Effects of Light and Heavy Rare Earths on Anti-Degradation of Nodular Cast Iron

The effects of rare earths with different contents on anti-degradation of Y base heavy rare earths-magnesium and cerium base light rare earths-magnesium nodular cast iron were studied. Curves of the relationship between the spheroidization grade of liguid iron treated by different nodulizers and holding time were obtained. The results show that the more the remains of the rare earth, the longer the anti-degradation time, the liquid iron was treated either by Y-Mg-Si or by Ce-Mg-Si nodulizer. When the rare earth remains are above certain quantity, the spheroidization grade starts to decline. When liquid iron treated by either Y-Mg-Si or Ce-Mg-Si nodulizer with proper remains of rare earths about 0.04% 0.06%（mass fraction）, the anti-degradation is the best, and the remains of Mg being about 0.04% -0.07% （mass fraction）. Rare earths-Mg nodulizer with moderate RE remains is better than that of Mg-Si nodulizer in anti-degradation property. However, Y-Mg-Si nodulizer with moderate remins of Re is better than Ce-Mg-Si nodulizer. Sometimes Ce-Mg- Si nodulizer can be used for the production of heavy section nodular cast iron.

Round Top Mountain rhyolite(Texas, USA), a massive, unique Y-bearing-fluorite-hosted heavy rare earth element(HREE) deposit

Round Top Mountain in Hudspeth County, west Texas, USA is a surface-exposed rhyolite intrusion enriched in Y and heavy rare earth elements （HREEs）, as well as Nb, Ta, Be, Li, F, Sn, Rb, Th, and U. The massive tonnage, estimated at well over 1 billion tons, of the deposit makes it a target for recovery of valuable yttrium and HREEs （YHREEs）, and possibly other scarce ele-ments. Because of the extremely fine grain size of the mineralized rhyolite matrix, it has not been clear which minerals host the YHREEs and in what proportions. REE-bearing minerals reported in the deposit included bastn？site-Ce, Y-bearing fluorite, xeno-time-Y, zircon, aeschynite-Ce, a Ca-Th-Pb fluoride, and possibly ancylite-La and cerianite-Ce. Extended X-ray absorption fine struc-ture （EXAFS） indicated that virtually all of the yttrium, a proxy for the HREEs, resided in a coordination in the fluorite-type crystal structure, rather than those in the structures of bastn？site-Ce and xenotime-Y. The YREE grade of the Round Top deposit was just over 0.05%, with 72%of this consisting of YHREEs. This grade was in the range of the South China ionic clay deposits that supply essentially all of the world’s YHREEs. Because the host Y-bearing fluorite is soluble in dilute sulfuric acid at room temperature, a heap leaching of the deposit appeared feasible, aided by the fact that 90%-95%of the rock consists of unreactive and insoluble feld-spars and quartz. The absence of overburden, remarkable consistency of mineralization grade throughout the massive rhyolite, prox-imity （a few km） to a US interstate highway, major rail systems and gas and electricity, temperate climate, and stable political location in the world’s largest economy all enhanced the potential economic appeal of Round Top.

Local concentration of middle and heavy rare earth elements in the col on the weathered crust elution-deposited rare earth ores

This present study focused on investigating the content and relative enrichment multiple of rare earth elements（REEs） in different terrain of weathered ore body, and the value of light rare earth elements/middle and heavy rare earth elements（LREEs/HREEs）, in order to understand the mobilization and redistribution of HREEs, Furthermore, the abrasion pH was investigated as well, The results show that the average contents of HREEs in the knap, ridge and col are 37.26, 61.71, and 271.3 μg/g, respectively. The value of LREEs/HREEs is decreased from 16.78 to 7.914 between knap and col and the relative enrichment multiple of HREEs is as follows： CCol-HREEs 〉 CRidge-HREEs 〉 0. It is indicated the HREEs is concentrated in the col and the enrichment degree of HREEs is stronger than the ridge and the knap. Rare earth elements fractionation is exhibited in the different terrain of weathered ore body. Based on this study, the finding that HREEs concentrate in the lower terrain of weathered crust elution-deposited rare earth ores, such as in the col, would become a marker or indicator to search for middle and heavy rare earth enriched zone.

Study on the diffusion kinetics of adsorption of heavy rare earth with Cyanex272-P507 impregnated resin

Kinetics of adsorption of heavy rare earth with Cyanex272-P507 impregn ated resin was studied. The influences of temperature,concentration,granularit y of resin on the exchange degree were investigated by the limited bath method. The result showed that the controlling factor of RE3+/H+ diffusion on Cyanex272-P507 extraction resin was particles diffusion. The process of diffuse kinetics f itted well with the expression developed by Body model. The apparent activation energy was determined as 23.20 kJ/mol. The reaction order was 0.452. In addition,the constant of particles diffusion(D0) was 1.352×10-8 m2/S and the entropy of diffusion was-47.055 J/(mol·K).

Extractant(2,3-dimethylbutyl)(2,4,40-trimethylpentyl) phosphinic acid(INET-3) impregnated onto XAD-16 and its extraction and separation performance for heavy rare earths from chloride media

（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 H2SO4.

Solid-phase extraction and separation of heavy rare earths from chloride media using P227-impregnated resins

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.

Extraction and separation of heavy rare earths from chloride medium byα-aminophosphonic acid HEHAPP

The extraction and separation of heavy rare earths（REs） using newly synthesized a-aminophosphonic acid extractant 2-ethylhexyl-3-（2-ethylhexylamino）pentan-3-yl phosphonic acid（HEHAPP, HA） in nheptane were investigated from chloride medium. The extraction stoichiometries of lanthanum, gadolinium, yttrium and lutetium are determined to be REA3 by the slope analysis method. The favorable separation factors of adjacent heavy REs（Ⅲ）,i.e. β（Y/Ho）, β（Er/Y）,β（Tm/Er）,β（Yb/Tm） and β（Lu/Yb）, are determined to be1.87,1.36, 3.21,3.22 and 1.93, respectively, when extracted from a binary system at proper condition. The loading capacities of HA for Ho, Er, Yb and Lu increase in the order Ho 〈 Er 〈 Yb 〈 Lu with the values being 0.201, 0.205, 0.216 and 0.229 mol/L, respectively. So HA would be a potential extractant for the separation of heavy REs（Ⅲ）. Among inorganic acids such as H2 SO4, HNO3 and HCl, HCl is tested to be the most effective stripping agent.

Effect of Cycling Loaded Rare Earths on Stripping Process in P507 Extraction System

P507 （HEH [EHP]） is an important extractant for the separation of rare earth and is widely used in industry. Since the complexes of heavy rare earth ions with saponified P507 are so stable that the rare earth ions are difficult to be exchanged and stripped by H^＋ ions. Thus, the cycled extractant loads certain amount of heavy rare earth ion after stripped by acid. This amount of rare earth ions loaded in blank organic phase is named as the ＂cycling loaded rare earth ions （CLREs）＂. In the separation process of Tm^3＋, Yb^3 ＋, and Lu^3 ＋ , the amount of CLREs carl be more than 10% of the normal capacity of saponifiedorganic phase. In fact, CLREs affect the separation efficiency and decrease the purity of the products. Based on the extracting-stripping equilibrium and mass balance, the influence of different process parameters on the amount of CLREs was studied by computer simulation. The results indicate that higher acid consumption and more stripping stages are required to eliminate CLREs. For an industrial practice, however, the acid consumption and the number of stripping stage can be designed by choosing an economic process and controlling CLREs at a reasonable level.

Reaction mechanism between Al_(2)O_(3)–MgO refractory materials and rare earth high-carbon heavy rail steel

Submerged entry nozzle(SEN)clogging is a major problem affecting the production quality of rare earth steel,and finding a suitable refractory outlet can significantly reduce production costs.To explore the relationship between refractory composition and interface interaction,unprotected coated Al_(2)O_(3)–MgO refractories and SiO2-coated Al_(2)O_(3)–MgO refractories were added to rare earth high-carbon heavy rail steel under laboratory conditions,and the Al_(2)O_(3)–MgO refractory was found to be more suitable.The results show that,from the epoxy resin side to the refractory side,the contour of the refractory interface reaction layer can be divided into two main layers:an iron-rich reaction layer and an iron-poor reaction layer.Calculations based on the spherical model suggest that the adhesion force is proportional to the size of the refractory particles and inclusions,and the same result applies to the surface tension.Controlling the inclusions at a smaller size has a specific effect on alleviating the erosion of refractories.Combined with the erosion mechanism of Al_(2)O_(3)–MgO refractories,the interface reaction mechanism between Al_(2)O_(3)–MgO refractories and molten steel was proposed,which provides ideas for solving SEN clogging.

A separation processing for industrial rare earth feed solution by phosphonium ionic liquid type saponification strategy

A novel ionic liquid type saponification processing based on quaternary phosphonium type bifunctional IL was developed for yttrium separation from ion-adsorbed rare earth deposit.The extractabilities of（[trihexyl（tetradecyl）phosphonium][sec-octylphenoxy acetate]（[P_（6,6,6,14）][SOPAA]） were pronouncedly higher than those of sec-octylphenoxy acetic acid（HSOPAA）,a mixture of HSOPAA and[P_（6,6,6,14）]Cl for rare earth elements（REEs）.The ion association extraction mechanism contributed to avoiding the numerous saponification procedures using alkali and resulting in saponification wastewater.After 13 stages of extraction and 6 stages of scrubbing sections,the Y（Ⅲ） was successfully separated from industrial heavy RREs feed,the purity of Y（Ⅲ） in raffinate was approximately to be 98.9%.Stripping by distilled water was effectively achieved for REEs,which contributed to the decreased consumption of acid to a considerable extent.

Tb doping induced enhancement of anomalous Hall effect in NiFe films

Tbx（Ni0.8Fe0.2）1-x films with x ≤ 0.14 are fabricated and the anomalous Hall effect is studied. The intrinsic anomalous Hall conductivity and the extrinsic one from the impurity and phonon induced scattering both increase with increasing x. The enhancement of the intrinsic anomalous Hall conductivity is ascribed to both the weak spin–orbit coupling enhancement and the Fermi level shift. The enhancement of the extrinsic term comes from the changes of both Fermi level and impurity distribution. In contrast, the in-plane and the out-of-plane uniaxial anisotropies in the Tb Ni Fe films change little with x. The enhancement of the Hall angle by Tb doping is helpful for practical applications of the Hall devices.

Loading capacity and emulsification phenomena of HREE extraction by dialkylphosphinic acids with different β,γ,δ-substituents

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.

Effect of grain boundary diffusion of terbium on mode of mechanical fracture of sintered NdFeB magnets

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.

The role ofβ,γ,δ-substituent of dialkylphosphinic acids in HREE extraction and separation behaviors

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)).

Structural properties and crystal orientation of polycrystalline Gd films

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.

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 developing the process,reducing the consumption of heavy rare earth elements(Tb),and improving the coercivity of sintered Nd-Fe-B magnets.

Estimating REY content of eastern Kentucky coal samples based on their associated ash elements

Coal and coal combustion byproducts can be considered as an alternative source of rare earth elements and yttrium （REY）. The study of relationships between REY and other main coal properties could have several advantages such as estimating REY content of coal particles and designing beneficial extraction method. In this investigation, inter-correlations between REY content with coal parameters （proximate and ash elements） for a wide range of eastern Kentucky coal samples （708 records） were explored. Results demonstrate that zircon and monazite are the main source of heavy and light rare earth elements （HREE and LREE）, respectively. Zr has the highest correlation with Y and Th has the strength relationship with Ce and La. In general, LREE have higher interaction with coal ash content in comparison with HREE. Results indicated that REY can be estimated quite satisfactorily by using their associated elements in coal ash.

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 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.

Yttrium chloride-modified Au/AC catalysts for acetylene hydrochlorination with improved activity and stability

The addition of yttrium chloride(YCl) to an activated carbon-supported Au catalyst(Au/AC) can markedly promote the catalytic performance of acetylene hydrochlorination to the vinyl chloride monomer(VCM), The structure and physicochemical features of the YCl-modified catalysts(Y-Au/AC)were measured by X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction, CH-temperature programmed desorption, and scanning transmission electron microscopy.The presence of YClwas found suppressing the reduction of highly oxidized Au(δ=1,3) to metallic Au~0 dependently and thus retard the agglomeration of Au nanoparticles during the reaction. In addition,the additive of YClto the Au/AC catalyst greatly inhibits the coke deposition on the catalyst surface. The optimized catalyst with an atomic ratio of Y/Au = 5(1 wt% Au loading weight) yields an 87.8% acetylene conversion and almost 100% selectivity for VCM under the reaction of GHSV(CH) = 800 hat 180 ℃.The durability test indicates that the 5 Y-1 Au/AC catalyst maintains high catalytic activity for more than2300 h at 30 hGHSV(CH) and 180 ℃, indicating great promise as a non-mercury catalyst for PVC manufacture.