A study of the behaviour of titanium in acidic solution. Part 1 — Anodic behaviour and behaviour in “ababdoned” conditions

Sinigaglia, D.; Taccani, G.; Vicentini, B.

doi:10.1002/maco.19730241203

Cited by 14 publications

(8 citation statements)

References 38 publications

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“…5 demonstrate that as the pH decreases, im increases and Em becomes increasingly positive (noble). These qualitative observations have been reported by many investigators for both chloride and sulfate solutions (31,(33)(34)(35). However, attempts to establish quantitative relationships among ira, Era, and pH have been very limited in number, and not successful.…”

Section: ~Oo I I I I I 1 I I I I ~ I' I --supporting

confidence: 62%

“…[25]- [34], the steady-state current density is given by Eq. [35] 3 (k29 + k31a(H+)N) -}-4N (k33 -5 ks4M) [35] [ (1/PQR) -5 (1/PQ) -5 (l/P) -5 1 -5 N - The electrolyte-coupled active-passive system just described contains all of the chemical and electrochemical elements present in localized corrosion and, consequently, serves to demonstrate in a quantitative fashion the critical roles played by Ti (III), Ti (IV), and C1-ions in determining the cessation or propagation of localized corrosion. In a true localized corrosion system, the time required to generate C4" increases as a consequence of mass transport limitations.…”

Section: Spontaneous Cessation O] Localized Corrosion and The Role Os...mentioning

confidence: 99%

“…The systematic reduction of Eq. [35] to correspond to the results contained in Eq. [5]- [7] requires very few assumptions.…”

Section: [41]mentioning

confidence: 99%

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Anodic Dissolution and Passivation of Titanium in Acidic Media: III . Chloride Solutions

Kelly

1979

J. Electrochem. Soc.

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The electrochemical behavior of titanium in deoxygenated acidic chloride solutions, with and without additions of Ti(III) and Ti(IV) ions, has been determined and compared with that observed in acidic sulfate media. A monolayer mechanism has been developed for the active‐state dissolution and passivation of titanium in acidic media. According to this mechanism, the metal is oxidized in a sequence of one‐electron charge‐transfer reactions which results in the formation of adsorbed reaction intermediates corresponding to each of the relevant valence states of titanium (+1, +2, +3, +4) and which leads to Ti(III) ions in solution in the active and active‐passive transition regions. The mechanism is in quantitative agreement with the experimental results for both chloride and sulfate media. In acidic chloride solutions, as well as in acidic sulfate solutions, the rates of oxidation at a passive titanium surface of Ti(III) ions in solution to Ti(IV) and of reduction at an active‐state surface of Ti(IV) ions in solution to Ti(III) are directly proportional to the concentrations of Ti(III) and Ti(IV), respectively. The reduction of Ti(IV) at an active surface is responsible for the fact that, at a critical concentration of Ti(IV), an active‐state surface passivates. In localized corrosion systems, active and passive surfaces are in simultaneous contact with the electrolyte within the occluded cell, and the aforementioned oxidation and reduction reactions serve to couple the active‐state and passive‐state electrochemical systems. Such electrolyte‐coupled active‐passive systems are capable of generating the critical concentration of Ti(IV) required to passivate the active‐state surface, a fact which explains random spontaneous cessation of localized corrosion (self‐healing). The critical concentration of Ti(IV) is much greater in chloride solutions than in sulfate media and takes much longer to attain. Consequently, the halide ion functions as a promoter of localized corrosion.

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Section: ~Oo I I I I I 1 I I I I ~ I' I --supporting

confidence: 62%

Section: Spontaneous Cessation O] Localized Corrosion and The Role Os...mentioning

confidence: 99%

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Anodic Dissolution and Passivation of Titanium in Acidic Media: III . Chloride Solutions

Kelly

1979

J. Electrochem. Soc.

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“…The dissolution of the titanium oxide film in sulphuric acid is thermodynamically possible [23] and was experimentally observed by Sinigaglia et al [24]. From a theoretical point of view, there are only two phenomena, diffusion and migration, that may be responsible for the thickening of the film.…”

Section: Electrochemical Aspectsmentioning

confidence: 99%

Self-colour anodizing of titanium

et al. 1982

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Relations between the co lo urs and the electro chemical parameters (current density, quantity o f electricity and température of the electrolyte) durin g the an odization of titan ium sheets were studied in a 1 M H2SO 4 solution. Mathematical théories were developed for the kin etics of growth of the an odic film an d for the colours of this film. Thèse théories show that the relation between the growth an d the colour of the film is complicated. Nevertheless, it was possible to fin d expérimen tal con dition s that led to un iform an d well-defin ed colours.

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“…(i) An active state in which the titanium is oxidized to form soluble Ti(III) ions. In this area, previously reported works have focused on the kinetics and mechanism of the hydrogen evolution reaction, hydride formation and its role in the behaviour of titanium, the kinetics and mechanism of anodic titanium dissolution [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20], the effects of added redox couples and various oxidants, as well as the role of alloying elements.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical behaviour of titanium in H2SO4–MnSO4 electrolytes

Utomo

Donne

2006

Electrochimica Acta

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The corrosion of titanium in H 2 SO 4 electrolytes (0.001-1.0 M) at temperatures from ambient to 98°C has been investigated using steady state polarization measurements. Four distinct regions of behaviour were identified; namely, active corrosion, the active-passive transition, passive region and the dielectric breakdown region. The active corrosion and active passive transition were characterized by anodic peak current (i m) and voltage (E m), which in turn were found to vary with at 98°C,-58 mV at 80°C and-28 mV at 60°C. The activation energy for titanium corrosion, determined from temperature studies, was found to be 67.7 kJ mol-1 in 0.1 M H 2 SO 4 and 56.7 kJ mol-1 in 1.0 M H 2 SO 4. The dielectric breakdown voltage (E d) of the passive TiO 2 film was found to vary depending on how much TiO 2 was present. The inclusion of Mn 2+ into the H 2 SO 4 electrolyte, as is done during the commercial electrodeposition of manganese dioxide, resulted in a decrease in titanium corrosion current, possibly due to Mn 2+ adsorption limiting electrolyte access to the substrate.

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A study of the behaviour of titanium in acidic solution. Part 1 — Anodic behaviour and behaviour in “ababdoned” conditions

Cited by 14 publications

References 38 publications

Anodic Dissolution and Passivation of Titanium in Acidic Media: III . Chloride Solutions

Anodic Dissolution and Passivation of Titanium in Acidic Media: III . Chloride Solutions

Self-colour anodizing of titanium

Electrochemical behaviour of titanium in H2SO4–MnSO4 electrolytes

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