Mechanism of the Electrolytic Deposition of Titanium


ONE of the commercial methods of manufacturing pure titanium metal involves the high-temperature electrolysis of either K2TiF6, TiCl4 or TiCl3 in a molten alkali halide eutectic. Several such processes have been in operation for some time, and certain details of the preparative techniques have been published1. The mechanism of these electrolytic methods has, however, remained in doubt. Of the two possibilities, (1) primary deposition of a titanium ion, complex or otherwise, on to a suitable cathode, or (2) secondary deposition where the titanium species are reduced by electrolytically produced alkali metal, the latter has seemed more probable because of the amorphous nature of the resultant titanium. It is true that fairly large dendritic crystals of titanium are produced during the electrolysis, but such dendrites are also found in the commercial preparation of titanium where TiCl4 is reduced with liquid sodium. The current–voltage relations observed during electrolysis are also in keeping with a predominantly secondary process.

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  1. 1

    Cordner and Worner, Aust. J. App. Sci., 2, 351 (1951). Worner, Wells and Worner, J. Electrochem. Soc., 100, 18 (1953). Bett, Hickman, Willis and Worner, Inst. Min. Metall. Symposium No. 21 (1956). Brenner and Senderoff, J. Electrochem. Soc., 100, 223C (1953). Titan Co., Inc., B.P. 682,919 (1952). Shawinigan Water-Power Co., B.P. 678,807 (1952). Smart (I.C.I.), B.P. 698,151 (1952). Drossbach, Z. Elektrochem., 57, 556 (1953). Steinberg, Siebert and Wainer, J. Electrochem. Soc., 101, 63 (1954). Steinberg, Siebert, Corlton and Wainer, J. Electrochem. Soc., 102, 332 (1955). Kawane, J. Electrochem. Soc. (Japan), 22, 662 (1954). Okada, Kawane and Takahashi, Bull. Eng. Res. Inst. Kyoto Univ., 6, 57 (1954).

  2. 2

    Hills and Inman (in preparation).

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