A kinetic study of the leaching of a low-grade niobium–tantalum ore by concentrated KOH solution

A kinetic study of the leaching of a low-grade niobium–tantalum ore by concentrated KOH solution under atmospheric pressure has been investigated. The effects of reaction temperature, KOH concentration, agitation speed, particle size and alkali-to-ore mass ratio on the dissolution rate of niobium were examined. It was found that the dissolution rate of niobium is significantly influenced by the temperature, particle size and concentration of KOH solution. The experimental data were well interpreted with a shrinking core model under diffusion control through the product layer. By using the Arrhenius expression, the apparent activation energy for the dissolution of niobium was evaluated. Finally, on the basis of the shrinking core model, the following rate equation was established:$1-3(1-X_{\text{b}}{)}^{2/3}+2(1-X_{\text{b}})=\frac{k_0}{R^2}{\mathrm{e}}^{-\frac{72200}{R\prime T}}·t\text{.}$     

Effect of Tb(III) on the unfolding of ciliate Euplotes octocarinatus centrin induced by guanidine hydrochloride

To understand the unfolding of ciliate Euplotes octocarinatus centrin (EoCen), the glycine positioned at 115, the sixth residue of the loop of the protein's third EF-hand, was mutated into tryptophan (Trp). Intrinsic fluorescence and Tb(III) binding properties of wild type EoCen and G115W mutant were monitored by fluorescence spectra in 10 mmol/L Hepes. The emission maximum of EoCen was 306 nm and mutation had no impact on the Tb(III) binding properties. The properties of G115W were investigated by fluorescence, far-UV circular dichroism (CD) spectra and fluorescence decays in the absence or in the presence of 6 mol/L guanidine hydrochloride (GdnHCl). For the increase in polarity of micro-environment around Trp residue, the emission maximum of apoG115W at 343 nm is shifted to 359 nm in 6 mol/L GdnHCl. Also the secondary structure is lost nearly and fluorescence lifetime decreases in 6 mol/L GdnHCl. The unfolding of G115W induced by GdnHCl was assessed by using the model of structural element. The unfolding of proteins is a sequential reaction, namely two-transition, three-state process. The first transition belongs to the unfolding of the C-terminal domain, and the second transition is assigned to the unfolding of the N-terminal domain. The $\Delta 〈\Delta G_{\text{total}}^0\left({\text{H}}_2\text{O}\right)〉$ was used to determine the effect of Tb(III) on the stability of apoprotein. The $〈\Delta G_{\text{total}}^0\left({\text{H}}_2\text{O}\right)〉$ for Tb₂-G115W has a less increase of 0.68 kJ/mol compared with apoG115W, proving Tb(III) situated at C-terminal has negligible impact on the stability of protein. Whereas the $〈\Delta G_{\text{total}}^0\left({\text{H}}_2\text{O}\right)〉$ for Tb₄-G115W has a rise of 1.29 kJ/mol compared with Tb₂-G115W, manifesting Tb(III) located at low affinity sites has considerable influence on protein stability, mainly stabilizing the N-terminal domain.     

CeO2 nanoscale particles: Synthesis,characterization and photocatalytic activity under UVA light irradiation

CeO_2 nanoparticles(NPs) were synthesized in alkaline medium via the homogeneous precipitation method and were subsequently calcined at 80 ℃/24 h(assigned as CeO_2-80) and 500 ℃/2 h(assigned as CeO_2-500). The as-prepared materials and the commercial ceria(assigned as CeO_2-com) were characterized using TGA-MS, XRD, SEM-EDX, UV-vis DRS and IEP techniques. The photocatalytic performances of all obtained photocatalysts were assessed by the degradation of Congo red azo-dye(CR) under UVAlight irradiation at various environmental key factors(e.g., reaction time and calcination temperature).Results reveal that CeO_2 compounds crystalize with cubic phase, CeO_2-500 exhibits smaller crystallite size(9 nm vs 117 nm) than that of bare CeO_2-com. SEM analysis shows that the materials are sphericallike in shape NPs with strong assembly of CeO_2 NPs observed in the CeO_2-500 NPs. EDX analysis confirms the stoichiometry of CeO_2 NPs. UV-vis DRS measurement reveals that, CeO_2-500 NPs exhibits a red-shift of absorption band and a more narrow bandgap(2.6 eV vs 3.20 eV) than that of bare CeO_2-com. On the contrary, Urbach energy of Eu is found to be increased from 0.12 eV(CeO_2-com) to 0.17 eV(CeO_2-500),highlighting an increase of crystalline size and internal microstrain in the CeO_2-500 NPs sample. Zeta potential(IEP) of CeO_2-500 NPs is found to be 7.2. UVA-light-responsive photocatalytic activity is observed with CeO_2-500 NPs at a rate constant of 10×10~(-3) min~(-1), which is four times higher than that of CeO_2-com(K_(app)=2.4×10~(-3) min~(-1)) for the degradation of CR. Pseudo-first-order kinetic model gives the best fit. On the basis of the energy band diagram positions, the enhanced photocatalytic performance of CeO_2-500 nano-catalyst can be ascribed to O_2~-, 'OH and R'~+ as the primary oxidative species involved in the degradation of RC under UVA-light irradiation.     

Rare earth （Eu2＋,ce3＋） activated BaAIESi2O8 blue emitting phosphor

Blue emitting rare earth（Eu2＋,Ce3＋） doped BaAl2Si2O8 phosphors were synthesized by combustion methods at 600 oC. BaAl2Si2O8： Eu2＋ phosphor showed isolated broad blue emission band at 455 nm, when it was excited with the wavelength of 329 nm. Whereas BaAl2Si2O8：Ce3＋ phosphor exhibited blue emission band at 442 nm, under 303 nm excitation wavelength. These observed emission bands of Eu2＋ and Ce3＋ ions corresponded to 5d-4f allowed transitions. The position of emission band was calculated by using the equationE=Q[1-〔V/4〕^1/V）]× 10 （nEar/80）Also the spin orbit splitting difference in the ground state levels of Ce3＋ ion was studied by Gaussian curve fitting. Broad absorption and emission bands in blue regions made prepared phosphors a promising blue host for the white-LEDs.     

Characterization of p precipitate phase in Mg-7Gd-5Y-1Nd-0.5Zr alloy

As reported in our previous works,a Mg-7Gd-5Y-1Nd-0.5Zr alloy recently developed exhibited remarkable age-hardening responses and excellent mechanical properties at both room and elevated temperatures.In Mg-7Gd-5Y-1Nd-0.5Zr alloy,the β precipitate phase was assumed to be one of the main strengthening phases in peak-aged samples.This study aimed to determine the crystal structure and orientation relationship of the β precipitate phase in Mg-7Gd-5Y-1Nd-0.5Zr alloy using transmission electron microscopy and high-resolution electron microscopy.The results indicated that the β precipitate had a face-centered cubic structure with a lattice parameter of a=2.22 nm.The orientation relationship between the β precipitate phase and the α-Mg matrix was(12)β$$$$(100)α,[110] β/[0001] α.The β plates formed on prismatic planes could play an important role in alloy strengthening by proving effective barriers to gliding dislocations.A single β plate often contained several domains of(11)β twin-related variants.A composition of Mg 5(Y0.4Gd0.4Nd0.2) was suggested for the β phase in Mg-7Gd-5Y-1Nd-0.5Zr alloy.     

Structural properties and catalytic performance of the LaCuZn mixed oxides for CO2 hydrogenation to methanol

A series of La-Cu-Zn-O mixed oxide catalysts were synthesized by a co-precipitation method and calcined under different temperatures. The XRD, BET, TPR, N_2 O-adsorption, XPS, SEM and TPD techniques were carried out to measure the aimed catalysts. The results indicated that the chemical environment of lanthanum element changes with the increase of calcination temperature. The La_2 CuO_4 perovskite structure is obtained at the temperature higher than 823 K and the special copper species appear in the perovskites due to the special structure property. The catalysts with La_2 CuO_4 perovskite structure show higher methanol selectivity compared with the mixed copper catalyst. For the perovskite catalysts, the conversion of CO_2 changes with the same tendency of the copper species ratio((Cu~(α+)+Cu~0)/(Cu_(Total))%), which implied both Cu~(α+) and Cu~0 are important active sites in the perovskite catalyst for the reaction.     

Comparative studies on Y(III) and Dy(III) extraction from hydrochloric and nitric acids by Cyanex 572 as a novel extractant

Extraction of Y(III) and Dy(III) from hydrochloric and nitric acids by Cy-572 in kerosene was studied. The factors affecting the extraction were separately investigated. The stoichiometry of the extracted species was deduced on the basis of slope analysis method. Evaluation of extraction equilibrium and stripping investigation was studied as well as saponification effect of Cy-572. The composition of the extracted metal species in the organic phase was found to be $\overline{{[\text{MA}}_3·{\left(\text{HA}\right)}_3]}$ for Y(III) or Dy(III) in both media. 1.0 mol/L HCl is the best stripping agent for each metal ion from the studied acidic media in one step. Saponified Cy-572 does not exhibit any selectivity towards the extraction of Y(III) or Dy(III) from both HCl and HNO₃ solutions. Based on the obtained results, the data were compared and the separation feasibility between lanthanides and Y(III) in the two media was discussed.     

Magnetic properties and large magnetocaloric effects of GdPd intermetallic compound

With the intention to explore excellent magnetocaloric materials, the intermetallic compound GdPd was synthesized by arc melting and heat treatment. The microstructure, magnetic and magnetocaloric properties of the intermetallic compound of GdPd were investigated by X-ray diffraction(XRD), scanning electron microscopy(SEM) and the physical property measurement system(PPMS). A large reversible magnetocaloric effect is observed in GdPd accompanied by a second order magnetic phase transition from paramagnetism to ferromagnetism at ～39 K. The paramagnetic Curie temperature(θp) and the effective magnetic moment(μ_(eff))are determined to be 34.7 K and 8.12 μ_B/Gd,respectively. The maximum entropy change(|△S_M~(Max)|) and the relative cooling power(RCP) under a field change of 5 T are estimated to be 20.14 J/(kg·K) and 433 J/kg, respectively. The giant reversible magnetocaloric effects(both the large△S_M and the high RCP) together with the absence of thermal and field hysteresis make the GdPd compound an attractive candidate for low-temperature magnetic refrigeration.     

How minor structural changes generate major consequences in photophysical properties of RE coordination compounds;resonance effect,LMCT state

Lanthanide coordination compounds of the formula Na[Ln(L)_4](1 Ln),where Ln=La~(3+),Eu~(3+),Gd~(3+),Tb~(3+),L=[L]~-and HL=dimethyl(4-methylphenylsulfo nyl)amidophosphate,were synthesized.Their structural and spectro scopic properties were discussed in detail based on X-ray diffraction measurements,IR spectroscopy,absorption and emission spectroscopy at 293 and 77 K and theoretical calculations of the intramolecular energy transfer(IET) rates.DFT calculations were used to investigate the 1 Ln electronic properties re quired to calculate the transition rates.30 and 22 pathways of intramolecular nonradiative energy transfer were examined in the case of 1 Eu and 1 Tb,respectively.It is shown that the main pathway for sensitization of the lanthanide emission is either the triplet(1 Eu) or singlet(1 Tb) transfer,occurring mainly through the exchange mechanism.The energy rates for energy transfer from S_1 and T_1 equal W_S=1.53 × 10~5 s~(-1)(1 Eu),W_T=5.14 × 10~6 s~(-1)(1 Eu) and W_S=4.09 × 10~7 s~(-1)(1 Tb),W_T=6.88 × 10~5 s~(-1)(1 Tb).The crucial role of the 7 F5 level in the energy transfer process of 1 Tb and the participation of the LMCT state in the depopulation of the ligand singlet state of 1 Eu were demonstrated.The influence of the resonance effect on the splitting of the~7 F_1 level in 1 Eu was analyzed.By comparing the properties of 1 Ln with the properties of 2 Ln coordination compounds,sharing the same ligand and crystallizing in the same crystallographic system(monoclinic),but with a different space group,it is demonstrated how slight structural changes can affect the photophysical properties of Ln compounds.     

Co-substitution of zirconium and neodymium on hyperfine interactions and AC susceptibility of SrFe_(12)O_(19) nanohexaferrites

This study presents the influence of Zn and Nd co-substitution on structure,morphology,AC susceptibility and ZFC-FC magnetizations of Sr nanohexaferrites(NHFs),SrFe_(12-x)(Zn,Nd)_xO_(19)(0.0≤x≤1.0),which was produced by sol-gel approach.XRD powder patterns,scanning electron microscopy(SEM) and high-resolution transmission electron spectroscopy(HR-TEM) approve the synthesis of Sr M-type hexaferrite.Mossbauer spectra show that Zn~(2+)ions occupy 2 b and 4f_1 sites while Nd~(3+)ions locate at 2 a,4f_2 and 12 k sites.The magnetic properties of the produced Sr-NHFs were investigated also by ZFC-FC magnetizations and AC susceptibility.According to the M_(FC)-M_(ZFC) results(between 2 and 400 K),no blocking temperature was detected which indicates the ferromagnetic(FM) behavior of NHFs.At lower temperatures,a super-spin glass like behavior is discerned.The AC susceptibility indicates that the magnetic interactions are improved due to the inclusion of low content(x=0.1) of Nd~(3+)and Zn~(2+)ions into the Sr-NHFs.However,with further increasing the Nd~(3+)and Zn~(2+)contents(x=0.9),the magnetic interactions are weakened.     

Development of a microfluidic-chip system based on parallel flow for intensified Gd(III) extraction from nitrate media using cationic extractant

Microfluidic solvent extraction (micro SX) of gadolinium was conducted using a mono- and di-ester mixture (MDEHPA) as the cationic extractant. A microfluidic YY channel was fabricated using CO₂-laser technique in a glass microchip used as the extraction system. Compared with batch extraction, extraction kinetic is found fast, and extraction equilibrium is attained within 15 s. Stoichiometry of the extracted complex is found to be Gd(NO₃)₃·3MDEHPA using log–log plot method. Additionally, the operating parameters and overall volumetric mass transfer coefficient $\left(k_{\mathrm{L}}\alpha \right)$ were investigated to determine the mass transfer performance. Optimal condition of microextraction for gadolinium using response surface methodology was determined (feed solutions 31 mg/L adjusted to pH value 2.5, extractant concentration 2.9 vol% and extraction time 13.5 s). In optimal condition, gadolinium extraction yield is obtained 95.5%. Findings of this study approve simplicity, portability, effectiveness, swiftness, and environmental friendliness microfluidic solvent extraction process and reveal that micro SX is useful in the field of extraction strategic metals present at low concentrations, which are otherwise not technically amenable or economically feasible to extract using current traditional methods.     

Enhanced thermal stability of Ce_(0.33)Zr_(0.55)(LaNdY)_(0.12)O_2 mixed oxides prepared by sulfate-aided coprecipitation method

Ceria-zirconia based mixed oxides(CZs) have been applied in three-way catalysts(TWCs) for their high surface area and oxygen storage capacity(OSC).In this work,enhanced thermal stability of Ce_(0.33)Zr_(0.55)(LaNdY)_(0.12)O_2 mixed oxides was realized via a facile and scalable approach,namely,sulfateaided coprecipitation method was labelled as CZ-S.Sulfate ion(SO_4~(2-)) was added into raw solution in the form of sulfuric acid and acted as coordination agent.The control sample was prepared by conventional coprecipitation method without sulfuric acid added and labelled as CZ.The promotion effect of sulfate ion was analyzed systematically by X-ray diffraction(XRD),transmission electron microscopy(TEM),scanning electron microscopy(SEM),N_2 adsorption-desorption,Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),OSC and hydrogen temperatureprogrammed reduction(H_2-TPR) analysis.XRD and high resolution TEM results reveal that CZ-S have homogeneous distributions of elements.TEM and SEM images show that fresh samples of CZ-S have narrower distributions of grain sizes and larger pore sizes than those of CZ.Through cross analysis of structure and morphology of CZ and CZ-S,we find that the introduction of sulfate ions results in uniform distributions of elements,narrows distributions of grain sizes,and enables the formation of secondary loose packing of sub-particles,which lead to enhanced thermal stability of the samples of CZ-S upon aging process at high temperature.After aging treatment at 1100℃ for 10 h,aged samples of CZ-S present larger specific surface areas and pore volumes than the aged sample prepared by conventional coprecipitation method without sulfate ions added.Furthermore,the aged sample of CZ-S2(SO_4~(2-)/Zr=1)possesses the highest specific surface area of 21.9 m2/g and the biggest pore volume of 0.035 mL/g among all aged samples.