Stress Corrosion Cracking

SCC is the brittle cracking of a metal due to the result of combined

effects from localized corrosion and a tensile stress.

Stress Corrosion Cracking

Stress Corrosion Cracking

Characteristic
Most of areas unaffected
Specific to certain environments
Brass - SCC in solutions with ammonia.
Steel - SCC in caustic (high pH), amine solutions.
Stainless steels and aluminium alloys - SCC in solutions containing chlorides.
Ti-alloys - SCC in nitric acid or methanol.
Can be Intergranular (Al-Cu, Cu base alloys) transgranular (Mg alloy or

18/8SS) or mixed mode of cracking.

Residual stresses due to cold working, welding etc.,
Compressive stress does not cause
Threshold stress is required

Mechanism

Mechanism

Mechanism

Mechanism

Mechanism

Mechanism
Mechanism
Electrochemical theory
Fissures at weak points of oxide film favour anodic
dissolution & initiation of SCC
Stress sorption theory
Adsorption of ions on metal weakens metal atom bond

Control
(Material + Environment+ Tensile Stress)
1. Lower stress level below the threshold value (annealing,
thickening the section)
2. Eliminate critical species
3. Apply cathodic protection
4. Add inhibitor (Phosphate in boilers)

Hydrogen Embrittlement
Brittle mechanical failure caused by penetration and diffusion of atomic hydrogen
into the crystal structure of an alloy.
(e.g) boiler tubes, plating, crude oil pipe lines pickling
Steels in oil and gas industry

Formation of cavities in the

steel due to hydrogen blistering

Failure of wall of a hydrofluoric

alkylisation plant due to
hydrogen blistering

Source of Hydrogen
Corrosion process
H+ + e H

H2O + e H+ + OH

H-bearing environment (heat treatment, wielding or other manufacturing

process)
Decomposition of water vapour or steam on hot surfaces.
The corrosion reactions in presence of hydrogen sulphides
Anodic reaction:

Fe Fe2+ + 2e

Dissociation reaction:
H2S H+ + HSHS- H+ + SCathodic reaction :
2H+ + 2e 2H 2H2 (gas)

Posions - Presence of S2- and As3+ delay the recombination of H atoms.

P, Sb, Se, Te and Cyanide are other poisons.

Fe (Surface) + H2S (gas) FeS (Surface) + 2H (solution)

Hydrogen Induced Cracking (HIC) The corrosion damage is in the
form of blisters and / or internal cracks in absence of STRESS
Sulfide stress Cracking (SSC) Presence of STRESS

Mechanism
Weakening of the metallic bond strength by the dissolve H.
Diffusion of atomic H into metal and forms molecular H2 in voids/defects
forms blisters. This build up high pressure causes rupture.
Diffusion of atomic H into metal and reacts with alloying elements to
form brittle hydrides

Prevention of HE
Modification of environments
Use of materials resistant to HE (High strength materials with low inclusion/voids)

Corrosion Fatigue
Brittle failure of an alloy caused by fluctuating stress in a corrosive environment.
(Different from SCC)
(e.g) Sucker rods & drilling rods in oil wells rail vehicle springs, motor shaft working in
corrosive environment
Characteristics
Large smooth area and a small corroded area
Specific to high strength materials
Transgranular failure
Endurance limit is decreased by corrosive agent
Fatigue occurs when a material is subjected to repeated loading and unloading.

Mechanism
Deep pits are initially formed
Cracks initiates & propagates across the metal
The frquency of cyclic stress is important. Lower frequency leads to
greater crack propagation per cycle.
Prevention
Lowering the general corrosion rate will delay or prevent CF.
Addition of inhibitors
Barrier coating (Coating Zn, Cr, Ni, Cu & nitride)
Reduce cyclic stresses by shot peening

Dealloying
Also known as Selective Leaching or Selective dissolution or Parting
Removal of one element from an alloy leaving an altered residual structure.
Dezincification:
Selective removal of Zn from Brass with its yellow colour and its colour
changes to red (copper colour)

Graphitization
Selective dissolution of iron from Grey cast iron (E.g. Water pipes buried in soil)
Graphite flakes are cathodic to iron, and corrosion is localized to iron which starts
leaching (becomes a porous mass) and leaves a rich residue of graphite flakes.

Characteristics
Loss of mechanical strength without change in shape
It leaves a porous structure
White cast iron does not undergo since C is present as Fe3C but leaves
behind a network of graphite flakes
Mechanism
C is present as graphite form
Potential difference exists between graphite and iron
Local cell promotes corrosion of iron.
Prevention
Coal tar epoxy coating on metal to prevent graphitization
Tackling at desgin stage
Cupro-nickel or addition of 1% Sn to 70-30 brass reduces.
Addition of 2% Al to Brass also prevents

Fretting Corrosion
Loaded metal surfaces under relative motions in the presence of corrosive
environment. e.g) Ball bearing, electrical switch gear
Discolour & deep pit formation
Relative motion small as 10-8 cm

Mechanism
Wear Oxidation Rupture causes metal removal and oxidation
Oxidation wear oxide layer ruptured and oxide debris formed
Exposed metal is further oxidized
Prevention
Lubricate with low viscosity
Increase hardness
Use gaskets to absorb vibration
Roughen the surface

Cavitation Damage
Corrosion caused by impact of air bubbles in a medium (e.g) Marine
propellers, boiler tubes
Pitting type of appearance and surface roughening
Mechanism
Repeated formation of bubbles act as hammer and remove metal.
Prevention
Metal must be high Corr. Resistant.
Coating with neoprene
Use dense high strength tensile material.

Erosion-Corrosion

Erosion-Corrosion
A = Erosion - corrosion
B = Cavitation erosion corrosion
C = Turbulent flow corrosion

Cavitation
erosion
Laminar
flow

Corrosion
C

Turbulent
flow
Erosion

Types of Flow
turbulent flow

laminar flow (parabolic profile)

y
x

notional profile in the absence of

friction at the pipe walls

Fully developed velocity profiles in a circular section pipe

Types of Flow
(a)

inlet

laminar flow

(b)

inlet

entry zone unstable flow

turbulence

v ()

turbulent layer

intermediate
layer
laminar layer

y
laminar sub - layer

x CRIT

Hydrodynamic (prandl) boundary layers near the surface of a flat plate formed by a uniform
fluid velocity such that turbulent flow can develop

boundary layers

entry length

boundary layers merge and

become fully developed

Fully developed laminar flow

Development of a hydrodynamic boundary layer for solution flowing through a tube

Influence of fluid velocity on NAB

corrosion performance
0.8

Corrosion rate mm/year

0.75

Max. recommended
in-service velocity

0.6

0.5

0.4

0.2

0.05
0.0
0

1
Tidal

5 m/s

7.62m/s

3 m/s
30.5

Critical velocity is not well defined for NAB. In seawater service conditions a maximum
flow rate of 5 m/s is normally recommended

Corrosion rate vs Velocity

Protective film integrity

Protective oxide film on NAB
prevents corrosion
approx. 800 nm
complex layers of CuO, Cu2O and
Al2O3
Level of protective film damage is
dependent on particle impact angle
Mechanical removal and/or rupture
enables charge transfer at varying
rates
Recovery aspects then become
important (system dependent)

Ductile erosion mechanisms

For a ductile material, the

erosion mechanisms are (1)
+ (2) microcutting, (3) plastic
deformation depending on
the angle of impingement.

Brittle erosion mechanism

Crack
systems
e.g. oxides at splat boundaries

Fracture toughness plays an important role.

Can depend on direction (perpendicular/transverse to coating / substrate
interface).

Synergy
T=E+C+S
or
S=T-(E+C)
where
T is material loss under erosion-corrosion
E is material loss by pure mechanical erosion processes
C is solids free flow corrosion
S is synergy, the difference between erosion-corrosion (T) and the summation
of erosion (E) and corrosion (C).
Synergistic effects can be:
Negative (equivalent to extra safety factor)
Positive (additional safety factor required)

Zero Resistance
Ammeter
Microbial
Induced
Corrosion
Immediately after immersion, a metal surface
undergoes a sequence of biological and
chemical changes that lead to the formation of a
biofilm which is causative for corrosion .

Microbial Induced Corrosion

A biofilm is
heterogeneous in
nature and the
distribution of
microorganisms is
not uniform:

highly complex structures containing

voids, microbial clusters or layers.
diffusion in biofilms is dependent on
flow conditions and structure.

Slime, extracellular polymeric substances

(EPS) - enzymes, proteins, nutrients, trapped
inorganic material possible modification of
oxygen reduction mechanisms

Sulphate Reducing Bacteria

Biofilms and galvanic corrosion

Copper alloys are more resistant to biofouling than most metals due to the toxicity of
the released copper-ions.
When coupled to other metals the release of copper-ions can be greatly reduced.
The ennoblement of passive metals, such as titanium and stainless steels is welldocumented:

This ennoblement has been related to the formation of aerobic biofilms, although
the mechanism governing the processes is still a subject of much debate.
Biofilms on titanium have been reported to catalyse the cathodic reduction of
oxygen thus increasing the overall cathodic efficiency.

References
S.N.Banerjee, An Introduction to Corrosion Science and Corrosion Inhibition,
Oxonian Press P.Ltd., New Delhi, 1985.
Zaki Ahmad, Principles of Corrosion Engineering & Corrosion Control, Butterworth
Heinemann, 2006.

M.G.Fontana & N.D. Greene, Corrosion Engineering, McGraw Hill, New York ,
1978.

L.L.Shrier Corrosion, Vol. I & II, Butterworth Heinemann, 1994.

H.H.Uhlig and R.W.Revie, Corrosion and Corrosion Control, A Wiley Inter

Science Publication John Wiley & Sons, New York, 3rd Edition, 1985

and etc.