Passive film properties

The nature, the growth rate, and the stabdity of electrochemicaUy passivated [21,22] and air-formed films [23] have been investigated in acidic and borate bufler solutions. The passive film properties were found to depend on the passivation potential [24,25], solution temperature [26], solution pH [24], and time of exposure in the corrosive media... 

For stainless steels [3c], the chromium content is obviously one of the major parameters which controls the passive film properties and then the pitting resistance, at least for some conditions of passive film formation. This is illustrated in standard conditions by the results shown in Figure 3. Other oxidizable elements, such as silicon, which is present at the level of some tenths of a weight % in industrial AISI 430 or 304 t5 e steels, can also enter the passive film and improve the pitting resistance. 

More generally, it should be pointed out that, whatever the pit nucleation mechanism, the survival probability of a pit nucleus (or even of a pit embryo) depends on the state of the surrounding passive film, since different passive films formed on the same alloy do not exhibit the same pitting resistance. The distribution of potentials and electric charges around the pit nucleus should likely provide a better assessment of the intensity of the anodic reactions than the average potential difference V and are probably a function of both the pitting site characteristics and the surrounding passive film properties [3i]. 

As outlined above, electron transfer through the passive film can also be cmcial for passivation and thus for the corrosion behaviour of a metal. Therefore, interest has grown in studies of the electronic properties of passive films. Many passive films are of a semiconductive nature [92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102 and 1031 and therefore can be investigated with teclmiques borrowed from semiconductor electrochemistry—most typically photoelectrochemistry and capacitance measurements of the Mott-Schottky type [104]. Generally it is found that many passive films cannot be described as ideal but rather as amorjDhous or highly defective semiconductors which often exlribit doping levels close to degeneracy [105]. 

Passivating inhibitors act in two ways. First they can reduce the passivating current density by encouraging passive film formation, and second they raise the cathodic partial current density by their reduction. Inhibitors can have either both or only one of these properties. Passivating inhibitors belong to the group of so-called dangerous inhibitors because with incomplete inhibition, severe local active corrosion occurs. In this case, passivated cathodic surfaces are close to noninhibited anodic surfaces. 

Nickel and nickel alloys possess good resistance to sea-water in conditions where the protective properties of the passive film are fully maintained. As pointed out above, Ni-30 Cu Alloy 400, in contrast to its behaviour in acidic solution, normally forms a protective film in neutral and alkaline environments, including sea-water this alloy and its age hardening variant... 

The local dissolution rate, passivation rate, film thickness and mechanical properties of the oxide are obviously important factors when crack initiation is generated by localised plastic deformation. Film-induced cleavage may or may not be an important contributor to the growth of the crack but the nature of the passive film is certain to be of some importance. The increased corrosion resistance of the passive films formed on ferritic stainless steels caused by increasing the chromium content in the alloy arises because there is an increased enhancement of chromium in the film and the... 

Kinetic stability of lithium and the lithiated carbons results from film formation which yields protective layers on lithium or on the surfaces of carbonaceous materials, able to conduct lithium ions and to prevent the electrolyte from continuously being reduced film formation at the Li/PC interphase by the reductive decomposition of PC or EC/DMC yielding alkyl-carbonates passivates lithium, in contrast to the situation with DEC where lithium is dissolved to form lithium ethylcarbonate [149]. EMC is superior to DMC as a single solvent, due to better surface film properties at the carbon electrode [151]. However, the quality of films can be increased further by using the mixed solvent EMC/EC, in contrast to the recently proposed solvent methyl propyl carbonate (MPC) which may be used as a single sol-... 

The corrosion resistance of lithium electrodes in contact with aprotic organic solvents is due to a particular protective film forming on the electrode surface when it first comes in contact witfi tfie solvent, preventing further interaction of the metal with the solvent. This film thus leads to a certain passivation of lithium, which, however, has the special feature of being efiective only while no current passes through the external circuit. The passive film does not prevent any of the current flow associated with the basic current-generating electrode reaction. The film contains insoluble lithium compounds (oxide, chloride) and products of solvent degradation. Its detailed chemical composition and physicochemical properties depend on the composition of the electrolyte solution and on the various impurity levels in this solution. 

MIC depends on the complex structure of corrosion products and passive films on metal surfaces as well as on the structure of the biofilm. Unfortunately, electrochemical methods have sometimes been used in complex electrolytes, such as microbiological culture media, where the characteristics and properties of passive films and MIC deposits are quite active and not fully understood. It must be kept in mind that microbial colonization of passive metals can drastically change their resistance to film breakdown by causing localized changes in the type, concentration, and thickness of anions, pH, oxygen gradients, and inhibitor levels at the metal surface during the course of a... 

The corrosion of stainless steel in 0.1 mol-1 NaCl solutions at open circuit potential was studied in detail by Bruesch et al. [106] using XPS in combination with a controlled sample transfer system [38]. It was verified by XPS analysis that the passivating film contains chromium oxide. The position and the height of the Cr concentration maximum depends critically on the bulk chromium content of the steel. Significant variations in the electrode passivation properties were observed at a Cr concentration of 12%, while the film behaviour was found to be rather independent of the other components like Mo, Ni, Cu. From the fact that the film structures and... 

The nature of the passive film has been the object of innumerable further studies with arguments over its thickness, composition, structure and electronic properties raging. What has become very clear is that that removal from solution and drying of the passivated electrode alters the film profoundly and any studies of the film ex situ must be treated with considerable caution. For that reason we will concentrate here primarily on in situ studies or at the least those studies carried out on passive films that retain their hydration. 

First application of Mossbauer spectroscopy in electrochemistry the properties of passive films are due to their amorphous character. 

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