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.     

Electrochemical Investigation on the Formation of Dy-Fe Alloy in Molten Chlorides

ＥｌｅｃｔｒｏｃｈｅｍｉｃａｌＩｎｖｅｓｔｉｇａｔｉｏｎｏｎｔｈｅＦｏｒｍａｔｉｏｎｏｆＤｙＦｅＡｌｏｙｉｎＭｏｌｔｅｎＣｈｌｏｒｉｄｅｓＬｉｕＧｕａｎｋｕｎ（刘冠昆），ＴｏｎｇＹｅｘｉａｎｇ（童叶翔），ＨｏｎｇＨｕｉｃｈａｎ（洪惠婵），Ｙａｎｇ...     

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.     

Electrochemical properties of gadolinium on liquid gallium electrode in LiClKCl eutectic

This work presents the electrochemical properties of gadolinium(Gd), a significant rare earth element in spent nuclear fuel(SNF), in the LiCl-KCl eutectic. To explore thermodynamic properties of Gd at the liquid gallium(Ga) electrode, experiments were performed both on the inert tungsten(W) and liquid gallium(Ga) electrode at different temperatures in a range from 723 to 823 K, which show that the Gd metal can be oxidized to Gd(Ⅲ) by exchanging of 3 electrons. Electrochemical techniques including cyclic voltammetry(CV), open circuit potential(OCP), potentiostatic electrolysis and galvanostatic electrolysis were utilized to detect the electrochemical behavior and evaluate standard apparent potential of the Gd(Ⅲ)/Gd couple,and E_(Gd(Ⅲ)/Gd)~*=-3.456 + 6.2×10~(-4)T(±0.046)( vs Cl_2/Cl~-) is obtained.In addition, electromotive force(EMF) and coulometric titration were employed to calculate the activity and activity coefficient of Gd in metal Ga. After calculation, the activity is 1.791×10~(-15) at 723 K and function of activity coefficient and temperature is lgγ = 3.485-10927/T(±0.0875).     

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

Ｔｈｅｎｉｃｋｅｌｍｅｔａｌｈｙｄｒｉｄｅ（ＮｉＭＨ）ｓｙｓｔｅｍｉｓａｔｒａｃｔｉｖｅａｓａｓｅｃｏｎｄａｒｙｂａｔｅｒｙｂｅｃａｕｓｅｏｆｉｔｓｈｉｇｈｅｎｅｒｇｙｄｅｎｓｉｔｙａｎｄｌｏｗｌｅｖｅｌｏｆｐｏｌｕｔｉｏｎ．ＡＢ５ｔｙｐｅｈｙ...     

Combined influence of Ce(Ⅲ) and iodide ions for corrosion protection of AA 2024-T3 in acidic to neutral chloride-rich environments:Electrochemical and surface characterization studies

It has been reported that trivalent cerium salts are effective inhibitors for corrosion of AA2024-T3 in neutral to alkaline co rrosive enviro nments,but poor in acidic environments.In this study,work was done for extending corrosion resistance provided by Ce(NO₃)₃ to acidic pHs as low as 2.5 through the addition of iodide ions.To this end,potentiodynamic polarization was used to ascertain the optimum Ce(Ⅲ)concentration for the inhibition of AA2024-T3 corrosion in 3.5%NaCl s...     

Synthesis and Crystal Structure of RE[CH_2(CH_2)_4CONC_4H_9]_3(NO_3)_3(RE=Dy,La)

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＲＥ［ＣＨ２（ＣＨ２）４ＣＯＮＣ４Ｈ９］３（ＮＯ３）３（ＲＥ＝Ｄｙ，Ｌａ）ＷａｎｇＨａｎｚｈａｎｇ（王汉章），ＸｕＱｉｎｇｆｅｎｇ（徐庆锋），ＱｉａｎＰｕ（钱朴）ＳｕｎＪｉａｎｐｉｎｇ（孙建...     

Luminescent properties of dysprosium(III) ions in LaAlO_3 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 rela...     

Molten salt synthesis of Z-scheme CeO2/C3N4 photocatalysts with excellent properties for removal of organic pollutants: Characterization,kinetics and mechanisms

In this work,we firstly synthesized a CeO₂/C₃N₄ photocatalyst with Z-scheme heterojunction by a facile LiC-KCI molten salt method.The synthesized catalyst has an excellent quality for removing organic pollution of dyes and antibiotics in wastewater.As an example,the CeCN-1:5 prepared with a mass ratio of Ce₂(CO₃)₃·xH₂O:C₃H₃N₆=1:5 exhibits a methylene blue(MB) removal capacity of 100%with...     

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 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.     

Nd(III)在NaF-KF熔盐钨电极上电化学行为

钕铁硼磁体中稀土元素钕占据较大比重,从钕铁硼废料回收稀土有重大意义。为进一步了解钕在高温下氟化物熔盐的行为,本文在1 063 K采用NaF-KF(摩尔比2:3)电解质体系,加入质量分数为1%的NdF₃,以Pt为参比电极,钨棒为对电极,用循环伏安法等电化学暂态测试研究了Nd(III)在惰性钨电极上的电化学过程,探究Nd(III)的还原机理。结果显示:Nd(III)于NaF-KF-NdF₃熔盐中在惰性钨电极上的电化学还原过程是受扩散控制的不可逆的一步反应:Nd(III)+3e-=Nd,1 063 K时循环伏安法得到Nd(III)的扩散系数为2.107×10-5 cm2/s,钕的成核机制为瞬时成核。      

Preparation of Mg-Yb alloy film by electrolysis in the molten LiCl-KCl-YbCl_3 system at low temperature

The electrochemical behavior of Yb3+ and electrodeposition of Mg-Yb alloy film at solid magnesium cathode in the molten LiCl-KCl-YbCl3(2 wt.%) system at 773 K was investigated.Transient electrochemical techniques,such as cyclic voltammetry,chronopotentiometry and chronoamperometry were used in order to explore the deposition mechanism of Yb.The reduction process of Yb3+ is stepwise reactions which are single-electron and double-electron reversible charge transfer reactions.The speed control step was a diffusion-controlled step which is caused by concentration polarization.The microstructures of Mg-Yb alloy film were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM) and EPMA area analysis.A very thin Mg2Yb alloy film(～200 nm) was formed by potentiostatic electrolysis at ?1.85 V(vs.Ag/AgCl) for 12 h.A much thicker Mg2Yb alloy film(～450 μm) was obtained at ?2.50 V(vs.Ag/AgCl) for 2.5 h.The corrosion resistance of magnesium can be enhanced by electrochemical formation of Mg-Yb alloy film on its surface.     

Calculation of RECl_3-CaCl_2-LiCl Phase Diagrams(RE=La, Ce, Pr, Nd)

ＣａｌｃｕｌａｔｉｏｎｏｆＲＥＣｌ_３－ＣａＣｌ_２－ＬｉＣｌＰｈａｓｅＤｉａｇｒａｍｓ（ＲＥ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ）ＱｉａｏＺｈｉ－Ｙｕ（乔芝郁）；ＸｉｎｇＸｉａｎ－Ｒａｎ（邢献然），ＤｕａｎＳｈｕ－Ｚｈｅｎ（段淑贞）（ＤｅｐａｒｔｍｅｎｔｏｆＰｈ...     

Impact of La3+ substitution on electrical,magnetic, dielectric and optical properties of Ni0.7Cu0.1Zn0.2LaxFe2–xO4 (0 < x < 0.035) system

The oxalate co-precipitation method was used to synthesize the La³⁺ substituted Ni–Cu–Zn (La–NCZ) nanoferrites having chemical composition Ni_0.7Cu_0.1Zn_0.2La_xFe_2–xO₄ (x = 0, 0.015, 0.025 and 0.035). DC resistivity study of nanoferrites shows both the conducting and semiconducting behaviour. The room temperature DC electrical resistivity of Ni–Cu–Zn (NCZ) nanoferrites decreases, whereas Curie temperature increases with increasing La³⁺ content. In the temperature range of 30–170 °C nanoferrites show p-type semiconducting behavior except x = 0.015; thereafter, they show n-type behaviour. The frequency dispersive initial permeability (μ_i) associated with its real and imaginary (μ′ and μ") parts are attributed to the domain wall movement and magnetic spin resonant. The μ_i, μ′ and μ" of La–NCZ nanoferrites are higher than those of pure NCZ nanoferrite. Dielectric constant (ε′), dielectric loss (ε″) and AC resistivity (ρ_AC) of La–NCZ nanoferrites show normal dielectric behaviour. It is found that ε′ of NCZ nanoferrites decreases with the increasing content of La³⁺ ions. The bandgap energy of La–NCZ nanoferrites is achieved in the range 1.36–1.70 eV confirming the semiconducting nature of materials.     

Synthesis and photoluminescent properties of Sm~(3+)-activated La_3Si_6N_(11) as an orange-red emitting phosphor

A series of Sm³⁺-doped La₃Si₆N₁₁phosphor materials we re synthesized by a high temperature solid-state reaction method.The crystal structure,micro structure,photoluminescence properties,decay curves as well as thermal quenching properties of the as-prepared phosphors were investigated systematically.The excitation spectra contain a wide asymmetric band below 350 nm originating from the host absorption,several sharp excitation peaks in the range of 300-550 nm corresponding to f-f transition of Sm³⁺.Under the excitation of 369 and 414 nm light,the phosphors exhibit strong narrow-band orangered emission peaked at 605 nm.The average decay time of La_2.99Si₆N₁₁:0.01 Sm³⁺sample is fitted to be0.38 ms and the CIE coordinates were calculated to be(0.6105,0.3833).For water resistance,La₃Si₆N₁₁:Sm³⁺is better than K₂SiF₆:Mn⁴⁺phosphor.After soaking in deionized water for 300 min,the La₃Si₆N₁₁:Sm³⁺sample retains approximately 80%of its initial relative emission intensity.When the temperature rises to 423 K(150℃),the emission intensity of La_2.99Si₆N₁₁:0.01 Sm³⁺sample remains 85%in co mparison to that of room tempe rature.The activation energy was calculated to be 0.63253 eV,which is higher than those of Sm³⁺-activated oxide phosphors,indicating that the phosphor has relatively good thermal stability.     

Relaxor behavior and superior ferroelectricity of Y2O3-doped (Ba0.98Ca0.02) (Ti0.94Sn0.04Zr0.02)O3 lead-free ceramics

To upgrade the electric properties of lead-free piezoceramics, (1–x)(Ba_0.98Ca_0.02Ti_0.94Sn_0.04Zr_0.02)O₃-xY₂O₃ (abbreviated as (1–x)BCTSZ-xY, x = 0 mol%, 0.02 mol%, 0.04 mol%, 0.06 mol%, 0.08 mol% and 0.1 mol%) ceramics were successfully synthesized by traditional solid-state sintering method. The phase structure and microstructure of ceramics were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and piezoresponse force microscopyeramics (PFM). The electric properties of ceramics were researched through piezoelectric, dielectric and ferroelectric test instruments. The results show that all samples have pure perovskite structure and favorable electric properties. The optimal electric properties which especially include superior ferroelectric properties are gained when Y₂O₃ content is 0.06 mol% (d₃₃ = 419 pC/N, k_p = 52%, T_c = 89.5 °C, ε_r = 26900, tanδ = 2.86%, P_r = 14.41 μC/cm², E_c = 1.8 kV/cm). Moreover, the temperature-dependent dielectricity of samples shows apparent relaxor behavior under different frequencies. The Curie–Weiss law further proves that all samples are typical relaxor ferroelectrics, and the relaxor degree of samples decreases with increase of Y₂O₃ content. In conclusion, Y₂O₃ plays a significant role in enhancing electric properties of BCTSZ ceramics.     

Solvent extraction of Ce(III) and Pr(III) with P507 using SiC foam as a static mixer

Extraction reactor is a major research area of interest within the field of rare earths extraction and separation. SiC foam offers excellent material characteristics as well as three-dimensional (3-D) reticulated structure; however, very little research has been carried out on its application in extraction reactor so far. In this work, a static mixer reactor based on SiC foam was designed and demonstrated to extract and separate Ce(III) and Pr(III) from nitric acid media by using 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (P507) as extractant. The structure–performance relationship between SiC foam and extraction performance was studied by experiment combined with computational fluid dynamics (CFD) simulation. The experiment data are in good agreement with the simulation results. Contrast experiment by using a Kenics mixer was carried out, and SiC foam shows better extraction and mass transfer performance. Using the optimal structural SiC foam (pore size D = 2.3 mm, open porosity ε = 85%, foam length L = 80 mm), high extraction efficiency η (Pr(III): 94.6%, Ce(III): 88.5%) and separation factor β (2.27) between Ce(III) and Pr(III) is achieved at a high total throughput of 200 mL/min. Besides, overall volumetric mass transfer coefficient K_La of Pr(III) and Ce(III) are 0.519 and 0.378 s^?1 at the residence time τ of 3.6 s, respectively, which reach the high level of microchannel reactors and are better than conventional extractors and other static mixers. SiC foam is found to be applicable as a static mixer for efficient and high-throughput extraction and separation of rare earths.     

Electrochemical Behavior of Nd~(3 ) and Ho~(3 ) in LiCl-KCl Eutectic Melt

ＥｌｅｃｔｒｏｃｈｅｍｉｃａｌＢｅｈａｖｉｏｒｏｆＮｄ３＋ａｎｄＨｏ３＋ｉｎＬｉＣｌＫＣｌＥｕｔｅｃｔｉｃＭｅｌｔＺｈａｏＭｉｎｓｈｏｕ（赵敏寿），ＬｕＸｉａｎｇｐｉｎｇ（吕翔平），ＬｉａｎｇＪｉｎ（梁金）（ＬａｂｏｒａｔｏｒｙｏｆＲａｒｅＥａｒｔ...     

Kinetics and thermodynamics modeling of Nd(III) removal from aqueous solution using modified Amberlite XAD7

New adsorbent material was obtained by modification of commercial Amberlite XAD7 with thiourea that represents a non-toxic, cheap and environmentally friendly extractant. Prepared adsorbent was used for removal of neodymium ions from aqueous solutions. Thiourea modified Amberlite involved in this study shows good adsorption capacities (74.3 mg/g) and excellent efficiency during Nd removal process. In order to elucidate the mechanism of the Nd adsorption process kinetic, thermodynamic and equilibrium studies were performed, establishing this way which kinetic model better describes the Nd adsorption process. Moreover the thermodynamic studies prove that the Nd adsorption on thiourea modified Amberlite XAD7 is an endothermic and spontaneous process.