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稀土学报（英文版）
稀土学报（英文版）

徐光宪

月刊

1002-0721

jrechina@263.net xtxb@grinm.com

010-62014832

100088

北京新街口外大街2号中国稀土学报编辑部

稀土学报（英文版）/Journal Journal of Rare EarthsCSCDCSTPCD北大核心EISCI
查看更多>>本学报是由中国稀土学会主办、北京有色金属研究总院承办、北京大学协办的综合性学术刊物。它涉及的主要内容有稀土化学与湿法冶金；稀土金属学与湿法冶金；稀土新材料（磁性材料、超导材料、纳米材料等）；稀土固体物理与固体化学；稀土应用研究；稀土分析检测；稀土地质、矿物和选矿等。主要栏目有综合评述、学术论文、研究快报及研究简报等。
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    Syntheses of new di-nuclear and tetra-nuclear lanthanide 9-anthracenecarboxylates:Magnetocaloric effect,slow magnetic relaxation and luminescent properties

    Xing LiuRuonan YangLu ZhangJian Zhou...
    1101-1109页
    查看更多>>摘要：Lanthanide complex-based materials with magnetic and luminescent properties have received a great deal of attention,owing to their importantly potential applications in diverse fields.In this work,the 9-anthracenecarboxylic acid(9-Haca)as bridging ligand was applied in combination with optically activeπ-conjugated 2,4,6-tri(2-pyridyl)-1,3,5-triazine(tptz)to construct a series of new di-nuclear and tetra-nuclear lanthanide 9-anthracenecarboxylates[La2(9-aca)6(tptz)2(μ-H2O)]·0.25H2O(1),[Ln2(9-aca)6(tptz)2(H2O)2]·0.5AQ·CH3COOH2H2O[Ln=Sm(2a),Eu(2b),Gd(2c),Tb(2d),Dy(2e),Tm(2f);AQ=9,10-anthracenedione]and[Ln4(9-aca)10(tptz)2(CH3COO)2]·H2O[Ln=Eu(3a),Gd(3b),Dy(3c)].1 displays a di-nuclear centrosymmetric moiety[La2(9-aca)6(tptz)2(µ-H2O)]built up from two complex[La(9-aca)2(tptz)]groups bridged by one H2O molecule and two syn-syn-µ2-η1:η1-9-aca-bridging li-gands,while 2a-2f are isostructural and comprise another di-nuclear centrosymmetric moieties[Ln2(9-aca)6(tptz)2(H2O)2]based on two complex[Ln(9-aca)2(tptz)(H2O)]groups connected by two syn-syn-μ2-η1∶η1-9-aca-bridging ligands.3a-3c are isostructural and show tetra-nuclear centrosymmetric moieties[Ln4(9-aca)10(tptz)2(CH3COO)2]containing three types of coordination modes of 9-aca-ligands.The present compounds offer the only examples of lanthanide 9-anthracenecarboxylates decorated by optically active tptz.Magnetic investigations of 2a,2c-2f,and 3b-3c indicate that 3c is typical of slow relaxation of the magnetization,while 2c and 3b show significant magnetocaloric effect(MCE)with the value of-△Sm of 5.26 J/(kg·K)at 4 K and 15.65 J/(kg·K)at 2 K(△H=7 T),respectively.The luminescent properties were also studied and reveal that the characteristic luminescent properties of the π-conju-gated aromatic ligands are introduced into magnetic lanthanide 9-anthracenecarboxylates,simulta-neously exhibiting slow magnetic relaxation(or MCE)and luminescent properties.
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    Growth,optical dispersion and magnetic behavior of Dy3+doped yttrium iron garnet crystals

    Yating FangHui ShenYudie MaShijie Liao...
    1110-1117页
    查看更多>>摘要：Y3Fe5O12(YIG)crystals are highly desirable for the fabrication of mid-infrared isolators with the rapid growth of optical communications,although it is rather challenging to grow large size and high-quality single crystals.Dy3+doping is expected to improve the optical and magneto-optical properties.However,high quality Dy:YIG crystals and the adjustment of Dy3+on the structure and optical behavior of YIG crystal remain unclear,impeding its practical applications.Herein,a series of Y3-xDyxFe5O12(x=0,0.5,1.0,1.5,3)solid solution crystals was grown by the flux-Bridgman method and single crystals up to 25 mm were obtained.With the introduction of Dy3+,lattice parameters are gradually enlarged from 1.2379 nm(YIG)to 1.2420 nm(DyIG).Typical Dy3+absorption peaks are observed around 1070,1265 and 1670 nm.The refractive index decreases from 2.37(500 nm)to 2.10(2500 nm)for YIG crystal,and it reduces from 2.47(500 nm)to 2.16(2500 nm)for DyIG crystal.The optical bandgaps remain almost unchanged for Dy∶YIG crystals.The optical dispersion of the refractive indices was finely fitted by the Wemple and DiDomenico(WDD)and the Sellmeier models,respectively.With the increase of Dy3+content,the saturation magnetization(Ms)decreases significantly from 23.62 emu/g(YIG)to 5.33 emu/g(DyIG).Small coercive field is persisted for this system,endowing small external magnetic field.These results provide valuable references for the manipulation of rare earths on the properties of magneto-optical crystals,which is beneficial to the design of high-performance garnet crystals for the applica-tion of optical switching and non-reciprocal related devices.
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    ⅢA-ⅡB multicomponent perovskite rare earth ferrites with promising electromagnetic wave absorption properties

    Yanyan HeTao ChenYanyu PanMinzhong Huang...
    1118-1127页
    查看更多>>摘要：Perovskite-type rare-earth ferrites(REFeO3)are promising materials for absorbing electromagnetic(EM)wave pollution.However,insufficient dielectric loss and poor impedance matching are key factors that limit the broader implementation of REFeO3.Herein,a series of multicomponent perovskite-type ferrites with strong EM wave absorption capabilities was prepared.Through the synergistic effect of chemical constitution regulation and entropy regulation,optimization of the dielectric loss and impedance matching is achieved by strengthening the structural defect mechanism,thus further adjusting the EM wave absorption performance.Compared with(LaGdSmNdBa)FeO3(HE-1)and(LaGdPrSmNdBa)FeO3(HE-2),(LaGdBa)FeO3(ME-1)and(LaGdSmBa)FeO3(ME-2)exhibit favorable performance,with optimal minimum reflection loss(RLmin)of-56.35 dB(at 11.12 GHz)and-63.25 dB(at 7.22 GHz)and effective absorption bandwidth(EAB)of 4.46 and 4.72 GHz,respectively.This multicomponent design provides a new strategy for the development of EM wave absorption materials.
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    Enhancement of coercivity,permeability,and dielectric properties of Co0.2Zn0.3Ni0.5EuxFe2-xO4 ferrites for memory and high frequency devices

    I.SardarM.D.HossainM.S.SikderM.N.I.Khan...
    1128-1135页
    查看更多>>摘要：Spinel cubic ferrites have huge applications in memory and high frequency devices.For the improvement of these modern devices,the magnetic coercivity,permeability,and dielectric properties of a ferrite are the important issues.This article focuses on improving the magnetic coercivity,magnetic permeability,and dielectric properties of Co0.2Zn0.3Ni0.5EuxFe2-xO4 ferrites,where x=0.00,0.06,and 0.10.The X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),field emission scanning electron mi-croscopy(FESEM),energy dispersive X-ray(EDX),vibrating sample magnetometer(VSM),and an impedance analyzer were used to characterize the structural,magnetic,and dielectric properties of the samples.The XRD patterns indicate the formation of spinel cubic structure of the samples with a sec-ondary peak(EuFeO3)for Eu doped samples.The densities and porosities of the samples follow an in-verse trend,where the doped samples'lattice parameters are increased with the increment of rare earth Eu concentration.The FTIR analysis also proves the spinel cubic phase of the samples.The average grain size of the ferrites is obtained via FESEM images,and it is increased from 121 to 198 nm.VSM analysis confirms that doping of the Eu content also changes other hysteresis loop properties of Co0.2Zn0.3-Ni0.5EuxFe2-xO4 ferrites.Particularly,the coercivity of the Eu doped samples is greater than that of the mother alloy(x=0.00).The EDX study shows that there is no impurity contamination in the ferrites.The permeability and dielectric measurements show an improved quality factor of the Eu-doped samples with low magnetic and dielectric losses.Frequency dependent resistivity and impedance analysis also show the improved nature.From the observed properties of the samples,all the investigated ferrites might be strong candidates for potential applications in memory devices,magnetic sensors,and high frequency applications.
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    Hydrogen and nitrogen absorption properties of Ce-added Zr2(Fe1-xNix)alloys

    Kai YinXiaopeng Liu
    1136-1141页
    查看更多>>摘要：To improve the nitriding resistance of Zr2Fe alloy,the Ce-added Zr2(Fe1-xNix)(x=0,0.15,0.3,0.5)alloys were prepared by magnetic levitation melting method.The effects of Ni substitution for Fe on the phase structure,hydrogen and nitrogen absorption properties of the alloys were investigated by X-ray diffraction,scanning electron microscopy and p-c isotherm measurements.The experimental results show that Ni substitution can effectively inhibit the formation of both α-Zr and ZrFe2 phases and pro-mote the formation of C16 structure Zr2(Fe,Ni)phase,causing Ni-substituted alloys to exhibit low ni-trogen absorption rate and capacity.At 623 K under 0.5 MPa nitrogen pressure,the nitrogen absorption capacity of Ce-added Zr2(Fe0.5Ni0.5)alloy reaches to 0.8 mL/g,much lower than that of Zr2Fe alloy(1.5 mL/g).Ni substitution decreases the crystal cell volume of the C16 Zr2(Fe,Ni)phase,resulting in an increase in the hydrogen absorption equilibrium pressure.At 623 K under 0.05 MPa hydrogen pressure,the hydrogen absorption capacity decreases from 1.46 wt％of Zr2Fe alloy to 1.41 wt％of Ce-added Zr2(Fe0.5Ni0.5)alloy.
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    Theoretical probe into universal tetrad effect for complexation discrepancy between lanthanide elements and organophosphoric extractant diethyl phosphoric acid

    Haifeng ZhengYanling LiXuyi ZhangJinglu Han...
    1142-1148页
    查看更多>>摘要：The deep understanding of 4f-correlated electron motion behavior is experimentally limited due to similar physicochemical properties of rare earth elements(REEs).While the solvent extraction behavior originating from the continuous occupation of 4f electrons along the lanthanide family provides a particular platform to probe the 4f electrons motion behavior and its correlations to their versatile functions.Herein,the complexation between REEs and the prototypical extractant of diethyl phosphoric acid(DEP)was substantially studied based on quantum mechanical calculation.The results firstly show that the average bond lengths between Ln and six coordinated oxygen atoms are consistent with lanthanide contraction phenomenon,and gadolinium break effect is also obviously observed.Secondly,the"tetrad effect"is figured out based on the subtle discrepancy of 4f electrons occupation,namely La-Nd,Sm-Eu,Gd-Dy and Ho-Lu.Specifically,the main composition is 4f5d6p for La-Nd,while the discrepancy is due to the increasing electrons in the 5d shell,while it is 4f5d for Pm-Eu.For Gd-Dy,their 4f orbitals accept little electrons and the donating electrons flow into 6s5d subshells due to the half-filled stability and the enhancement of shielding effect.The electrons donate into 5d6p subshells due to multiply electrons occupation of 4f orbitals for Ho-Lu.These detailed analyses obviously clarify the"tetrad effect"along the lanthanide family due to the different variation of 4f orbital occupation.It is expected that these microscopic understandings provide important guidance for the separation of REEs and the design of new extractants.
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    Selective leaching of calcium from mechanically activated mixed rare earth concentrate

    Jiang LiuBingxue ChenYuanqi FengYijun Cao...
    1149-1156页
    查看更多>>摘要：The loss of rare earths(REs)takes place during the pre-decalcification process of mixed rare earth concentrate.In an effort to reduce such RE loss,a novel idea to improve the leaching selectivity of Ca to REs by applying selective mechanical activation was proposed.First,regarding the key minerals affecting the leaching selectivity of Ca to REs,the differences in the mechanical activation behaviors of CaF2 and REFCO3 were studied,and we find that the lattice strain of CaF2 increases from 0.21％to 0.42％,whereas that of REFCO3 increases from 0.31％to 0.40％.Notably,CaF2 demonstrates a larger lattice strain than REFCO3,indicating greater mechanical activation energy storage and higher leaching activity.Next,the HCl leaching process was studied.A significant leaching selectivity of Ca to REs,from 21.6 to 35.1,is achieved through mechanical activation.The Ca leaching rate reaches 80.7％when the RE loss is 2.3％in the activated sample.This study provides an novel approach for achieving selective extraction of specific components via mechanical activation pretreatment.
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    Comparison of extraction abilities of deep eutectic solvents and aqueous acid solutions for extraction of rare earths and transition metals

    Svetlana DrogobuzhskayaMargarita FrolovaAndrey ShishovNikita Tsvetov...
    1157-1164页
    查看更多>>摘要：In recent years,deep eutectic solvents have attracted increasing interest as effective extractants for the separation of both organic substances and metals from various objects.Acid-based deep eutectic solvents are most often used as extractants for the extraction of metals.In this work,for the first time,the extraction efficiency of transition metals and rare earth elements(Y,Zr,Nb,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Hf and Ta)from mining tailings and Na,K,Ca,Mg,Cu,Fe,Mn,Pb,Ba,Ni and Sr from biodiesel samples using acidic deep eutectic solvents and saturated aqueous solutions of the same acids(malonic,malic,tartaric and citric)is compared.For this,deep eutectic solvents based on acids and their aqueous saturated solutions were prepared and studied.The prepared mixtures were analyzed by IR spectroscopy to confirm the formation of eutectic solvents.Properties such as the density and viscosity of the resulting mixtures were also investigated,as this can be of key importance for the efficiency of metal extraction.The extraction of rare earth metals from mining tailings took a long time(up to several days),while the extraction of metals from fuel took no more than 30 min.Atomic emission spectral methods were used as an analysis method.It is shown that the extraction efficiency with aqueous solutions is better than that with eutectic solvents,which casts doubt on the need for deep eutectic solvents use in this area.
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    Direct microwave leaching conditions of rare earth elements in fluorescent wastes

    A.BilenB.BirolM.N.Saridede?.S.Kaplan...
    1165-1174页
    查看更多>>摘要：The luminescent phosphor powder in the fluorescent lamp constitutes 2％of the lamp's weight.It can be mentioned that fluorescent wastes are a crucial raw material to produce rare earth oxides.In the present study,microwave leaching process was conducted to dissolve rare earth elements yttrium(Y),europium(Eu),and remaining rare earth elements(REEs)present in the phosphor powder of the fluorescent lamp,and the yields were compared.In the microwave leaching process,the effects of the temperature(80-160℃),acid type(hydrochloric acid(HCl),nitric acid(HNO3),sulphuric acid(H2SO4)),acid concen-tration(0.5-6 mol/L),solid to liquid ratio(0.1:10-0.5:10)and reaction time(5-90 min)parameters on leaching efficiencies of varying rare earth elements and calcium were investigated.The highest yield was obtained in the direct microwave leaching of fluorescent waste with the experimental conditions of 6 mol/L HCl,160 ℃,0.1:10 solid-to-liquid ratio(S:L),and 90 min.Activation energy calculations were made,and kinetic models of the reactions were obtained,and it is observed that Y and Eu dissolution is diffusion-controlled,on the other hand,lanthanum(La),cerium(Ce),and terbium(Tb)were examined to be chemical reaction controlled.Moreover,calcium(Ca)and gadolinium(Gd)seem coherent with the mixed model.Concurrently,mathematical models of all experimental studies are created with the response surface Box-Behnken method and the correlation coefficients of all the models are over 90％.
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    Mass transfer in heap leaching of weathered crust elution deposited rare earth ore with Al2(SO4)3 solution

    Jingqun YinDedong ZengJun TianYaqing Weng...
    1175-1181页
    查看更多>>摘要：In order to increase efficiency and avoid NH4+-N pollution in the leaching process of weathered crust elution-deposited rare earth ores,the mass transfer in heap leaching with Al2(SO4)3 solution was simulated with column elution and experimentally optimized.The results indicate that the leaching yield is also up to 99％for leaching with aluminum sulfate instead of ammonium sulfate.The optimal flow rate is 60 mL/h,the height equivalent to a theoretical plate(HETP)is 1.29 mm correspondingly.The peak value position of RE3+is 60 mL/h,Fe3+is 100 mL/h,however,Al3+is 150 mL/h,and the heap leaching process has kinetic separation effect.
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