Shell Global Solutions

Corrosion
M285 Diagnosis of Engineering Failures Course
Petronas, KL, May 2009

David Knowles
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Shell Global Solutions International B.V., 2009. All rights reserved.

CORROSION
CORROSION PRINCIPLES
Electrochemical mechanism
Effect of environment/variables

FORMS OF CORROSION
9 Main types
Examples
DIAGNOSIS OF CORROSION
Procedure
Identification

CORROSION : ELECTROCHEMICAL MECHANISM

OXIDATION
PROCESS
(LOSS e- )

ANODE

IONIC
MIGRATION

REDUCTION
PROCESS
(GAIN e- )

CATHODE

ELECTRON
MIGRATION

ANODIC REACTION :

M - 2e- = M2+ (in solution)

CATHODIC REACTION :
2H+ + 2e- = H2

(acids)
O2 + 2H2O + 4e- = 4OH- (waters)
Me3+ + e- = Me2+
(ion reduction)

CORROSION : DISSIMILAR METALS

GALVANIC COUPLES
A
C v

Noble metal is cathode

Base metal is anode
Critical factor is the relative
size of the anodic/cathodic
areas which determines the
current density

GALVANIC SERIES
Noble: Titanium alloys (passive)
Nickel alloys
(passive)
Stainless steel (passive)
Silver
Copper alloys
Lead and tin alloys
Nickel alloys
(active)
Stainless steel (active)
Cast irons
Structural steel
Zinc alloys
Aluminium alloys
Base: Magnesium alloys

CORROSION : SINGLE METALS OR ALLOYS

METALLIC FEATURES
Active sites become anodic
4

1 = Structural differences between

grains (via stress, stacking or
composition)
2 = Grain boundaries
3 = Inclusions
4 = Macro/micro discontinuities in
surface films

ENVIRONMENT FEATURES
Variations in the concentration
of reducible species promote the
cathodic reaction (reduction) at
areas of high concentration, and
the anodic reaction (oxidation corrosion) at areas of low
concentration.
nb. Crevice corrosion
(Oxygen concentration cell)

CORROSION : SINGLE METALS OR ALLOYS

CORROSION : SINGLE METALS OR ALLOYS

CORROSION : INFLUENCE OF THE ENVIRONMENT

CONDUCTIVITY OF THE
SOLUTION
An electrolyte is required to
conduct electrical current
between the anode and
cathode.
Salt water.

AGGRESSIVE IONS
Breakdown protective films
or prevent their formation.
Chlorides.

DISSOLVED GASES
1. Oxygen
Provides a reducible species
for the cathodic reaction.
O + 2H O + 4e- = 4OH2

2. Sulphur Trioxide (Condensate)

Carbon Dioxide (Sweet)
Hydrogen Sulphide (Sour)
Acidify water for the cathodic
reduction of hydrogen.
2H+ + 2e- = H
2

CORROSION : EFFECT OF PHYSICAL VARIABLES

TEMPERATURE

VELOCITY

Rule-of-thumb guide
indicates that the corrosion
rate doubles for every 10C
rise in temperature.

Stagnant or low flow rates

usually give low corrosion
rates but pitting is more
likely.

Decreases gas solubility in

open systems.

Corrosion rates generally

increase with velocity.

High velocities and/or

suspended solids and gas
bubbles can lead to:

PRESSURE
Increases gas solubility.

- Erosion / corrosion
- Impingement attack
- Cavitation

CORROSION : EFFECT OF pH
pH is a measure of the degree of acidity or
alkalinity of an aqueous solution
pH = - log10 [H+]
where [H+] = Hydrogen ion concentration
NEUTRAL
0
RATE

ACIDITY

1 = NOBLE METALS
2 = ACID-SOLUBLE METALS
2

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ALKALINITY
3

3 = METALS WITH AMPHOTERIC OXIDES

4 = STEEL
4

pH

10

CORROSION : MAIN FORMS

GENERAL CORROSION
GALVANIC CORROSION
PITTING CORROSION
CREVICE CORROSION
SELECTIVE CORROSION
CONDENSATE CORROSION
MICROBIAL CORROSION
EROSION CORROSION
STRESS CORROSION
HYDROGEN DAMAGE

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CORROSION : MAIN FORMS

GENERAL CORROSION
Uniform thinning.
Can predict rates through
simple immersion tests.
Maintainable if the correct
control measures are
applied:
- Resistant materials
- Coatings
- Inhibitors
- Cathodic Protection
Examples:
- Atmospheric corrosion
- Acid corrosion

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General Corrosion

13

General Corrosion

14

General Corrosion

15

CORROSION : MAIN FORMS

GENERAL CORROSION
Uniform thinning.
Can predict rates through
simple immersion tests.
Maintainable if the correct
control measures are
applied:
- Resistant materials
- Coatings
- Inhibitors
- Cathodic Protection
Examples:
- Atmospheric corrosion
- Acid corrosion

GALVANIC CORROSION
Requires materials with
different corrosion potentials, a
common electrolyte and a
common electrical path.
Less resistant metal becomes
the anode (corrodes).
Dependent on potential
difference between the metals,
their relative areas and the
environment.
Examples:
- Riveted/bolted plates
- Metallic coatings
- (Stray current corrosion)

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Galvanic Corrosion

17

Galvanic Corrosion

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CORROSION : MAIN FORMS

GALVANIC SERIES IN SEAWATER

METAL
Platinum
Gold
Graphite
Titanium
Incoloy 825
S/S Type 316/317
Monel 400
S/S Type 304/321
Silver
Nickel

POTENTIAL
+ 0.7
+ 0.6/0.7
+ 0.2
+ 0.1
0.0
0.0/- 0.1
0.0/- 0.1
0.0/- 0.1
- 0.1
- 0.1/- 0.2

METAL
Cupro-Nickel
S/S Types 400
Bronzes
Copper
Brasses
Cast Iron
Mild Steel
Aluminium
Zinc
Magnesium

POTENTIAL
-

0.2
0.2/- 0.3
0.2/- 0.3
0.3
0.4
0.6
0.6
0.9
1.0
1.6

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CORROSION : MAIN FORMS

PITTING CORROSION
Localised attack where
electrochemical driving force
is concentrated in specific
areas.
Process is autocatalytic.
Perforation of components
can occur in a short time.
Environments:
Chlorides:
- Breakdown passive films
Concentration cells:
- Differential aeration
- Crevices
- Porous corrosion products
- Scales & sludges (SRBs)

CREVICE CORROSION
Crevices promote the
formation of concentration
cells.
Particularly serious in
oxygenated systems.
Limited supply of oxygen in
the crevice makes it anodic
to the surroundings.
Examples:
- Narrow openings
- Cracks
- Metal joints
- Flanges
- Nuts, bolts and washers
- Deposits and fouling

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Crevice Corrosion

21

Crevice Corrosion

22

Crevice Corrosion

23

Crevice Corrosion

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CORROSION : MAIN FORMS

PITTING/CREVICE CORROSION RESISTANCE
(in quiet seawater)
Stainless steels (300/400 series)
Steels with scale
Nickel
Aluminium

Poor
1000 m/y

Low carbon alloy steels

Stainless steel (Type 316)
Ni-Cu alloy (Monel)
Anodised aluminium

Fair
600 m/y

Cast irons
Copper & copper alloys
High-nickel stainless steels
Ni-Cr-Fe alloys (Inconel)

Good
200 m/y

Ni-Cr-Mo alloys (Hastelloy)

Titanium

Excellent
0 m/y

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CORROSION : MAIN FORMS

SELECTIVE CORROSION
Dealloying
Removal of specific elements
from an alloy by corrosion.
Favoured by stagnant
conditions.

Examples:
- Dezincification
- Dealuminification
- Denickelification
- Graphitisation

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Selective Corrosion: Dezincification

27

Selective Corrosion: Denickelification

28

CORROSION : MAIN FORMS

SELECTIVE CORROSION

SELECTIVE CORROSION

Dealloying

Intergranular Corrosion

Removal of specific elements

from an alloy by corrosion.
Favoured by stagnant
conditions.

Compositional differences
(enrichment/depletion of
alloying elements, impurities)
can make grain boundaries
more reactive than the matrix.
Grain boundaries and
surrounding areas become
anodic and preferentially
corrode.
Net effect is a reduction in
material strength.

Examples:
- Dezincification
- Dealuminification
- Denickelification
- Graphitisation

Examples:
- Weld decay (Sensitisation)

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CORROSION : MAIN FORMS

CONDENSATE CORROSION
Strong mineral acids (nitric,
sulphuric) can condense from
combustion gases causing
significant corrosion of
associated equipment.
Condensation takes place up
to the dewpoint temperature.
The higher the temperature,
the more concentrated the
acid.
Problem areas:
- Diesel engines (valves,
injectors, liners, bearings).
- Industrial boilers (ducting,
economisers, air heaters).

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Condensate Corrosion

31

Condensate Corrosion

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Condensate Corrosion

33

Condensate Corrosion

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Condensate Corrosion

35

Condensate Corrosion

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CORROSION : MAIN FORMS

CONDENSATE CORROSION
Strong mineral acids (nitric,
sulphuric) can condense from
combustion gases causing
significant corrosion of
associated equipment.
Condensation takes place up
to the dewpoint temperature.
The higher the temperature,
the more concentrated the
acid.
Problem areas:
- Diesel engines (valves,
injectors, liners, bearings).
- Industrial boilers (ducting,
economisers, air heaters).

MICROBIAL CORROSION
Sulphate reducing bacteria
remove hydrogen from
cathodic areas to reduce
sulphates to sulphides; this
stimulates the anodic reaction
(i.e. corrosion).
Thiobacilli oxidise sulphur
and hydrogen sulphide and
thereby create acid
conditions.
The two species are
extremely active together.
Example:
- Tank bottom corrosion

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Microbial Corrosion

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CORROSION : MAIN FORMS

EROSION CORROSION
With increasing flow
velocity, pitting decreases
and general corrosion
predominates.
Film adherence becomes
important.
Stainless steels and highnickel alloys have tough
films.
Turbulence in the flow can
cause specific erosioncorrosion problems:
- Impingement attack
- Cavitation

Impingement attack:
- Breakdown of protective
film by turbulence, particles
or gas bubbles.
- Horse-shoe shaped pits.

Cavitation:
- Collapse of vapour-filled
cavities caused by pressure
changes or vibrations.
- Hemispherical pits, sharply
outlined and free from
corrosion product (sponge).
Examples:
- Pump impellers
- Flow lines (valves, elbows)
- Heat exchanger tubes

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Erosion Corrosion: Impingement Attack

40

Erosion Corrosion: Impingement Attack

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Erosion Corrosion: Cavitation

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Erosion Corrosion: Impingement Attack

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CORROSION : MAIN FORMS

STRESS CORROSION
Corrosion Fatigue
Cyclic stress.
Fatigue is accelerated by
corrosion (20% life reduction
with steel).
Failure can occur at a stress
level well below the fatigue
limit of the material.
Multiple crack initiation where
one predominates (others
appear blunt-nosed).
Generally transgranular crack
propagation (intergranular at
high stresses).

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Corrosion Fatigue

45

Corrosion Fatigue

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CORROSION : MAIN FORMS

STRESS CORROSION

STRESS CORROSION

Corrosion Fatigue

Stress Corrosion Cracking

Cyclic stress.
Fatigue is accelerated by
corrosion (20% life reduction
with steel).
Failure can occur at a stress
level well below the fatigue
limit of the material.
Multiple crack initiation where
one predominates (others
appear blunt-nosed).
Generally transgranular crack
propagation (intergranular at
high stresses).

Static tensile stress (applied,

residual, thermal, etc.).
Stress has to be above a
threshold value for different
alloy/corrosive environment
combinations (can be as low
as 10% yield stress).
Cracking is branched and
perpendicular to the applied
stress (brittle in appearance).
Generally intergranular crack
propagation (transgranular
cracking also occurs).

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CORROSION : MAIN FORMS

STRESS CORROSION CRACKING

Examples:
Season cracking of brass cartridges.
Caustic cracking of steel boilers.

Materials & Environments:

Carbon steel

High strength steel

Stainless steel
(Austenitic)
Brass

Hot nitrates
Caustic solutions
Carbonate/bicarbonate
Seawater
H2S
Aqueous electrolytes (with H2S)
Acidic chlorides
Hot chlorides
Seawater
H2S
Ammonia solutions

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CORROSION : DIAGNOSIS
1. Check history and environment
2. Corrosion products - colour
- analyse
3. Appearance and location of the attack:
General
- Acid/alkali attack
Localised - Galvanic
- Turbulence
- Differential aeration
Pitting
- Cavitation (hemispherical)
- Impingement (elongated)
- SRBs (smell)
- Chlorides
Cracking - Corrosion fatigue (blunt-nosed/transgranular)
- Stress corrosion (branched/intergranular)
Selective - De-alloying
- Intergranular attack

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