Cathodic processes at electrolysis of chloride and chloride-fluoride melts of zirconium

Polyakova, L. P.; Stangrit, P.T.

doi:10.1016/0013-4686(82)80092-3

Cited by 27 publications

(12 citation statements)

References 7 publications

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“…Concerned with chloride-fluoride system, Polyakova et al [1] found that in NaCl-KCl-ZrCl 4 melt with the addition of sodium fluoride and also in NaCl-KCl-K 2 ZrF 6 , KCl-K 2 ZrF 6 and KCl-KF-K 2 ZrF 6 melts, the electrochemical reduction of zirconium occurs reversibly in a four-electron step reaction: Zr 4+ + 4e → Zr. Chen et al [2] suggested that the electrochemical reaction of zirconium in chloride-fluoride melts with less fluoride is a double two-electron reduction process, but with higher fluoride concentration the main zirconium complex ions are directly reduced to metallic zirconium.…”

Section: Introductionmentioning

confidence: 98%

“…Polyakova et al [1] and Chen et al [2] considered that the cathodic reduction of Zr 4+ in chloride melt occurred by the mechanism of Zr 4+ → Zr 2+ → Zr with the formation of soluble zirconium dichloride. However, Basile et al [3] proposed that the cathodic reduction of zirconium in chloride melts comprises two-electroreduction reactions Zr 4+ → Zr 2+ → Zr with the formation of insoluble zirconium dichlorides, and its disproportion gives zirconium powder and regenerates the complex M 2 ZrCl 6 .…”

Section: Introductionmentioning

confidence: 99%

“…The molten salt electrochemistry of zirconium in alkali chloride and chloride-fluoride systems has been investigated by several researchers [1][2][3][4][5][6][7], but the electrochemical reduction mechanisms presented by different authors are dissimilar.…”

Section: Introductionmentioning

confidence: 99%

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Electrochemical behavior of zirconium in molten NaCl-KCl-K2ZrF6 system

Wu¹,

Zhang²,

Chen³

et al. 2011

Rare Metals

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The electrochemical reduction of Zr 4+ (complex) ions in NaCl-KCl-K 2 ZrF 6 molten salt on Pt electrode was investigated using cyclic voltammetry and square wave voltammetry at 1023 K. Two cathodic reduction peaks related to Zr 4+ /Zr 2+ and Zr 2+ /Zr steps were observed in the cyclic voltammograms. The result was also confirmed by square wave voltammetry. The diffusion coefficient of Zr 4+ (complex) ions at 1023 K in NaCl-KCl-K 2 ZrF 6 melt, measured by cyclic voltammetry, is about 4.22×10 −6 cm 2 /s. The characterization of the deposits obtained by potentiostatic electrolysis at different potentials was investigated by XRD, and the results were well consistent with the electrochemical reduction mechanism of Zr 4+ (complex) ions.

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Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Electrochemical behavior of zirconium in molten NaCl-KCl-K2ZrF6 system

Wu¹,

Zhang²,

Chen³

et al. 2011

Rare Metals

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“…It is known that the redox behavior of Zr in fluorides or mixed salts with a small additive of fluoride is simpler than chlorides salt. However, the higher melting point (typically over 973 K) and increase of corrosion rate by fluoride additive 5 can be huge obstacles for industrialization and commercialization.…”

Section: Introductionmentioning

confidence: 99%

Zirconium metal recovery from irradiated radioactive zirconium alloy via chloride‐basedelectrorefining and thermal decomposition ofZrCl

Hur

Jeon

Jeong

et al. 2021

Intl J of Energy Research

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Summary Chloride salt–based decontamination methods for neutron‐irradiated radioactive zirconium alloys have been designed to directly recover metallic Zr. Previous studies have shown that ZrCl is co‐deposited with Zr at a low current density on the cathode, while sparse and low‐purity Zr is obtained with the application of a high current density. We propose a process to prepare high‐purity Zr metal involving the electrochemical recovery of ZrCl and thermal decomposition of ZrCl to Zr. Electrodeposition of ZrCl in a LiCl‐KCl‐ZrCl4 system by controlling the cathode potential at −1.1 V (vs Ag/AgCl, −2.3 V vs Cl2/Cl−) was performed at 723 K to produce ZrCl and confirm the morphology of deposition. Dense and layered depositions adhered to the cathode were introduced to a vacuum distillation furnace after washing with pyridine solvent. The optimized condition of the thermal decomposition process was deduced by experimental results using X‐ray diffraction, scanning electron microscopy, Raman spectroscopy, and inductively coupled plasma‐optical emission spectrometry. Furthermore, the crystallographic phase transition of Zr into a face‐centered cubic structure during the thermal decomposition was also observed by crystallographic analysis. Quantitative evaluation of electrodeposition of ZrCl and production Zr by thermal decomposition was discussed.

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“…WU [9] studied the electrochemical behavior of zirconium in LiCl-KCl-K2ZrF6 melt at 1023 K. It showed that the electrochemical reduction of Zr 4+ ions is a diffusion-controlled reversible electrochemical reaction, and Zr 4+ is reduced in the two-step transfer of Zr 4+ → Zr 2+ → Zr and the diffusion coefficient of Zr ion in the system is 4.22×10 -6 cm 2 •s -1 . Polyakova [10] found that in NaCl-KCl-ZrCl4 melt with the addition of NaF, the electrode reaction of zirconium occurs reversibly in a four-electron step reaction: :Zr 4+ + 4e -→Zr. Chen [11] considered the electrochemical behavior of zirconium in chloride-fluoride melts.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical behavior of zirconium in the (NaCl-KCl-NaF- ZrO2) molten salt

Ma¹,

Wu²,

Li³

et al. 2018

Proceedings of the 2017 3rd International Forum on Energy, Environment Science and Materials (IFEESM 2017)

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Abstract. As a refractory metal, zirconium has a wide range of applications in many fields. The method of electrode position to produce metal zirconium is more available, it is important to study the behavior of zirconium in the molten salt. The electrochemical reaction mechanism and electrocrystallization process of zirconium in the NaCl-KCl-NaF-ZrO2 molten salt were studied at 973 K by means of cyclic voltammetry, chronopotentiometry, and chronoamperometry techniques. The results show that the electrochemical reaction process of zirconium in the NaCl-KCl-NaF-ZrO2 molten salt system is a reversible process and controlled by ion diffusion rate. Zirconium ion in this system is reduced to Zr(0) in only one step and the diffusion coefficient of Zr ion in the system is 3.274×10 -5 cm 2 •s -1 . The electrocrystallization process of zirconium is an instantaneous hemispheroid three-dimensional nucleation process.

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Cathodic processes at electrolysis of chloride and chloride-fluoride melts of zirconium

Cited by 27 publications

References 7 publications

Electrochemical behavior of zirconium in molten NaCl-KCl-K2ZrF6 system

Electrochemical behavior of zirconium in molten NaCl-KCl-K2ZrF6 system

Zirconium metal recovery from irradiated radioactive zirconium alloy via chloride‐basedelectrorefining and thermal decomposition ofZrCl

Electrochemical behavior of zirconium in the (NaCl-KCl-NaF- ZrO2) molten salt

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