Structure and electrochemical characteristics of RENi3 alloy

The RENi3 (RE = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Y) series compounds have been prepared by arc melting constituent elements under Ar atmosphere. X-ray diffraction (XRD) analysis reveals that the as-prepared alloys have different lattice parameters and cell volumes, depending on different rare earth (RE) element. The electrochemical characteristics, including the electrochemical capacity, P-C isotherms, high rate chargeability (HRC) and high-rate dischargeability (HRD), of these alloys have been studied through the charge-discharge recycle testing at different temperatures, charge currents and discharge currents. The results show that YNi3 has the largest cell volume, smallest density, and moreover, it shows more satisfactory electrochemical characteristics than other alloys, including discharge capacity, HRC, HRD and low temperature dischargeablity.

Separation of yttrium from heavy lanthanide by CA-100 using the complexing agent

The selective extraction of yttrium front heavy lanthanide by liquid-liquid extraction using CA-100 in the presence of the complexing agent, such as EDTA, DTPA, and HEDTA was investigated. The extraction of heavy lanthanide in the present of the complexing agent was Suppressed when compared to that of Y because of the masking effect, but the selective extraction of Y was enhanced. All complexing agents formed 1: 1 complex with rare earth elements (RE), and only free rare earth ions could take part in the extraction. The condition for separation was obtained by exploring the effects of the complexing agent concentration, the extractant concentration, pH and the equilibration time on the extraction of the heavy rare earth elements.

Synergistic extraction of rare earths by mixture of bis(2,4,4-trimethylpentyl)phosphinic acid and Sec-nonylphenoxy acetic acid

Synergistic extraction of trivalent rare earths (RE=Sc, Y, La, Gd, Yb) from hydrochloride medium using mixture of bis(2,4,4-trimethylpentyl)phosphinic acid (HL, Cyanex272) and Sec-nonylphenoxy acetic acid (HA, CA-100) in n-heptane has been studied. The synergistic enhancement coefficients were observed for La (1.30), Gd (1.97), Y (3.59), Yb (8.21) and Sc (14.41). The results indicated yttrium was extracted into n-heptane as YH(5)A(4)L(4) mixed species instead of Y(HL2)(3), Y(OH)(2)A(HA)(3) which were extracted by Cyanex272 and CA-100, respectively. A cation exchange mechanism was proposed and further clarified by IR spectra. The equilibrium constants, formation constants and thermodynamic functions such as Delta G, Delta H and Delta S were determined. The Cyanex272 + CA-100 system not only enhanced the extraction efficiency of RE but also improved the selectivities significantly. The mutual separation factors of these ions suggested the mixture system would be of practical value in extraction and separation of rare earths.

A new hydrometallurgical process for extracting rare earths from apatite using solvent extraction with P-350

In this paper, a new process is proposed to recover rare earths from nitric acid leaching of apatite without interfering with the normal route for fertilizer production using solvent extraction with dimethyl heptyl methyl phosphonate CH3P(O)(OC8H17)(2) (P-350, B). In the present work, the leaching conditions are studied. In selected condition, apatite was dissolved in 20% (v/v) nitric acid solution at 60-70 degrees C while agitating. The most suitable acidity for extraction is 0.4 M HNO3. More than 98% of rare earths in apatite can be recovered using countercurrent extraction process with six stages when phase ratio = 0.5, and defluorination is unnecessary. The influences of phase ratio, stage number, acidity and salting-out agent on extractabilities Of P-350 are studied. The results show that rare earths can be separated with P-350 from Ca, P, Fe and other impurities. Mixed rare earth oxides (REO) of which purity is more than 95% with yield over 98% can be obtained.

Selective separation of yttrium by CA-100 in the presence of a complexing agent

The selective separation of Y from yttrium solution containing small heavy rare earth (HRE) impurities (Ho, Er, Tm, Yb, Lu) by liquid-liquid extraction using CA-100 in the presence of a water-soluble complexing agent of ethylenediaminetetraacetic acid (EDTA) was experimentally studied at 298K. Experiments were carried Out in two feeds, Feed-I: [RE](f) = 4.94 x 10(-3) M, Y = 98.5%, HRE (Ho, Er, Tm, Yb, Lu) = 1.5%; Feed-II: [RE](f) = 4.94 x 10(-3) M, Y = 99.9%, HRE (Ho, Er, Tm, Yb, Lu) = 0.1%, as a function of equilibrium pH (pH(eq)), the concentration ratio of [EDTA]:[HRE impurities]. It was shown that the extraction of HRE in the presence of EDTA was suppressed when compared to that of Y because of the masking effect, while the selective extraction of Y was enhanced and the separation factors increased to maximum at appropriate condition for Feed-I: Y/Ho = 1.53, Y/Er = 3.09, Y/Tm = 5.61, Y/Yb = 12.04, Y/Lu = 27.51 at pH 4.37 and [EDTA]:[HRE impurities] = 4: 1, for Feed-II: Y/Ho = 1.32, Y/Er = 1.91, Y/Tm = 2.00, Y/Yb = 3.05, Y/Lu = 3.33 at pH 4.42 and [EDTA]: [HRE impurities] = 8:1. The separation and purification of Y by this method was discussed.

Synergistic extraction of rare earths(III) from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and di-(2-ethylhexyl)-2-ethylhexylphosphonate

The synergistic effect of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 (HPMBP, HA) and di-(2ethylhexyl)-2-ethylhexylphosphonate (DEHEHP, B) in the extraction of rare earths (RE) from chloride solutions has been investigated. Under the experimental conditions used, there was no detectable extraction when DEHEHP was used as a single extractant while the amount of RE(III) extracted by HPMBP alone was also low. But mixtures of the two extractants at a certain ratio had very high extractability for all the RE (III). For example, the synergistic enhancement coefficient was calculated to be 9.35 for Y3+, and taking Yb3+ and Y3+ as examples, RE3+ is extracted as RE(OH)A(2).B. The stoichiometry, extraction constants and thermodynamic functions such as Gibbs free energy change Delta G (-17.06kJmol(-1)), enthalpy change Delta H (-35.08kjmol(-1)) and entropy change Delta S (-60.47JK(-1)mol(-1)) for Y3+ at 298 K were determined. The separation factors (SF) for adjacent pairs of rare earths were calculated. Studies show that the binary extraction system not only enhances the extraction efficiency of RE(III) but also improves the selectivity, especially between La(III) and the other rare earth elements.

Langmuir-Blodgett films based on europium-substituted heteropolytungstate and their luminescence properties

Several new hybrid organic-inorganic Langmuir-Blodgett (LB) films containing europium-substituted hetero-polytungstate Eu (XW11O39)(2)''(-) (X=Ge, Si, B) were successfully obtained using LB technique. When the heteropolytungstate anions are dissolved in the subphase, dimethyldioctadecylammonium bromide compression isotherms have been modified, which shows that the polyanions interact with the monolayer. Y-type LB films were obtained from the systems. Low-angle X-ray has shown that these LB films have well-defined lamella. The LB films were characterized by luminescence spectra and the characteristic luminescence behavior for europium-substituted heteropolytungstate complexes and their LB films were discussed. The results of excitation spectra indicate that the energy could be effectively transferred from ligands to the Eu3+ ions in the LB films and the luminescence efficiency could be greatly increased. The results of luminescence spectra indicate that the formations of hybrid organic-inorganic LB films have a great effect on the luminescence of europium-substituted heteropolytungstate. The lifetime shortening was observed in LB films.

Recent progress in the studies of endohedral metallofullerenes

This overview presents the recent progress in the area of endohedral metallofullerenes in the past several years. The important results have been summarized as follows: (1) Many metals including Group 3 metals, most of the lanthanide series elements, and Group 2 metals have been encapsulated into a fullerene cage to form mono-, di-, and trimetallofullerenes by using the arc-evaporation technique. (2) Some endohedral metallofullerenes such as Group 3 metals, most of the lanthanide series elements, Group 2 metals, and some of their isomers have been successfully isolated and purified by a two-step or several-step HPLC technique. By using high-temperature and high-pressure extraction with pyridine, Ln@C-80, Ln@C-82, and Ln2@C-80 for most rare-earth metals have been selectively extracted in high yield (about 1% of the saw soot) from fullerenes and other size metallofullerenes. (3) The endohedral nature of metallofullerenes such as Y@C-82, Sc2@C-84, and Sc@C-82 has been finally confirmed by synchrotron X-ray powder diffraction. The symmetries and the structures of metallofullerenes such as Ca@C-82(III), La-2@C-80(I-h), Sc-2@C-84(D-2d), and Sc-2@C-84(C-s) have been confirmed by NMR measurements. (Lb) The information on the electronic structures and properties of endohedral metallofullerenes has been obtained by various spectrometric means Such as EPR, W-vis-MR, XPS, CV. It is generally accepted that three-electron transfer is favorable when M = Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu but Sc, Eu, Sm, Yb, Tm, Ca, Sr, Ba prefer to donate two electrons to the fullerene cages. (5) Several chemical reactions of endohedral metallofullerenes have been reported in which reagents are disilacyclopropane, digermacyclopropane, diphenyldiazomethane, and trifluoroacetic acid. (6) Mass spectrometry provided the crucial evidence that led to the discovery of metallofullerenes in 1985 and has always played a key role in their identification and characterization, Ion-mobility measurements of gas-phase ions have obtained the information of structures and the formation mechanism of endohedral metallofullerenes. till Theoretical calculations on the endohedral metallofullerenes have made an important contribution to the studies on the symmetry of the cage, the position of metal atom(s) inside the cage, the number of electronic transfer between metal atom(s) and fullerene cage, etc. (C) 2000 Elsevier Science S.A. All rights reserved.

Species of lanthanum in Wistar rat liver

The metabolic accumulation and species of lanthanum in Wistar rat liver were investigated by ICP-MS, gel exclusion chromatography and ultrafiltration after the rats were fed by low dose of lanthanum for a long time. It was found that the content of La in the liver increased regularly with arise of dose and time of drug delivery. After the administration was stopped for a certain time a part of lanthanum in the liver Tvas metabolized, but;the metabolic rate was very slow, The lanthanum in rat liver was distributed in the soluble protein with molecular weight: of more than 60000 mostly. Rare Earth existed in the six elution peaks separated by Sephacryl S-200. The amount of lanthanum in the first elution fraction is the largest, which was 88 percent in the whole content of lanthanum in proteins with molecular weight more than 60000.

Synthesis, luminescence, energy transfer and Langmuir-Blodgett films of amphiphilic complexes of rare earths with monooctadecyl phthalate

Three new amphiphilic rare earth complexes with only two organic long chains Ln (MOP)(2)Cl (MOP=monooctadecyl phthalate, Ln=Eu, Tb, Gd) were synthesized and characterized by elemental analysis. The complexes (Eu, Tb) showed good luminescence property with long fluorescence lifetime, whereas the intensity and lifetime of Tb complex are greater than those of Eu complex, By measuring the triplet energy levels of ligand based on energy transfer mechanism, above phenomena have been well explained. The Langmuir films of the complexes on the air/water interface were also studied and the results show that all of them have good film-forming property.

pH-potentiometric study on rare earths and calcium binary and ternary complexes with DL-malic acid and L-hydroxyproline

The stability constants of M-L binary system and M-L-L' (M = La3+ similar to Yb3+, Y3+ and Ca2+; L= DL-malic aicd, L' = L-hydroxyproline) ternary system were determined by pH-(0)-tentiometric method under the simulating physiological condition(37 degrees C, I=0.15 mol/L NaCl). The complex species MpLqLr'H-s(abbr as pqrs) in the sytems were ascertained by program COMPLEX. The results show that there are three species(1101, 1100 and 1200) in M-L binary system and one species(1010) in M-L' binary system. In addition to the above four species, a new species, 1112 was found in the M-L-L' ternary system, which is the only species of mixed ligands. Rare earth ions form more stable complexes than calcium ion does and the stability differences between their complexes in the ternary system are less than that in the binary system. The distributions of all the species in La-L-L' ternary system vs pH are discussed.

Physico-chemical properties and catalytic behavior of LnSrNiO(4) mixed oxides for NO decomposition

A series of LnSrNiO(4)(A(2)BO(4), Ln = La, Pr, Nd, Sm, Gd) mixed oxides with K2NiF4 structure, in which A-site(Sr) was partly substituted by individual light rare earth element, was prepared. The solid state physico-chemical properties including crystal structure, defect structure, IR spectrum, valence state of H-site ion, nonstoichiometric oxygen, oxygenous species, the properties of oxidation and reduction etc. as well as the catalytic behavior for NO decomposition on these mixed oxides were investigated. The results show that all of these mixed oxide catalysts have high activity for the direct decomposition of NO(at 900 degrees C the conversion of NO is more than 90%). The effect of the substitution of light rare earth elements at A-site on catalytic behavior for NO decomposition was elucidated.

The photophysical properties of binary and ternary complexes of rare earths with conjugated carboxylic acids and 1,10-phenanthroline

Results of photophysical properties of the complexes of Gd3+, Eu3+ and Tb3+ with conjugated carboxylic acids (3,4-funandicarboxylic acid and nicotinic acid) and 1,10-phenanthroline are reported. Whether between central ions and ligands or between the two ligands, it is found that the intramolecular energy efficiency is a sensitive function of the relative positions of the resonance energy levels of the central ions and the lowest triplet states of the ligands. Couplings of rare earth ions to the ligands are discussed in detail. (C) 1997 Elsevier Science S.A.

Luminescent properties of Ba-3(PO4)(2):Eu, Tb phosphors

Luminescence of europium (III), europium(II) and terbium(III) has been observed in Ba-3(PO4)(2):Eu, Tb phosphors which are synthesized in air atmosphere. The valence state of europium is influenced by amount of terbium. It is notable that the relative intensity of the emission spectra peaks corresponding to Eu2+ is increased if the amount of Tb3+ is increased. These phenomena can be explained by an electron transfer mechanism. We predict a new kind of two-rare-earth codoped trichromatic phosphors in Ba-3(PO4)(2) matrix.

The spectral properties of BaB8O13:Eu,Tb phosphors

The luminescence properties of BaB8O13:xEu,yTb phosphors which were synthesized in air atmosphere have been studied. The emissions of europium(III), terbium(III) and europium(II) have been observed in BaB8O13:xEu, yTb phosphors. Electron paramagnetic resonance (EPR) studies were carried out. The intensities of EPR peaks of europium(II) are increased if terbium(III) is increased in BaB8O13:Eu3+,yTb(3+) phosphors. So the valence state of europium is influenced by terbium(III). These phenomena can be explained by an electron transfer mechanism. We found a new kind of method to prepare trichromatic phosphor that two rare earth ions activated in a BaB8O13 matrix.