Mechanism of Crevice Corrosion

The mechanism of crevice corrosion of stainless steels in chloride-containing solutions follows

three stages.

First Stage

It is also called incubation or oxygen depletion stage, during which oxygen inside the gap is
consumed through the corrosion reactions occurring on passive stainless steel, namely, oxygen
reduction and passive film growth, as follows:

The rate of reactions equals the slowest one, which is the passivity current density of the metal,
ip (mA/m2 .

How long this stage takes depends on two parameters: passivity current density, i p, and crevice
volume, i.e., maximum available oxygen mass inside crevice. It appears evident that the most influencing
and decisive parameter is the passivity current density, which in turn is function of composition of
stainless steel—in short, of PREN, pH and temperature (see Chap. 5, Fig. 5.21).

It has to be considered that when passivity current density is very low, in spite of the tiny gap,
some oxygen diffusion, i.e., oxygen renewal, becomes possible, therefore the incubation has never an
end: accordingly, crevice can never start.

For an estimation of the duration of this stage reference can be made to Oldfield and Sutton
(1978a, b) and to Oldfield (1987).

Second Stage

The second stage starts once oxygen is completely depleted in the crevice. The elimination of
oxygen inside the crevice brings stainless steel in active condition, as schematically below
 Fig. Potential change inside crevice during first stage: conditions inside (IN) and outside (OUT)
the interstice

During this stage, two important processes take place: inside the crevice, metal ions
concentration can exceed 1 M, so hydrolysis reactions take place:

and pH drops to very low values, such as below 2 (mainly for the contribution of chromium), hence
impeding repassivation; outside crevice, oxygen reduction increases alkalinity, therefore strengthening
passivity.

Third Stage

Third stage is when macrocell current becomes stationary. Macrocell current can be calculated
as reported in Lazzari (2017) as seen for pitting in Chap. 11:

where icorr is the corrosion current density (mA/m2), ic is the cathodic current density (mA/m 2), Sa
is the anodic surface (m2), and Sc is the cathodic surface (m2).

It is important to emphasize that for crevice corrosion the driving voltage is expected to be
lower than that of pitting due to the higher ohmic drop contribution through the narrow gap. As rule of
thumb, it could be considered about a half of that adopted for pitting corrosion; hence, a value as low as
0.2 V. In aerated seawater, crevice corrosion rate varies between 1 and 5 mm/year regardless the
stainless steel grade.

For several aspects, crevice corrosion can be compared to pitting and some authors consider
crevice a particularly severe form of pitting or a pitting just initiated; others consider pitting a particular
form of crevice corrosion, arguing that the main difference is a matter of size (crevice corrosion in
something macroscopic whilst pitting is microscopic). In any case, experience tells that environmental
conditions, which cause pitting, cause also crevice corrosion, instead the opposite is not always true.