Abstract
To investigate the electrodeposition mechanism of Ti4+, electrochemistry experiments were conducted using a KF–KCl–K2Ti6O13 molten salt at a Cu electrode at 950 °C. Transient electrochemical techniques such as cyclic voltammetry (CV) and square-wave voltammetry were used in this study. The main phases and compositions of the product were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectrometry (EDS). The resulting product has the structure of metallic Ti. The results indicate that Ti4+ is reduced to metallic Ti by a two-step mechanism, corresponding to the reduction pathway: Ti4+ → Ti2+ → Ti. Moreover, Cu–Ti alloy could be obtained by the potentiostatic electrolysis at a Cu electrode.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Jahedi M, Zahiri S, Gulizia S. Direct manufacturing of titanium parts by cold spray. Mater Sci Forum. 2009;618–619:505.
Ning XH, Asheim H, Ren HF, Jiao SQ, Zhu HM. Preparation of titanium deposit in chloride melts. Metall Mater Trans B. 2011;42(6):1181.
Wan MP, Zhao YQ, Zeng WD. Phase transformation kinetics of Ti-1300 alloy during continuous heating. Rare Met. 2015;34(4):233.
Wang YL, Hui SX, Liu R, Ye WJ, Yu Y, Kayumov R. Dynamic response and plastic deformation behavior of Ti–5Al–2.5Sn ELI and Ti–8Al–1Mo–1V alloys under high-strain rate. Rare Met. 2014;33(2):127.
Boccaccini AR, Gerhardt LC, Rebeling S, Blaker JJ. Fabrication, characterisation and assessment of bioactivity of poly (D, L lactid acid) (PDLLA)/TiO2 nanocomposite films. Compos Part A: Appl Sci Manuf. 2005;36(6):721.
Qu W, Wlodarski W, Austin M. Microfabrication and reliability study of sapphire based Ti/Pt-electrodes for thin-film gas sensor applications. Microelectron J. 2000;31(7):561.
Wang B, Liu KR, Chen JS. Reaction mechanism of preparation of titanium by electro-deoxidation in molten salt. Trans Nonferrous Met Soc China. 2011;21(10):2327.
Kroll W. The production of ductile titanium. Trans Am Electrochem Soc. 1940;78(1):35.
Fray DJ, Chen GZ. Reduction of titanium and other metal oxides using electrodeoxidation. Mater Sci Technol. 2002;20(3):295.
Chen GZ, Fray DJ, Farthing TW. Direct electrochemical reduction of titanium dioxide to titanium in molten calcium chloride. Nature. 2000;407(6802):361.
Nagesh CR, Ramachandran CS. Electrochemical process of titanium extraction. Trans Nonferrous Met Soc China. 2007;17(2):429.
Xu Q, Deng LQ, Wu Y, Ma T. A study of cathode improvement for electro- deoxidation of Nb2O5 in a eutectic CaCl2-NaCl melt at 1073 K. J. Alloys Compd. 2005;396(1–2):288.
Suzuki RO. Calciothermic reduction of TiO2 and in situ electrolysis of CaO in the molten CaCl2. J Phys Chem Solids. 2005;66(2):461.
Jiao SQ, Zhu HM. Electrolysis of Ti2CO solid solution prepared by TiC and TiO2. J Alloys Compd. 2007;438(1):243.
Wang QY, Li Y, Jiao SQ, Zhu HM. Producing metallic titanium through electro-refining of titanium nitride anode. Electrochem Commun. 2013;2013(35):135.
Zhang LL, Wang SB, Jiao SQ, Huang K, Zhu HM. Electrochemical synthesis of titanium oxycarbide in a CaCl2 based molten salt. Electrochim Acta. 2012;75:357.
Chen GS, Masazumi O, Takeo O. Electrochemical studies of titanium ions (Ti4+) in equimolar KCl-NaCl molten salts with 1 wt% K2TiF6. Electrochim Acta. 1987;32(11):1637.
Wurm JG, Gravel L. The mechanism of titanium production by electrolysis of fused halide baths containing titanium salts. J Electrochem Soc. 1957;104(5):301.
Polyakov LP, Strangrit PT, Polyakov EG. Electrochemical study of titanium in chloride-fluoride melts. Electrochim Acta. 1986;31(2):159.
Zou XL, Lu XG, Zhou ZF, Li CH. Direct electrosynthesis of Ti5Si3/TiC composites from their oxides/C precursors in molten calcium chloride. Electrochem Commun. 2012;21:9.
Mukhopadhyay I, Aravinda CL, Freyland W. Electrodeposition of Ti from TiCl4 in the ionic liquid l-methyl-3-butyl-imidazolium bis (trifluoro methyl sulfone) imide at room temperature: study on phase formation by in situ electrochemical scanning tunneling microscopy. Electrochim Acta. 2005;50(6):1275.
Castrillejo Y, Bermejo MR, Barrado AI, Pardo R, Barrado E, Martinez AM. Electrochemical behaviour of dysprosium in the eutectic LiCl–KCl at W and Al electrodes. Electrochim Acta. 2005;50(10):2047.
Castrillejo Y, Bermejo MR, Barrado E, Martinez AM. Electrochemical behaviour of erbium in the eutectic LiCl–KCl at W and Al electrodes. Electrochim Acta. 2006;51(10):1941.
Brisard GM, Zenati E. Underpotential deposition of lead on copper (111) -a study using a single-crystal rotating-ring electrode and ex situ low- energy- electron diffraction and auger-electron spectroscopy. Langumuir. 1995;11(6):2221.
Ge M, Gewirth AA. In situ atomic force microscopy of under-and over potentially deposited cadmium on Cu(111). Surf Sci. 1994;324(2):140.
Bard AJ, Faulkner LR. Electrochemical Methods: fundamentals and applications. New York: Wiley; 1980. 162.
Massot L, Chamelot P, Bouyer F, Taxil P. Electrodeposition of carbon films from molten alkaline fluoride media. Electrochim Acta. 2002;47(12):1949.
Polyakova LP, Taxil P, Polyakov EG. Electrochemical behaviour and codeposition of titanium and niobium in chloride-fluoride melts. J Alloys Compd. 2003;359(1–2):244.
Christie JH, Turner JA, Osteryoung RA. Square wave voltammetry at the dropping mercury electrode: theory. Anal Chem. 1977;49(13):1899.
Acknowledgments
This study was financially supported by the State Key Development Program for Basic Research of China (973 Program, Grant No. 2013CB632606-1).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Zhao, K., Wang, YW., Peng, JP. et al. Electrochemical preparation of titanium and titanium–copper alloys with K2Ti6O13 in KF–KCl melts. Rare Met. 36, 527–532 (2017). https://doi.org/10.1007/s12598-016-0708-5
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12598-016-0708-5