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Shell Global Solutions Corrosion M285 Diagnosis of Engineering Failures Course Petronas, KL, May 2009 David

Shell Global Solutions

Corrosion
Corrosion

M285 Diagnosis of Engineering Failures Course

Petronas, KL, May 2009

David Knowles

Neither the whole nor any part of this document may be reproduced or distributed in any form or by any means (electronic, mechanical, reprographic, recording or otherwise) without the prior written consent of the copyright owner.

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

CORROSION
CORROSION

CORROSION PRINCIPLES

Electrochemical mechanism

Effect of environment/variables

FORMS OF CORROSION

9 Main types

Examples

DIAGNOSIS OF CORROSION

Procedure

Identification

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

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CORROSION : ELECTROCHEMICAL MECHANISM IONIC OXIDATION PROCESS (LOSS e - ) MIGRATION REDUCTION PROCESS (GAIN
CORROSION : ELECTROCHEMICAL MECHANISM
IONIC
OXIDATION
PROCESS
(LOSS e - )
MIGRATION
REDUCTION
PROCESS
(GAIN e - )
ANODE
CATHODE
ELECTRON
MIGRATION
ANODIC REACTION :
M 2+
M -
2e -
=
(in solution)
CATHODIC REACTION : 2H + + = (acids) H 2 + 2e - 2H 2
CATHODIC REACTION :
2H +
+
=
(acids)
H 2
+
2e -
2H 2 O +
4e -
= 4OH -
(waters)
O 2
Me 3+ + e -
= Me 2+
(ion reduction)

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CORROSION : DISSIMILAR METALS GALVANIC COUPLES GALVANIC SERIES C v A Noble: Titanium alloys Nickel
CORROSION : DISSIMILAR METALS
GALVANIC COUPLES
GALVANIC SERIES
C
v A
Noble:
Titanium alloys
Nickel alloys
(passive)
(passive)
Stainless steel
(passive)
Silver
Copper alloys
Lead and tin alloys
Nickel alloys
(active)
Stainless steel
(active)
• Noble metal is cathode
Cast irons
• Base metal is anode
• Critical factor is the relative
size of the anodic/cathodic
Structural steel
Zinc alloys
Aluminium alloys
areas which determines the
Base:
Magnesium alloys
current density
Structural steel Zinc alloys Aluminium alloys areas which determines the Base: Magnesium alloys current density 4

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CORROSION : SINGLE METALS OR ALLOYS METALLIC FEATURES ENVIRONMENT FEATURES Active sites become anodic 4
CORROSION : SINGLE METALS OR ALLOYS
METALLIC FEATURES
ENVIRONMENT FEATURES
Active sites become anodic
4
4
1
3
2
Variations in the concentration
of reducible species promote the
cathodic reaction (reduction) at
areas of high concentration, and
the anodic reaction (oxidation -
1
= Structural differences between
corrosion) at areas of low
concentration.
grains (via stress, stacking or
composition)
nb. Crevice corrosion
2
= Grain boundaries
(Oxygen concentration cell)
3
= Inclusions
4
= Macro/micro discontinuities in
surface films
2 = Grain boundaries (Oxygen concentration cell) 3 = Inclusions 4 = Macro/micro discontinuities in surface

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CORROSION : SINGLE METALS OR ALLOYS
CORROSION : SINGLE METALS OR ALLOYS

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CORROSION : SINGLE METALS OR ALLOYS
CORROSION : SINGLE METALS OR ALLOYS

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CORROSION : INFLUENCE OF THE ENVIRONMENT CONDUCTIVITY OF THE DISSOLVED GASES SOLUTION 1. Oxygen •
CORROSION : INFLUENCE OF THE ENVIRONMENT
CONDUCTIVITY OF THE
DISSOLVED GASES
SOLUTION
1. Oxygen
• An electrolyte is required to
conduct electrical current
between the anode and
• Provides a reducible species
for the cathodic reaction.
cathode.
O 2 + 2H 2 O + 4e - = 4OH -
• Salt water.
2. Sulphur Trioxide (Condensate)
Carbon Dioxide (Sweet)
AGGRESSIVE IONS
Hydrogen Sulphide (Sour)
• Breakdown protective films
or prevent their formation.
• Acidify water for the cathodic
reduction of hydrogen.
• Chlorides.
2H + + 2e - = H 2
prevent their formation. • Acidify water for the cathodic reduction of hydrogen. • Chlorides. 2H +

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CORROSION : EFFECT OF PHYSICAL VARIABLES TEMPERATURE VELOCITY • “Rule-of-thumb” guide indicates that the
CORROSION : EFFECT OF PHYSICAL VARIABLES
TEMPERATURE
VELOCITY
• “Rule-of-thumb” guide
indicates that the corrosion
rate doubles for every 10°C
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.
PRESSURE
• High velocities and/or
suspended solids and gas
bubbles can lead to:
• Increases gas solubility.
- Erosion / corrosion
- Impingement attack
- Cavitation
and gas bubbles can lead to: • Increases gas solubility. - Erosion / corrosion - Impingement

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CORROSION : EFFECT OF pH
CORROSION : EFFECT OF pH

pH is a measure of the degree of acidity or

alkalinity of an aqueous solution

pH

=

- log 10 [H + ]

where [H + ] = Hydrogen ion concentration

0

RATE

ACIDITY

NEUTRAL

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ALKALINITY

14

1

2

1 = NOBLE METALS 2 = ACID-SOLUBLE METALS

3 = METALS WITH AMPHOTERIC OXIDES 4 = STEEL

3

4

pH

14 1 2 1 = NOBLE METALS 2 = ACID-SOLUBLE METALS 3 = METALS WITH AMPHOTERIC
14 1 2 1 = NOBLE METALS 2 = ACID-SOLUBLE METALS 3 = METALS WITH AMPHOTERIC

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CORROSION : MAIN FORMS
CORROSION : MAIN FORMS

GENERAL CORROSION

GALVANIC CORROSION PITTING CORROSION

CREVICE CORROSION

SELECTIVE CORROSION

CONDENSATE CORROSION

MICROBIAL CORROSION

EROSION CORROSION STRESS CORROSION HYDROGEN DAMAGE

SELECTIVE CORROSION CONDENSATE CORROSION MICROBIAL CORROSION EROSION CORROSION STRESS CORROSION HYDROGEN DAMAGE 11
SELECTIVE CORROSION CONDENSATE CORROSION MICROBIAL CORROSION EROSION CORROSION STRESS CORROSION HYDROGEN DAMAGE 11

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CORROSION : MAIN FORMS GENERAL CORROSION • Uniform thinning. • Can predict rates through simple
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
General Corrosion

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General Corrosion
General Corrosion

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General Corrosion
General Corrosion

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CORROSION : MAIN FORMS GENERAL CORROSION GALVANIC CORROSION • Uniform thinning. • Requires materials with
CORROSION : MAIN FORMS
GENERAL CORROSION
GALVANIC CORROSION
• Uniform thinning.
• Requires materials with
different corrosion potentials, a
• Can predict rates through
common electrolyte and a
simple immersion tests.
common electrical path.
• Maintainable if the correct
control measures are
applied:
• Less resistant metal becomes
the anode (corrodes).
- Resistant materials
• Dependent on potential
- Coatings
difference between the metals,
- Inhibitors
- Cathodic Protection
Examples:
their relative areas and the
environment.
Examples:
- Atmospheric corrosion
- Riveted/bolted plates
- Acid corrosion
- Metallic coatings
- (Stray current corrosion)
- Atmospheric corrosion - Riveted/bolted plates - Acid corrosion - Metallic coatings - (Stray current corrosion)

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Galvanic Corrosion
Galvanic Corrosion

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Galvanic Corrosion
Galvanic Corrosion

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CORROSION : MAIN FORMS GALVANIC SERIES IN SEAWATER METAL POTENTIAL METAL POTENTIAL Platinum + 0.7
CORROSION : MAIN FORMS
GALVANIC SERIES IN SEAWATER
METAL
POTENTIAL
METAL
POTENTIAL
Platinum
+
0.7
Cupro-Nickel
- 0.2
Gold
+
0.6/0.7
S/S Types 400
- 0.2/- 0.3
Graphite
+ 0.2
Bronzes
- 0.2/- 0.3
Titanium
Incoloy 825
+
0.1
Copper
- 0.3
0.0
Brasses
- 0.4
S/S Type 316/317
Monel 400
0.0/- 0.1
Cast Iron
Mild Steel
- 0.6
0.0/- 0.1
- 0.6
S/S Type 304/321
0.0/- 0.1
Aluminium
- 0.9
Silver
-
0.1
Zinc
- 1.0
Nickel
-
0.1/- 0.2
Magnesium
- 1.6
0.6 S/S Type 304/321 0.0/- 0.1 Aluminium - 0.9 Silver - 0.1 Zinc - 1.0 Nickel
0.6 S/S Type 304/321 0.0/- 0.1 Aluminium - 0.9 Silver - 0.1 Zinc - 1.0 Nickel

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CORROSION : MAIN FORMS PITTING CORROSION CREVICE CORROSION • Localised attack where electrochemical driving force
CORROSION : MAIN FORMS
PITTING CORROSION
CREVICE CORROSION
• Localised attack where
electrochemical driving force
• Crevices promote the
formation of concentration
is concentrated in specific
cells.
areas.
• Process is autocatalytic.
• Particularly serious in
oxygenated systems.
• Perforation of components
can occur in a short time.
• Limited supply of oxygen in
the crevice makes it anodic
to the surroundings.
Environments:
Chlorides:
Examples:
- Breakdown passive films
- Narrow openings
Concentration cells:
- Cracks
- Differential aeration
- Metal joints
- Crevices
- Flanges
- Porous corrosion products
- Nuts, bolts and washers
- Scales & sludges (SRB’s)
- Deposits and fouling
- Porous corrosion products - Nuts, bolts and washers - Scales & sludges (SRB’s) - Deposits

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Crevice Corrosion
Crevice Corrosion

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Crevice Corrosion
Crevice Corrosion

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Crevice Corrosion
Crevice Corrosion

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Crevice Corrosion
Crevice Corrosion

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CORROSION : MAIN FORMS
CORROSION : MAIN FORMS

PITTING/CREVICE CORROSION RESISTANCE

(in quiet seawater)

Stainless steels (300/400 series) Steels with scale Nickel Aluminium

Poor 1000 µm/y

Low carbon alloy steels

 

Stainless steel (Type 316)

Fair

Ni-Cu alloy (Monel)

600 µm/y

Anodised aluminium

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

Good

200 µm/y

Ni-Cr-Mo alloys (Hastelloy) Titanium

Excellent 0 µm/y

steels Ni-Cr-Fe alloys (Inconel) Good 200 µm/y Ni-Cr-Mo alloys (Hastelloy) Titanium Excellent 0 µm/y 25

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CORROSION : MAIN FORMS SELECTIVE CORROSION Dealloying • Removal of specific elements from an alloy
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
Selective Corrosion: Dezincification

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Selective Corrosion: Denickelification
Selective Corrosion: Denickelification

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CORROSION : MAIN FORMS SELECTIVE CORROSION SELECTIVE CORROSION Dealloying Intergranular Corrosion • Removal of
CORROSION : MAIN FORMS
SELECTIVE CORROSION
SELECTIVE CORROSION
Dealloying
Intergranular Corrosion
• Removal of specific elements
from an alloy by corrosion.
• Compositional differences
(enrichment/depletion of
alloying elements, impurities)
• Favoured by stagnant
can make grain boundaries
conditions.
more reactive than the matrix.
Examples:
- Dezincification
• Grain boundaries and
surrounding areas become
- Dealuminification
anodic and preferentially
- Denickelification
corrode.
- Graphitisation
• Net effect is a reduction in
material strength.
Examples:
- Weld decay (Sensitisation)
- Graphitisation • Net effect is a reduction in material strength. Examples: - Weld decay (Sensitisation)

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CORROSION : MAIN FORMS CONDENSATE CORROSION • Strong mineral acids (nitric, sulphuric) can condense from
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
Condensate Corrosion

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Condensate Corrosion
Condensate Corrosion

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Condensate Corrosion
Condensate Corrosion

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Condensate Corrosion
Condensate Corrosion

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Condensate Corrosion
Condensate Corrosion

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Condensate Corrosion
Condensate Corrosion

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CORROSION : MAIN FORMS CONDENSATE CORROSION MICROBIAL CORROSION • Strong mineral acids (nitric, sulphuric) can
CORROSION : MAIN FORMS
CONDENSATE CORROSION
MICROBIAL CORROSION
• Strong mineral acids (nitric,
sulphuric) can condense from
combustion gases causing
significant corrosion of
• Sulphate reducing bacteria
remove hydrogen from
cathodic areas to reduce
sulphates to sulphides; this
associated equipment.
stimulates the anodic reaction
(i.e. corrosion).
• Condensation takes place up
to the dewpoint temperature.
• The higher the temperature,
the more concentrated the
acid.
Problem areas:
• Thiobacilli oxidise sulphur
and hydrogen sulphide and
thereby create acid
conditions.
- Diesel engines (valves,
injectors, liners, bearings).
• The two species are
extremely active together.
Example:
- Industrial boilers (ducting,
- Tank bottom corrosion
economisers, air heaters).
active together. Example: - Industrial boilers (ducting, - Tank bottom corrosion economisers, air heaters). 37

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Microbial Corrosion
Microbial Corrosion

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CORROSION : MAIN FORMS EROSION CORROSION Impingement attack: • With increasing flow velocity, pitting decreases
CORROSION : MAIN FORMS
EROSION CORROSION
Impingement attack:
• With increasing flow
velocity, pitting decreases
and general corrosion
predominates.
- Breakdown of protective
film by turbulence, particles
or gas bubbles.
- Horse-shoe shaped pits.
Cavitation:
• Film adherence becomes
important.
• Stainless steels and high-
nickel alloys have tough
- Collapse of vapour-filled
cavities caused by pressure
changes or vibrations.
- Hemispherical pits, sharply
films.
outlined and free from
• Turbulence in the flow can
cause specific erosion-
corrosion problems:
corrosion product (sponge).
Examples:
- Pump impellers
- Impingement attack
- Flow lines (valves, elbows)
- Cavitation
- Heat exchanger tubes
Examples: - Pump impellers - Impingement attack - Flow lines (valves, elbows) - Cavitation - Heat

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Erosion Corrosion: Impingement Attack
Erosion Corrosion: Impingement Attack

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Erosion Corrosion: Impingement Attack
Erosion Corrosion: Impingement Attack

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Erosion Corrosion: Cavitation
Erosion Corrosion: Cavitation

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Erosion Corrosion: Impingement Attack
Erosion Corrosion: Impingement Attack

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CORROSION : MAIN FORMS STRESS CORROSION Corrosion Fatigue • Cyclic stress. • Fatigue is accelerated
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
Corrosion Fatigue

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Corrosion Fatigue
Corrosion Fatigue

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CORROSION : MAIN FORMS STRESS CORROSION STRESS CORROSION Corrosion Fatigue Stress Corrosion Cracking • Cyclic
CORROSION : MAIN FORMS
STRESS CORROSION
STRESS CORROSION
Corrosion Fatigue
Stress Corrosion Cracking
• Cyclic stress.
• Static tensile stress (applied,
residual, thermal, etc.).
• Fatigue is accelerated by
corrosion (20% life reduction
• Stress has to be above a
with steel).
• Failure can occur at a stress
level well below the fatigue
limit of the material.
threshold value for different
alloy/corrosive environment
combinations (can be as low
as 10% yield stress).
• Cracking is branched and
• Multiple crack initiation where
one predominates (others
appear blunt-nosed).
perpendicular to the applied
stress (brittle in appearance).
• Generally transgranular crack
propagation (intergranular at
high stresses).
• Generally intergranular crack
propagation (transgranular
cracking also occurs).
at high stresses). • Generally intergranular crack propagation (transgranular cracking also occurs). 47

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CORROSION : MAIN FORMS
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

H 2 S

Aqueous electrolytes (with H 2 S)

Acidic chlorides Hot chlorides Seawater

H 2 S

Ammonia solutions

S Aqueous electrolytes (with H 2 S) Acidic chlorides Hot chlorides Seawater H 2 S Ammonia

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CORROSION : DIAGNOSIS 1. Check history and environment 2. Corrosion products - colour - analyse
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)
- SRB’s (smell)
- Chlorides
Cracking
- Corrosion fatigue (blunt-nosed/transgranular)
Selective
- Stress corrosion (branched/intergranular)
- De-alloying
- Intergranular attack

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