(2,3-Dimethylbutyl)(2,4,40-trimethylpentyl)phosphinic acid(INET-3) was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl(Pre-XAD-16) to prepare the solvent impregnated res...(2,3-Dimethylbutyl)(2,4,40-trimethylpentyl)phosphinic acid(INET-3) was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl(Pre-XAD-16) to prepare the solvent impregnated resins SIRs-INET-3/XAD-16 and SIRs-INET-3/Pre-XAD-16. The molecular weight distribution of the low molecular weight(LMW) polymers washed off by ethyl alcohol during XAD-16 pretreatment was determined by gel permeation chromatography(GPC). The macroporous resins(XAD-16 & Pre-XAD-16), the corresponding solvent impregnated resins(SIRs-INET-3/XAD-16 &SIRs-INET-3/Pre-XAD-16) and the PVA coated SIRs-INET-3/Pre-XAD-16 with boric acid as cross-linking agent were characterized by FT-IR, SEM-EDS and TGA. The effects of XAD-16 pretreatment and PVA coating technology on RE(III) adsorption equilibrium time, INET-3 losses during extraction and adsorption capacity were investigated. The adsorption kinetics, selectivity and stripping behaviors of SIRs-INET-3/XAD-16 were further studied. The washed off LMW polymers had the Mn of 36,656, Mw of 40,310 and polydispersity coefficient of 1.10. The SIRs-INET-3/XAD-16 had shorter equilibrium time,less INET-3 loss and more Tm(III) adsorption capacity than the SIRs-INET-3/Pre-XAD-16. The PVA coated SIRs-INET-3/Pre-XAD-16 had less INET-3 loss and more Tm(III) adsorption capacity but longer equilibrium time than the uncoated SIRs-INET-3/Pre-XAD-16. The adsorption of RE(III) on the SIRsINET-3/XAD-16 followed the pseudo-second-order kinetic model. The Tm(III) accumulative adsorption amounts onto SIRs-INET-3/XAD-16 after eight extraction stages was 23.6 mg/g. The separation factors of adjacent heavy RE(III) β_(Er/Ho), β_(Tm/Er), β_(Yb/Tm) and β_(Lu/Yb) values were 1.76, 2.59, 2.56 and 1.19,respectively. The adsorbed Lu(III) onto the SIRs-INET-3/XAD-16 can be stripped completely by 1.0 mol/L H_2SO_4.展开更多
A solid-phase extraction resin SIRs-P227/XAD-7 HP was prepared by impregnating extractant P227 onto macroporous resin XAD-7 HP beads. SIRs-P227/XAD-7 HP beads were characterized by Fourier transform infrared spectrosc...A solid-phase extraction resin SIRs-P227/XAD-7 HP was prepared by impregnating extractant P227 onto macroporous resin XAD-7 HP beads. SIRs-P227/XAD-7 HP beads were characterized by Fourier transform infrared spectroscopy(FTIR) and scanning electron microscopy(SEM) equipped with energy-dispersive spectroscopy(EDS). The adsorption kinetics, particle size effect,adsorption isotherm, pH_(equilibrium)–lg D relationship(where D is distribution coefficient), desorption, adsorption selectivity for heavy rare earths, and impurity ions were studied. The results showed that the adsorption kinetics of Lu(III) on the SIRs-P227/XAD-7 HP beads fitted the Morris–Weber model best. The adsorbance decreased as the particle size increased. The pH_(equilibrium)–lg D relationship fitted well with a straight line, and the slope was 1.56. The experimental data fitted well with Langmuir adsorption.The calculated maximum adsorption capacity was23.8 mg·g^(-1), while the experimental datum was22.7 mg·g^(-1) at the given conditions. The adsorbed Lu(III)can be easily stripped by 0.1 mol·L^(-1) HCl. The adsorption selectivity of SIRs-P227/XAD-7 HP for heavy REs exhibited the following order: Lu>Yb>Tm>Er>Ho. The adjacent heavy rare earth(RE) separation factors β_(Lu/Yb),β_(Yb/Tm), β_(Tm/Er), and β_(Er/Ho)were 1.57, 3.00, 3.03, and 2.23,respectively, at liquid/solid ratio(L/S) equal to 3:20. The adsorption selectivity for impurity ions exhibited the followingorder:Fe >Lu>Tm>Zn>Mg>Ca>Ho>Co>Ni>Cu>Al.展开更多
The relationship between dialkylphosphinic acid structure and their loading capacity for HREEs and emulsification phenomena has rarely been studied.In this paper,we took Lu extraction as an example to study the effect...The relationship between dialkylphosphinic acid structure and their loading capacity for HREEs and emulsification phenomena has rarely been studied.In this paper,we took Lu extraction as an example to study the effect of β,γ,δ-substituents of dialkylphosphinic acids on their loading capacity and anti-emulsification performance for HREEs.To discuss conveniently,the dialkylphosphinic acids were classified into two groups:β-substituent group(P208,INET-1,P218,USTB-1 and P227)and γ,δ-substituent group(P218,P2132 and Cyanex 272).For β-substituent group extractants,their loading capacities are in the order P208(299.7 mg/L)≈INET-1(299.5 mg/L)>P218(270.8 mg/L)>>USTB-1(163.1 mg/L)>P227(151.4 mg/L),while their anti-emulsification/gelation performances are just in the opposite order P227>USTB-1>P218>P208≈INET-1 under the studied conditions.For γ,δ-substituent group extractants,their loading capacities are in the order P218(270.8 mg/L)>P2132(192.3 mg/L)>Cyanex272(131.7 mg/L),while the anti-emulsification performance of P218 is better than those of P2132 and Cyanex 272.The loading capacity data given in the parentheses are obtained through repeatedly extracting Lu from ~4×10^(-4)mol/L of Lu aqueous feed solution with initial pH of 2.40 by 0.01 mol/L extractant at phase ratio A/O of 1:1.展开更多
Grain boundary diffusion process(GBDP)is a widely used method of increasing the coercivity of sintered NdFeB magnets.In this study,the effects of the GBDP on the bending strength and microhardness of sintered NdFeB ma...Grain boundary diffusion process(GBDP)is a widely used method of increasing the coercivity of sintered NdFeB magnets.In this study,the effects of the GBDP on the bending strength and microhardness of sintered NdFeB magnets and the fracture mode were investigated.Results show that the bending strength of magnets is reduced by pickling and heat treatment and greatly recove rs after heavy rare earth element(Tb)grain boundary diffusion.The pickling and the heat treatment cause a slight decrease in microhardness.Compared with the recovery of the bending strength,the hardness decreases after the GBDP.The fracture mode of bended magnets changes from intergranular to transgranular.This study helps in further improving the mechanical and magnetic properties of sintered NdFeB magnets.展开更多
Heavy rare earth element(HREE)separation has always been a great challenge.The kind of dialkylphosphinic acids is recognized as the third generation of organophosphorous acid extractants.However,detailed relationship ...Heavy rare earth element(HREE)separation has always been a great challenge.The kind of dialkylphosphinic acids is recognized as the third generation of organophosphorous acid extractants.However,detailed relationship betweenβ-substituent(especially when it changes from H to methyl,and further to ethyl)and their extraction behaviors and selectivity for HREEs have rarely been reported.Besides,there are also few reports on effect ofγ,δ-substituent on HREE extraction and separation.In this paper,we synthesized five and collected two dialkylphosphinic acids with differentβ,γ,δ-substituents(from H to ethyl).These extractants were divided into two groups to discuss their extraction behaviors and selectivity for HREEs:β-substituent group(P208,INET-1,P218,USTB-1 and P227)andγ,δ-substituent group(P218,P2132 and Cyanex 272).To evaluate and compare their extractabilities,P507 was used as a reference and Tm,Yb,Lu were extracted with 0.01 mol/L of these extractants from single Tm,Yb and Lu solutions(~4×10^(-4)mol/L)at different initial pH.Besides,pH_(0.5)(Tm),pH_(0.5)^(Yb)and pH_(0.5)^(Lu)values and their differences(ΔpH_(0.5)^(Tm-Yb),ΔpH_(0.5)^(Yb-Lu),ΔpH_(0.5)^(Tm-Lu))for each extractant were given to roughly evaluate their separation performance for Tm,Yb and Lu.To further investigate the selectivity of these extractants for HREEs,Tb,Dy,Ho,Er,Tm,Yb and Lu were extracted from their mixed solution with initial pH of 4.00 at phase ratio A/O of 2:1,1:1 or 1:2.Their HREE separation performance is mainly discussed based on the adjacent HREE separation factors(β_(N+1/N))and their average value(β_(Tb-Lu)).展开更多
To get a systematic understanding about dependence of deposition conditions on properties of Gd films,a series of Gd films were prepared under different Ar gas pressures:0.5,0.7,1.0,and 1.5 Pa,and another series of Gd...To get a systematic understanding about dependence of deposition conditions on properties of Gd films,a series of Gd films were prepared under different Ar gas pressures:0.5,0.7,1.0,and 1.5 Pa,and another series of Gd films were prepared under different substrate temperatures:25,100,200,350,and 500℃.The effects of the deposition time,Ar pressure,and substrate temperature on microstructures and crystal orientation were investigated by grazingincidence X-ray diffraction(GIXRD)and transmission electron microscopy(TEM).The experimental results show that low Ar pressure and plenty deposition time will contribute to the formation of Gd hcp phase,which has better magnetic properties such as higher Curie temperature and bigger magnetic moment,and high substrate temperature can diminish the inner stress in Gd films and promote lattice parameters closer to those of the ideal Gd hcp-structure.展开更多
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
The grain boundary diffusion(GBD) technology was used to prepare high performance Nd-Fe-B sintered magnets by NdH3 and TbH3 nanoparticle diffusion.The factors affecting the coercivity of GBD magnets include distributi...The grain boundary diffusion(GBD) technology was used to prepare high performance Nd-Fe-B sintered magnets by NdH3 and TbH3 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.展开更多
基金Project supported by the National Natural Science Foundation of China(21301104)the State Key Laboratory of Chemical Engineering(SKLCh E-14A04)the Fundamental Research Funds for the Central Universities(FRFTP-16-019A3)
文摘(2,3-Dimethylbutyl)(2,4,40-trimethylpentyl)phosphinic acid(INET-3) was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl(Pre-XAD-16) to prepare the solvent impregnated resins SIRs-INET-3/XAD-16 and SIRs-INET-3/Pre-XAD-16. The molecular weight distribution of the low molecular weight(LMW) polymers washed off by ethyl alcohol during XAD-16 pretreatment was determined by gel permeation chromatography(GPC). The macroporous resins(XAD-16 & Pre-XAD-16), the corresponding solvent impregnated resins(SIRs-INET-3/XAD-16 &SIRs-INET-3/Pre-XAD-16) and the PVA coated SIRs-INET-3/Pre-XAD-16 with boric acid as cross-linking agent were characterized by FT-IR, SEM-EDS and TGA. The effects of XAD-16 pretreatment and PVA coating technology on RE(III) adsorption equilibrium time, INET-3 losses during extraction and adsorption capacity were investigated. The adsorption kinetics, selectivity and stripping behaviors of SIRs-INET-3/XAD-16 were further studied. The washed off LMW polymers had the Mn of 36,656, Mw of 40,310 and polydispersity coefficient of 1.10. The SIRs-INET-3/XAD-16 had shorter equilibrium time,less INET-3 loss and more Tm(III) adsorption capacity than the SIRs-INET-3/Pre-XAD-16. The PVA coated SIRs-INET-3/Pre-XAD-16 had less INET-3 loss and more Tm(III) adsorption capacity but longer equilibrium time than the uncoated SIRs-INET-3/Pre-XAD-16. The adsorption of RE(III) on the SIRsINET-3/XAD-16 followed the pseudo-second-order kinetic model. The Tm(III) accumulative adsorption amounts onto SIRs-INET-3/XAD-16 after eight extraction stages was 23.6 mg/g. The separation factors of adjacent heavy RE(III) β_(Er/Ho), β_(Tm/Er), β_(Yb/Tm) and β_(Lu/Yb) values were 1.76, 2.59, 2.56 and 1.19,respectively. The adsorbed Lu(III) onto the SIRs-INET-3/XAD-16 can be stripped completely by 1.0 mol/L H_2SO_4.
基金financially supported by the National Natural Science Foundation of China(Nos.51974026 and 21301104)the National Key R&D Program of China(No.2018YFC1900604)the Fundamental Research Funds for the Central Universities(No.FRF-TP-16019A3)。
文摘A solid-phase extraction resin SIRs-P227/XAD-7 HP was prepared by impregnating extractant P227 onto macroporous resin XAD-7 HP beads. SIRs-P227/XAD-7 HP beads were characterized by Fourier transform infrared spectroscopy(FTIR) and scanning electron microscopy(SEM) equipped with energy-dispersive spectroscopy(EDS). The adsorption kinetics, particle size effect,adsorption isotherm, pH_(equilibrium)–lg D relationship(where D is distribution coefficient), desorption, adsorption selectivity for heavy rare earths, and impurity ions were studied. The results showed that the adsorption kinetics of Lu(III) on the SIRs-P227/XAD-7 HP beads fitted the Morris–Weber model best. The adsorbance decreased as the particle size increased. The pH_(equilibrium)–lg D relationship fitted well with a straight line, and the slope was 1.56. The experimental data fitted well with Langmuir adsorption.The calculated maximum adsorption capacity was23.8 mg·g^(-1), while the experimental datum was22.7 mg·g^(-1) at the given conditions. The adsorbed Lu(III)can be easily stripped by 0.1 mol·L^(-1) HCl. The adsorption selectivity of SIRs-P227/XAD-7 HP for heavy REs exhibited the following order: Lu>Yb>Tm>Er>Ho. The adjacent heavy rare earth(RE) separation factors β_(Lu/Yb),β_(Yb/Tm), β_(Tm/Er), and β_(Er/Ho)were 1.57, 3.00, 3.03, and 2.23,respectively, at liquid/solid ratio(L/S) equal to 3:20. The adsorption selectivity for impurity ions exhibited the followingorder:Fe >Lu>Tm>Zn>Mg>Ca>Ho>Co>Ni>Cu>Al.
基金Project supported by the National Natural Science Foundation of China(51974026,21301104)the State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization。
文摘The relationship between dialkylphosphinic acid structure and their loading capacity for HREEs and emulsification phenomena has rarely been studied.In this paper,we took Lu extraction as an example to study the effect of β,γ,δ-substituents of dialkylphosphinic acids on their loading capacity and anti-emulsification performance for HREEs.To discuss conveniently,the dialkylphosphinic acids were classified into two groups:β-substituent group(P208,INET-1,P218,USTB-1 and P227)and γ,δ-substituent group(P218,P2132 and Cyanex 272).For β-substituent group extractants,their loading capacities are in the order P208(299.7 mg/L)≈INET-1(299.5 mg/L)>P218(270.8 mg/L)>>USTB-1(163.1 mg/L)>P227(151.4 mg/L),while their anti-emulsification/gelation performances are just in the opposite order P227>USTB-1>P218>P208≈INET-1 under the studied conditions.For γ,δ-substituent group extractants,their loading capacities are in the order P218(270.8 mg/L)>P2132(192.3 mg/L)>Cyanex272(131.7 mg/L),while the anti-emulsification performance of P218 is better than those of P2132 and Cyanex 272.The loading capacity data given in the parentheses are obtained through repeatedly extracting Lu from ~4×10^(-4)mol/L of Lu aqueous feed solution with initial pH of 2.40 by 0.01 mol/L extractant at phase ratio A/O of 1:1.
基金Project supported by the National Key Research and Development Program of China(2021YFB3502902)the Key Research and Development Program of Ningbo(2021Z024)。
文摘Grain boundary diffusion process(GBDP)is a widely used method of increasing the coercivity of sintered NdFeB magnets.In this study,the effects of the GBDP on the bending strength and microhardness of sintered NdFeB magnets and the fracture mode were investigated.Results show that the bending strength of magnets is reduced by pickling and heat treatment and greatly recove rs after heavy rare earth element(Tb)grain boundary diffusion.The pickling and the heat treatment cause a slight decrease in microhardness.Compared with the recovery of the bending strength,the hardness decreases after the GBDP.The fracture mode of bended magnets changes from intergranular to transgranular.This study helps in further improving the mechanical and magnetic properties of sintered NdFeB magnets.
基金Project supported by the National Natural Science Foundation of China (51974026,21301104)the State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization。
文摘Heavy rare earth element(HREE)separation has always been a great challenge.The kind of dialkylphosphinic acids is recognized as the third generation of organophosphorous acid extractants.However,detailed relationship betweenβ-substituent(especially when it changes from H to methyl,and further to ethyl)and their extraction behaviors and selectivity for HREEs have rarely been reported.Besides,there are also few reports on effect ofγ,δ-substituent on HREE extraction and separation.In this paper,we synthesized five and collected two dialkylphosphinic acids with differentβ,γ,δ-substituents(from H to ethyl).These extractants were divided into two groups to discuss their extraction behaviors and selectivity for HREEs:β-substituent group(P208,INET-1,P218,USTB-1 and P227)andγ,δ-substituent group(P218,P2132 and Cyanex 272).To evaluate and compare their extractabilities,P507 was used as a reference and Tm,Yb,Lu were extracted with 0.01 mol/L of these extractants from single Tm,Yb and Lu solutions(~4×10^(-4)mol/L)at different initial pH.Besides,pH_(0.5)(Tm),pH_(0.5)^(Yb)and pH_(0.5)^(Lu)values and their differences(ΔpH_(0.5)^(Tm-Yb),ΔpH_(0.5)^(Yb-Lu),ΔpH_(0.5)^(Tm-Lu))for each extractant were given to roughly evaluate their separation performance for Tm,Yb and Lu.To further investigate the selectivity of these extractants for HREEs,Tb,Dy,Ho,Er,Tm,Yb and Lu were extracted from their mixed solution with initial pH of 4.00 at phase ratio A/O of 2:1,1:1 or 1:2.Their HREE separation performance is mainly discussed based on the adjacent HREE separation factors(β_(N+1/N))and their average value(β_(Tb-Lu)).
基金financially supported by the National Natural Science Foundation of China(No.5150010868)。
文摘To get a systematic understanding about dependence of deposition conditions on properties of Gd films,a series of Gd films were prepared under different Ar gas pressures:0.5,0.7,1.0,and 1.5 Pa,and another series of Gd films were prepared under different substrate temperatures:25,100,200,350,and 500℃.The effects of the deposition time,Ar pressure,and substrate temperature on microstructures and crystal orientation were investigated by grazingincidence X-ray diffraction(GIXRD)and transmission electron microscopy(TEM).The experimental results show that low Ar pressure and plenty deposition time will contribute to the formation of Gd hcp phase,which has better magnetic properties such as higher Curie temperature and bigger magnetic moment,and high substrate temperature can diminish the inner stress in Gd films and promote lattice parameters closer to those of the ideal Gd hcp-structure.
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 National Natural Science Foundation of China(51971005,51371002)the National Key Research and Development Program of China(2018YFC1903405)+1 种基金International S&T Cooperation Program of China(2015DFG52020)Program of Top Disciplines Construction in Beijing(PXM2019_014204_500031)。
文摘The grain boundary diffusion(GBD) technology was used to prepare high performance Nd-Fe-B sintered magnets by NdH3 and TbH3 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.