Crevice Corrosion

cdcorrosion.com
ssina.com
dreiym.com
spearindustrial.com
 Thermodynamics of corrosion – Differential aeration cell
Oxygen concentration cell –

O2 + 4e- + 2H2O à 4OH-

§ Nernst eq. at 298K, half cell potentials E1 and E2 for the two
electrodes 1 and 2 having oxygen partial pressures 𝑝 𝑂! " and
𝑝 𝑂! !
#.#%& () ! "
𝐸" = 𝐸# − log
' * (# $

0.059 [𝑂𝐻 # ]$
𝐸! = 𝐸 " − log( )
4 𝑝 𝑂! !
2 1
Assuming same pH
Same electrode (iron) in O2 "."'( ) *
containing and O2 absent 𝐸% - 𝐸! = log( ! ")
$ ) *! !
environments
If 𝑝 𝑂! % < 𝑝 𝑂! ! , 𝐸% − 𝐸! < 0 , 𝐸% < 𝐸! à specimen 1
with lower oxygen content more anodic (more negative)
2
than specimen 2 (cathodic)
Initiation of Crevice Corrosion

O2 + 2H2O+ 4e− →4OH− differential oxygen cell

difference in O2 concentration between the bulk solution and the sheltered crevice has two effects
 E0 = 1.228 V vs. SHE for O2 + 2H2O+ 4e− →4OH−

At a pH of 7.0, when the concentration of dissolved O is 15 mg/L (often

the case for bulk solutions) E(O ) = 1.596 V vs. SHE.2
2
When the concentration of dissolved O within a crevice is 1 mg/L, then
2
E(O ) = 1.579 V vs. SHE
2

Variation of the oxygen concentration within crevices on a Cr-containing stainless steel

 Brief recap of concentration polarization curves..

Schematic Evans diagrams for O2 reduction and OH– oxidation Schematic Evans diagrams for Fe in aqueous solutions where
the oxygen reduction reaction is diffusion controlled. The
intersection of the oxygen reduction and iron dissolution curves
gives the corrosion potential and the corrosion rate
limiting current density iL for O2 reduction within the
crevice is decreased relative to that for the bulk
solution. Why ?

Concentration C of dissolved O2 decreases within the

crevice

iL decreases according to
 only a 25 mV difference in the electrode potential
between open iron and iron in crevices in 0.6 M
NaCl !

But this difference is enough to initiate corrosion

within the crevice !!

the electrode potential for metal within the crevice

becomes more negative with time before levelling off

Establishment of steady-state potentials for open iron and iron within crevices in 0.6 M NaCl
Note that the electrode potential for creviced iron is more negative than that for open iron
 • the limiting cathodic density is less for the creviced
iron than for open iron.

• limiting cathodic rate is suppressed to a constant value

for crevice heights between 0.13 and 0.50 mm.

• crevice height of 0.50 mm is significant because it is

approximately the thickness of the oxygen diffusion
layer near the metal surface.

• δ of the diffusion layer and can be calculated to be

0.65 mm for iron in NaCl solutions.

• when the crevice height is comparable to the thickness

of the oxygen diffusion layer, diffusion of oxygen into
the crevice is impeded

Cathodic polarization curves for open iron and iron in crevices • rate of oxygen reduction is decreased
in 0.06 M NaCl. The numbers in the figure refer to crevice
heights
crevice corrosion electrochemical cell
Propagation of Crevice Corrosion
• changes in the electrolyte composition within the
crevice

• crevice electrolyte become acidic

• contain concentrated amounts of cations discharged

from the alloy

• In chloride solutions, the internal electrolyte within the

crevice become concentrated in chloride ions

• sufficiently aggressive to break down passive film

• changes in the composition of the crevice electrolyte

occur because of narrow geometrical character,

• allows only restricted exchange between crevice and

bulk electrolytes

• Fe2+ ions formed within crevice on iron do not easily

diffuse out of the crevice due to the crevice geometry
Example - Chromium contained within a crevice of 0.5 cm2 area and 0.2 mm in height corrodes at the rate of 1 μA/cm2. What is
the pH within the crevice after 10 days if Cr corrodes as Cr3+, and Cr3+ ions hydrolyze to form Cr(OH)3? Assume that all Cr3+
ions produced by crevice corrosion remain within the crevice.

The amount of Cr3+ ions produced is given by

 crevice pH decreases with increasing Cr content in the
Fe-Cr alloy

Cr ion concentration in the crevice increases, reaches a

constant value

pH of crevice hydrolysis reactions determines local pH

Crevice pH of Fe−Cr binary alloys as a function of the

chromium content of the alloy. Data are also shown for two
Fe−Cr−Ni alloys
Area Effects in Crevice Corrosion

• rate of crevice corrosion increases with an increase in the area of open metal outside the crevice
• area of the external (open) metal increases, the total current for oxygen reduction also increases

Schematic Evans diagrams showing the effect of external area Effect of the area outside the crevice on the weight loss
on the rate of crevice corrosion of an Fe-17% Cr steel inside a crevice in natural
seawater.
 Can a parallel be drawn for area effect in propagation
stage of crevice corrosion with that of galvanic
corrosion ?

Schematic Evans diagrams showing the effect of increasing cathode area on the corrosion rate of a copper/iron couple when the
O2 reduction reaction is under diffusion control. The intersection of the anodic and cathodic polarization curves defines the
corrosion potential and the corrosion rate.
Protection Against Crevice Corrosion

1. Use of corrosion inhibitors, such as chromates, dichromates, nitrites, or phosphates

2. Cathodic protection (using anodes located outside the crevice)

3. Design considerations to minimize the existence of crevices

Continuous welds in (b) are preferable to intermittent welds in Discharge valves can be re-designed as in (b)
(a) because intermittent welds introduce additional crevices to prevent crevice corrosion under deposits