Electrochemical study of titanium in chloride-fluoride melts

Polyakova, L. P.; Stangrit, P.T.; Polyakov, E. G.

doi:10.1016/0013-4686(86)87102-x

Cited by 39 publications

(20 citation statements)

References 3 publications

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“…At the same time, it is also reasonable to assume that the complex of Ti(IV) with the coordination number of 6, TiF 6 2À , is dominating the concentration of Ti(IV). We can dene the equilibrium constant of the complex as in eqn (12).…”

Section: Faraday Discussion Papermentioning

confidence: 99%

“…Investigations on the inuence of uoride have been studied for years. [8][9][10][11][12] However, a concrete value has not been provided, and the mechanism is still ambiguous. The present work contains new results of a study on the measurement of titanium ions in equilibrium with metallic titanium in NaCl-KCl melt with the addition of uoride, and the inuence of uoride ion is analysed for the formation of the complexes of TiF i 3Ài and TiF i 2Ài .…”

Section: Introductionmentioning

confidence: 99%

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The influence of fluoride ions on the equilibrium between titanium ions and titanium metal in fused alkali chloride melts

Song

Wang

et al. 2016

Faraday Discuss.

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KF is employed as a source of fluoride ions added to the melt to disclose the influence of fluoride on the disproportionation reactions of titanium ions, 3Ti(2+) = 2Ti(3+) + Ti, and 4Ti(3+) = 3Ti(4+) + Ti. The results reveal that the equilibrium transferred to the right direction for the first reaction and the apparent equilibrium constant increased sharply, mainly because of the formation of coordination compounds: TiFi(3-i). The accurate values of the equilibrium constants referring to the formation reactions of Ti(3+) + iF(-) = TiFi(3-i) (i = 1-6) in NaCl-KCl melt at 1023 K were evaluated with a best fit least squares method. It is also revealed that the stable states of the coordination compounds are TiF(2+), TiF2(+), TiF4(-) and TiF6(3-). Moreover, the Gibbs free energies for complex formation were estimated. Ti(2+) was undetectable when the concentration of fluoride ion was high enough. The equilibrium constant for the formation reaction, Ti(4-) + 6F(-) = TiF6(2-), was evaluated. The equilibrium constant, Kc2, for the disproportionation reaction 4Ti(3+) = 3Ti(4+) + Ti, in chloride melt was determined as 0.015.

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Section: Faraday Discussion Papermentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The influence of fluoride ions on the equilibrium between titanium ions and titanium metal in fused alkali chloride melts

Song

Wang

et al. 2016

Faraday Discuss.

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“…Niobium was intended to diffuse into the titanium matrix and work as a crack arrester. The fundamental aspects of the electrochemistry and electrodeposition of titanium in molten salts have been investigated by several authors [4][5][6][7][8][9] and are not reproduced here. For more information, a review by Girginov et al [10] should be consulted.…”

Section: Introductionmentioning

confidence: 99%

Deposition of titanium on SiC fibres from chloride melts

Gussone

Hausmann

2011

J Appl Electrochem

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The present study examined the feasibility of producing titanium matrix composites based on a molten salt fibre coating process. It is demonstrated that sufficiently thick and coherent titanium coatings can be deposited on SiC fibres in LiCl-KCl-TiCl 2 at 700 K. One important aspect of the study was the behaviour of the substrate during electrolysis. Therefore, additional features related to carbon-coated SiC fibres and carbonaceous substrates in general are outlined. The morphologies and microstructures of electrolytically coated SiC fibres were investigated by scanning electron microscopy and compared to fibres coated by a physical vapour deposition technique. The cause and relevance of the growth failures that were observed in this study are also discussed.

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“…42 Using the values of the function Ψ T obtained from the Eq. 4 and the diffusion coefficients, 9,18,44 the standard rate constants of charge transfer were calculated by Eq. 2.…”

Section: Resultsmentioning

confidence: 99%

“…7 In this regard, studies of the electrochemical behavior of titanium complexes are of undoubted interest. [5][6][7][8][9][10][11][12][13][14][15][16][17][18] At the same time, the presence of alkaline earth metal cations in molten alkali metal halides leads to significant changes in the kinetic and transport properties of titanium containing melts. [19][20][21] To monitor such changes, it is advisable to use quantum-chemical simulations.…”

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confidence: 99%

Study of the Electron Transfer in Titanium Containing Melts by Electrochemical and Quantum-Chemical Methods

Stulov

Vetrova

Kremenetsky

et al. 2021

J. Electrochem. Soc.

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The electron transfer mechanism in a titanium containing system was investigated by electrochemical and quantum-chemical methods. The kinetics of charge transfer for the Ti(IV)/Ti(III) redox couple in the (NaCl–KCl)equimol–NaF (10 wt%)-K2TiF6 melt with addition of Ca2+ cations was studied by cyclic voltammetry. The standard rate constants of charge transfer (k s ) were calculated by Nicholson’s method. The increase values of the k s reaching the maximum at mole ratio Ca2+/Ti(IV) equals 1:1 was found. Values of activation energy for system with Ca2+ cations are considerably less than activation energies of the system without Ca2+ cations. The quantum-chemical calculations were performed using the Firefly quantum-chemical package by methods of the density functional theory. Structures with a high probability of the electron transfer from the cathode to the titanium complex were found. Using the Frontier molecular orbital method made it possible with a small amount of computer time to determine the structure of the transition state of the TiF6 2− complex. The calculated activation energy of the electron transfer was in a good agreement with experimentally determined value.

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Electrochemical study of titanium in chloride-fluoride melts

Cited by 39 publications

References 3 publications

The influence of fluoride ions on the equilibrium between titanium ions and titanium metal in fused alkali chloride melts

The influence of fluoride ions on the equilibrium between titanium ions and titanium metal in fused alkali chloride melts

Deposition of titanium on SiC fibres from chloride melts

Study of the Electron Transfer in Titanium Containing Melts by Electrochemical and Quantum-Chemical Methods

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