Synergistic extraction of rare earths using acid-base coupling extractants of calix[4]arene carboxyl derivative and primary amine N1923

Synergistic effect in the extraction of rare earth (RE) metals by the acid-base coupling (ABC) extractants of calix[4]arene carboxyl derivative Bu-t[4]CH2COOH (H(4)A) and primary amine N1923 (RNH2) has been investigated. The extraction of RE was enhanced by the addition of sodium cations into the aqueous phase not only in the extraction system of Bu-t[4]CH2COOH alone but also in the mixture of Bu-t[4]CH2COOH and N1923. The separation factors (SFs) indicating the extraction selectivity of adjacent RE elements became higher in the mixture system.

Synthesis of Tributylphosphate Capped Luminescent Rare Earth Phosphate Nanocrystals in an Ionic Liquid Microemulsion

Uniform rare earth phosphate (REPO4, RE = La-Tb) nanocrystals were successfully synthesized in a properly designed TBP/[Omim]Cl/H2O (tributylphosphate/1-octyl-3-methyl-imidazolium chloride/water) microemulsion system. The phosphoryl groups anchored the TBP molecules oil the surfaces of the nanocrystals, and this made the nanocrystals easily dispersed in some imidazolium-based ILs. LaPO4:Eu3+ and CePO4:Tb3+ nanocrystals capped with TBP showed bright red and green emission under UV excitation, with enhanced emission intensity and lifetimes compared with the uncapped ones.

Rare Earth Pyrophosphates: Effective Catalysts for the Production of Acrolein from Vapor-phase Dehydration of Glycerol

Vapor-phase dehydration of glycerol to produce acrolein was investigated at 320 A degrees C over rare earth (including La, Ce, Nd, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu) pyrophosphates, which were prepared by precipitation method. The most promising catalysts were characterized by means of XRD, FT-IR, TG-DTA, BET and NH3-TPD measurements. The excellent catalytic performance of rare earth pyrophosphate depends on the appropriate surface acidity which can be obtained by the control of pH value in the precipitation and the calcination temperature, e.g. Nd-4(P2O7)(3) precipitated at pH = 6 and calcined at 500 A degrees C in the catalyst preparation.

Investigation of Chemical Bond Characteristics, Thermal Expansion Coefficients and Bulk Moduli of alpha-R2MoO6 and R2Mo2O7 (R = rare earths) by Using a Dielectric Chemical Bond Method

Theoretical researches are performed on the alpha-R2MoO6 (R = Y, Gd, Tb Dy, Ho, Er, Tm and Yb) and pyrochlore-type R2Mo2O7 (R = Y, Nd, Sm, Gd, Tb and Dy) rare earth molybdates by using chemical bond theory of dielectric description. The chemical bonding characteristics and their relationship with thermal expansion property and compressibility are explored. The calculated values of linear thermal expansion coefficient (LTEC) and bulk modulus agree well with the available experimental values. The calculations reveal that the LTECs and the bulk moduli do have linear relationship with the ionic radii of the lanthanides: the LTEC decreases from 6.80 to 6.62 10(-6)/K and the bulk modulus increases from 141 to 154 GPa when R goes in the order Gd, Tb Dy, Ho, Er, Tm, and Yb in the alpha-R2MoO6 series; while in the R2Mo2O7 series, the LTEC ranges from 6.80 to 6.61 10(-6)/K and the bulk modulus ranges from 147 to 163 GPa when R varies in the order Nd, Sm, Gd, Tb and Dy.

Bonding Characteristics, Thermal Expansibility, and Compressibility of RXO4 (R = Rare Earths, X = P, As) within Monazite and Zircon Structures

Systematically theoretical research was performed on the monazite- and zircon-structure RXO4 (R = Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; X = P, As) series by using the chemical bond theory of dielectric description. The chemical bond properties of R-O and X-O bonds were presented. In the zircon phase, the covalency fractions of X-O bonds increased in the order of V-O < As-O < P-O, which was in accordance with the ionic radii and electronegative trends, and the covalency fractions of R-O bonds varied slightly due to the lanthanide contraction. While in the monazite phase, both R-O and X-O bonds were divided into two groups by their covalency fractions.

Solvent impregnated resin prepared using task-specific ionic liquids for rare earth separation

A novel bifunctional task-specific ionic liquid (TSIL), i.e. [trialkylmethylammonium][sec-nonylphenoxy acetate] ([A336] [CA-100]) was impregnated on intermediate polarized XAD-7 resin, and the prepared solvent impreganated resin (SIR) was studied for rare earth (RE) separation. Adsorption ability of the SIR was indicated to be obviously higher than that prepared by [A336][NO3] because of the functional anion of [A336][CA-100]. Adsorption kinetics, adsorption isotherm, separation and desorption of the SIR were also studied.

Chemical bond characteristics, thermal expansion property and compressibility of AR(2)O(4) (A = Ca, Sr, Ba; R = rare earths)

Theoretical researches were performed on the CaFe2O4-type binary rare earth oxides AR(2)O(4) (A = Ca, Sr, Ba; R = rare earths) by using chemical bond theory of dielectric description. The chemical bond properties of these crystals were explored, and then the thermal expansion property and compressibility were studied. The theoretical values of linear thermal expansion coefficient (LTEC) and bulk modulus were presented. The calculations revealed that the LTECs and the bulk moduli do have linear relationship with the ionic radii of the rare earths. In the cases of Sc and Y, both the LTEC and bulk modulus values are larger than the lanthanide series. We attribute this to the difference in the electronic configuration between Sc (Y) and lanthanide series. For SrY2O4 and BaY2O4 crystals, the theoretical values of LTEC and bulk modulus agree well with experimental ones.

Extraction and separation of rare earths from chloride medium with mixtures of 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester and sec-nonylphenoxy acetic acid

BACKGROUND: 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (HEHEHP, H(2)A(2)) has been applied extensively to the extraction of rare earths. However, there are some limitations to its further utilization and the synergistic extraction of rare earths with mixtures of HEHEHP and another extractant has attracted much attention. Organic carboxylic acids are also a type of extractant employed for the extraction of rare earths, e.g. naphthenic acid has been widely used to separate yttrium from rare earths. Compared with naphthenic acid, sec-nonylphenoxy acetic acid (CA100, H2B2) has many advantages such as stable composition, low solubility, and strong acidity in the aqueous phase. In the present study, the extraction of rare earths with mixtures of HEHEHP and CA100 has been investigated. The separation of the rare earth elements is also studied.

Solvent extraction study of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid with Cyanex301 or Cyanex302

The extraction of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid (CA100) with bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex301) or bis(2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex302) in n-heptane has been studied. The synergistic enhancement of the extraction of lanthanum (III) by mixtures of CA100 with Cyanex301 has been investigated using the methods of slope analysis and constant mole. The extracted complex of lanthanum (III) is determined. The logarithm of the equilibrium constant is calculated as - 1.41. The formation constants and the thermodynamic functions, Delta H, Delta G, and Delta S have also been determined.

Solvent extraction of rare earths from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and sec-octylphenoxyacetic acid

The extraction of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid (CA100) with bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex301) or bis(2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex302) in n-heptane has been studied. The synergistic enhancement of the extraction of lanthanum (III) by mixtures of CA100 with Cyanex301 has been investigated using the methods of slope analysis and constant mole. The extracted complex of lanthanum (III) is determined. The logarithm of the equilibrium constant is calculated as - 1.41. The formation constants and the thermodynamic functions, Delta H, Delta G, and Delta S have also been determined.

Adhesive strength of new thermal barrier coatings of rare earth zirconates

La2Zr2O7 (LZ) and La-2(Zr0.7Ce0.3)(2)O-7 (LZ7C3) as novel candidate materials for thermal barrier coatings (TBCs) were prepared by electron beam-physical vapor deposition (EB-PVD). The adhesive strength of the as-deposited LZ and LZ7C3 coatings were evaluated by transverse scratch test. Meanwhile, the factors affecting the critical load value were also investigated. The critical load value of LZ7C3 coating is larger than that of LZ coating, whereas both values of these two coatings are lower than that of the traditional coating material, i.e. 8 wt% yttria stabilized zirconia (8YSZ). The micro-cracks formed in the scratch channel can partially release the stress in the coating and then enhance the adhesive strength of the coating. The width of the scratch channel and the surface spallation after transverse scratch test are effective factors to evaluate the adhesive strength of LZ and LZ7C3 coatings.

Rare Earth Fluorides Nanowires/Nanorods Derived from Hydroxides: Hydrothermal Synthesis and Luminescence Properties

In this paper, we reported the synthesis of nearly monodisperse and well-defined one-dimensional (1D) rare earth fluoride(beta-NaREF4) (RE = Y, Sm, Eu, Gd, Tb, Dy, and Ho) nanowires/nanorods by in situ acid corrosion and anion exchange approach using RE(OH)(3) as precursors via a facile hydrothermal route. X-ray diffraction (XRD), energy-dispersive X-ray (EDX) spectroscopy. scanning electron microscopy (SEM), transmission electron microscopy (TEM). high-resolution transmission electron microscopy (HRTEM), and photoluminescence(PL)spectroscopy were used to characterize the samples. The results show that the as-prepared rare earth fluoride (beta-NaREF4) nanowires/nanorods preserve the basic morphology of the initial RE(OH)(3) precursors.

Synthesis and characterization of monodisperse spherical SiO2@RE2O3 (RE = rare earth elements) and SiO2@Gd2O3:Ln(3+) (Ln = Eu, Tb, Dy, Sm, Er, Ho) particles with core-shell structure

Spherical SiO2 particles have been coated with rare earth oxide layers by a Pechini sol-gel process, leading to the formation of core-shell structured SiO2@RE2O3 (RE = rare earth elements) and SiO2@Gd2O3:Ln(3+) (Ln = Eu, Tb, Dy, Sm, Er, Ho) particles. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL), and cathodoluminescence spectra as well as lifetimes were used to characterize the resulting SiO2@RE2O3 (RE = rare earth elements) and SiO2@Gd2O3:Ln(3+) (Eu3+, Tb3+, Dy3+, Sm3+, Er3+, Ho3+) samples. The obtained core-shell phosphors have perfect spherical shape with narrow size distribution (average size ca. 380 nm), smooth surface and non-agglomeration. The thickness of shells could be easily controlled by changing the number of deposition cycles (40 nm for two deposition cycles).

Rare-earth metal complexes stabilized by amino-phosphine ligand. Reaction with mesityl azide and catalysis of the cycloaddition of organic azides and aromatic alkynes

Stoichiometric reactions between mesityl azide (MesN(3), Mes = 2,4,6-C6H2Me3) and amino-phosphine ligated rare-earth metal alkyl, LLn(CH2SiMe3) (2)(THF) (L = (2,6-C6H3Me2)NCH2C6H4P(C6H5)(2); Ln = Lu (1a), Sc (1b)), amide, LLu(NH(2,6-(C6H3Pr2)-Pr-i))(2)(THF) (2) and acetylide at room temperature gave the amino-phosphazide ligated rare-earth metal bis(triazenyl) complexes, [L(MesN(3))]Ln[(MesN(3))-(CH2SiMe3)](2) (Ln = Lu (3a); Sc (3b)), bis(amido) complex [L(MesN3)] Lu[NH(2,6-C6H3 Pr-i(2))](2) (4), and bis(alkynyl) complex (5) (L(MesN(3))Lu (C CPh)(2))(2), respectively. The triazenyl group in 3 coordinates to the metal ion in a rare eta(2)-mode via N-beta and N-gamma atoms, generating a triangular metallocycle. The amino-phosphazide ligand, L(MesN(3)), in 3, 4 and 5 chelates to the metal ion in a eta(3)-mode via N-alpha and N-gamma atoms. In the presence of excess phenylacetylene, complex 3a isomerized to 3', where the triazenyl group coordinates to the metal ion in a eta(3) mode via Na and Ng atoms.

Reactivity of Rare-Earth Metal Complexes Stabilized by an Anilido-Phosphinimine Ligand

Treatment of anilido-phosphinimine-ligated yttrium mono(alkyl) complex 1a, LY(CH2Si(CH3)(3))(THF) (L = o-(2,6-(C6H3Pr2)-Pr-i)NC6H4P(C6H4)(C6H5)N(2,4,6-C6H2Me3)), with 2 equiv of phenylsilane in DME afforded methoxy-bridged complex 2, [LY(mu-OCH3)](2), via the corresponding hydrido intermediate. When excess isoprene was added to the mixture of la and phenylsilane, a eta(3)-isopentene product, 3, LY(CH2C(CH3)=CHCH3)(THF), was isolated. A lutetium chloride, LLuCl(DME) (4), was generated through the reaction of lutetium mono(alkyl) complex 1b, LLu(CH2Si(CH3)(3))(THF), with [Ph3C]-[B(C6F5)(4)]center dot LiCl accompanied by the formation of [Li(DME)(3)](+)[B(C6F5)(4)](-). Metathesis reaction of 1b with excess AlMe3 at room temperature gave a methyl-terminated counterpart, 5, LLu(CH3)(THF)(2). In all these reactions, the Ln-C-phenyl bonds of complexes 1 remained untouched.