Simultaneous Determination of Trace Rare Earth Elements and Other Elements in High Purity Terbium Oxide (Tb_4O_7) by ICP-AES After HPLC Separation Using P507 Resin

This article describes a new method for the simultaneous determination of trace rare earth elements (REEs) and non rare earth elements (NREEs) in high purity terbium oxide by ICP-AES after HPLC separation using P507 resin. The chromatographic separation of the analytes from the matrix using dilute nitric acid as mobile phase was studied. The experimental results showed that a favorable separation of trace metals (Cu and Gd) from the matrix (Tb) can easily be achieved by elution with dilute nitric acid within 25 min. The proposed method was applied to the determination of trace metals (Ca, Cu, Mg, Mn, Ni, Si, La, Ce, Pr, Nd, Sm, Eu and Gd) in high purity terbium oxide. The detection limits (DLs) for the analytes ranged from 0.4-4.0 μg\5g -1, and the recoveries are from 78%-105%.

Analysis of rare earth elements in high purity europium oxide

Five trace impurities as Ce, Pr, Sm, Gd, and Dy are separated from europium oxide with P507 extraction resin by extraction chromatography. When determined simultaneously by ICP-AES, the impurities show their recovery ratios between 88% and 105%. A lower than 10% relative standard deviation of these elements is obtained when their contents in europium oxide are 5μg/g. The satisfactory results indicate this simple method is sensitive and accurate. It has been employed in the analysis of these five rare earth elements in 99.99% europium oxide.

STUDY OF ADSORPTION OF RARE EARTH ELEMENTSBY FERRIC OXIDE GEL

A new secondary ore of rare earth was discovered in the Southwest of China. It is a kind of product of the weathered mineral. The rare earth elements (REE) in it exist probably as ionic characteristic adsorption state in manganesian and ferric oxide colloid mineral, and one bearer of REE is amorphous ferric oxide gel. It is neessary to study the binding state of rare earth elements on manganesian and ferric oxide in order to utilize comprehensively the rare earth resources and avoid latent influence on the environment resulting from the fact that highcontent rare earth elements are carried into soil by the mineral efflorescence. A simulating adsorption test of rare earth ions in weak acid media is carried out with ferric oxide gel prepared by sol-gel method. The experimental results show that the characteristics of adsorption isotherm correspond well with the Flory-Huggins equation, but deviated from the Langmuir equation. The standard molar adsorption Gibbs function, standard molar adsorption entropy and standard molar adsorption enthaply are calculated. The measurements of the point of zero charge and isoelectric point show occurrence of the characteristic adsorption. It has been proved that the OH group on the skeleton of ferric oxide gel is the innate cause of the characteristic adsorption.

Direct Determination of Rare Earth Impurities in High Purity Europium Oxide by ICP-MS

A novel inductively coupled plasma mass spectrometry method for direct determination of trace rare earth impurities in high purity europium oxide (Eu_2O_3) was developed. The spectral interference,matrix effect,instrument parameters fluctuation were investigated and the optimized experimental conditions were established. Under the selected conditions,the detection limits of the method are 3～7 ng·L (-1),the RSD is varied between 2.1%～8.4%,and the percentage recovery is ranged from 90% to 113% for the analytes. The solid detection limit for gross amount of 13 rare earth impurities is 0.19 μg·g (-1) when the matrix (Eu) concentration of 0.1 mg·ml (-1) was chosen. Compared with the reported methods in the literature,this method has several attractive features: simple,small sample amount required,no internal standard and matrix matching requirements.

The Characteristics of Adsorption and Desorption of Rare Earth Elements by the Main Types of Soils of China

The adsorption-desorption behavior of the mixed rare earth elements(RE)on the main types of soils of China,kaolinite and synthetic oxides was studied.The isothermal adsorption of RE was fitted to Langmuir.Freundlich and Temkin equations.The main factors determining the RE adsorption capacity of the soils are the type of clay mineral and the content of amorphous iron oxide in the soils.The above two fac- tors and the pH of soil determine the RE adsorption ability of the soils.The soil and synthetic iron,manga- nese oxides strongly adsorb RE specifically.

Fractionation characteristics of rare earth elements(REEs) linked with secondary Fe, Mn, and Al minerals in soils

Soil secondary minerals are important scavengers of rare earth elements(REEs) in soils and thus affect geochemical behavior and occurrence of REEs. The fractionation of REEs is a common geochemical phenomenon in soils but has received little attention, especially fractionation induced by secondary minerals. In this study, REEs(La to Lu and Y) associated with soil-abundant secondary minerals Fe-, Al-, and Mn-oxides in 196 soil samples were investigated to explore the fractionation and anomalies of REEs related to the minerals. The results show right-inclined chondrite-normalized REE patterns for La–Lu in soils subjected to total soil digestion and partial soil extraction. Light REEs(LREEs) enrichment features were negatively correlated with a Eu anomaly and positively correlated with a Ce anomaly. The fractionation between LREEs and heavy REEs(HREEs) was attributed to the high adsorption affinity of LREEs to secondary minerals and the preferred activation/leaching of HREEs.The substantial fractions of REEs in soils extracted byoxalate and Dithionite-Citrate-Bicarbonate buffer solutions were labile(10 %–30 %), which were similar to the mass fraction of Fe(10 %–20 %). Furthermore, Eu was found to be more mobile than the other REEs in the soils, whereas Ce was less mobile. These results add to our understanding of the distribution and geochemical behavior of REEs in soils, and also help to deduce the conditions of soil formation from REE fractionation.

Behavior and mechanism of graphene oxide-tris(4-aminophenyl)amine composites in adsorption of rare earth elements

Three-dimensional(3D)graphene oxide-tris(4-aminophenyl)amine(GO-TAPAx:y)composites with different GO-to-TAPA mass ratios(x:y)were prepared by a facile one-step ultrasonic treatment.GOTAPAx:y composites were characterized by scanning electron microscopy(SEM),nitrogen(N2)adsorption-desorption isotherms,Fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS)and thermogravimetric analysis(TGA).Behavior and mechanism of GO-TAPAx:yco mposites for the adsorption of rare earth elements(REEs)were investigated.The adso rption capacities of GO-TAPA1;2 composite for Yb^3+,Er^3+,Nd^3+,La^3+and Y^3+are 30.88,26.52,20.60,11.24 and 10.52 mg/g,respectively.Effects of some important parameters including GO-to-TAPA mass ratios,contact time,reaction temperature and initial Yb^3+concentration on the adsorption were evaluated in detail.FTIR spectral and XPS analyses show that the metal complexations and ion exchanges between nitrogen/oxygen-containing species of the adsorbents and REEs are involved in the adsorption procedure besides the conventional adsorption based on specific surface area,indicating the introduction of specific molecules onto GO is beneficial to its adsorption ability.The convenient reusability and applicability of GO-TAPAx:y composites toward real samples also demonstrate their feasibility in the enrichment of REE ions.

Specific Adsorption and Its Mechanisms of Rare Earth Elements by Soils and Oxides

There have been many studies on the adsorption-desorption behavior of heavy metals such as Cu, Zn, Co, Ni, Cd and Pb by soils in China and abroad, and their adsorption mechanisms have also been sought. The above research has demonstrated that the synthetic or soil oxides like Fe, Mn and Al oxides adsorb heavy metals specifically and their specific adsorption is greatly affected by the ambient pH. The proposed mechanisms for explaining the above phenomena are as follows: ion hydrolysis-adsorption, outer or in-

Determination of REE,U,Тh,Ba,and Zr in simulated hydrogeological leachates by ICP-AES after matrix solvent extraction

A fast, reliable and precise method for the determination of Ba, Zr, Th, U, La, Ce, Eu, Hf and Gd in leaching solutions containing up to 1 mol/L FeCl3 by inductively coupled plasma-atomic emission spectrometry（ICP-AES） was described.Liquid-liquid extraction with diethyl ether was applied for selective and quantitative extraction of the iron with a decontamination factor of 65000.The study has enabled the determination of rare earth elements, U, Th Ba, and Zr, from the solution with high iron content with detection limits in the range of 1-24 ng/ml and a precision of 0.9%-4.6 % relative standard deviation.The developed method was simple and was adopted for implementation in a glove box for handling radioactive materials.

Effect of rare earth elements(La,Y,Pr)in multi-element composite perovskite oxide supports for ammonia synthesis

A series of BaCe0_(3)modified with different rare earth elements(La,Y,Pr)were synthesized by coprecipitation and calcination and the effect of rare earth elements for catalytic ammonia synthesis under mild conditions was studied.The ammonia synthesis performance tests show that 2.5%Ru/BaCe_(0.9)La_(0.1)O_(3-δ)catalyst(All the percentages of Ru in this article are in mass fraction)exhibits the highest ammonia synthesis rate(34 mmol/(g·h))at 3 MPa,450℃,and no sign of deactivation after 100 h of reaction.H_(2)-TPR and XPS analyses indicate that the introduction of La increases the amount of oxygen vacancies of the catalyst,which is beneficial to increasing the electron density of Ru surface.HRTEM analysis shows that the Ru particle size is reduced greatly after La is introduced,which facilitates the catalyst generating more Bs-type sites(active sites of Ru species for N=N dissociation).CO_(2)-TPD analysis indicates that BaCe_(0.9)La_(0.1)O_(3-δ)has stronger basicity,which promotes electrons transfer from support to Ru.This work provides an effective method for design and synthesis of Ru-based multi-element composite perovskite oxide catalysts.

Determination of Trace Impurities of Rare Earth Elements in High Purity Yttrium Oxide by ICPMS

Determination of trace rare earth elements(REEs)in 99. 999% purity yttrium oxide using the inductively coupled plasma mass spectrometric technique (ICPMS) has been developed. Instrumental parameters and factors affecitng analytical results have been studied and then optimized.Samples are analyzed directly following an acid digestion without separation or preconcentration and with limit of detection of 0. 003～0. 02 ng/ml, precision of ±5. 4%(cofficient of variation)and recovery of 90～115%. Correction for isobaric interferences from oxide ions and hydroxide ions is made mathematically. Special internal standard procedures are used to compensate drift in metal:metal oxide ratios and sensitivity. The analytical results of several samples are accurate as compared with inductively coupled plasma atomic emission spectrometry (ICPAES) and spark source mass spectrometry (SSMS).

SPECTRAL VARIATION AND CHARACTERISTICS OF LOW VALENCY RARE EARTH IONS IN COMPLEX OXIDESⅢ.EFFECT OF THE CRYSTAL ENVIRONMENT AND CHEMICAL FACTORS ON LUMINESCENCE PROPERTIES OF EUROPIUM (Ⅱ) ION

In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.

Coal and coal byproducts:A large and developable unconventional resource for critical materials—Rare earth elements

Rare earth elements（REEs） are critical materials and provide significant values to national security,energy production, environmental protection and economic growth. The supply of REEs in U.S. solely relies on import as domestic production of REEs was ceased because of the environmental concerns during mining and lack of competitiveness. Nonetheless, unconventional REEs-containing resources,including produced water. acid mine drainage, and coal and coal byproducts（C＆CBs） contain significant amounts of REEs. However, the concentrations of REEs in these resources are several orders of magnitude lower than that of REEs ores. Thus, extraction of REEs from these materials is challenging. Here we report REEs extraction with environmentally friendly method that successfully concentrated REEs from312 ppm in fly ash to 99.4% in the final product. Especially, the five critically important REEs（Dy, Eu, Nd.Tb. and Y） account for up to ～63% of the total weight of all REEs in the final 99.4%-purity product. Coal fly ash is one of the major solid coal utilization byproducts, representing great potential resources for REEs extraction. Extraction of REEs from these unconventional resources could be the way to secure domestic supply of these critical materials.

Optical and electrical conductivity properties of rare earth elements(Sm, Y, La, Er) co-doped CeO_(2)

In this research,un-doped CeO_(2) and Ce_(0.85)La_(0.10)MO_(0.05)O_(2)(M:Sm,Er,Y) compounds were synthesized by hydrothermal method and the multi-functional properties are reported.Oxygen defects were created with the additives of rare earth ions.The electrical and luminescence behaviors of the synthesized compounds were investigated in accord with the types of additives.The synthesized products were characterized by X-ray diffraction(XRD) analysis,Brunauer-Emmett-Teller(BET) measurement,UV-vis diffuse reflectance spectroscopy(DRS),scanning electron microscopy(SEM),photoluminescence(PL)spectroscopy and electrochemical impedance spectroscopic(EIS).All synthesized compounds are found to be nano-structured and have cubic phase.The total conductivity of all samples was calculated.Hence,the total conductivity of un-doped CeO_(2),Ce_(0.85)La_(0.10)Y_(0.05)O_(2),Ce_(0.85)La_(0.10)Er_(0.05)O_(2) and Ce_(0.85)La_(0.10)Sm_(0.05)O_(2) is found to be 2.07×10^(-10),5.70×10^(-4),1.0×10^(-3) and 0.0747 S/cm,respectively.Also,bandgap energy(E_(g)) of these samples calculated from UV visible absorption spectra is discussed,and the optical results show variation between 3.2 and 2.15 eV.Additionally,the luminescence properties of the compounds were investigated and different emissions occur depending on the additive type.Accordingly,photoluminescent emission spectra of Ce_(0.85)La_(0.10)Y_(0.05)O_(2),Ce_(0.85)La_(0.10)Er_(0.05)O_(2) and Ce_(0.85)La_(0.10)Sm_(0.05)O_(2) phosphors indicate that these phosphors have red,green and orange-red colors,respectively.

Compilation of Q－data and Simulation of Q－spectra in Rare Earth Elements Analysis by Using ICP－AES

This paper developed a method,called compilation of Q-data and simulation of Q-spectra,combining experimental data with the aid of a microcomputer to predict and correct spectral interferences in rare-earth elements analysis by using ICP-AES. Raw spectral data of each element were obtained through experiments, followed by removing noise with Kalman smoothing and spectral averaging, and correcting the shifts of wavelength. These processed data were eventually transformed into Q-data and used in spectral simulation and intenference correction. Some fundamental problems in simulation and correction were investigated and the results indicates that Q-data are accurate enough for the correction of spectral interferences when the interferences are not too strong, and that spectral simulation is practicable in routine analysis. It is a convenient, rapid and accurate way to deal with spectral interferences in REE analvsis.

Morphology, chemical compositions and size distribution of rare earth oxides in pure iron

The pure iron was melted and deoxidized by metallic Al and rare earth elements La, Ce and Y respectively at 1600℃ in a vertical resistance furnace. The morphology, chemical composition and size distribution of the inclusions in deoxidized liquid iron have been investigated by using of SEM and image-analysis techniques. The investigated results show that the deoxidation products in molten iron are complex inclusions of rare earth oxide or A12O3 combined with FeO finely distributed. The proper holding time and rapid cooling rate can make inclusions finer. La, Y and Al are more effective than Ce for obtaining finely distributed inclusions.

Determination of Non-Rare Earth Impurities in High Purity Lanthanum Oxide by Inductively Coupled Plasma Atomic Emission Spectrometry after HPLC Separation Using P507 Resin

A new method for the determination of trace non-rare earth elements (NREEs) impurities in high-purity lanthanum oxide by HPLC combined with ICP-AES is proposed. The chromatographic retention behaviors of matrix (La) and NREEs were studied using 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate (P507) chelating resin as the stationary phase and dilute nitric acid as the mobile phase. It is found that the use of pH 1.7 nitric acid enables effective elution of NREEs from HPLC column, but the lanthanum remains on the column. The experimental results show that a favorable separation between matrix lanthanum and NREEs can be obtained within 15 min. The method proposed is applied to the determination of 8 NREEs impurities in high-purity La2O3. The recoveries of 8 NREEs are in the range of 90 % similar to 110 %.

A New Ternary Fluorescent Europium Complex with Bis(Diphenyl Phosphine Oxide) Methane and Thenoyltrifluoroacetone

A fluorescent ternary europium complex containing bis (diphenyl phosphine oxide) methane which functioned as both a neutral and anion ligand, and thenoyltrifluoroacetonato anion was synthesized and characterized by elemental analysis, DTA TG analysis, UV Vis, FT IR and MS spectroscopy. The chemical formula is proved to be Eu(TTA)(MPPO)(HMPPO)·(NO 3)·2H 2O. Its luminescence quantum efficiency(in acetonitrile, 26 3%) is approximately the same as that of the commonly used red emission luminescent compound, Eu(TTA) 3(TPPO) 2 (TPPO is triphenyl phosphine oxide). The new complex has comparatively long fluorescence lifetime.

Influence of additive element on surface oxide film of A356 alloy

The influences of RE-modification and Sr-modification on the hydrogen content and surface oxide film of A356 aluminum alloy melt were investigated. The hydrogen content of the melt was measured by reduce pressure test. The phases in the surface oxide film were analyzed by X-ray diffractometry (XRD), and the morphology of the surface oxide film was observed by scanning electronic microscopy (SEM). The results show that RE-modification reduces the hydrogen content of A356 aluminum alloy greatly. Contrarily, Sr-modification increases the hydrogen content remarkably. After being treated with RE, a large number of LaAl11O18 consisting of Al2O3 and La2O3, are generated in the surface oxide film of A356 alloy. The surface oxide film of Sr-modification is almost composed of Al2SrO4. According to the results of SEM, the surface oxide film of Sr-modification is very easy to crack, destroy the continuity and compactness of surface oxide film, accelerate the vapor diffusing into the melt, consequently, increase the hydrogen content of A356 alloy melt significantly. But RE-modification makes the surface oxide film compact, and restrains the aluminum exposed to water, so reduces the hydrogen content of A356 alloy melt.

稀土元素原子发射光谱及其谱线干扰的高分辨率ICP-AES研究 Ⅳ铕、钆基体对其他稀土元素的光谱干扰

本文是系列工作的第四部分。利用光栅刻线为 3 60 0条 /mm的顺序扫描高分辨率ICP AES光谱仪研究了铕 (Eu)和钆 (Gd)分别作为基体时对其他 14个稀土元素共 66条“首选分析线”的光谱干扰情况 ,获得了相应的光谱干扰轮廓和其他光谱干扰信息 。