Rare earth（RE） metals and their alloys have attracted considerable practical interests due to their functional properties. Because of their negative deposition potentials, RE metals cannot be electrochemically depos...Rare earth（RE） metals and their alloys have attracted considerable practical interests due to their functional properties. Because of their negative deposition potentials, RE metals cannot be electrochemically deposited from aqueous media. Using molten salt as medium provides a unique opportunity for the electrowinning and electrorefining of high-purity RE metals, as well as for the electrochemical formation of their alloys and intermetallic compounds. Certainly, the electrochemical behaviors of RE metals and their alloys have been investigated in a number of different molten salts comprising all-fiuorides,all-chlorides and mixed chloride-fiuoride media. Based on the results, RE and their alloys were produced by molten salt electrolysis. In this paper, the developments of preparation of RE metals and their alloys by electrolysis in molten salts in recent years were systematically summarized on both the local and international levels. Attention was paid mainly to the electrodeposition of RE metals and their alloys, including RE-Mg, RE-Al, RE-Ni, RE-Co,RE-Cu, RE-Fe and RE-Zn alloys.展开更多
The work concerned the electrochemical behaviors of Y（Ⅲ） on W and Ni electrodes in molten LiCl-KCl salts by a series of electrochemical techniques. The electrochemical reaction of Y（Ⅲ） to Y（0） proceeded in a o...The work concerned the electrochemical behaviors of Y（Ⅲ） on W and Ni electrodes in molten LiCl-KCl salts by a series of electrochemical techniques. The electrochemical reaction of Y（Ⅲ） to Y（0） proceeded in a one-step reduction process with the exchange of three electrons, Y（Ⅲ）＋3e^–→Y（0）. Compared with the cyclic voltammogram and square wave voltammogram obtained on W electrode, the reduction potential of Y（Ⅲ） on Ni electrode was observed at less negative potential than the one of Y（Ⅲ） to give pure Y metal on W electrode, which revealed the occurrence of underpotential deposition of Y（Ⅲ） on Ni electrode. Electromotive force（emf） measurements were performed to calculate the relative partial molar Gibbs energies and activities of Y in Y-Ni alloys. The standard Gibbs energies of formation for different Y-Ni intermetallic compounds were also estimated. The different Y-Ni alloys were formed by potentiostatic electrolysis at different potentials and characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, and energy dispersive spectrometry（EDS）. It was found that four intermetallic compounds, YNi5, Y2Ni7, YNi3 and YNi2, were selectively produced by controlling applied potential.展开更多
An electrochemical study of dysprosium（III） on Bi film electrode was carried out in eutectic LiCl-KCI melts by transient and steady state electrochemical techniques.The results of transient electrochemical technique...An electrochemical study of dysprosium（III） on Bi film electrode was carried out in eutectic LiCl-KCI 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 DyBi3/5 and DyBi phases展开更多
The electrochemical behaviour of magnesium（Ⅱ） and the formation mechanism of Mg-Ni alloys on Ni electrode were studied in LiCl-KCl eutectic using various electrochemical techniques. Cyclic voltammogram and square-w...The electrochemical behaviour of magnesium（Ⅱ） and the formation mechanism of Mg-Ni alloys on Ni electrode were studied in LiCl-KCl eutectic using various electrochemical techniques. Cyclic voltammogram and square-wave voltammogram revealed that under-potential deposition of magnesium occurred on Ni electrode because Mg-Ni alloy compounds were formed. The thermodynamic properties of the Mg-Ni intermetaUics, Mg2Ni and MgNi2, were determined using open circuit chronopotentiometry in the temperature range of 8186893 K. Moreover, the Mg-Ni alloys were produced by potentiostatic and galvanostatic electrolysis under different conditions and characterized by means of scanning electron microscopy（SEM） equipped with energy dispersive spectrometry（EDS） and X-ray diffraction（XRD）. The experimental results indicate that Mg-Ni intermetaUic compounds can be selectively produced by potentiostatic electrolysis.展开更多
This work presents a new method for preparation of samarium alloy. Using A1 rod as anode, electrochemical formation of Sm-A1 alloy on Mo electrode from Sm203 in LiC1- KC1-MgC12-KF molten salts was investigated. Samari...This work presents a new method for preparation of samarium alloy. Using A1 rod as anode, electrochemical formation of Sm-A1 alloy on Mo electrode from Sm203 in LiC1- KC1-MgC12-KF molten salts was investigated. Samarium mainly exists in the form of A12Sm in Li-Mg matrix, and the concentration of Sm in this alloy runs up to be as high as 34.7%. The reaction of samarium preparation appears like a replacement reaction. The new preparation method makes possible a high samarium content in electrochemical deposition of Sm-A1 alloy. Using A1 rod as anode consumedly decreased, the electrolytic cell voltage, and facilitated Sm deposition from Sm203. This preparation method uses 8m203 as raw materials to gain samarium alloy directly, which could revolutionize the industrial production of samarium alloys.展开更多
The electrochemical formation processes of holmium-cobalt alloys on cobaltcathode in molten HoCl_3-KCl were investigated by cyclic voltammetry and open current potential-timecurve alter potentiostatic electrolysis. Th...The electrochemical formation processes of holmium-cobalt alloys on cobaltcathode in molten HoCl_3-KCl were investigated by cyclic voltammetry and open current potential-timecurve alter potentiostatic electrolysis. The structure of Ho-Co alloys' films deposited on cobaltelectrode by potentiostatic electrolysis was characterized by X-ray diffraction. The standard Gibbsfree energies of formation for the intermetallic compounds of Ho and Co were determined. Thediffusion coefficient and diffusion activation energy of Ho atom in the alloy phase were calculatedto be 10^(-10) -10^(-11) cm^2/s and 96.0 kJ/mol, respectively, from the current-time curve atpotential step.展开更多
Cyclic voltammetry, open circuit potential— time curve after potentiostatic electrolysis and potential step chronoamperometry were used to investigate the electrochemical formation processes of holmium-copper alloys ...Cyclic voltammetry, open circuit potential— time curve after potentiostatic electrolysis and potential step chronoamperometry were used to investigate the electrochemical formation processes of holmium-copper alloys on copper cathode in molten HoCl3-KCl. Intermetallic compounds HoCu5, HoCu4, HoCu2 and HoCu are formed in sequence and then the metallic Ho is deposited when Ho3+ is reduced on copper electrode in molten KCl-HoCl3 at 1066 K. The first charge-transfer reaction is reversible. The structure of holmium-copper alloy film deposited on copper electrode by potentiostatic electrolysis was characterized by X-ray diffraction. The standard free energies of formation for the intermetallic compounds HoCu5, HoCu4, HoCu2 and HoCu are - 95.5, - 92.6, - 73.8 and - 44.0 kJ/mol, respectively. The diffusion coefficient and diffusion activation energy of Ho atom in the alloy are estimated to be 10-10- 10-11 cm2/s and 75.35 kJ/mol, respectively, from the chronoamperometry data.展开更多
基金financially supported by Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, the National Natural Science foundation of China (Nos. 11675044, 21271054, 11575047 and 21173060)the Major Research Plan of the National Natural Science Foundation of China (Nos. 91326113 and 91226201)the Fundamental Research Funds for the Central Universities (No. HEUCF2016012)
文摘Rare earth（RE） metals and their alloys have attracted considerable practical interests due to their functional properties. Because of their negative deposition potentials, RE metals cannot be electrochemically deposited from aqueous media. Using molten salt as medium provides a unique opportunity for the electrowinning and electrorefining of high-purity RE metals, as well as for the electrochemical formation of their alloys and intermetallic compounds. Certainly, the electrochemical behaviors of RE metals and their alloys have been investigated in a number of different molten salts comprising all-fiuorides,all-chlorides and mixed chloride-fiuoride media. Based on the results, RE and their alloys were produced by molten salt electrolysis. In this paper, the developments of preparation of RE metals and their alloys by electrolysis in molten salts in recent years were systematically summarized on both the local and international levels. Attention was paid mainly to the electrodeposition of RE metals and their alloys, including RE-Mg, RE-Al, RE-Ni, RE-Co,RE-Cu, RE-Fe and RE-Zn alloys.
基金Project supported by the National Natural Science Foundation of China(21271054,11575047,21173060,11675044),the Major Research Plan of the National Natural Science Foundation of China(91326113,91226201)the Fundamental Research Funds for the Central Universities(HEUCF2016012)
文摘The work concerned the electrochemical behaviors of Y（Ⅲ） on W and Ni electrodes in molten LiCl-KCl salts by a series of electrochemical techniques. The electrochemical reaction of Y（Ⅲ） to Y（0） proceeded in a one-step reduction process with the exchange of three electrons, Y（Ⅲ）＋3e^–→Y（0）. Compared with the cyclic voltammogram and square wave voltammogram obtained on W electrode, the reduction potential of Y（Ⅲ） on Ni electrode was observed at less negative potential than the one of Y（Ⅲ） to give pure Y metal on W electrode, which revealed the occurrence of underpotential deposition of Y（Ⅲ） on Ni electrode. Electromotive force（emf） measurements were performed to calculate the relative partial molar Gibbs energies and activities of Y in Y-Ni alloys. The standard Gibbs energies of formation for different Y-Ni intermetallic compounds were also estimated. The different Y-Ni alloys were formed by potentiostatic electrolysis at different potentials and characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, and energy dispersive spectrometry（EDS）. It was found that four intermetallic compounds, YNi5, Y2Ni7, YNi3 and YNi2, were selectively produced by controlling applied potential.
基金Project supported by the National Natural Science Foundation of China(11675044,11575047,21790373,21271054,21173060)the Major Research plan of the National Natural Science Foundation of China(91326113,91226201)
文摘An electrochemical study of dysprosium（III） on Bi film electrode was carried out in eutectic LiCl-KCI 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 DyBi3/5 and DyBi phases
基金Supported by the National Natural Science Foundation of China（Nos.11675044, 11575047, 21790373 and 21271054）, the Major Research Plan of the National Natural Science Foundation of China（Nos. 91326113, 91226201） and the Fundnmental Research Funds for the Central Universities, China（No.HEUCFP201790）.
文摘The electrochemical behaviour of magnesium（Ⅱ） and the formation mechanism of Mg-Ni alloys on Ni electrode were studied in LiCl-KCl eutectic using various electrochemical techniques. Cyclic voltammogram and square-wave voltammogram revealed that under-potential deposition of magnesium occurred on Ni electrode because Mg-Ni alloy compounds were formed. The thermodynamic properties of the Mg-Ni intermetaUics, Mg2Ni and MgNi2, were determined using open circuit chronopotentiometry in the temperature range of 8186893 K. Moreover, the Mg-Ni alloys were produced by potentiostatic and galvanostatic electrolysis under different conditions and characterized by means of scanning electron microscopy（SEM） equipped with energy dispersive spectrometry（EDS） and X-ray diffraction（XRD）. The experimental results indicate that Mg-Ni intermetaUic compounds can be selectively produced by potentiostatic electrolysis.
基金supported by the National Natural Science Foundation of China (Grant No.21173060)the Basic Research Foundation of Harbin Engineering University of China (No.HEUFT08030)
文摘This work presents a new method for preparation of samarium alloy. Using A1 rod as anode, electrochemical formation of Sm-A1 alloy on Mo electrode from Sm203 in LiC1- KC1-MgC12-KF molten salts was investigated. Samarium mainly exists in the form of A12Sm in Li-Mg matrix, and the concentration of Sm in this alloy runs up to be as high as 34.7%. The reaction of samarium preparation appears like a replacement reaction. The new preparation method makes possible a high samarium content in electrochemical deposition of Sm-A1 alloy. Using A1 rod as anode consumedly decreased, the electrolytic cell voltage, and facilitated Sm deposition from Sm203. This preparation method uses 8m203 as raw materials to gain samarium alloy directly, which could revolutionize the industrial production of samarium alloys.
文摘The electrochemical formation processes of holmium-cobalt alloys on cobaltcathode in molten HoCl_3-KCl were investigated by cyclic voltammetry and open current potential-timecurve alter potentiostatic electrolysis. The structure of Ho-Co alloys' films deposited on cobaltelectrode by potentiostatic electrolysis was characterized by X-ray diffraction. The standard Gibbsfree energies of formation for the intermetallic compounds of Ho and Co were determined. Thediffusion coefficient and diffusion activation energy of Ho atom in the alloy phase were calculatedto be 10^(-10) -10^(-11) cm^2/s and 96.0 kJ/mol, respectively, from the current-time curve atpotential step.
文摘Cyclic voltammetry, open circuit potential— time curve after potentiostatic electrolysis and potential step chronoamperometry were used to investigate the electrochemical formation processes of holmium-copper alloys on copper cathode in molten HoCl3-KCl. Intermetallic compounds HoCu5, HoCu4, HoCu2 and HoCu are formed in sequence and then the metallic Ho is deposited when Ho3+ is reduced on copper electrode in molten KCl-HoCl3 at 1066 K. The first charge-transfer reaction is reversible. The structure of holmium-copper alloy film deposited on copper electrode by potentiostatic electrolysis was characterized by X-ray diffraction. The standard free energies of formation for the intermetallic compounds HoCu5, HoCu4, HoCu2 and HoCu are - 95.5, - 92.6, - 73.8 and - 44.0 kJ/mol, respectively. The diffusion coefficient and diffusion activation energy of Ho atom in the alloy are estimated to be 10-10- 10-11 cm2/s and 75.35 kJ/mol, respectively, from the chronoamperometry data.
