1

1
Pitting and crevice
corrosion
2
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Pitting
Pitting corrosion is a localized form of
corrosion by which cavities or "holes" are
produced in the material. Pitting is
considered to be more dangerous than
uniform corrosion damage because it is
more difficult to detect, predict and
design against.
image source: Corrosion Doctors , www.corrosion-doctors.org
3
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
A pit
general attack
(small pits)
deep pit
(anode)
intact
(cathode)
An aluminum
A92519 specimen
exposed to a 3,5%
NaCl solution for
seven days. The
width of the
picture is
approximately 1
mm.
image source: Corrosion Doctors , www.corrosion-doctors.org
4
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Causes of pitting
Localized chemical or mechanical
damage to the protective oxide film.
Low dissolved oxygen concentrations
and high concentrations of chloride (as
in seawater)
Localized damage to, or poor
application of, a protective coating
The presence of non-uniformities in
the metal structure of the component,
e.g. inclusions.
2
5
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Passive metals pit
Pitting corrosion on a stainless steel bar
exposed to an alkaline solution loaded
with chlorides.
image source: Prof. Dr. H. Bhni, www.ibwk.baum.ethz.ch
6
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Morphology of pitting
narrow/deep
pits
elliptical pits
shallow pits
mesa attack
image source: Corrosion Doctors , www.corrosion-doctors.org
7
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Morphology of pitting
(continued)
subsurface
pits
undercutting
pits
vertical grain
attack
horizontal
grain attack
image source: Corrosion Doctors , www.corrosion-doctors.org 8
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Background: theory of
differential aeration
|
p
o
t
e
n
t
i
a
l

/

V




+
log I / A
F
e

F
e

2+ +
2
e

o
n
a
n
o
d
e
a
n
d
c
a
th
o
d
e
couple
corr
E
=
to
ta
l a
n
o
d
ic
to
ta
l c
a
th
o
d
ic
=
couple
corr
I
O
2
+

2
H
2
O

+

4
e

-

4
O
H

o
n

a
n
o
d
e
O
2 +
2
H
2O
+
4
e

-

4
O
H

-
o
n
c
a
th
o
d
e
anode
corr
E
cathode
corr
E
3
9
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Anode acidifies
due to depletion of oxygen anode acidifies:
Fe
2+
+ 2H
2
O Fe(OH)
2
+ 2H
+
leading to even more iron dissolution
soluble
10
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Cathode passivates
due to rapid oxygen reduction on the
cathode and a more alkaline solution :
O
2
+ 2H
2
O + 4e
-
4OH

it passivates
11
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
An active/passive
differential aeration cell
|
p
o
t
e
n
t
i
a
l

/

V




+
log I / A
F
e

F
e

2+ +
2
e

o
n
a
c
id
ifie
d
a
n
o
d
e
couple
corr
E
couple
corr
I
O
2 +
2
H
2O
+
4
e

-

4
O
H

o
n
p
a
s
s
iva
te
d
c
a
th
o
d
e
F
e

F
e

2
+
+

2
e

o
n

p
a
s
s
i
v
a
t
e
d

c
a
t
h
o
d
e
12
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Under deposit pitting of
passive metals
stainless steel
passive
film
stuff
O
2
+ 2H
2
O + 4e
-
4OH

Fe Fe
2+
+ 2e
-
4
13
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Under deposit acidification
due to the depletion of oxygen and due to
increasing concentrations of dissolved iron
under the deposit, the solution acidifies:
Fe
2+
+ 2H
2
O Fe(OH)
2
+ 2H
+
leading to activation (active dissolution) of
iron under the deposit and rapid growth of a pit
soluble
14
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Pit:
a differential aeration cell
|
p
o
t
e
n
t
i
a
l

/

V




+
log I / A
F
e

F
e

2+ +
2
e

in
th
e
p
it
couple
corr
E
couple
corr
I
O
2 +
2
H
2O
+
4
e

-

4
O
H

a
ro
u
n
d
th
e
p
it
F
e

F
e

2
+
+

2
e

a
r
o
u
n
d

t
h
e

p
i
t
15
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Under deposit pit growth
passive
film
stuff
O
2
+ 2H
2
O + 4e
-
4OH

Fe Fe
2+
+ 2e
-
pitting aggravated by a large cathode/anode ratio
16
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
stainless steel
Chloride induced pitting of
passive metals
passive
film
FeOOH
FeOOH + Cl
-
FeOCl + OH

5
17
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Chloride induced pit
growth
passive
film
O
2
+ 2H
2
O + 4e
-
4OH

Fe Fe
2+
+ 2e
-
pitting aggravated by a large cathode/anode ratio
18
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Chloride induced pitting of
passive metals
|
p
o
t
e
n
t
i
a
l

/

V




+
log (current density) / (A m
-2
)
without Cl
-
with Cl
-
19
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Prevention of pitting
decrease:
chloride content
acidity
temperature
increase:
flow / mixing
surface cleaning
eliminate
suspended solids
dead legs / stagnant sections
add inhibitors
material selection
20
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Crevice corrosion
Crevice corrosion is a localized form of
corrosion usually associated with
stagnant solutions in shielded areas such
as those formed under gaskets, washers,
insulation material, fastener heads,
surface deposits, disbonded coatings,
threads, lap joints, clamps, etc.
image source: Corrosion Doctors, www.corrosion-doctors.org
6
21
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Example of crevice corrosion
Crevices corrosion of a S30400 stainless
steel washer after 30 days in 0.5 FeCl3 +
0.05 M NaCl solution
image source: Corrosion Doctors, www.corrosion-doctors.org 22
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Another example of crevice
corrosion
Stainless steel bolt used in seawater after 5 years
of exposure.
image source: George Dinwiddie,
www.alberg30.org
23
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Crevice corrosion of
passive metals
passive
film
Fe Fe
2+
+ 2e
-
stainless steel
O
2
+ 2H
2
O + 4e
-
4OH

crevice corrosion aggravated by a

large cathode/anode ratio
24
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
Crevice corrosion of
passive metals
due to depletion of oxygen and due to
increasing concentrations of dissolved iron in
the crevice, the solution acidifies:
Fe
2+
+ 2H
2
O Fe(OH)
2
+ 2H
+
leading to activation (active dissolution) in
the crevice
soluble