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Pitting and crevice corrosion 1
Pitting and crevice
corrosion
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A pit Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion general attack
A pit
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
general attack
deep pit
(small pits)
(anode)
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
An aluminum
A92519 specimen
exposed to a 3,5%
NaCl solution for
seven days. The
width of the
picture is
approximately 1
mm.
environments
intact
Corrosion mitigation
(cathode)
image source: Corrosion Doctors , www.corrosion-doctors.org
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Pitting Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion Pitting corrosion is
Pitting
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
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.
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
image source: Corrosion Doctors , www.corrosion-doctors.org
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Causes of pitting Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion •
Causes of pitting
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
• Localized chemical or mechanical
damage to the protective oxide film.
• Low dissolved oxygen concentrations
and high concentrations of chloride (as
in seawater)
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
• 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.
environments
Corrosion mitigation
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Passive metals pit Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion Pitting
Passive metals pit
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
Pitting corrosion on a stainless steel bar
exposed to an alkaline solution loaded
with chlorides.
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
image source:
Prof. Dr. H. Böhni, www.ibwk.baum.ethz.ch
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Morphology of pitting (continued) subsurface Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of
Morphology of pitting
(continued)
subsurface
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
pits
undercutting
pits
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
vertical grain
attack
environments
Corrosion mitigation
horizontal
grain attack
image source:
Corrosion Doctors , www.corrosion-doctors.org
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Morphology of pitting Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion narrow/deep
Morphology of pitting
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
narrow/deep
pits
elliptical pits
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
shallow pits
environments
Corrosion mitigation
mesa attack
image source:
Corrosion Doctors , www.corrosion-doctors.org
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- – O + 2H O + 4e 4OH on anode 2 2 - - O
-
O
+ 2H O + 4e
4OH
on anode
2
2
-
-
O
2
2
4OH
on cathode
+ 2H O + 4e
total cathodic =
Background: theory of
differential aeration
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
cathode
E
corr
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
couple
E
corr
anode
E
corr
environments
couple
Corrosion mitigation
I
corr
log I / A
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on anode and cathode
Fe Fe
2+
+ 2e
= total anodic
|
potential / V
+
Anode acidifies Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion … due
Anode acidifies
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
… due to depletion of oxygen anode acidifies:
soluble
Fe
2+
+ 2H O Fe(OH)
+ 2H
+
2
2
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
… leading to even more iron dissolution
environments
Corrosion mitigation
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- – O 2 + 2H 2 O + 4e 4OH on passivated cathode An active/passive
-
O
2
+ 2H
2
O + 4e
4OH
on passivated cathode
An active/passive
differential aeration cell
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
couple
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
E
corr
environments
couple
Corrosion mitigation
I
corr
log I / A
11
2+
+ 2e
Fe Fe
on acidified anode
|
potential / V
+
Fe Fe
2+
+ 2e
on passivated cathode
Cathode passivates Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion … due
Cathode passivates
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
… due to rapid oxygen reduction on the
cathode and a more alkaline solution :
-
O
+ 2H O + 4e
4OH
2
2
… it passivates
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
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Under deposit pitting of passive metals Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms
Under deposit pitting of
passive metals
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
O 2 + 2H 2 O + 4e - 4OH –
passive
stuff
film
passivity
galvanic corrosion
Fe Fe 2+ + 2e -
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
stainless steel
environments
Corrosion mitigation
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Under deposit acidification Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion …
Under deposit acidification
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
… due to the depletion of oxygen and due to
increasing concentrations of dissolved iron
under the deposit, the solution acidifies:
soluble
Fe
2+
+ 2H O
Fe(OH)
+
2H
+
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
2
2
environments
… leading to activation (active dissolution) of
iron under the deposit and rapid growth of a pit
Corrosion mitigation
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Under deposit pit growth
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
O 2 + 2H 2 O + 4e - 4OH –
passive
stuff
film
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
Fe Fe 2+ + 2e -
environments
Corrosion mitigation
pitting aggravated by a large cathode/anode ratio
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- – O around the pit 2 2 4OH + 2H O + 4e Pit: a
-
O
around the pit
2
2
4OH
+ 2H O + 4e
Pit:
a differential aeration cell
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
couple
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
E
corr
environments
couple
Corrosion mitigation
I
corr
log I / A
14
2+
+ 2e
Fe Fe
in the pit
|
potential / V
+
Fe Fe
2+
+ 2e
around the pit
Chloride induced pitting of passive metals Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms
Chloride induced pitting of
passive metals
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
FeOOH + Cl - FeOCl + OH –
passive
film
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
FeOOH
stainless steel
environments
Corrosion mitigation
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Chloride induced pit growth Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
Chloride induced pit
growth
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
O 2 + 2H 2 O + 4e - 4OH –
passive
film
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
Fe Fe 2+ + 2e -
environments
Corrosion mitigation
pitting aggravated by a large cathode/anode ratio
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Prevention of pitting
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
• decrease:
– chloride content
– acidity
– temperature
• increase:
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
– flow / mixing
– surface cleaning
• eliminate
– suspended solids
– dead legs / stagnant sections
environments
Corrosion mitigation
• add inhibitors
• material selection
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Chloride induced pitting of passive metals Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms
Chloride induced pitting of
passive metals
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
without Cl -
with Cl -
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
log (current density) / (A m -2 )
Corrosion mitigation
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|
potential / V
+
Crevice corrosion Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion Crevice corrosion
Crevice corrosion
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
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.
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
image source: Corrosion Doctors, www.corrosion-doctors.org
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Example of crevice corrosion Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
Example of crevice corrosion
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
Crevices corrosion of a S30400 stainless
steel washer after 30 days in 0.5 FeCl3 +
0.05 M NaCl solution
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
environments
Corrosion mitigation
image source: Corrosion Doctors, www.corrosion-doctors.org
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Crevice corrosion of
passive metals
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
O 2 + 2H 2 O + 4e - 4OH –
passive
film
Fe Fe 2+ + 2e -
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
stainless steel
environments
Corrosion mitigation
crevice corrosion aggravated by a
large cathode/anode ratio
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Another example of crevice corrosion Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of
Another example of crevice
corrosion
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 bolt used in seawater after 5 years
of exposure.
image source:
George Dinwiddie,
www.alberg30.org
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Crevice corrosion of passive metals Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of
Crevice corrosion of
passive metals
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
Corrosion rate
measurements
Various forms of
corrosion
… due to depletion of oxygen and due to
increasing concentrations of dissolved iron in
the crevice, the solution acidifies:
soluble
passivity
galvanic corrosion
pitting/crevice
corrosion
cracking
erosion corrosion
corrosion
Fe
2+
+ 2H O
Fe(OH)
+
2H
+
2
2
environments
… leading to activation (active dissolution) in
the crevice
Corrosion mitigation
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