Pitting

Pitting and 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

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.

Corrosion mitigation

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A pit
Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

Causes of pitting
Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

general attack (small pits)

deep pit (anode)

An aluminum A92519 specimen exposed to a 3,5% NaCl solution for seven days. The width of the picture is approximately 1 mm.

Corrosion mitigation

intact (cathode)
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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.

Corrosion mitigation

Passive metals pit

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

Morphology of pitting
Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

Pitting corrosion on a stainless steel bar exposed to an alkaline solution loaded with chlorides.

narrow/deep pits

elliptical pits

shallow pits

Corrosion mitigation

Corrosion mitigation

mesa attack
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Morphology of pitting
(continued)
Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

subsurface pits

Background: theory of differential aeration

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

O2 + 2H 2O

potential / V

undercutting pits vertical grain attack horizontal grain attack

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+ 4e

cathode E corr

4 OH on c atho tota de l ca thod ic =

O2 + 2H2O + 4e - 4OH on anode

couple corr

anode E corr

2e e 2+ + d Fe d catho n Fe node a ic nod on a tal a = to

couple I corr

Corrosion mitigation

Corrosion mitigation

log I / A
8

Anode acidifies
Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

Cathode passivates
Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

due to depletion of oxygen anode acidifies:

soluble

due to rapid oxygen reduction on the cathode and a more alkaline solution :

Fe2+ + 2H2O Fe(OH)2 + 2H+

leading to even more iron dissolution

O2 + 2H2O + 4e - 4OH
it passivates

Corrosion mitigation

Corrosion mitigation

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An active/passive differential aeration cell

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

Under deposit pitting of passive metals

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion

on passivated cathode

+ 2e

2+

on p

O2 + 2H 2O
assiv a ted

+ 4e

Fe Fe

cath ode

4 OH

O2 + 2H2O + 4e - 4OH
stuff

potential / V

couple corr

Fe

e F
cid on a

2+

+ 2e
ano

ified

de

passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

passive film

Fe Fe 2+ + 2e stainless steel

Corrosion mitigation

couple I corr

Corrosion mitigation

log I / A
11 12

Under deposit acidification

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

Pit: a differential aeration cell

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

Fe Fe 2+ + 2e

around the pit

due to the depletion of oxygen and due to increasing concentrations of dissolved iron under the deposit, the solution acidifies:
soluble

O2 + 2H 2O

+ 4e

4 OH

arou

nd t h

e pit

potential / V

Fe2+ + 2H2O Fe(OH)2 + 2H+

leading to activation (active dissolution) of iron under the deposit and rapid growth of a pit
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couple E corr

2e 2+ + Fe pit Fe in the

Corrosion mitigation

Corrosion mitigation

couple I corr

log I / A
14

Under deposit pit growth

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion

Chloride induced pitting of passive metals

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

O2 + 2H2O + 4e 4OH
stuff

FeOOH + Cl - FeOCl + OH
passive film

passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

passive film

FeOOH
stainless steel

Fe Fe 2+ + 2e pitting aggravated by a large cathode/anode ratio

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Corrosion mitigation

Corrosion mitigation

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Chloride induced pit growth

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion

Chloride induced pitting of passive metals

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

O2 + 2H2O + 4e - 4OH

without Cl -

passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

passive film

Fe Fe 2+ + 2e pitting aggravated by a large cathode/anode ratio

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potential / V

with Cl -

Corrosion mitigation

Corrosion mitigation

log (current density) / (A m-2)

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Prevention of pitting
Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

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

decrease:
chloride content acidity temperature

increase:
flow / mixing surface cleaning

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.

eliminate
suspended solids dead legs / stagnant sections

Corrosion mitigation

add inhibitors material selection

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Corrosion mitigation

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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

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

Crevices corrosion of a S30400 stainless steel washer after 30 days in 0.5 FeCl3 + 0.05 M NaCl solution

Corrosion mitigation

Corrosion mitigation

Stainless steel bolt used in seawater after 5 years of exposure.

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Crevice corrosion of passive metals

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion

Crevice corrosion of passive metals

Introduction Electrochemical thermodynamics Electrochemical kinetics Corrosion rate measurements Various forms of corrosion
passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

O2 + 2H2O + 4e - 4OH

due to depletion of oxygen and due to increasing concentrations of dissolved iron in the crevice, the solution acidifies:
soluble

passive film

passivity galvanic corrosion pitting/crevice corrosion cracking erosion corrosion corrosion environments

Fe Fe

2+

+ 2e

Fe2+

+ 2H2O Fe(OH)2 + 2H+

stainless steel crevice corrosion aggravated by a large cathode/anode ratio

Corrosion mitigation

Corrosion mitigation

leading to activation (active dissolution) in the crevice

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