Electrochemical behavior of Dy(III) on bismuth film electrode in eutectic LiCl-KCl melts

An electrochemical study of dysprosium (III) on Bi film electrode was carried out in eutectic LiCl-KCl melts by transient and steady state electrochemical techniques. The results of transient electrochemical techniques showed that the reduction of Dy (III) appears at a more positive value than the one detected on W electrode owing to the formation of Bi-Dy intermetallic compounds through electrochemical deposition of Dy on bismuth film electrode. The thermodynamic properties of the formation for Dy-Bi intermetallics were estimated by a steady state electrochemical method in a temperature range of 713–803 K. Furthermore, the electrochemical preparation of Bi-Dy alloys was conducted by galvanostatic electrolysis at different current intensities. The Bi-Dy alloys, characterized by scanning electron microscopy equipped with energy dispersive spectrometry and X-ray diffraction, are comprised of DyBi_3/5 and DyBi phases.     

Evolution of microstructures and optical properties of gadolinium oxide with oxygen flow rate and annealing temperature

In this study, the effects of oxygen flow rate and annealing temperature on Gd_2 O_3 structures and optical properties were systematically analyzed. Gd_2 O_3 films were deposited on both quartz and ZnS substrates by magnetron sputtering and then annealed under vacuum at 700, 800 and 900℃, Restructure and phase transformation from cubic to monoclinic occur at different temperatures depending on the oxygen flow rate. The optical band gap, which is more sensitive to the annealing temperature than oxygen flow rate changes from 5.32 to 5.65 eV. The refractive index is approximately 1.75 at 550 nm and is adjustable by the oxygen flow rate. The transmittance of the ZnS substrate with Gd_2 O_3 film exceeds 80% and reaches82% at the 7.5-9.5 μm range. When ZnS is coated on both sides, the transmittance is increased to approximately 90%. Our results indicate that Gd_2 O_3 films are promising new candidates for anti-reflective coatings in the infrared region.     

Effect of erbium on properties and microstructure of Al-Si eutectic alloy

Eutectic Al-12.6 wt.%Si alloys with various contents of the rare earth dement Er were prepared by the conventional casting technique.The effect of Er on the microstructure and properties of the eutectic Al-Si alloys was investigated using optical microscopy,scanning electron microscopy as well as the friction and wear tests.It was found that the addition of Er obviously improved the anti-wear properties,and reduced the friction coefficient of the alloys.The appropriate addition of Er would change the size and shape of the eutectic silicon,and thereby refine the microstructure of the Al-Si alloys.The refinement mechanism was also discussed.     

Electrochemical behavior of dysprosium(III) in eutectic LiF-DyF3 at tungsten and copper electrodes

Electrochemical behavior of dysprosium (Dy) ions in LiF-DyF₃ (24 mol%) was investigated by cyclic voltammetry, chronoamperometry and chronopotentiometry. Dy‐Cu alloy samples were prepared by constant-potential electrolysis in LiF-DyF₃ (24 mol%) at the Cu electrode. The Cu₅Dy and Cu phases were characterized by an X-ray diffractometer and a scanning electron microscope equipped with an energy dispersive spectrometer. The results show that the reduction of Dy(III) ions in a LiF-DyF₃ (24 mol%) molten salt system is found to be a quasi-reversible diffusion-controlled process which occurs via a one-step reaction involving the transfer of three electrons. The electro-crystallization processes of the Dy metal at the W electrode and the mode of nucleation confirm that progressive nucleation is dominant at high concentrations of Dy ions in the LiF-DyF₃ salt. At lower concentrations, the instantaneous nucleation of Dy with three-dimensional growth of the nuclei is dominant.     

Self-polymerization and co-polymerization kinetics of gadolinium methacrylate

Gadolinium methacrylate(Gd(MAA)_3) was synthesized by using gadolinium oxide and methacrylic acid as the starting materials and its self-polymerization kinetic was studied based on non-isothermal and isothermal analysis. Moreover, the monomer reactivity ratios of methyl methacrylate(MMA) and Gd(MAA)_3 were evaluated by using Kelen-Tiidos method. The thermal neutron shielding properties of PMMA and poly(MMA-co-Gd(MAA)3) were calculated by MCNP program. The results show that the selfpolymerization of Gd(MAA)3 can be initiated by thermal and free radical and its activation energy is103.35 kJ/mol or 58.55 kJ/mol correspondingly in the solid state or aqueous solution. The polymerization rate,R_p,under low conversion at 65 ℃ is expressed as R_p = K[M]~(1.05)[I]~(0.60). The reactivity ratios of r_1(MMA) and r_2(Gd(MAA)_3) are 0.225 and 1.340, respectively. The ability of thermal neutron shielding of poly(MMA-co-Gd(MAA)_3) is increased by gadolinium contents and is far better than PMMA.     

Optical analysis and separation of trivalent lanthanides in deep eutectic solvents

Deep eutectic solvents(DESs) were used for luminescence measurements in quantitative analysis of trivalent lanthanide ions and as solvents for light rare earth elements(LREE) in solid-liquid separation.The spectroscopic characteristics of lanthanide chlorides LnCl_3(Ln=Eu,Tb),respectively their aquo complexes,are described in a comprehensive study that demonstrates the significant enhancement of the phosphorescence emission intensity in DESs as polar and weakly coordinating solvent.Several DESs stabilize the lanthanide ion luminescence against changes in temperature and moisture,which is advantageous compared with the use of ionic liquids.Small amounts of water lead in certain eutectic systems even to a further increase in phosphorescence emission intensity.By investigating the solubility of lanthanide sesquioxides Ln_2 O_3(Ln=La,Nd,Sm,Eu,Gd,Tb,Dy) in DESs,selectivities are identified that may be of use for the separation of LREE.     

Effect of reduced graphene oxide-supported copper addition on electrochemical properties of La0.7Mg0.3Ni2.8Co0.5 electrodes

The reduced graphene oxide-supported copper(Cu@rGO) nanocomposite was introduced to improve the electrochemical properties of La_(0.7)Mg_(0.3)Ni_(2.8)Co_(0.5)alloy electrodes.Experimental results show that adding Cu@rGO nanocomposite with mass fractions of x wt%(x=0,3,6 and 9) to the alloy electrodes provides electrodes with maximum discharge capacities of 368.9 mAh/g(x=0),373.2 mAh/g(x=3),407.3 mAh/g(x=6) and 398.6 mAh/g(x=9),and high-rate dischargeabilities at a discharge current density of1200 mA/g of 40.5%(x=0),64.0%(x=3),82.0%(x=6) and 76.0%(x=9).The addition of Cu@rGO nanocomposite also provides alloy electrodes with hydrogen diffusion coefficients of 3.7×10~(-10) cm~2/s(x=0),4.1×10~(-10) cm~2/s(x=3),4.2×10~(-10) cm~2/s(x=6) and 4.0×10~(-10) cm~2/s(x=9).Clearly,the addition of 6 wt%Cu@rGO nanocomposite not only increases the electrochemical capacity of La_(0.7)Mg_(0.3)Ni_(2.8)Co_(0.5) alloy electrodes,but also improves their electrochemical kinetic properties.     

Effect of nano-TiC dopant size on magnetic properties and corrosion resistance of hot-deformed NdFeB

Effects of dopant size on the magnetic properties and corrosion behavior of hot-deformed NdFeB with the intergranular additions of nano-TiC were investigated using X-ray diffraction (XRD), X-ray photoelectron spectrometer (XPS), scanning electron microscopy (SEM), electrochemical and magnetic measurement technologies. Additions of 50 nm-TiC, unlike 30 nm- and 40 nm-TiC, are found to increase the magnetic energy product and comprehensive magnetic properties, due in main to the improvement of magnet orientation by more strip-shaped Nd-rich phases. Nano-TiC dopants especially with a size of 40 nm can increase the electrochemical corrosion resistance of magnets. It is attributed to the hindrance of additives on the reaction channel formation and their barrier effect on the oxidations of Nd and Fe. For 40 nm-TiC doped magnet, the charge transfer resistance in electric double layer structure reaches 15000 Ω?cm² that is one order of magnitude higher than other cases, which is responsible for the lowest corrosion current density and accordingly the best anti-corrosion properties.     

Doping effect of rare-earth (lanthanum,neodymium and gadolinium) ions on structural,optical, dielectric and magnetic properties of copper nanoferrites

Copper and rare earth-doped (RE = La, Gd, Nd) CuFe_1.85RE_0.15O₄ nanoferrites were prepared using the sonochemical method. The effective doping of rare-earth (La³⁺, Nd³⁺, Gd³⁺) ions with copper nanoferrites was confirmed by X-ray diffraction. The tetrahedral and octahedral sites of the nanoferrites were identified through the Fourier transform infrared spectra. The doping of rare-earth elements enhances the optical bandgap energy of the nanoferrites that are observed through Ultraviolet–DRS spectra. The oxidation state of the elements Cu 2p, La 3d, Nd 3d, Gd 3d, Fe 2p and O 1s was analyzed. Scanning electron microscopy images indicate a spherical morphology with agglomeration to some elongate. The values of dielectric constant and conductivity decrease considerably due to doping rare-earth ions in copper nanoferrites. Low saturation magnetization and high coercivity values of rare earth-doped copper nanoferrites are observed from the typical hysteresis curves.     

Coercivity enhancement of nanocrystalline hot-deformed Nd-Fe-B magnets by low-melting eutectic MM-Cu(MM=La,Ce,Pr,Nd) alloys addition

MM_(85)Cu_(15)(MM = La,Ce,Pr,Nd) eutectic alloys were added into the hot-deformed Nd-Fe-B magnets to enhance the coercivity.It is found that three endothermic peaks occur on the differential scanning calorimetry curve of the MM-Cu melt-spun ribbons at 432.2,451.1 and 516.5℃.The peaks substantially correspond to three types of MM-Cu low-melting eutectic phase.The coercivity of magnets increases when the MM-Cu content is lower than 4 wt%,and then keeps almost no change with the content further increasing to 5 wt%.The coercivity of the hot-deformed magnets with 4 wt% and without MM-Cu addition is 948 and 683 kA/m,respectively.Nearly all the platelet-shaped grains are isolated by the thickened intergranular phase after MM-Cu addition.Moreover,the average grain size of the magnets with MM-Cu addition decreases compared with that of the magnet without MM-Cu addition.Scanning electron microscopy images show that the areal fraction of the RE-rich grain boundary phase increases from 8.6% to 15.1% after MM-Cu addition.The La,Ce together with Cu and Ga aggregate at the grain boundary regions separating neighboring grains and smoothing the grain boundaries.Therefore,both the thickened grain boundary and decreased mean grain size result in the enhancement of coercivity after MM-Cu eutectic alloy addition.     

Voltammetric determination of venlafaxine as an antidepressant drug employing Gd2O3 nanoparticles graphite screen printed electrode

Graphite screen printed electrode modified with Gd_2 O_3 nanoparticles(Gd_2 O_3/SPE) was developed for the determination of venlafaxine(VF). The Gd_2 O_3 nanoparticles were thoroughly characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and X-ray diffraction(XRD) analyses. To study the electrochemical behaviour of venlafaxine cyclic voltammetry(CV), chronoamperometry(CHA)and differential pulse voltammetry(DPV) were employed. These studies reveal that the oxidation of venlafaxine is facilitated at Gd_2 O_3/SPE. After optimization of analytical conditions, analysis of venlafaxine using the modified electrode in 0.1 mol/L PBS(pH 7.0) demonstrates that the peak currents corresponding to venlafaxine vary linearly with its concentration in the range of 5.0 ×10~(-6)-9.0 × 10~(-4) mol/L. The detection limit(S/N = 3) of 2.1 × 10~(-7) mol/L is obtained for venlafaxine using DPV. The prepared modified electrode benefits from advantages such as simple preparation method, high sensitivity and low detection limit.Moreover, the evaluation of practical applicability of this proposed method is successful in the identification of venlafaxine in pharmaceutical formulations, urine and water samples.     

Influence of Gadolinium with Small Content on Recrystallization Behaviour inSilver-Gold Alloys

Ag-Aualloyisatypicalis0morphousbinnyalloysystem.TheeffectofAucontent(<5%)inAg-Aualloysonrecrystallizati0ntemperaturehasbeenstudiedinRef.[1].Itwasf0undthatoftherelationshipwasdifferentfr0mthat0ftheCucofitentonrecrystallizati0ntemperatureinAg-Cualloyswhichisalindteds0lublealloysys-t..'2].InRefs.[3]and[41theinfluenceofsmal1additi0n0fGdandSm0ntherecrysta]iIza-tionbehavi0r0fAg-Cu.alloyshasbeenstudied,respectively.InthispaPertheresultsab0uttheialluence0fsmallGdadditi0nontherecrystal-lizationb…     

Thermodynamic properties of liquid Cd-Pb-Sn solutions and analytical calculation of the phase diagram

Abstract

The relative partial thermodynamic properties of Cd in liquid Cd-Pb-Sn alloys have been investigated in the temperature range 680–840K by an emf technique. Data have been represented by general , power series expansions in the composition variables, and the liquidus surfaces when Cd or Sn are the primary crystallization products have been calculated analytically.

Résumé

Les propriétés thermodynamiques partielles du cadmium dans les alliages Cd-Pb-Sn liquide ont été étudiées dans une fourchette de température comprise entre 680 et 840K par la mesure de force électromotrice. Les données sont représentées par un développement en série des variables de composition. Les surfaces du liquidus ont été calculces analytiquement dans le cas où le cadmium ou l' étain est le produit prima ire de cristallisation.     

Enhancement of terbium efficiency by gallium and copper co-doping in (Pr,Nd)-Fe-B sintered magnets

It is well known that Tb substitution for (Pr, Nd) in (Pr, Nd)-Fe-B based sintered magnetic materials is an effective way to increase intrinsic coercivity, but it is not quite clear whether the increment depends on the different matrix phases with various doping ingredient or not, which is essential to develop high quality magnets with high coercivity more efficiently and effectively with economic consumption of expensive Tb and other costly heavy rare earths. In this paper, we investigated the efficiency of Tb substitution for magnetic property in (Pr, Nd)-Fe-B sintered permanent magnets by co-doping Ga and Cu elements. It is shown that Ga and Cu co-doping can effectively improve the efficiency of Tb substitution to increase the thermal stability and the coercivity. The intrinsic coercivity increases up to 549 and 987 kA/m respectively by 1.5 wt% and 3.0 wt% Tb substitution in Ga and Cu co-doped magnets while the intrinsic coercivity increases up to only 334 and 613 kA/m respectively by the same amounts of Tb substitution in non-Ga and low-Cu magnets. In other words, it demonstrates that there is about 329–366 kA/m linear equivalent enhancement of intrinsic coercivity by 1.0 wt% Tb substitution for (Pr, Nd) in Ga and Cu co-doped magnets. The temperature coefficients of both intrinsic coercivity β and remanence α at 20–150 °C by 3.0 wt% Tb substitution for the magnets with Ga and Cu co-doping are −0.47%/K and −0.109%/K respectively, and in contrast those values are −0.52%/K and −0.116%/K respectively for the non-Ga and low-Cu magnets. It is the principal reason for more efficient enhancement of magnetic property by Tb substitution in the Ga and Cu co-doped magnets in which Tb atoms are expelled from triple junction phases (TJPs) to penetrate into the grain boundary phases (GB phases) and thus modify the grain boundary. It is prospected that the efficiency of Tb substitution would rely on different matrix phases with various doping constituents.     

LiCl-KCl熔盐La^3+在钨电极上的电化学还原机理

以LiCl-KCl为电解质体系,LaCl3为原料,利用循环伏安法、计时电位法和计时电流法研究773K时镧离子在钨电极上的电化学还原过程。结果表明,在773K、50%KCl-50%LiCl-2%LaCl3的熔盐体系中,镧离子在钨电极上还原是一步转移3个电子反应(La^3++3e→La),相对于Ag/AgCl电极析出电位为-2.05V;镧在钨电极析出过程中出现成核极化现象,且通过循环伏安和计时电流法可判断镧离子在钨电极上的析出还原过程为受扩散控制的准可逆反应,扩散系数D=6.36×10^-5 cm^2/s。     

Manufacturing Process,Electrochemical Properties and Structures of Ml(NiMnTiCo)_5 Hydrogen Storage Alloys

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Effect of Dy-substitution on structural and magnetic properties of MnZn ferrite nanoparticles

This paper describes the structural and magnetic properties of Dy-substituted Mn-Zn ferrite nanoparticles. Mn-Zn-Dy ferrite nanoparticles of the composition Mn_(0.5)Zn_(0.5)Dy_xFe_(2-x)O_4(x=0.05, 0.1,0.15 and 0.2) were synthesized by a facile chemical co-precipitation method. The samples were characterized through X-ray diffraction(XRD), transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FTIR), vibrating sample magnetometer(VSM) and Curie temperature. The XRD patterns confirm the synthesis of single crystalline phase of Mn-Zn-Dy ferrite nanoparticles. Lattice parameter increases with increase in Dy-substitution which confirms the replacement of Fe~(3+) ions by Dy~(3+) ions.Crystallite size is of the order of 6-8 nm for all these samples. The particle sizes observed from TEM analysis are in good agreement with the XRD values. The magnetic measurements show superparamagnetic nature of the samples. The saturation magnetization decreases with increase in Dyconcentration and can be correlated to modifications in the A-B exchange interactions as a result of the structural modifications due to Dy-substitution. The Curie temperature for Mn_(0.5)Zn_(0.5)Fe_2 O_4 nanoparticles is 124 ℃ and decreases up to 84 ℃ with the increase in the Dy-concentration. The decrease in Curie temperature can be attributed to the weakening of the superexchange interaction between A-site and B-site as a result of Dy-substitution. The low value of Curie temperature and higher value of thermomagnetic coefficient k_T shown by these samples makes them suitable for the preparation of temperature sensitive ferrofluid for heat transfer applications.     

Electrochemical synthesis,structure characterization and magnetic properties of Tb_xFe_7Co_3(x=0,0.6,0.8) nanowires

Highly ordered Tb_xFe_7 Co_3(x=0,0.6,0.8) nanowires were synthesized in alumina templates by electrochemical deposition method.Here,the effects of Tb content and annealing treatment on the phase composition,morphology,crystalline structure and magnetic properties were investigated.The asdeposited Tb_0 Fe_7 Co_3 nanowires comprise Fe_7 Co_3 phase.While after adding Tb,the diffraction peaks slightly shift left,indicating the infiltration of Tb atoms into Fe_7 Co_3 phase.After annealing,Tb_0 Fe_7 Co_3 nanowires still consist of Fe_7 Co_3 phase with a slight enhancement on coercivity.While the annealed nanowires with Tb doped present a complex phase composition containing Fe3 Tb,Fe_2 Tb,Co_3 Tb,Co_(17)Tb_2,TbFeO_3 and Fe_2 O_3 phases distribute in the central portion,and Co_(0.72)Fe_(0.28) at the nanowire outer walls.The annealed Tb_xFe_7 Co_3(x=0.6,0.8) nanowires show higher magnetic performance owing to the formation of hard magnetic phases,the interfacial elastic coupling between hard and soft phases and the coherent Fe3 Tb/Co_3 Tb interface which restrain the domain wall motion.To be specific,the coercivity and remanence ratio of TbxFe_7 Co_3(x=0.6,0.8) nanowires significantly enhance with increasing Tb content.     

Single phase A_2B_7-type La-Mg-Ni alloy with improved electrochemical properties prepared by melt-spinning and annealing

La-Mg-Ni alloys were prepared by melt-spinning with different cooling rates and followed by annealing.Elevation of the cooling rate leads to refinement of the grains size and increasing of the abundance of LaNis.Annealing is favorable to formation of the A_2 B_7-type phase and promotes the discharge capacity,cycling stability and high rate discharge ability of the as-spun alloys.Phase constitution of the annealed alloys is found to be closely related to the microstructure of the as-spun alloys.A single phase A_2 B_7-type microstructure is obtained in the annealed alloy which is attributed to the lower abundance of the LaNis of the original alloy spun with lower cooling rate.Formation of the single phase A_2 B_7-type microstructure is also ascribed to the isolated and homogeneous distribution of the morphology of the as-spun alloy.The single phase alloy presents higher discharge capacity and better cycling stability compared with other annealed alloys.     

Synthesis and luminescent properties of BaGd2O4:Eu3+ phosphors with highly efficient red-emitting

The BaGd_(2-2 x)Eu_(2 x)O_4(BG, x = 0.01-0.09) phosphors were successfully synthesized via the sol-gel method,and BaY_(2-2 y)Eu_(2 y)O_4(BY, y = 0.005-0.07) phosphors were included for comparison. The pure phase BG phosphors with the ordered CaFe_2 O_4-type structure are obtained by annealing at 1300℃ for5 h. The phosphors with uniform particle size of 120 nm and good dispersion display typical Eu~(3+)emission with the strongest peak at 613 nm(~5 D_0→~7 F_2 transition of Eu3+) under optimal excitation band at 262 nm(CTB band). The presence of Gd~(3+) excitation bands on the PLE spectra monitoring the Eu3+emission directly proves an evidence of Gd~(3+)-Eu~(3+) energy transfer. Owing to the concentration quenching, the optimum content of Eu3+ addition is 5 at%(x = 0.05), and the quenching mechanism is determined to be the exchange reaction between Eu3+. All the BG samples have similar color coordinates and temperature of(0.64 ± 0.02, 0.36 ± 0.01) and 2000 ± 100 K,respectively. The lifetime value of BaGd_(1.9)Eu_(0.1)O_4 for 613 nm is fitted to be 2.19 ± 0.01 ms, and the Eu~(3+) concentration does not change the lifetime significantly. Owing to the Gd~(3+)-Eu~(3+) energy transfer, the luminescent intensity of the BaGd_(1.9)Eu_(0.1)O_4 phosphor is better than BY system. The BG system served as a new type of phosphor is expected to be widely used in lighting and display areas.