Pitting

Pitting corrosion is a localized form of

Introduction
Electrochemical corrosion by which cavities or "holes" are
produced in the material. Pitting is
Pitting and crevice
thermodynamics
Electrochemical
kinetics considered to be more dangerous than
Corrosion rate uniform corrosion damage because it is
corrosion measurements
Various forms of more difficult to detect, predict and
corrosion
 passivity
design against.
 galvanic corrosion
 pitting/crevice
corrosion
 cracking
 erosion corrosion
 corrosion
environments
Corrosion mitigation

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A pit Causes of pitting

Introduction
Electrochemical
general attack deep pit Introduction
Electrochemical
• Localized chemical or mechanical
thermodynamics (small pits) (anode) thermodynamics damage to the protective oxide film.
Electrochemical Electrochemical
kinetics
An aluminum
kinetics • Low dissolved oxygen concentrations
A92519 specimen
Corrosion rate
exposed to a 3,5%
Corrosion rate and high concentrations of chloride (as
measurements measurements
Various forms of NaCl solution for Various forms of in seawater)
corrosion seven days. The corrosion
• Localized damage to, or poor
 passivity  passivity
width of the
 galvanic corrosion
 pitting/crevice picture is
 galvanic corrosion
 pitting/crevice
application of, a protective coating
corrosion
 cracking
approximately 1 corrosion
 cracking
• The presence of non-uniformities in
 erosion corrosion mm.  erosion corrosion the metal structure of the component,
 corrosion  corrosion
environments environments e.g. inclusions.
Corrosion mitigation intact Corrosion mitigation
(cathode)
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3 4

1
 Passive metals pit Morphology of pitting
Introduction
Electrochemical
Pitting corrosion on a stainless steel bar Introduction
Electrochemical narrow/deep
thermodynamics exposed to an alkaline solution loaded thermodynamics
pits
Electrochemical Electrochemical
kinetics with chlorides. kinetics
Corrosion rate Corrosion rate
measurements measurements
Various forms of Various forms of elliptical pits
corrosion corrosion
 passivity  passivity
 galvanic corrosion  galvanic corrosion
 pitting/crevice  pitting/crevice
corrosion corrosion
 cracking
 erosion corrosion
 cracking
 erosion corrosion
shallow pits
 corrosion  corrosion
environments environments
Corrosion mitigation Corrosion mitigation
mesa attack
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Morphology of pitting Background: theory of

(continued) differential aeration
Introduction
subsurface Introduction O2 +
Electrochemical pits Electrochemical 2H
2O
thermodynamics thermodynamics
+ 4e -
Æ4

O2 + 2H2O + 4e - Æ 4OH – on anode

+
Electrochemical Electrochemical OH -
kinetics kinetics on c
tota atho
Corrosion rate Corrosion rate l ca de
undercutting thod
measurements measurements ic =
Various forms of pits Various forms of
cathode
E corr

potential / V
–
corrosion corrosion
2+ +
2e e
 passivity  passivity d
 galvanic corrosion  galvanic corrosion E couple
Æ Fe d catho
n
corr Fe node a ic
 pitting/crevice
vertical grain  pitting/crevice
on a nod
tal a
corrosion corrosion
attack = to
anode
 cracking  cracking E corr
 erosion corrosion  erosion corrosion
 corrosion  corrosion
environments environments
couple
Corrosion mitigation
horizontal Corrosion mitigation I corr
grain attack |
log I / A
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2
 Anode acidifies Cathode passivates
Introduction Introduction
Electrochemical Electrochemical … due to rapid oxygen reduction on the
thermodynamics thermodynamics
Electrochemical … due to depletion of oxygen anode acidifies: Electrochemical
cathode and a more alkaline solution :
kinetics kinetics
soluble
O2 + 2H2O + 4e - Æ 4OH –
Corrosion rate Corrosion rate
measurements measurements
Various forms of
corrosion
Fe2+ + 2H2O Æ Fe(OH)2 + 2H+ Various forms of
corrosion
 passivity  passivity … it passivates
 galvanic corrosion  galvanic corrosion
 pitting/crevice … leading to even more iron dissolution  pitting/crevice
corrosion corrosion
 cracking  cracking
 erosion corrosion  erosion corrosion
 corrosion  corrosion
environments environments
Corrosion mitigation Corrosion mitigation

9 10

An active/passive Under deposit pitting of

differential aeration cell passive metals
Introduction Introduction
O2 +
on passivated cathode
+ 2e –

Electrochemical 2H Electrochemical
2O
thermodynamics + 4e thermodynamics
O2 + 2H2O + 4e - Æ 4OH –
+

on p -
Electrochemical assiv Æ4 Electrochemical
OH
2+

kinetics a ted – kinetics

cath
Fe Æ Fe

Corrosion rate ode Corrosion rate

measurements measurements
–
Various forms of
+ 2e
Various forms of
passive stuff
potential / V

corrosion 2+ corrosion
e
 passivity
E couple
corr Fe ÆF de
 passivity film
ano
Fe Æ Fe 2+ + 2e -
 galvanic corrosion  galvanic corrosion
 pitting/crevice cid ified  pitting/crevice
corrosion on a corrosion
 cracking
 erosion corrosion
 cracking
 erosion corrosion
stainless steel
 corrosion  corrosion
environments environments
couple
Corrosion mitigation I corr Corrosion mitigation
|

log I / A
11 12

3
 Pit:
Under deposit acidification
a differential aeration cell
Introduction Introduction
O2 +

–
Electrochemical Electrochemical 2H
… due to the depletion of oxygen and due to

Fe Æ Fe 2+ + 2e
thermodynamics thermodynamics 2O + 4e

around the pit

+
Electrochemical increasing concentrations of dissolved iron Electrochemical
-
Æ4
OH –
kinetics
under the deposit, the solution acidifies: kinetics
arou
nd t
Corrosion rate Corrosion rate
h e pit
measurements measurements
Various forms of soluble Various forms of

potential / V
–
corrosion corrosion
2e
 passivity Fe2+ + 2H2O Æ Fe(OH)2 + 2H+  passivity couple
E corr 2+ +
Fe pit
 galvanic corrosion  galvanic corrosion Æ
Fe in the
 pitting/crevice  pitting/crevice
corrosion corrosion
 cracking  cracking
 erosion corrosion  erosion corrosion
 corrosion
environments
… leading to activation (active dissolution) of  corrosion
environments
Corrosion mitigation iron under the deposit and rapid growth of a pit Corrosion mitigation couple
I corr

|
log I / A
13 14

Chloride induced pitting of

Under deposit pit growth
passive metals
Introduction Introduction
Electrochemical Electrochemical
- –
thermodynamics
Electrochemical
O2 + 2H2O + 4e Æ 4OH thermodynamics
Electrochemical
kinetics kinetics FeOOH + Cl - Æ FeOCl + OH –
Corrosion rate Corrosion rate
measurements measurements
Various forms of
corrosion
passive stuff Various forms of
corrosion
passive
 passivity film  passivity film
 galvanic corrosion
 pitting/crevice
 galvanic corrosion
 pitting/crevice FeOOH
corrosion corrosion
 cracking
 erosion corrosion
 cracking
 erosion corrosion
stainless steel
 corrosion
environments
Fe Æ Fe 2+ + 2e -  corrosion
environments
Corrosion mitigation Corrosion mitigation

pitting aggravated by a large cathode/anode ratio

15 16

4
 Chloride induced pit Chloride induced pitting of
growth passive metals
Introduction Introduction
Electrochemical Electrochemical

+
without Cl -
thermodynamics
Electrochemical
O2 + 2H2O + 4e - Æ 4OH – thermodynamics
Electrochemical
kinetics kinetics
Corrosion rate Corrosion rate
with Cl -

potential / V
measurements measurements
Various forms of
corrosion
passive Various forms of
corrosion
 passivity film  passivity
 galvanic corrosion  galvanic corrosion
 pitting/crevice  pitting/crevice
corrosion corrosion
 cracking  cracking
 erosion corrosion  erosion corrosion
 corrosion
Fe Æ Fe 2+ + 2e -  corrosion

|
environments environments
Corrosion mitigation Corrosion mitigation log (current density) / (A m-2)

pitting aggravated by a large cathode/anode ratio

17 18

Prevention of pitting Crevice corrosion

Crevice corrosion is a localized form of
Introduction • decrease: Introduction
corrosion usually associated with
Electrochemical Electrochemical
thermodynamics – chloride content thermodynamics stagnant solutions in shielded areas such
Electrochemical – acidity Electrochemical
as those formed under gaskets, washers,
kinetics kinetics
– temperature
Corrosion rate Corrosion rate insulation material, fastener heads,
measurements • increase: measurements
surface deposits, disbonded coatings,
Various forms of Various forms of
corrosion – flow / mixing corrosion threads, lap joints, clamps, etc.
 passivity – surface cleaning  passivity
 galvanic corrosion  galvanic corrosion
 pitting/crevice • eliminate  pitting/crevice
corrosion corrosion
 cracking – suspended solids  cracking
 erosion corrosion
 corrosion
– dead legs / stagnant sections  erosion corrosion
 corrosion
environments • add inhibitors environments
Corrosion mitigation Corrosion mitigation
• material selection
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5
 Another example of crevice
Example of crevice corrosion
corrosion
Introduction Introduction
Electrochemical Crevices corrosion of a S30400 stainless Electrochemical
thermodynamics
Electrochemical
steel washer after 30 days in 0.5 FeCl3 + thermodynamics
Electrochemical
kinetics 0.05 M NaCl solution kinetics
Corrosion rate Corrosion rate
measurements measurements
Various forms of Various forms of
corrosion corrosion
 passivity  passivity
 galvanic corrosion  galvanic corrosion
 pitting/crevice  pitting/crevice
corrosion corrosion
 cracking  cracking
 erosion corrosion  erosion corrosion
 corrosion  corrosion
environments environments Stainless steel bolt used in seawater after 5 years
Corrosion mitigation Corrosion mitigation
of exposure.
image source: George Dinwiddie,
www.alberg30.org
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Crevice corrosion of Crevice corrosion of

passive metals passive metals
Introduction Introduction
Electrochemical O2 + 2H2O + 4e - Æ 4OH – Electrochemical
… due to depletion of oxygen and due to
thermodynamics thermodynamics
Electrochemical Electrochemical increasing concentrations of dissolved iron in
kinetics kinetics
the crevice, the solution acidifies:
Corrosion rate Corrosion rate
measurements passive measurements
soluble
Various forms of
corrosion
film Various forms of
corrosion
-
 passivity
 galvanic corrosion
Fe Æ Fe 2+ + 2e  passivity
 galvanic corrosion
Fe2+ + 2H2O Æ Fe(OH)2 + 2H+
 pitting/crevice  pitting/crevice
corrosion corrosion
 cracking  cracking
 erosion corrosion  erosion corrosion
 corrosion
environments stainless steel
 corrosion
environments
… leading to activation (active dissolution) in
Corrosion mitigation Corrosion mitigation the crevice
crevice corrosion aggravated by a
large cathode/anode ratio 23 24