Electrode process of La(Ⅲ) in molten LiCl-KCl

The electrode process of La(Ⅲ) at Mo electrode in the molten LiCl-KCl for temperatures ranging from 683 K to 773 K was studied by cyclic voltammetry and chronopotentiometry,respectively.The results showed that in the molten LiCl-KCl,reduction of La(Ⅲ) occurred in a step with a global exchange of three electrons.Cyclic voltammetry studies indicated that at a sweep rate lower than 0.2 V/s,the electroreduction of La(Ⅲ) to lanthanum metal was reversible and controlled by diffusion of La(Ⅲ).However,the process b...     

Electrochemical behavior of cerium ion in molten LiCI-KCI

The electrode process of cerium(Ⅲ) on the Mo electrode in eutectic LiCl-KCl melt was investigated by electrochemical transient techniques in the temperature range of 673-783 K,respectively.These results unanimously indicated that the reduction process of cerium(Ⅲ) to cerium metal was a single step exchanging three electrons which was controlled by diffusion of cerium(Ⅲ).Diffusion coefficients(D Ce(Ⅲ)) in eutectic LiCl-KCl melt were determined by cyclic voltammetry,chronopotentiometry and square wave voltammetry.An empirical diffusion coefficient function depending on temperature was proposed:lnD Ce(Ⅲ) =-2.129-5704/T.The formal potentials(Eθ’ Ce(Ⅲ)/Ce(0) versus Ag/AgCl reference electrode) at different temperatures were obtained from chronopotentiometry,which were-2.10 V(673 K) and-2.07 V(733 K),respectively.     

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。     

An in-situ Raman spectroscopic study on potential-pO~(2-) phase diagram of lanthanum in LiCl-KCl eutectic melt

The oxidative reaction between lanthanum trichloride and oxide ion was studied in the molten LiCl-KCl eutectic at 773 K by in-situ Raman spectroscopy using an yttria-stabilized zirconia electrode in conjunction with electrochemical methods.The formation of lanthanum oxychloride,LaOCl(s),was confirmed by studying the vibrational properties of crystalline LaOCl and X-ray diffraction analysis.The solubility product of LaOCl in the LiCl-KCl molten eutectic at 773 K is found to be pK_(sp)(LaOCl)=7.569±0.100,by combining the results of Raman spectroscopy and potentiometric titration with the addition of barium oxide.The use of Raman spectroscopic quantitation of dissolved lanthanum ions in the system allows faster and more accurate determination of the stable phase of lanthanum as well as the solubility product of LaOCl compared with that measured by potentiometric titration only.Based on experimentally obtained pK_(sp) and standard equilibrium potentials,the potentialpO~(2-) phase diagram of lanthanum in the molten LiCl-KCl eutectic was reported.     

Electrochemical formation of Mg–La–Mn alloys by coreduction of Mg(II), La(III) and Mn(II) in LiCl+KCl molten salts

In the present work, cyclic voltammetry (CV), square wave voltammetry (SWV) and chronopotentiometry (CP) were used to investigate the electrochemical coreduction behaviors of La(III) and Mg(II) as well as La(III), Mg(II) and Mn(II) on Mo electrode in LiCl + KCl molten salts. CV and SWV results exhibit that the coreduction mechanism of La (III) and Mg(II) on Mo electrode is that La(III) is reduced and Mg–La intermetallic compound is formed, leading to the deposition potential of La(III) shifting to more positive one. The electrochemical signals pertaining to the formation of metallic La, Mg and Mn as well as Mg–La intermetallic compound are also observed by coreduction of La(III), Mg(II), and Mn(II) in LiCl + KCl molten salt on the inert Mo electrode. However, the electrochemical signals associated with the formation of La–Mn and Mg–Mn alloys are not observed, which means that the depolarization effect of La(III) and Mg(II) does not occur on pre-deposited Mn electrode. The Mg–La–Mn alloys were formed by co-deposition of La(III), Mg(II), and Mn(II) on Mo electrode at various concentration ratios of La(III) and Mg(II). The results of scanning electron microscopy equipped with energy dispersive spectroscopy and X-ray diffraction displays that the Mg–La–Mn alloys are comprised of La–Mg compound Mg₁₇La₂, Mg and Mn phases. The concentration ratio of La(III) and Mn(II) has few effects on the alloy composition.     

Absorption behavior of lattice oxygen in Ce_(0.8)Y_(0.2)O_(2-δ) at intermediate temperature

The absorption behavior of lattice oxygen for Ce_(0.8)Y_(0.2)O_(2-δ)(YDC) crystal was investigated. Combined with TG-DSC, XRD, Raman and XPS characterization, lattice oxygen absorption occurs at intermediate temperature(from 500 to 800 ℃),which is related to the oxygen vacancies consumption,and no phase change is observed in this process. In electric conductivity relaxation(ECR) experiment, prolonged oxygen diffusion process is observed above 600 ℃, which may be caused by oxygen absorption process. And through ECR experiments,the bulk diffusion coefficient D_(chem) and surface exchange coefficient K_(ex) for YDC dense sample are measured as 6,5×10~(-5)-2×10~(-4)cm~2/s and K_(ex)=2×10~(-4)-9×10~(-4)cm/s at intermediate temperature range.     

Activation parameters of high-temperature creep in polycrystalline nickel at ambient and high pressures

Polycrystalline specimens of pure nickel were deformed in uniaxial compression at temperatures of 1000–1550 K, strain rates of 1×10⁻⁵-3×10⁻³s⁻¹ and pressures of 0.1–1500 MPa, in order to determine the activation parameters of high temperature creep. Experiments at 0.1 MPa were conducted in an MTS apparatus with the specimen immersed in a molten heat-treating salt to prevent oxidation. The data show a decreasing power-law stress exponent with decreasing normalized steady-state flow stress (σ/G), approaching the “natural law” value of n=3 at normalized stresses <10⁻⁴. In contrast, the activation energy is constant over our range of temperatures (T/T_m = 0.55−0.90), and is indistinguishable from the activation energy of self-diffusion (284 kJ/mol). High pressure experiments were conducted in a modified piston-cylinder apparatus using the same molten heat-treating salt for the confining medium. The small activation volume could not be resolved; however, the trend of the high pressure data parallels that of the 0.1 MPa data with a systematic offset, and is consistent with the measured activation volume of self diffusion. Specimens deformed at 0.1 MPa exhibited significant strain-enhanced grain growth; this effect is greatly reduced under hydrostatic pressure, whereas subgrain size was less affected.     

Electrochemical behaviour of erbium and preparation of Mg-Li-Er alloys by codeposition

The electrodeposition of erbium on molybdenum electrodes and the formation of Mg-Li-Er alloys were investigated in LiCl-KCl molten salts. At a molybdenum electrode, the electroreduction of Er (III) proceeded in a one-step process involving three electrons. The diffu-sion coefficient of erbium ions in the melts was determined by cyclic voltammetry, chronopotentiometry and chronoamperometry respectively. Cyclic voltammograms (CVs) showed that the underpotential deposition (UPD) of lithium on pre-deposited Mg-Er alloy led to the formation of a Mg-Li-Er alloy. X-ray diffraction (XRD) indicated that Er5Mg24 phase was formed via potentiostatic electrolysis. Scanning electron microscopy (SEM) showed that Er atoms mainly concentrated at the grain boundaries while Mg element evenly located in the alloy.     

Trace detection of Ce3+ by adsorption strip voltammetry at a carbon paste electrode modified with ion imprinted polymers

To develop a convenient method for sensitive and selective determination of Ce3+ in aqueous phase with complicated matrices, a carbon paste electrode(CPE) modified with ion imprinted polymers(IIPs) were fabricated. The polymers were prepared by precipitation polymerization using Ce3+ as template, allyl phenoxyacetate(APA) as monomer, ethylene glycol dimethacrylate(EGDMA) as crosslinker and azobisisobutyronitrile(AIBN) as initiator under the molar ratio of Ce3+, APA and EGDMA as 1:4:40, respectively. Ce~(3+) was detected directly by differential pulse adsorptive stripping voltammetry(DPASV) and its oxidation peak appears at about 0.93 V. All parameters affecting the sensor's response are optimized and a calibration curve is plotted at a linear range of 1.0 × 10~(-6)-1.0 x 10~(-5) mol/L and 1.0×10~(-5)-2.0 × 10~(-4)mol/L with the detection limit of 1.5 × 10~(-7) mol/L. All other rare earth ions have no interference with the determination of Ce~(3+) even at a concentration 500 times higher than that of Ce~(3+).This sensor was successfully applied to determination of Ce~(3+) in two catalyst sample solutions with RSD≤3.3%(n = 5)and recoveries in the range of 99.2%-106.5% at our optimal conditions.     

Cathodic reduction process of Al–Cu–Y alloy in fluoride-oxide eutectic system via molten salt electrolysis

Al-Cu-Y alloys were prepared by molten salt electrolysis in fluoride-oxide system composed of electrolyte(Na_3 AlF_6-AlF_3-LiF-MgF_2) and oxide(Al_2 O_3-CuO-Y_2 O_3). Cathodic reduction process of Al_2 O_3,CuO and Y_2 O_3 were analyzed by cyclic voltammetry and chronoamperometry. Components and phase composition of alloy samples prepared by potentiostatic electrolysis were characterized by scanning electron microscopy and energy dispersive spectroscopy. The results show that the Al-Cu-Y alloy can be prepared in the AIF_3-NaF-5 wt%LiF-5 wt%MgF2(NaF/AlF_3 = 2.2, molecular ratio) eutectic system with mixed oxide(Al_2 O_3-CuO-Y_2 O_3) through 2 h at the conditions of a temperature of 1208 K, cell voltage3.0 V, cathode current density 0.7 A/cm~2. Al(Ⅲ) and Cu(Ⅱ) ions can be reduced to zero valence Al(0) and Cu(0) directly on carbonaceous electrode surface by instantaneous nucleation, respectively, the reduction process is controlled by diffusion. The reduction potential of Y(Ⅲ) ions is close to the active ions of fluoride melts, but strengthened phase AI3 Y can be formed through electrochemical reduction and alloyed process with active Al(Ⅲ) and Cu(Ⅱ) ions, meanwhile, the Al_2 Cu and Al_3 Y phases are distributed at the grain boundary of Al matrix.     

Electrodeposition of magnesium-yttrium alloys by molten salt electrolysis

Electrodeposition of magnesium-yttrium alloys from molten salts was studied by electrochemical techniques. LiF-YF₃ was electrolyte system with magnesium oxide and Yttrium oxide as raw materials. It was proved that Mg²⁺ and Y³⁺was deposited more prior than other ions during cyclic voltammetry and potential step measurement at 1050 °C. Voltammograms showed Mg²⁺ could be deposited at ?0.5 V, and Y³⁺ could be deposited at ?0.7 V on tungsten electrode compared with platinum electrode. The sedimentation of Mg²⁺ was more positive about 230 mV than that of other ions in electrolyte. The electrolytic codeposition of yttrium and magnesium was 0.58 V on condition that the weight ratio of Y₂O₃/MgO was 4:1. Chronopotentiogram indicated that the process of electrodeposition of magnesium-yttrium alloys on tungsten electrode was controlled by diffusion of ions from electrolyte to electrode interface. It was feasible to prepare Magnesium-Yttrium alloys by controlling content of ions in molten salt electrolyte.     

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.     

The Electrochemical Formation of Ni-Tb Intermetallic Compounds on a Nickel Electrode in the LiCl-KCl Eutectic Melts

The work presents an electrochemical study on the formation of Ni-Tb intermetallic compounds in the LiCl-KCl-TbCl₃ melts on tungsten and nickel electrodes at 773 K (500 °C) by electrochemical techniques. For a tungsten electrode, cyclic voltammetry and square-wave voltammetry showed that the electrochemical reduction of Tb(III) proceeded in a one-step process involving three electrons at ?2.06 V (vs Ag/AgCl). For a nickel electrode, the reduction potential of Tb(III)/Tb was observed at more positive values than those on W electrode by cyclic voltammetry, due to the formation of Ni-Tb intermetallic compounds. Square-wave voltammetry and open-circuit chronopotentiometry put into evidence the formation of intermetallic compounds at around ?1.27, ?1.63, and ?1.88 V, respectively. Three alloy samples were obtained by potentiostatic electrolysis on a Ni electrode at various potentials and analyzed by X-ray diffraction, scanning electron micrograph, and energy-dispersive spectrometry. The analysis results confirmed the formation of Ni₁₇Tb₂, Ni₅Tb, and Ni₂Tb alloy compounds.     

Thermodynamic Calculation on Calcium Treatment for 26CrMo4S/2 Steel

Because CaSi core wire was not fed in external refining process for 26CrMo4S/2 steel making, it was found that the molar ratio of calcium versus alumina was very low and subsequently resulted in generation of much more non-metallic inclusions. Hence, it was reasonable to sugguest feeding appropriate amount of Ca core wire. Before the performance, the thermodynamic calculation had been carried out to obtain the theoretical amount of Ca wire to be fed. According to the practical data from steel plant and the thermodynamic data, it was calculated that only when 1.38 × 10^–4[%Al]_T^2/3 ≥ [%Ca]_T ≥ 4.97×10^–5[%Al]_T^2/3 in molten steel the Al₂O₃ inclusions could be properly modified.     

1723K下熔渣中Ni~(2+)和Fe~(2+)离子共存时的电化学行为

利用MgO部分稳定的ZrO_2固体电解质管集成构建以Pt,O_2(空气)|ZrO_2作为参比电极的新型可控氧流电解池,采用循环伏安CV、方波伏安SWV、恒电位电解PE等方法,并结合热力学计算与显微观察、能谱分析,研究1 723K高温下SiO_2-CaO-MgO-Al_2O_3熔渣中共存的Ni~(2+)、Fe~(2+) 离子在Ir电极上的电化学行为。结果表明:熔渣系中FeO与NiO之间存在较弱的相互作用,但镍离子以Ni~(2+)存在,铁离子基本以Fe~(2+) 存在。进行方波伏安分析时,Ni~(2+)、Fe~(2+) 离子的还原峰电流对频率呈现不同的规律。Ni~(2+)在Ir电极上的电化学还原是扩散控制的一步两电子转移反应过程;Fe~(2+) 到Fe的电化学还原也是一步两电子转移反应过程,但Fe~(2+) 的还原明显受到Ni~(2+)还原的影响。基于循环伏安法,计算得到NiO、FeO的质量分数分别为3%、5%的熔渣中Ni~(2+)离子在1 723K下的扩散系数为(9.2±0.2)×10-6cm2/s。     

Cathodic behavior of scandium(III) on reactive copper electrodes in LiF–CaF2 eutectic molten salt

The electrochemical formation of Sc–Cu alloy was investigated in LiF–CaF₂ eutectic molten salt employing various electrochemical methods. Cyclic voltammetry and square wave voltammetry indicate that the reduction of scandium(III) on the tungsten electrode is a one-step reduction process with three electrons transfer. And underpotential deposition of scandium on the copper electrode occurs owing to the depolarization effect, i.e., forming Sc–Cu intermetallic compounds. The thermodynamic properties of the Sc–Cu intermetallic compounds ScCu₄, ScCu₂, and ScCu in the temperature range of 1153–1223 K were estimated by open-circuit chronopotentiometry. Moreover, the Sc–Cu alloys were prepared by potentiostatic electrolysis and characterized by optical microscope, X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. The results reveal that only Sc–Cu alloy composed of Cu-ScCu₄ can be synthesized at low cathodic current density and above eutectic temperature.     

NaCl-KCl-CaCl_2熔盐体系中Mg~(2+)在Mo电极上的阴极过程

采用钼电极,在973K的温度下,研究了MgCl2在三元NaCl-KCl-CaCl2熔融氯化物混合物中的电化学行为。采用方波伏安法(SWV)、循环伏安法(CV)、计时电流法(CA)和计时电位法(CP)研究Mg~(2+)在钼电极上的反应过程。结果表明,Mg~(2+)在钼电极上发生一步还原反应(Mg~(2+)+2e=Mg),是由扩散控制的可逆反应,镁在钼电极上的成核过程是瞬时成核,这与半球核的形成和生长机制是一致的。通过CV、CP和CA在973K的不同方法计算的Mg~(2+)扩散系数分别为1.09×10-5、1.24×10-5和3.23×10-5 cm2/s。在给定电位下阴极沉积产物为金属镁。     

Electrochemical studies on cerium(III) in molten fluoride mixtures

This study aims to determine the principal electrochemical characteristics of the electrodeposition of cerium metal from molten fluoride systems. The cathodic process of Ce³⁺ ions in LiF-NaF and LiF-NaF-CaF₂ molten salts was studied using electrochemical techniques as steady state and cyclic voltammetry methods. The decomposition potential (E_d) and the overvoltage(η) were determined for NaCeF₄ using current-potential curves under galvanostatic conditions. The E_d was found to be 2.025 V in LiF-NaF and 2.045 V in LiF-NaF-CaF₂. It was also found that the ohmic drop potential (EΩ) was not dependent on NaCeF₄ concentration and it rose as the current intensity increased. The overvoltage (η) was determined from the polarization curves and the Tafel coefficients and kinetic parameters were calculated on the assumption that the process constitutes of direct discharge of Ce³⁺, with no solvent-solute interaction. In order to elucidate the cathodic process the investigation by cyclic voltammetry technique was finally used. From the evolution of the voltammograms we concluded that the electrochemical reduction of Ce³⁺ ion was actually a reversible process on the molybdenum electrode and cathodic reduction of Ce³⁺ took place in one single step involving three electron exchanges.     

Solute diffusion in liquid nickel measured by pulsed ion beam melting

Measurements of liquid-phase diffusion coefficients for dilute tungsten and molybdenum in molten nickel were made using a pulsed ion-beam melting technique. A high-intensity beam of nitrogen ions is focused on the surface of a nickel substrate that was implanted with known concentration profiles of W and Mo. Melting of the surface to a depth of ∼1 μm allows broadening of the implant profiles while molten. Solute concentration-depth profiles were determined before and after melting using Rutherford backscattering spectrometry. Using a series of numerical simulations to estimate the melt history and diffusional broadening for mean liquid temperatures in the range 1755 to 2022 K, an effective diffusion coefficient is determined in each case by comparison to the measured depth profiles. This is found to be (2.4±0.2)×10⁻⁵ cm²/s for W and (1.6±0.4)×10⁻⁵ cm²/s for Mo, with an additional systematic uncertainty of ±0.5×10⁻⁵ due to instrumental and surface effects.     

Electrochemical co-reduction of Y(III) and Al(III) in a fluoride molten salt system and electrolytic preparation of Y–Al intermediate alloys

In this study, a molten salt co-reduction method was proposed for preparing Y–Al intermediate alloys and the electrochemical co-reduction behaviors of Y(III) and Al(III) and the reaction mechanism of intermetallic compound formation were investigated by transient electrochemical techniques. The results show that the reduction of Y(III) at the Mo electrode is a reversible electrochemical process with a single-step transfer of three electrons, which is controlled by the mass transfer rate. The diffusion coefficient of Y(III) in the fluoride salt at a temperature of 1323 K is 5.0238 × 10^?3 cm²/s. Moreover, the thermodynamic properties associated with the formation of Y–Al intermetallic compounds were estimated using a steady-state electrochemical method. Y–Al intermediate alloy containing 92 wt% yttrium was prepared by constant current electrolysis at 1323 K in the LiF–YF₃–AlF₃–Y₂O₃ (6 wt%)–Al₂O₃ (1 wt%) system at a cathodic current density of 8 A/cm² for 2 h. The Y–Al intermediate alloy is mainly composed of α-Y₂Al and Y phases. The development and application of this innovative technology have solved major technical problems, such as a long production process, high energy consumption, and serious segregation of alloy elements at this stage.