Solvent extraction of neodymium（III） from acidic nitrate medium using Cyanex 921 in kerosene

The extraction of neodymium(Ⅲ) from acidic nitrate medium was investigated using Cyanex 921 as extractant in kerosene. The metal concentration in the aqueous phase before and after extraction was determined spectrophotometrically by Arsenazo Ⅲ method. The complete equilibration was achieved in 15 min. The effects of shaking time, nitric acid concentration, nitrate concentration, extractant concentration, and temperature on the extraction were studied. The extraction of Nd(Ⅲ) was found to increase very slowly with increase in concentration of HNO3 in the range of 0.001-0.008 mol/L and then decreased when 0.01 mol/L HNO3 was used. The percentage of extraction was increased with increase in nitrate concentration from 0.01-0.45 mol/L and then decreased when nitrate concentration increased to 0.5 mol/L. Quantitative extraction of Nd(Ⅲ) (98%) was obtained from the aqueous phase containing 0.001 mol/L HNO3 and 0.1 mol/L KNO3 using 0.5 mol/L Cyanex 921. On the basis of slope analysis, the extracted complex in the organic phase was proposed to be Nd(NO3)3.2Cyanex 921. The extraction of Nd(III) was found to increase with increase in concentration of metal ion in the range of 0.001-0.05 mol/L from 0.001 mol/L HNO3 and 0.1 mol/L KNO3 with 0.1 mol/L Cyanex 921. The percentage of extraction of neodymium was found to decrease with increase in temperature. From temperature variation studies, the negative value of △H indicated the extraction reaction to be exothermic and the negative value of △S indicated the formation of a stable complex. Almost 100% Nd(Ⅲ) was recovered from the fully loaded organic phase using 0.002 mol/L H2SO4 and 0.01 mol/L HCl.     

Adsorption of Ce（Ⅳ） in nitric acid medium by imidazolium anion exchange resin

N-methylimidazolium functionalized anion exchange resin in NO3-form(RNO3) was prepared and used for adsorption of Ce(IV)in nitric acid medium.The adsorption amount increased with shaking time increasing and the adsorption equilibrium was obtained within 180min.Ce(IV) was partially reduced to Ce(III) and the reduction percent of Ce(IV) increased with shaking time increasing.But RNO3 was morestable than other resins due to the high resistance to oxidation.A little increase of adsorption amount was found with concentration of HNO3increasing.However,the reduction percent of Ce(IV) decreased with the increase of HNO3 concentration.The addition of NaNO3 decreasedthe adsorption amount of Ce(IV) on RNO3 due to the competitive anion exchange reaction.Ce(IV) was adsorbed on RNO3 in the form ofCe(IV) anion nitrato-complex.RNO3 and Ce(IV)-loaded RNO3 were characterized by fourier transform infrared(FT-IR) and thermogravimeric analysis(TGA).Ce(IV) could be easily separated from RE(III) solution by RNO3.     

Synthesis, structure and photoluminescent properties of a new Eu(Ⅲ) complex with 5-bromoisophthalic acid

The self-assembly of 5-bromoisophthalic acid (H2BIPA) with Eu(NO3)3·6H2O under the hydrothermal conditions gave a 3D coordination polymer, Eu2(BIPA)3(CH3CH2OH) (1), which was characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 displayed an unusual three-dimensional network of a rare (4,6)-connected (48.66.8)2(44.62)2(42.84) topology, which was different from Eu2(BDC)3(H2O)2 (BDC=isophthalate), because the -Br substituent of the isophthalate resulted in the different electronic effects and the steric hindrance to change the coordination modes of carboxylate groups in the assembled process. Moreover, the luminescent properties of 1 were also investigated in the solid state.     

Syntheses aod Crystal Structures of Rare Earth Complexes with Adamantanecarboxylic Acid, [LnL_3(HL)(H_2O)]_2·2EtOH·2H_2O (Ln=Nd (1), La (2))

Syntheses aod Crystal Structures of Rare Earth Complexes with Adamantanecarboxylic Acid, [LnL_3(HL)(H_2O)]_2·2EtOH·2H_2O (Ln=Nd (1), La (2))     

Synthesis, characterization and thermostability of tris（2,2,6,6-tetramethyl-3,5- heptanedionato）yttrium（III）

The metal-organic chemical vapor deposition (MOCVD) technique is a promising process for high temperature superconductor YBa2Cu3O7-δ(YBCO) preparation. In this technique, the purity, evaporation characteristics and thermostability of adopted precursors will decide the quality and reproducible results of YBCO film. In the present report, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)yttrium(III)(Y(TMHD)3) was synthesized by the interaction of yttrium nitrate hydrate with TMHD in methanol solution, and its structure was identified by FTIR, 1 H NMR, 13C NMR and EI-MS spectroscopy. Subsequently, the thermal property and the kinetics of decomposition were systematically investigated by non-isothermal thermogravimetric analysis methods (TGA) at different heating rates in streams of N2,and the average apparent activation energy of evaporation process was evaluated by the Ozawa, Kissinger and Friedman methods. The possible conversion function was estimated through the Coats-Redfern method to characterize the evaporation patterns and followed a phase boundary reaction mechanism by the contracting area equation with average activation energy of 88.9kJ/mol.     

Direct Spectroscopic Determination of Europium（ Ⅱ ） Concentration During Europium（ Ⅲ ） Electro-Reduction in Hydrochloric Acid Medium

Europiumis one of the most important rare earth(RE) element .It is widely used as a component ofcathode ray tubes , with screen coated with red phos-phor ,as phosphorescent pigments ,andinlaser optics .It can also be used as neutron-absorbing material .In…     

Synthesis and fluorescent properties of a novel europium（III） complex with terpyridine-capped poly（ethylene glycol）

Terpyridine-capped poly(ethylene glycol) (PEG) was synthesized as a novel polymeric ligand and rare earth complex was prepared from Eu(NO3)3 and the telechelic macromolecules. The structure of the complex was characterized by 1H NMR, FT-IR, UV-vis and fluores-cence spectroscopy. Strong fluorescent emission of the complex was observed at 593 and 616 nm upon the excitation of 300 nm. The fluo-rescent emission was quenched upon addition of trace amount of diethyl chlorophosphate (DCP). And the observed Ksv values for DCP were measured to be 0.568×103 and 0.89×103 L/mol for quenching at 593 and 616 nm, which indicated the detection limit for DCP was about 0.014 mmol/L. These results showed that the terpyridine-lanthanide complex could be an effective chemosensor with a potential application in the detection of organophosphates.     

Enhancing the performance of photovoltaic cells by using down-converting KCaGd（PO_4）_2：Eu~（3＋） phosphors

The goal of this work is aimed to improve the power conversion efficiency of single crystalline silicon-based photovoltaic (PV) cells by using the solar spectral conversion principle, which employed a down-converting phosphor to convert a high-energy ultraviolet photon to the less energetic red-emitting photons to improve the spectral response of Si solar cells. In this study, the surface of silicon solar cells was coated with a red-emitting KCaGd(PO4)2:Eu3+ phosphor by using the screen-printing technique. In addition to the investigation on the microstructure using scanning electron microscopy (SEM), we measured the short circuit current (Isc), open circuit voltage (Voc), and power conversion efficiency (η) of spectral-conversion cells and compared with those of bare solar cells as a reference. Preliminary experimental results revealed that in an optimized PV cell, an enhancement of (0.64+0.01)% (from 16.03% to 16.67%) in Δη of a Si-based PV cell was achieved.     

Enhanced adsorption behavior of Nd（Ⅲ） onto Dll3-Ⅲ resin from aqueous solution

An enhanced adsorption and desorption procedure of Nd(III) onto D113-III resin were prepared with various chemical methods.Batch studies were carried out with various pH,contact time,temperature and initial concentrations,and then column studies were conducted.The results showed that the optimal adsorption condition was at pH value of 6.90.The process was fast initially and arrived equilibriumwithin 60 h.The resin exhibited a high Nd(III) uptake as 232.56 mg/g at 298 K.The adsorption data fitted well with pseudo-second-order kinetic model.Thermodynamic parameters were studied,which indicated that the adsorption process was spontaneous and endothermic.Thomas model was delineated here to predict the breakthrough curves based on the experimental column study data.In the elution test,1 mol/LHCl solution could achieve a satisfactory elution rate,which indicated that D113-III resin could be regenerated and reused.Finally,the IRspectroscopic technique was undertaken,and a novel adsorption mechanism was proposed.     

Luminescent properties of dysprosium（Ⅲ） ions in LaAlO3 nanocrystallites

The absorption and emission spectra as well as decay time profile of Dy3+ ions in LaAlO3 nanocrystals were analyzed.The crystal structure of LaAlO3 was confirmed from XRD measurement.The emission peaks from blue to red came from main emitting level of dyspro-sium 4F9/2 to the ground and other excited levels of Dy3+ ions.Cross relaxation process led to non-radiative quenching of luminescence,so that the lifetime of the 4F9/2 energy level ions decreased with increasing amount of doped Dy3+ ions.The cross relaxation transfer rates were ex-perimentally determined as a function of Dy3+ concentration.     

Luminescent properties of red phosphors K2Ba（MoO4）2：Eu3＋ for white light emitting diodes

K2Ba(MoO4)2:Eu3+ phosphors were synthesized by solid-state reaction. The emission and excitation spectra of K2 Ba(MoO4)2:Eu3+ phosphors exhibited that the phosphors could be effectively excited by near ultraviolet (394 nm) and blue (465 nm) light, and emitted red light at 616 nm. The influence of Eu3+concentration, sintering temperature and charge compensators (K+, Na+ or Li+ ) on the emission intensity were investigated. The results indicated that concentration quenching of Eu3+ was not observed within 30mol.% Eu 3+, 600 oC was a suitable sintering temperature for preparation of K2 Ba(MoO4)2:Eu3+phosphors, and K+ ions gave the best improvement to enhance the emission intensity. The CIE chromaticity coordinates of K2 Ba(MoO4)2:0.05Eu3+phosphor were calculated to be (0.68, 0.32), and color purity was 97.4%.     

Influence of iron on phase and magnetic property of the LaFe_（11.6）Si_（1.4） compound

The phase relation, microstructure, Curie temperatures, hysteresis, and magnetocaloric effects of LaFex*11.6Si1.4 (x=0.96, 0.98, 1.0, and 1.02) compounds prepared by arc-melting and then annealed at 1423 K (1.5 h)+1523 K (4.5 h) were investigated. The main phase was NaZn13-type phase, the impurity phases included a small amount of α-Fe and LaFeSi phase in four samples. The crystal cell parameters of 1:13 phase increased from 1.1433(5) to 1.1454(4) nm with x increasing from 0.96 to 1.02, respectively. All samples kept the typical first-order magnetic transition. The increase of Fe strengthened IEM behavior, and led to the remarkable enhancement of MCE effect and negative slopes in Arrott plots around TC. The maximum ΔSM (T, H) under a low magnetic field (0-2 T) was 15.3, 16.8, 17.9, and 24.7 J/kg K with increasing of Fe content from x=0.96 to 1.02, respectively.     

Spectroscopic investigations on the effect of humic acid on the formation and solubility of secondary solid phases of Ln_2（CO_3）_3

The formation of secondary Ln(III) solid phases (e.g., Nd2(CO3)3 and Sm2(CO3)3) was studied as a function of the humic acid concentration in 0.1 mol/L NaClO4 aqueous solution in the neutral pH range (5-6.5). The solid phases under investigation were prepared by alkaline precipitation under 100% CO2 atmosphere and characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), time-resolved laser fluorescence spectroscopy (TRLFS), diffuse reflectance ultraviolet-visible (DR-UV-Vis), Raman spectroscopy, and solubility measurements. The spectroscopic data obtained indicated that Nd2(CO3)3 and Sm2(CO3)3 were stable and remained the solubility limiting solid phases even in the presence of increased humic acid concentration (0.5 g/L) in solution. Upon base addition in the Ln(III)-HA system, decomplexation of the previously formed Ln(III)-humate complexes and precipitation of two distinct phases occurred, the inorganic (Ln2(CO3)3) and the organic phase (HA), which was adsorbed on the particle surface of the former. Nevertheless, humic acid affected the particle size of the solid phases. Increasing humic acid concentration resulted in decreasing crystallite size of the Nd2(CO3)3 and increasing crystallite size of the Sm2(CO3)3 solid phase, and affected inversely the solubility of the solid phases. However, this impact on the solid phase properties was expected to be of minor relevance regarding the chemical behavior and migration of trivalent lanthanides and actinides in the geosphere.     

Synthesis and luminescence characteristics of terbium（III） activated NaSrBO3

The thermoluminescence (TL) and photoluminescence (PL) properties of the phosphor NaSrBO 3 :Tb 3+ were reported and discussed. The combustion technique was used for the synthesis of polycrystalline samples of NaSrBO 3 :Tb 3+ . The TL glow curve of the compound had a simple structure with a single peak at 434 K. TL sensitivity of the phosphor was found to be more than that of (LiF:Mg,Cu,P). The TL glow curve was studied as a function of concentration of dopant and dose of gamma ray irradiation. The kinetic parameters of the thermoluminescence of NaSrBO 3 : Tb 3+ were calculated employing the peak shape method. The photoluminescence (PL) properties of Tb 3+ doped in NaSrBO 3 were studied over the 200-400 nm excitation range. The excitation spectra of NaSrBO 3 :Tb 3+ consisted of single narrow band peaking at about 236 nm. The emission spectra monitored at 236 nm excitation consisted of a series of sharp lines peaking at 489, 544, 586 and 622 nm corresponding to the 5 D 4 → 7 F j (j=3,4,5,6) transitions within the 4f 8 configurations of Tb 3+ .     

Effect of Lanthanum（ Ⅲ ） on Cytosolic Free Calcium in Isolated Rabbit Mature Osteoclasts

Theformationandresorptionofboneismain tainedbytheinteractionsofosteoblasts(OBs)withos teoclasts(OCs),andafunctionalimbalancebetween themmaycausethelossofbonemass.OCsaremulti nucleatedcellsformedbythefusionofmononuclear progenitorsofthemonocyte macrophagef…     

Complexation of N＇- [1-（3-aminophenyl）ethylidine] isonicotinohydrazide with La3＋, Pr3＋, Nd3＋, Sm3＋, Eu3＋ and Gd3＋ ions and associated thermodynamics

A novel Schiff base N′-[1-(3-aminophenyl)ethylidine]isonicotinohydrazide was prepared and its complexation behavior towards some selected lanthanides had been studied employing pH-metric and calorimetric titration and spectral techniques. pH-metric studies were carried out for the trivalent La, Pr, Nd, Sm, Eu, and Gd complexes in 30% aqueous-dioxane medium at constant ionic strength of 0.05 mol/L NaClO4 and at different temperatures of 293, 303 and 313 K. The proton-ligand formation constants of the ligand indicated the presence of only one dissociable proton while the metal-ligand formation constants were compatible with the formation of 1:1 Ln(Ⅲ) complexes. The sta-bility of the complexes followed the order: La3+Gd3+, showing a break at gadolinium. The thermodynamic parame-ters, ΔG, ΔH and ΔS associated with protonation and complexation reactions were negative which suggested that all reactions were exother-mic and enthalpy-driven. Isothermal calorimetric studies of Gd3+-aeINH systems at 303 K also showed exothermic nature of the complexation reaction and formation of 1:1 complex in agreement with the pH-metric data. Formation of 1:1 complexes was confirmed by the characteriza-tion of Nd(Ⅲ) complex. A seven coordinated geometry was assigned for the complex based on its elemental and spectral data.     

Electrochemical behavior of Ce（III） in LiF-BaF2 melts

The electrochemical behavior of Ce(III) was investigated in the molten LiF-BaF2 (81 mol.%-19 mol.%) on a molybdenum elec-trode in the temperature range of 1098-1188 K using cyclic voltammetry and chronopotentiometry. It was observed that CeF3 could be re-duced into cerium metal in a reversible one-step process exchanging three electrons (Ce(III)+3e-→Ce(0)) at the operating temperatures on a molybdenum cathode. The electrochemical reduction process was controlled by the diffusion of Ce(III) in the solution. The Ce(III) diffusion coefficients were calculated at different temperatures and the values obeyed the Arrhenius law with an activation energy of 87.5 kJ/mol.     

Investigation of the crystal structure and magnetic properties of Nd_（3-x）GdxCo_（11）B_4 borides

Polycrystalline samples of pseudo-ternary intermetallic Nd3-xGdxCo11B4 (x=0,1,2,3) borides prepared by standard arc-melting were characterized by X-ray powder diffraction (XRPD),magnetization and differential scanning calorimetry (DSC) measurements. The X-ray diffraction patterns indicated the hexagonal Ce3Co11B4-type structure with P6/mmm space group for each composition. The substitution of Gd for Nd led to a decrease of the unit-cell parameters a and the unit-cell volume V,while the unit-cell parameter c increased linearly. Magnetic measurements indicated that all samples were ordered magnetically below the Curie temperature. The Curie temperatures increased as Nd was substituted by Gd. The saturation magnetization at 4 K decreased upon the Gd substitution up to x=1,and then increased.     

Growth and characterization of new laser crystal Nda3＋：ca2.85Gd0.1（VO4）2

The crystal growth, crystal defect, thermal properties and luminescence properties of Nd3+:Ca2.85Gd0.1(VO4)2 were investigated. Nd3+:Ca2.85Gd0.1(VO4)2 crystal grown by Czochraski method was green colored, and was not transparent, which was possibly due to residual impurities in V2O5, or due to the lack of oxygen in the growth process. And the Nd3+:Ca2.85Gd0.1(VO4)2 crystal had the existence of 180° do-mains. However, the annealing method could effectively decrease the crystal defect and greatly improve the quality of crystal. The average thermal expansion coefficients calculated were α⊥c=9.5767×10-6 K-1, α∥c=10.7647×10-6 K-1, respectively. The specific heat of Ca2.85Gd0.1(VO4)2 was 0.401 J/(g·K) at 330 K. The polarized absorption spectra and the polarized fluorescence spectra of Ca2.85Gd0.1(VO4)2 were measured at 330 K. Based on the Judd-Ofelt theory, the intensity parameter Ωλ (λ=2, 4, and 6), the radiation transition probabilities τrad, the stimulated-emission cross section σp in Nd3+:Ca2.85Gd0.1(VO4)2 crystal were calculated.