In this paper,the fracture behaviors and interface stresses of sintered Nd-Fe-B magnets were investigated.It was revealed that cracks propagated along the interfaces of Nd_(2)Fe_(14)B/Nd_(2)Fe_(14)B,Nd_(2)Fe_(14)B/Nd-...In this paper,the fracture behaviors and interface stresses of sintered Nd-Fe-B magnets were investigated.It was revealed that cracks propagated along the interfaces of Nd_(2)Fe_(14)B/Nd_(2)Fe_(14)B,Nd_(2)Fe_(14)B/Nd-rich phases and within Nd-rich phases.The misfits between 2:14:1 and Nd-rich phases were quantitatively determined,reflecting the concentration of interface stresses in magnet.Grain boundaries of magnet were reconstructed by diffusing Tb-containing and Tb-free sources,respectively.The Tb-rich shells at extensive layers of 2:14:1 grains caused lattice distortion,i.e.,internal stresses,resulting in the crack mode changing from intergranular to transgranular in near surfaces of Tb-containing diffused magnets.Therefore,the bending strengths were deteriorated although the coercivities were apparently enhanced.In the case of Tb-free Pr-Cu diffused magnet,the Pr and Cu elements were enriched at grain boundaries,and the misfits between 2:14:1 and Nd-rich phases were declined,lowering interface stresses and strengthening grain boundaries.The mechanical and magnetic properties of Pr-Cu diffused magnet were simultaneously improved.展开更多
Recovery of rare earth elements(REEs)from bulk Nd-Fe-B scrap by chlorination with NH_(4)Cl as a chlorinating agent has been reported to be an energy efficient and environmentally friendly method.However,the reaction m...Recovery of rare earth elements(REEs)from bulk Nd-Fe-B scrap by chlorination with NH_(4)Cl as a chlorinating agent has been reported to be an energy efficient and environmentally friendly method.However,the reaction mechanism and phase evolution of the low-temperature selective chlorination process of Nd-Fe-B sludge are not clear.In this paper,we systematically investigated the lowtemperature selective chlorination process of Nd-Fe-B sludge with NH4Cl by combining thermokinetic theoretical calculations and experiments,and revealed its reaction mechanism.The phase evolution during chlorination was determined by X-ray diffraction(XRD),scanning electron microscopy(SEM)and ene rgy-dispersive X-ray spectroscopy(EDS)characterization as well as co mputational analysis of the phase stability diagram of the M-O-Cl system.To determine the optimum chlorination conditions,the effects of chlorinating agent dosage,reaction temperature and reaction time on the reaction were investigated.The results show that the rare earth components in Nd-Fe-B sludge are selectively chlorinated to RECl3and the formation of REOCl is avoided in the temperature range of 300-420℃,while the iron components are preferentially oxidized to Fe2O3.The selective chlorination reaction is consistent with the unreacted shrinking core model,and the rate-controlling step of the reaction is the internal diffusion process of NH4Cl through the transition layer of the reactant product to the surface of the Nd-Fe-B sludge.The complete chlorination of REEs is successfully achieved and 99.8%of REEs are selectively extracted into the leaching solution under optimal chlorination conditions(300℃,2.5 times of stoichiometric amount,4 h).展开更多
In this study,DyF_(3)powder was sprayed onto the polar and side surfaces of the magnets to determine the anisotropic diffusion mechanism of Dy in the sintered Nd-Fe-B magnet.The coercivity and squareness of the magnet...In this study,DyF_(3)powder was sprayed onto the polar and side surfaces of the magnets to determine the anisotropic diffusion mechanism of Dy in the sintered Nd-Fe-B magnet.The coercivity and squareness of the magnet in which the diffusion of Dy is perpendicular to the c-axis(a-magnet)are lower than those of the magnet with the diffusion of Dy parallel to the c-axis(c-magnet).Compared with the c-magnet,the a-magnet has a longer Dy-enrichment region from the diffusion surface,where Dy is enriched in the 2:14:1 grain.By contrast,the Dy concentration in the grain boundaries beyond the Dy enrichment region is lower in the a-magnet.Moreover,the Dy shells beyond the Dy enrichment region in the a-magnet are distributed on the side surfaces of the 2:14:1 grains but not on the polar surfaces.Based on the micromagnetic simulation,the Dy shells on the polar surfaces of the grains are more effective in enhancing coercivity.According to first-principle calculations,Dy migrating through 001 into the Nd vacancy in the Nd_(2)Fe_(14)B crystal has a higher diffusion barrier,thus indicating that the lattice diffusion of Dy parallel to the c-axis is more difficult.展开更多
Neodymium-iron-boron(Nd-Fe-B)sludge is an important secondary resource of rare-earth elements(REEs).However,the state-of-the-art recycling method,i.e.,HCl-preferential dissolution faces challenges such as slow leachin...Neodymium-iron-boron(Nd-Fe-B)sludge is an important secondary resource of rare-earth elements(REEs).However,the state-of-the-art recycling method,i.e.,HCl-preferential dissolution faces challenges such as slow leaching kinetics,excessive chemical consumption and wastewater generation.In this work,the in situ anodic leaching of Nd-Fe-B sludge was developed to selectively recover REEs with high efficiency.The leaching rates of the REEs are 2.4-9.0 times higher using the in situ anodic leaching at the current density from 10 to 40 mA/cm^(2)than using conventional chemical leaching under the maintained pH of 3.7.Mechanism studies reveal that the anode-generated H~+plays the key role during the in situ anodic leaching process that locally increases the H^(+)concentration at the interface of sludge particles,accele rating the leaching kinetics.By achieving a total leaching efficiency of Nd-Fe-B sludge close to 100%and the Fe deposition efficiency in the range of 70.9%-74.3%,selective leaching of REEs is successfully realized and thus largely reduces chemical consumption.Additionally,a two-step recycling route involving electrolysis-selective precipitation was proposed that enables a stable REEs recovery of 92.2%with recyclable electrolyte.This study provides a novel and environmentally-friendly strategy for the efficient recovery of REEs from secondary resources.展开更多
The enhancement of coercivity in Nd-Fe-B sintered magnets modified by Pr_(58)Dy_(10)Cu_(32)alloy was investigated through scanning electron microscope(SEM)and in-situ magneto-optic Kerr effect(MOKE)microscopy.The modi...The enhancement of coercivity in Nd-Fe-B sintered magnets modified by Pr_(58)Dy_(10)Cu_(32)alloy was investigated through scanning electron microscope(SEM)and in-situ magneto-optic Kerr effect(MOKE)microscopy.The modification treatment resulted in the formation of a smooth and continuous weakly magnetic grain boundary layer and the(Nd,Pr,Dy)_(2)Fe_(14)B main phase with a high magnetocrystalline anisotropy field,leading to an increased coercivity of 23 kOe.MOKE observations revealed that the dynamic evolution of the maze domain area under an external magnetic field varied significantly between the original and modified magnets.Compared with the original magnets,the modified magnets exhibited a slower decrease in maze domain area during magnetization and a slower increase during reverse magnetization,contributing to the observed coercivity enhancement.展开更多
Commercial N52 sintered NdFeB magnets were processed by grain boundary diffusion(GBD)with Dy-Co-M(M=Cu,AI)alloys.The coercivity of magnets greatly increase to 17.62 and 18.83 kOe respectively when diffusing Dy_(58)Co_...Commercial N52 sintered NdFeB magnets were processed by grain boundary diffusion(GBD)with Dy-Co-M(M=Cu,AI)alloys.The coercivity of magnets greatly increase to 17.62 and 18.83 kOe respectively when diffusing Dy_(58)Co_(25)Cu_(17)and Dy_(58)Co_(25)Al_(17)alloys,which are obviously higher than that of Dy58Co42GBD-treated magnet with 16.64 kOe,Further thermal stability studies indicate that the thermal stability of Dy_(58)Co_(25)Cu_(17)and Dy_(58)Co_(25)Al_(17)GBD-treated magnets is further improved compared to the Dy58Co42GBD-treated magnet The results show that th e temperature coefficients of remanence(20-120℃)are reduced from-0.148%/℃to-0.134%/℃and-0.132%/℃by Dy_(58)Co_(25)Cu_(17)and Dy_(58)Co_(25)Al_(17)GBD-treatment,respectively.Besides,the irreversible magnetic flux losses(120℃)for Dy_(58)Co_(25)Cu_(17)and Dy_(58)Co_(25)Al_(17)diffusion magnets are 4.76%and 2.79%,respectively.Microstructural analyses demonstrate that the presence of Cu and Al elements reduces the excessive accumulation of Dy and Co on the surface in the diffusion magnets an d improves the diffusion depth and utilization of Dy and Co.Furthermore,the flow of Co from the triple junction phase to the thin grain boundary phase is promoted,which contributes to the uniform distribution of Co.In addition,the dynamic evolution of the magnetic domain structure during the temperature rise process was studied.This work provides insight into the preparation of high-performance and high-thermal stability magnets.展开更多
By developing high comprehensive performance((BH)_(max)+H_(cj)),Nd-Fe-B magnets can operate stably in high-temperature applications,greatly expanding the application scenarios of them.Unfortunately,there is a constrai...By developing high comprehensive performance((BH)_(max)+H_(cj)),Nd-Fe-B magnets can operate stably in high-temperature applications,greatly expanding the application scenarios of them.Unfortunately,there is a constraint relationship between coercivity(H_(cj))and maximum magnetic energy product((BH)_(max)),and an increase in H_(cj) always accompanies a decrease in(BH)_(max).Here,the excellent comprehensive magnetic performance of up to 86.54,namely(BH)_(max) of 42.33 MGOe and H_(cj) of 44.21 kOe,is unprecedented in the sintered Nd-Fe-B magnets.This magnet is obtained by designing a unique grain structure through micrometallurgical reactions to prepare a matrix with excellent comprehensive performance,and then by stepwise diffusion,the(BH)_(max) and H_(cj) of the magnet are simultaneously enhanced.The magnet prepared in this way has a“double-shell core”structure and Tb segregation distribution inside the core.The working temperature of the magnet in this work reached 280℃,providing a new approach for the development of high-performance Nd-Fe-B magnets.展开更多
基金supported by the National Natural Science Foundation of China(No.52271165)the National Key R&D Program of China(No.2022YFB3505501).
文摘In this paper,the fracture behaviors and interface stresses of sintered Nd-Fe-B magnets were investigated.It was revealed that cracks propagated along the interfaces of Nd_(2)Fe_(14)B/Nd_(2)Fe_(14)B,Nd_(2)Fe_(14)B/Nd-rich phases and within Nd-rich phases.The misfits between 2:14:1 and Nd-rich phases were quantitatively determined,reflecting the concentration of interface stresses in magnet.Grain boundaries of magnet were reconstructed by diffusing Tb-containing and Tb-free sources,respectively.The Tb-rich shells at extensive layers of 2:14:1 grains caused lattice distortion,i.e.,internal stresses,resulting in the crack mode changing from intergranular to transgranular in near surfaces of Tb-containing diffused magnets.Therefore,the bending strengths were deteriorated although the coercivities were apparently enhanced.In the case of Tb-free Pr-Cu diffused magnet,the Pr and Cu elements were enriched at grain boundaries,and the misfits between 2:14:1 and Nd-rich phases were declined,lowering interface stresses and strengthening grain boundaries.The mechanical and magnetic properties of Pr-Cu diffused magnet were simultaneously improved.
基金Project supported by the National Natural Science Foundation of China(52261037,52401251)Key Research Project of Jiangxi Province(20203ABC28W006)+2 种基金the Research Fund of Key Laboratory of Rare Earths,Chinese Academy of SciencesKey Laboratory of Ionic Rare Earth Re sources and Environment,Ministry of Natural Resources of the People's Republic of China(2022IRERE302)the Ganzhou Science and Technology Innovation Empowerment Youth"Jie bang Gua shuai"Project。
文摘Recovery of rare earth elements(REEs)from bulk Nd-Fe-B scrap by chlorination with NH_(4)Cl as a chlorinating agent has been reported to be an energy efficient and environmentally friendly method.However,the reaction mechanism and phase evolution of the low-temperature selective chlorination process of Nd-Fe-B sludge are not clear.In this paper,we systematically investigated the lowtemperature selective chlorination process of Nd-Fe-B sludge with NH4Cl by combining thermokinetic theoretical calculations and experiments,and revealed its reaction mechanism.The phase evolution during chlorination was determined by X-ray diffraction(XRD),scanning electron microscopy(SEM)and ene rgy-dispersive X-ray spectroscopy(EDS)characterization as well as co mputational analysis of the phase stability diagram of the M-O-Cl system.To determine the optimum chlorination conditions,the effects of chlorinating agent dosage,reaction temperature and reaction time on the reaction were investigated.The results show that the rare earth components in Nd-Fe-B sludge are selectively chlorinated to RECl3and the formation of REOCl is avoided in the temperature range of 300-420℃,while the iron components are preferentially oxidized to Fe2O3.The selective chlorination reaction is consistent with the unreacted shrinking core model,and the rate-controlling step of the reaction is the internal diffusion process of NH4Cl through the transition layer of the reactant product to the surface of the Nd-Fe-B sludge.The complete chlorination of REEs is successfully achieved and 99.8%of REEs are selectively extracted into the leaching solution under optimal chlorination conditions(300℃,2.5 times of stoichiometric amount,4 h).
基金supported by the National Natural Science Foundation of China(52361033)National Key Research and Development Program(2022YFB3505400)+1 种基金the Main Discipline and Technology Leaders Training Plan of Jiangxi Province(2022BCJ23007)the Jiangxi Province Postgraduate Innovation Project(YC2022-S693)。
文摘In this study,DyF_(3)powder was sprayed onto the polar and side surfaces of the magnets to determine the anisotropic diffusion mechanism of Dy in the sintered Nd-Fe-B magnet.The coercivity and squareness of the magnet in which the diffusion of Dy is perpendicular to the c-axis(a-magnet)are lower than those of the magnet with the diffusion of Dy parallel to the c-axis(c-magnet).Compared with the c-magnet,the a-magnet has a longer Dy-enrichment region from the diffusion surface,where Dy is enriched in the 2:14:1 grain.By contrast,the Dy concentration in the grain boundaries beyond the Dy enrichment region is lower in the a-magnet.Moreover,the Dy shells beyond the Dy enrichment region in the a-magnet are distributed on the side surfaces of the 2:14:1 grains but not on the polar surfaces.Based on the micromagnetic simulation,the Dy shells on the polar surfaces of the grains are more effective in enhancing coercivity.According to first-principle calculations,Dy migrating through 001 into the Nd vacancy in the Nd_(2)Fe_(14)B crystal has a higher diffusion barrier,thus indicating that the lattice diffusion of Dy parallel to the c-axis is more difficult.
基金Project supported by the Natural Science Foundation of Inner Mongolia Autonomous Region of China(2021BS02007,2022MS02014)the"Science and Technology Project of Ordos"Program(2021 CGI 17-9,2021 ZDI11-14)+2 种基金the National Natural Science Foundation of China(21971129,21961022,51903125,21661023)the"Inner Mongolia Autonomous Region 2022 Leading Talent Team of Science and Technology"Program(2022LJRC0008)China Postdoctoral Science Foundation(2018M640043,2019T120038)。
文摘Neodymium-iron-boron(Nd-Fe-B)sludge is an important secondary resource of rare-earth elements(REEs).However,the state-of-the-art recycling method,i.e.,HCl-preferential dissolution faces challenges such as slow leaching kinetics,excessive chemical consumption and wastewater generation.In this work,the in situ anodic leaching of Nd-Fe-B sludge was developed to selectively recover REEs with high efficiency.The leaching rates of the REEs are 2.4-9.0 times higher using the in situ anodic leaching at the current density from 10 to 40 mA/cm^(2)than using conventional chemical leaching under the maintained pH of 3.7.Mechanism studies reveal that the anode-generated H~+plays the key role during the in situ anodic leaching process that locally increases the H^(+)concentration at the interface of sludge particles,accele rating the leaching kinetics.By achieving a total leaching efficiency of Nd-Fe-B sludge close to 100%and the Fe deposition efficiency in the range of 70.9%-74.3%,selective leaching of REEs is successfully realized and thus largely reduces chemical consumption.Additionally,a two-step recycling route involving electrolysis-selective precipitation was proposed that enables a stable REEs recovery of 92.2%with recyclable electrolyte.This study provides a novel and environmentally-friendly strategy for the efficient recovery of REEs from secondary resources.
基金supported by the National Key Research and Development Program of China(Grant Nos.2021YFB3500300,2023YFB3507000,and 2023XYJG0001-01-03)the National Natural Science Foundation of China(Grant No.52171167)Inner Mongolia Northern Rare Earth Advanced Materials Technology Innovation Co.,Ltd.Project(Grant No.CXZX-B-202304-0004).
文摘The enhancement of coercivity in Nd-Fe-B sintered magnets modified by Pr_(58)Dy_(10)Cu_(32)alloy was investigated through scanning electron microscope(SEM)and in-situ magneto-optic Kerr effect(MOKE)microscopy.The modification treatment resulted in the formation of a smooth and continuous weakly magnetic grain boundary layer and the(Nd,Pr,Dy)_(2)Fe_(14)B main phase with a high magnetocrystalline anisotropy field,leading to an increased coercivity of 23 kOe.MOKE observations revealed that the dynamic evolution of the maze domain area under an external magnetic field varied significantly between the original and modified magnets.Compared with the original magnets,the modified magnets exhibited a slower decrease in maze domain area during magnetization and a slower increase during reverse magnetization,contributing to the observed coercivity enhancement.
基金Project supported by the National Key R&D Program of China(2022YFB3505003,2021YFB3502802)the Natural Science Foundation of Zhejiang Province(LQ23E010001)+3 种基金"Pioneer"and"Leading Goose"R&D program of Zhejiang(2022C01020)Key Research and Development Program of Ningbo City(2023Z093)Kunpeng Plan of Zhejiang ProvinceNingbo Top Talent Program。
文摘Commercial N52 sintered NdFeB magnets were processed by grain boundary diffusion(GBD)with Dy-Co-M(M=Cu,AI)alloys.The coercivity of magnets greatly increase to 17.62 and 18.83 kOe respectively when diffusing Dy_(58)Co_(25)Cu_(17)and Dy_(58)Co_(25)Al_(17)alloys,which are obviously higher than that of Dy58Co42GBD-treated magnet with 16.64 kOe,Further thermal stability studies indicate that the thermal stability of Dy_(58)Co_(25)Cu_(17)and Dy_(58)Co_(25)Al_(17)GBD-treated magnets is further improved compared to the Dy58Co42GBD-treated magnet The results show that th e temperature coefficients of remanence(20-120℃)are reduced from-0.148%/℃to-0.134%/℃and-0.132%/℃by Dy_(58)Co_(25)Cu_(17)and Dy_(58)Co_(25)Al_(17)GBD-treatment,respectively.Besides,the irreversible magnetic flux losses(120℃)for Dy_(58)Co_(25)Cu_(17)and Dy_(58)Co_(25)Al_(17)diffusion magnets are 4.76%and 2.79%,respectively.Microstructural analyses demonstrate that the presence of Cu and Al elements reduces the excessive accumulation of Dy and Co on the surface in the diffusion magnets an d improves the diffusion depth and utilization of Dy and Co.Furthermore,the flow of Co from the triple junction phase to the thin grain boundary phase is promoted,which contributes to the uniform distribution of Co.In addition,the dynamic evolution of the magnetic domain structure during the temperature rise process was studied.This work provides insight into the preparation of high-performance and high-thermal stability magnets.
基金supported by the National Key Research and Development Program of China(No.2021YFB3502802)Zhejiang Provincial Department of Science and Technology of China(No.2022C01020)+3 种基金the Key Research and Development Program of Ningbo City(No.2023Z093)Ningbo Natural Science Foundation(No.2023J344)the Natural Science Foundation of Zhejiang Province(No.LQ23E010001)Ningbo Young Science and Technology Innovation Leading Talents(No.2023QL040).
文摘By developing high comprehensive performance((BH)_(max)+H_(cj)),Nd-Fe-B magnets can operate stably in high-temperature applications,greatly expanding the application scenarios of them.Unfortunately,there is a constraint relationship between coercivity(H_(cj))and maximum magnetic energy product((BH)_(max)),and an increase in H_(cj) always accompanies a decrease in(BH)_(max).Here,the excellent comprehensive magnetic performance of up to 86.54,namely(BH)_(max) of 42.33 MGOe and H_(cj) of 44.21 kOe,is unprecedented in the sintered Nd-Fe-B magnets.This magnet is obtained by designing a unique grain structure through micrometallurgical reactions to prepare a matrix with excellent comprehensive performance,and then by stepwise diffusion,the(BH)_(max) and H_(cj) of the magnet are simultaneously enhanced.The magnet prepared in this way has a“double-shell core”structure and Tb segregation distribution inside the core.The working temperature of the magnet in this work reached 280℃,providing a new approach for the development of high-performance Nd-Fe-B magnets.
