Mechanical Aspects of Corrosion

Bob Cottis
Corrosion and Protection Centre,
UMIST
Mechanical Aspects of Corrosion

O Static stress
– stress-corrosion cracking
– hydrogen embrittlement
– liquid metal embrittlement
O Dynamic stress
– corrosion fatigue
– fretting corrosion
The Effect of Stress and Strain on
Corrosion
O Stress per se does not affect corrosion
processes much
O Plastic strain can have a large effect:
– increased dislocation density
– rupture of passive films
Stress-Corrosion Cracking

O Cracking of a metal under the combined

effects of a static stress and a specific
chemical environment
O Several possible mechanisms, still not fully
understood
O Cause of major industrial costs and safety
hazards
Stress-Corrosion Cracking

O Mechanisms
– Anodic dissolution
– Hydrogen embrittlement
– Film-induced cleavage
 Anodic Dissolution

1 The walls and tip of the crack are passive

2 The passive film at the crack tip is ruptured by the plastic
strain, and active corrosion occurs
3 The crack tip repassivates
4 Go back to 1
 Film-Induced Cleavage

1 The walls and tip of the crack are covered by a brittle film
(either an oxide film or a de-alloyed layer)
2 The film at the crack tip is ruptured by the plastic strain
3 The brittle crack continues into the metal
4 The crack is blunted by plastic strain
 Hydrogen Embrittlement

H H H H
H HH
H

1 Hydrogen produced by the cathodic reaction

2 Hydrogen diffuses to region of tri-axial tensile stress
ahead of the crack
3 Hydrogen causes brittle fracture
4 Crack blunts by plastic deformation as it runs out of
hydrogen
Hydrogen Embrittlement

O sources of hydrogen
– welding
– electroplating
– contact with gaseous hydrogen
– corrosion, especially in the presence of
sulphides
O higher strength materials are more
susceptible to hydrogen embrittlement
Hydrogen Induced Cracking

O Internal cracking of lower strength steels

(e.g. pipeline steels) due to high pressure
hydrogen collecting at inclusions.
Hydrogen Cracking

O Internal cracking of steels at higher

temperatures due to reaction of dissolved
hydrogen with carbon to form methane
Stress Corrosion Cracking Systems

O Brass and ammonia (often in local

atmospheres).
O Austenitic stainless steels and chloride
solutions (70oC).
O Carbon steels in caustic, carbonate/
bicarbonate, nitrate and phosphate.
O High strength aluminium alloys in water or
water vapour.
Stress-Corrosion Testing
Constant Load Testing

Stress

Threshold stress

log(Time to Failure)
Stress-Corrosion Testing

O Slow strain-rate testing (or constant

extension rate testing)
O Extend a plain or pre-cracked specimen at a
slow constant rate
O Then assess by
– fracture surface
– change in elongation or reduction in area
– time to failure
Stress-Corrosion Testing

O A measure
Fracture of the severity
mechanics testing
of the stress state at the
– apply a constant load to a pre-cracked
crack tip
specimenK = σ πa
– measure crack growth rate as a function of
stress intensity factor (K)
Fracture Mechanics Testing

log (crack growth rate)

Fastfracture
Fast fracturestarting
startingto
to
Plateau
occur
Plateau
occur crack
crack
as velocity
asKKvelocity
approachesKKIc
approaches Ic
typicalrange
typical rangeof ofvalues
values
Threshold 10
stress
10
-11 to 10–3
intensity
Threshold stress intensitym/s
-11 to 10
–3 m/s

factor,KKIscc
factor, Iscc

Stress Intensity Factor

Control of Stress-Corrosion

O Remove stress (often difficult, especially for

residual stresses)
O Avoid the necessary environment
O Apply electrochemical protection where
possible
O Use a different material
O Live with it
Liquid Metal Embrittlement

O Liquid metals can permeate down grain

boundaries and cause intergranular
cracking:
– mercury on brass and aluminium alloys
– liquid zinc on stainless steel
Corrosion Fatigue

O Metal fatigue results in crack propagation

due to a cyclic stress
O Corrosion makes both crack initiation and
propagation easier
Corrosion Fatigue - S-N Curve
Stress Amplitude

Air

Corrosion

log (cycles to failure, Nf)

Corrosion Fatigue - Crack Growth

log (Crack Growth Rate, da/dN)

Log (Stress Intensity Factor Range, −K

Fretting Corrosion

O Rubbing of two metals removes oxide film

and allows oxidation
O The oxide may also act as an abrasive
O Prevention of relative motion and allowing
larger relative movement may prevent the
problem