos.51774146 and 52071143)Guangdong Key Laboratory of Rare Earth Development and Applications(No.XTKY201801)Special Project for Capacity Building of Guangdong Academy of Sciences(No.2020GDSYL-20200402008)
文摘The magnetic performance of Nd-Fe-B magnets depends on their grain boundary structure.Intergranular addition and grain boundary diffusion(GBD)process are effective approaches for enhancing coercivity with low material cost.This review summarizes the development of grain boundary modification techniques with emphasis on our recent work using cost-effective non-rare earth(non-RE)sources for GBD.Up to now,heavy rare earth(HRE)based compounds,metals and light rare earth(LRE)based alloys have been successfully employed as the diffusion sources for coercivity enhancement.Inspired from the previous investigations on the intergranular addition of non-RE compounds and alloys for Nd-Fe-B magnets,in 2015,we firstly proposed a novel GBD process based on diffusion source of Mg O.After that,various non-RE diffusion sources have been developed.The fundamentals of non-RE additives and non-RE diffusion sources for hard magnetic properties enhancement of Nd-Fe-B magnets are summarized here based on both the experimental and computational results.In particular,the properties-microstructure relationships of non-RE GBD modified magnets are discussed.The non-RE alloys or compounds modify the composition and structure of the grain boundary by diffusing into the intergranular regions,resulting in enhanced coercivity and corrosion resistance.Recently,we used Al-Cr coatings for both coercivity enhancement and surface protection,which shortens the production process and makes non-RE diffusion sources more competitive.The opportunity and future directions for non-RE GBD are also discussed in this review.
基金Beijing Youth Top-notch Team Support Project of China (2018000021223TD10)Hebei Province Fund for Transformation of Major Science and Technology Achievements of China (19041029Z)Hebei Province International Science and Technology Cooperation Base Construction Project of China(20591002D)。
基金This work was supported by the National Natural Science Foundation of China(Nos.51590882,51631001,51672010),and the National Key R&D Program of China(No.2017YFA0206301).
文摘High-performance Nd2Fei4B magnets have been widely required in various fields recently due to the lightweight and miniaturization of devices.In this work,we synthesize Nd2Fei4B nanostructures with tunable magnetic properties through surfactant-assisted high energy ball milling(SAHEBM)process,achieving prominently enhanced coercivity by forming non-magnetic layers as grain boundary phase.When the reduction annealing process was carried out as pellet with Ca,the coercivity increased from 0.8 kOe to over 3 kOe as Nd2Fei4B powder,which is proved to be the contribution of the chemical diffusion of Nd elements and the formation of Nd-rich layer as magnetic insulating medium.In addition,two-dimensional graphene oxide(GO)was employed to build extra grain boundary,by which the coercivity of the core@dual-shell structure can achieve up to 8 kOe,tenfold of the original sample.The intrinsic mechanism indicated that the Nd-diffusion induced Nd-rich phase along with the reduced GO in the system could form non-magnetic layer as grain boundary and magnetically isolate the adjacent grains,significantly enhancing the exchange coupling effect.This work markedly opens up an effective approach for the chemical preparation of high-performance Nd2Fe14B nanostructured magnets,especially after post treatment,and gives an insight on the interactions at nanoscale.