Effect of alloying elements on the electronic properties of thin passive films formed on carbon steel, ferritic and austenitic stainless steels in a highly concentrated LiBr solution

The influence of alloying elements on the electrochemical and semiconducting properties of thin passive films formed on several steels (carbon steel, ferritic and austenitic stainless steels) has been studied in a highly concentrated lithium bromide (LiBr) solution at 25 °C, by means of potentiodynamic tests and Mott-Schottky analysis. The addition of Cr to carbon steel promoted the formation of a p-type semiconducting region in the passive film. A high Ni content modified the electronic behaviour of highly alloyed austenitic stainless steels. Mo did not modify the electronic structure of the passive films, but reduced the concentration of defects

Passive and transpassive behaviour of Alloy 31 in a heavy brine LiBr solution

The passive and transpassive behaviour of Alloy 31, a highly alloyed austenitic stainless steel (UNS N08031), has been investigated in a LiBr heavy brine solution (400 g/l) at 25 °C using potentiostatic polarisation combined with electrochemical impedance spectroscopy and Mott-Schottky analysis. The passive film formed on Alloy 31 has been found to be p-type and/or n-type in electronic character, depending on the film formation potential. The thickness of the film formed at potentials within the passive region increases linearly with applied potential. The film formed at transpassive potentials is thinner and more conductive than the film formed within the passive region. These observations are consistent with the predictions of the Point Defect Model for passive and transpassive films on metals and alloys

Passivity of AISI 321 stainless steel in 0.5 M H2SO4 solution studied by Mott–Schottky analysis in conjunction with the point defect model

The passivity of AISI 321 stainless steel in 0.5 M H2SO4 solution, in the steady-state condition, has been explored using electrochemical impedance spectroscopy (EIS) and Mott–Schottky analysis. Based on the Mott–Schottky analysis in conjunction with the point defect model (PDM), it was shown that the calculated donor density decreases exponentially with increasing passive film formation potential. The thickness of the passive film was increased linearly with the formation potential. These observations were consistent with the predictions of the PDM, noting that the point defects within the passive film are metal interstitials, oxygen vacancies, or both

The Mechanism of Transpassive Dissolution of AISI 321 Stainless Steel in Sulphuric Acid Solution

The transpassive dissolution mechanism of AISI 321 stainless steel in a 0.5 M sulphate solution was studied using electrochemical impedance spectroscopy (EIS). On the basis of the experimental results, surface charge approach, and point defect model, a kinetic model of the transpassive dissolution process is proposed. The transpassive film is modeled as a highly doped n-type semiconductor—insulator-p-type semiconductor structure. Injection of negative defects at the transpassive film/solution interface results in their accumulation as a negative surface charge. It alters the nonstationary transpassive film growth rate controlled by the transport of positive defects (oxygen vacancies). The model describes the process as dissolution of Cr as Cr (VI) and Fe as Fe (III) through the transpassive film via parallel reaction paths

Passivation behavior of a ferritic stainless steel in concentrated alkaline solutions

The passivation behavior of AISI 430 ferritic stainless steel was investigated in concentrated alkaline solutions in relation to several test parameters, using electrochemical techniques. Increasing solution pH (varying from 11.5 to 14.0) leads to an increase in the corrosion rate of the alloy. Mott–Schottky analysis revealed that passive films formed on AISI 430 ferritic stainless steel behave as n-type semiconductor and the donor densities increased with pH. Electrochemical impedance spectroscopy (EIS) results showed that the reciprocal capacitance of the passive film is directly proportional to its thickness, which decreases with pH increase. The results revealed that for this ferritic stainless steel in concentrated alkaline solutions, decreasing the solution pH offers better conditions for forming passive films with higher protection behavior, due to the growth of a much thicker and less defective film

EFFECT OF IMMERSION TIME ON THE ELECTROCHEMICAL BEHAVIOUR OF AISI 321 STAINLESS STEEL IN 0.1 M H2SO4 SOLUTION

In this study, effect of immersion time on the electrochemical behaviour of AISI 321 stainless steel (AISI 321) in 0.1 M H 2SO 4 solution under open circuit potential (OCP) conditions was evaluated by potentiodynamic polarization, Mott–Schottky analysis and electrochemical impedance spectroscopy (EIS). Mott–Schottky analysis revealed that the passive films behave as n-type and p-type semiconductors at potentials below and above the flat band potential, respectively. Also, Mott–Schottky analysis indicated that the donor and acceptor densities are in the range 1021 cm-3 and increased with the immersion time. EIS results showed that the best equivalent circuit presents two time constants: The high-medium frequencies time constant can be correlated with the charge transfer process and the low frequencies time constant has been associated with the redox processes taking place in the surface film. According to this equivalent circuit, the polarization resistance (interfacial impedance) initially increases with the immersion time (1 to 12 h), and then it is observed to decreases. This variation is fully accordance with potentiodynamic polarization result

Effect of solution pH on the electrochemical behaviour of AISI 304 austenitic and AISI 430 ferritic stainless steels in concentrated acidic media

In this study, the effect of solution pH on the electrochemical behaviour of AISI 304 austenitic and AISI 430 ferritic stainless steels at open circuit potential (OCP) in concentrated acidic solutions was studied. Polarization curves showed that the corrosion current density of both stainless steels increased with decreasing pH. Mott–Schottky analysis revealed that passive films formed on AISI 304 and AISI 430 stainless steels behave as n-type and p-type semiconductors and the donor and acceptor densities increased with decreasing pH. Electrochemical impedance spectroscopy (EIS) results showed that the reciprocal capacitance of the passive film is directly proportional to its thickness which decreases with decreasing pH. Thus for both austenitic and ferritic stainless steels in acidic solutions, increasing the solution pH offers better conditions for forming passive films with higher protection behaviour, due to the growth of much thicker and less defective films

Semiconducting behavior of the anodically passive films formed on AZ31B alloy

This work includes determination of the semiconductor character and estimation of the dopant levels in the passive film formed on AZ31B alloy in 0.01 M NaOH, as well as the estimation of the passive film thickness as a function of the film formation potential. Mott–Schottky analysis revealed that the passive films displayed n-type semiconductive characteristics, where the oxygen vacancies and interstitials preponderated. Based on the Mott–Schottky analysis, it was shown that the calculated donor density increases linearly with increasing the formation potential. Also, the electrochemical impedance spectroscopy (EIS) results indicated that the thickness of the passive film was decreased linearly with increasing the formation potential. The results showed that decreasing the formation potential offer better conditions for forming the passive films with higher protection behavior, due to the growth of a much thicker and less defective films

Investigation of the passive behaviour of AZ31B alloy in alkaline solutions

In this work, the passivity of AZ31B alloy in NaOH solutions was studied by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and Mott–Schottky analysis. Potentiodynamic polarization results indicated that decreasing NaOH concentration leads to decrease the corrosion rate of this alloy. EIS results showed that the reciprocal capacitance (1/C) of the passive film is directly proportional to its thickness which increases with decreasing NaOH concentration. Therefore, it is clear that dilute NaOH solutions offer better conditions for forming the passive films with higher protection behaviour, due to the growth of a much thicker and less defective films. The Mott–Schottky analysis revealed that the passive films displayed n-type semiconductive characteristics, where the oxygen vacancies and interstitials (over the cation vacancies) preponderated. Also, Mott–Schottky results showed that the donor densities evaluated from Mott–Schottky plots are in the range of 1020 cm−3 and decreased with decreasing NaOH concentration