Coupling between dissolution and passivation revisited – Kinetic parameters of anodic oxidation of titanium alloys in a fluoride-containing electrolyte

Bojinov, Martin; Stancheva, Mina

doi:10.1016/j.jelechem.2014.09.016

Cited by 24 publications

(17 citation statements)

References 44 publications

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“…30,31 The inductance exhibited by the impedance data in the mid frequency range can be assigned to the high frequency migration of major current carriers. 13 The charge transfer resistance increases with the potential, while the inductance (L 4 ) and the associated resistance(R 4 ) decrease with the potential. The capacitance (C 5 ) appearing at the low frequency is assigned either to the variation in film thickness with low frequency perturbations 19 or to the accumulation of fluoride ions in the metalfilm interface.…”

Section: Resultsmentioning

confidence: 99%

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A Kinetic Model for the Anodic Dissolution of Ti in HF in the Active and Passive Regions

Fasmin

Praveen

Ramanathan

2015

J. Electrochem. Soc.

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We investigated the anodic dissolution of polycrystalline titanium rotating disc electrode in 0.1 M hydrofluoric acid in active and passive regions using potentiodynamic polarization and electrochemical impedance spectroscopy. In the active region, complex plane plots of the impedance spectra exhibited three capacitive loops indicting the presence of at least two adsorbed intermediates. In the passive region, they exhibited a negative resistance and a low frequency inductive loop. The high frequency loops exhibit constant phase element behavior indicating that a heterogeneous 2D film with partial surface coverage is present in the active and passive regions. The impedance data was fit to a reaction model and a four step mechanism with two adsorbed intermediate species is proposed to explain the observed trends in the active and passive regions. The change in the surface coverage of the adsorbed intermediate species, with the overpotential is estimated. This model describes the dissolution of Ti via two parallel paths, viz. a chemical step and an electrochemical step. The onset of passivation ensues when the rate of TiO 2 film formation is more than that of its dissolution. Transpassive dissolution becomes dominant when the electrochemical dissolution from the bare surface becomes negligible. Titanium metal and its alloys are widely used in engineering applications and medical implants, due to their low density, high corrosion resistance and high strength.1 These materials possess excellent corrosion resistance in acidic media, through the formation of protective oxide film on the metal surface. In order to facilitate the attack of the passive oxide layer, solutions containing fluoride ions are used for the anodic dissolution of titanium. [2][3][4] The corrosion studies of titanium show that at low overpotentials, the dissolution is in active region, and at moderate overpotentials, surface passivation occurs. At high overpotentials, transpassive dissolution is observed.The dissolution mechanism of titanium in solutions, with and without fluoride ions have been characterized using various techniques. The dissolution of Ti in 10 M H 2 SO 4 was investigated using polarization and impedance techniques 5 and it was reported that the dissolved species is Ti 3+ . To the best of our knowledge, the earliest report on electrochemical studies of Ti dissolving in acidic fluoride ions was published by Kelly.6 Polarization studies show clear active, passive and transpassive regions. 6 The impedance spectrum was acquired in the transpassive region and was analyzed to show that the film thickness increased with the potential. 6 The impedance of Ti in solutions containing strong acids (H 2 SO 4 and HNO 3 ) along with 0.1 mM -10 mM hydrofluoric acid was analyzed 4 and a four step reaction mechanism involving Ti + , Ti 2+ and Ti 3+ adsorbed intermediate species and Ti 3+ dissolved species was proposed to explain the results. In each case, the spectra were acquired at only one potential. The confidence in the model identification wo...

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Section: Resultsmentioning

confidence: 99%

“…Recently, the anodic dissolution of Ti and its alloys in glycol with controlled H 2 O and fluoride concentration was studied. 13 When the presence of dissolved oxygen and water is limited, passive region is not seen in polarization curves. The oxide formation and dissolution is modeled using a kinetic model with vacancy conduction in the film.…”

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confidence: 99%

A Kinetic Model for the Anodic Dissolution of Ti in HF in the Active and Passive Regions

Fasmin

Praveen

Ramanathan

2015

J. Electrochem. Soc.

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“…It should be mentioned that in the literature, the combination of EIS and XPS has already been used for the estimation of film thickness, e.g. for Ni-based alloys [27], Ti alloys [28], or W [29]. From XPS measurements, these authors determined the thickness of the oxide film formed on the metal, which in turn was used for the simulation of EIS spectra.…”

Section: Film Formation and Xps Characterizationmentioning

confidence: 99%

Comparison of different methods for measuring the passive film thickness on metals

Benoît

Bataillon

Gwinner

et al. 2016

Electrochimica Acta

166

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International audienceIn situ electrochemical impedance spectroscopy (EIS) and ex situ X-ray photoelectron spectroscopy (XPS) measurements on electrogenerated zirconium oxide films on zirconium (Zr/ZrO2) were used to quantify the oxide film thickness and resistivity profiles through the oxide. The EIS analysis presented here takes advantage of the high-frequency domain at which the constant-phase element (CPE) behavior of the oxide film reverts to a capacitive response and the Cole-Cole representations of the complex capacitance to extract the high-frequency capacitance of the oxide film without reference to the nature of the timeconstantdistribution within the oxide film. The film thickness of the ZrO2 samples measured from the high-frequency capacitance of EIS were in good agreement with the thickness obtained from XPS. Moreover, the EIS analysis presented is based on the use of the integral solution of the power law model, which allows to obtain in one single EIS experiment, both the film thickness and the resistivity profile in the ZrO2 film. This work suggests a convenient graphical method to extract film properties and serves tovalidate a key assumption of the power-law model for interpretation of CPE parameters in terms of physical properties

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“…The dissolution in saliva of high concentrated fluoride agents can lead to the formation of a high concentration of hydrofluoric acid. In such conditions, a transition of titanium oxide into a soluble Ti-F complex is observed [28,29,36]. It is worth adding that the corrosion rate depends not only on the concentration of fluoride ions, but also on the pH in the oral media.…”

Section: Introductionmentioning

confidence: 99%

Influence of nanostructure on titanium corrosion resistance in fluoridated medium

Sotniczuk

Kuczyńska

Kubacka

et al. 2019

Materials Science and Technology

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Nanocrystalline titanium, mainly owing to its high corrosion resistance, mechanical strength to density ratio and biocompatibility, has a great application potential in dental implantology. However, fluoridated agents commonly used for oral hygiene could have a destructive influence on the titanium protective passive films and lead to the formation of local corrosion damages. In this work, the effect of nanostructuring on titanium corrosion resistance in the concentration of F− which is typical for toothpastes, was evaluated by different electrochemical and surface characterisation techniques. It was found that nanostructure influences beneficially on titanium corrosion resistance in fluoride solution. Furthermore, the lower increase in nanocrystalline titanium surface roughness in corrosion solutions indicates better stability of passive film formed on its surface. This paper is part of a thematic issue on Titanium.

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Coupling between dissolution and passivation revisited – Kinetic parameters of anodic oxidation of titanium alloys in a fluoride-containing electrolyte

Cited by 24 publications

References 44 publications

A Kinetic Model for the Anodic Dissolution of Ti in HF in the Active and Passive Regions

A Kinetic Model for the Anodic Dissolution of Ti in HF in the Active and Passive Regions

Comparison of different methods for measuring the passive film thickness on metals

Influence of nanostructure on titanium corrosion resistance in fluoridated medium

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