Stress corrosion cracking (SCC)

Combined action of applied tensile stress and a corrosive

environment on susceptible material.

Caused by either:
1. Residual internal stress in the metal:
Cold forming
Unequal cooling from high temperature

2. An externally applied stress:

Faulty design
Thermal effects (expansion or contraction)

Requirements for SCC

The following conditions are necessary for SCC:

Figure 7.1 Stress corrosion triangle

Stress corrosion cracking (SCC)

Causes rupture of the film

Occurs in three stages:
Initiation: Slow attack which produces a pit

Slow crack growth plus corrosion enhances

propagation
Rapid failure.

Cause of major industrial costs and safety hazards

Characteristics of SCC
Required stress, either residual or applied.

Occurs for stresses below the materials yield stress.

Generally all alloys susceptible to SCC
Cracks initiate and propagate period.
Conditions of cracking are specific to alloy and environments.
Can initiate and crack with little outside evidence of corrosion and no
warning before catastrophic failure.
Other forms of corrosion, such as pitting or crevice corrosion can
transition to SCC.
SCC cracks are microscopically brittle in appearance.
Stress corrosion cracks can be both intergranular and transgranular,
depends on alloy, stress level, environments.

Stress corrosion cracking can propagate either intergranualry or transgranulary

depends on the material properties and the mechanism of crack propagation

Intergranular SCC

Transgranular SCC

Factors important in SCC:

1- Environmental Factors:
aqueous solutions
Temperature
Electrochemical potential
Time

For example,
Brasses crack in NH3
Inconel-600 cracked in pure water at 300C.
Stainless Steels crack in chloride
2- Stress: The greater stress on material, the quicker it will crack.
In fabricated components, there are usually:
Residual stresses from cold working, welding, surface
treatment such as grinding, etc.
Applied stresses from the service, such as hydrostatic,
vapour pressure of contents, bending loads, etc.

Electrochemical dissolution theory

1- the dissolution or oxidation of the metal must be thermodynamically possible.

2- the protective film formed on the metal surface should be thermodynamically
stable.
3- On the basis 1 and 2 it has suggested that a critical potential exists which SCC
occurs.
The electrochemical dissolution mechanism was performed by measuring the
critical potentials for initiations of SCC of 18-8 stainless steels exposed to
magnesium chloride solutions boiling at 130C with and without inhibition
anion addition, Figures 7.2 and 7.3

7.2 Effect of applied potential on time to failure of stressed moderately coldrolled 188 stainless steel in magnesium chloride solution boiling at 130C

7.3 Effect of applied potential on time to failure of stressed moderately coldrolled 188 stainless steel in magnesium chloride solution with sodium
acetate additions, boiling at 130C (2% sodium acetate addition is inhibiting)

Initiation of SCC and critical potentials

For various metals and solutions, value of

critical potentials, immediately above (or
noble to) SCC initiations.

Figure 7.4 Effect of applied potential on stress-corrosion cracking of mild

steel in 170 g ammonium carbonate per liter, 70C.

Figure 7.4 Effect of applied potential on failure times of 0.09% C mild steel at
3 temperatures in 35% sodium hydroxide solution.

Prevention of SCC
1.

Lowering the stress below the threshold value if one exists.

This can be done by:
1. annealing in the case of residual stresses
2. thickening the section, or
3. reducing the load.

Plain carbon steels may be stress-relief annealed at 590

to 650C.
Austenitic stainless steels are frequently stress-relieved at
temperatures ranging from 820 to 930C.

2. Eliminating the critical environmental species by, e.g.

demineralization (salt removal).

3. Changing the alloy is one possible recourse if neither the

environment nor stress can be changed.
It is common practice to use Inconel (raising the nickel content)
when type 304 stainless steel is not satisfactory.
Although carbon steel is less resistant to general corrosion, it is
more resistant to SCC than are the stainless steels.
Thus, under conditions which tend to produce SCC, carbon
steels are often found to be more satisfactory than the
stainless steels.
Heat exchangers used in contact with seawaters are often
constructed of ordinary mild steel.

Chloride Stress Corrosion Cracking (CSCC)

Surface initiated cracks caused by environmental cracking of
300 Series SS and some nickel base alloys under the combined
action of tensile stress, temperature and an aqueous chloride
environment. The presence of dissolved oxygen increases the
probability for cracking.
A ffected Materials
a) All 300 Series SS are highly susceptible.
b) Duplex stainless steels are more resistant.
c) Nickel base alloys are highly resistant, but not immune

External cracking of Type 304SS instrument tubing under insulation

Factors affecting CSCC

Temperature : Increasing temperatures increase the susceptibility
to cracking.
Chloride content : Increasing levels of chloride increase the
likelihood of cracking.
pH: SCC usually occurs at pH values above 2. At lower pH values,
uniform corrosion generally predominates. SCC tendency
decreases toward the alkaline pH region.
Stress may be applied or residual. Highly stressed or cold worked
components, such as expansion bellows, are highly susceptible to
cracking.
Oxygen dissolved in the water normally accelerates CSCC.

 Alloy composition: Nickel content of the alloy has a

major affect on resistance. The greatest susceptibility
is at a nickel content of 8% to 12%. Alloys with nickel
contents above 35% are highly resistant and alloys
above 45% are nearly immune.
k) Low-nickel stainless steels, such as the duplex
(ferrite-austenite) stainless steels, have improved
resistance over the 300 Series SS but are not immune.
Carbon steels, low alloy steels and 400 Series SS are
not susceptible to CSCC

Morphology
The material usually shows no visible signs of
corrosion.
Characteristic stress corrosion cracks have
many branches and may be visually detectable
Metallography of cracked samples typically
shows branched transgranular cracks
Fracture surfaces often have a brittle
appearance.

Prevention / Mitigation
Use resistant materials of construction. Alloys with
nickel contents above 35% are highly resistant and
alloys above 45% are nearly immune.
Properly applied coatings under insulation.
Avoid designs that allow stagnant regions where
chlorides can concentrate or deposit.
A high temperature stress relief of 300 Series SS
after fabrication may reduce residual stresses.
However, consideration should be given to the
possible effects of sensitization that may occur.

Hydrogen induced failures

Hydrogen atoms may be produced on a metal surface in
an aqueous environment by a corrosion reaction, cathodic
protection, electroplating or acid pickling.
Some of the hydrogen atoms combine to form gaseous
molecular hydrogen on the metal surface and are
released to the environment. A portion of the atoms are
absorbed by the metal and this entry of hydrogen atoms
into the metal may have some very undesirable effects.
Hydrogen induced cracking (HIC\SOHIC\SCC) and
hydrogen embrittlement are two types of phenomena that
can occur.

HIC
Hydrogen induced cracks occur when atomic hydrogen diffuse
into the metal and then recombines as hydrogen molecules at
trap sites in the steel matrix such as inclusions and/or regions of
anomalous microstructure.
Cracking that connects adjacent hydrogen induced cracks on
planes in the metal, or near the metal surface is referred to as
stepwise cracking. The linking of the hydrogen induced cracks to
produce stepwise cracking is dependent upon local straining
between cracks filled with accumulated hydrogen under
pressure and the level of dissolved hydrogen in the metal
matrix.

Hydrogen-induced cracking (HIC)

Factors Affecting HIC

Steel composition : HIC is usually associated with low strength
ferritic plate steels used in the production of pipelines and
vessels. It is commonly found in steels with high impurity levels.
Environment: The degree of HIC is related to the hydrogen
concentration in the steel, which is dependent on partial
pressure of H2S, pH and temperature.
Stresses: No externally applied stress is needed for the
formation of hydrogen induced cracks.

Morphology
HIC normally occurs as planar defects aligned in the
rolling direction. Blisters can also form.

Prevention of HIC
Controlling the metal chemistry to minimise the
affects of inclusions or laminations. The risk of HIC
can be reduced by using HIC resistant steels with
low sulphur content (<0.003%).
Controlling corrosion with coating or inhibitors to
minimise the generation of hydrogen.

Stress Oriented Hydrogen Induced

Cracking (SOHIC)
SOHIC is similar to HIC but is a potentially more
damaging form of cracking which appears as arrays of
cracks stacked on top of each other.
SOHIC staggered small cracks are formed approximately
perpendicular to the principle stress (applied and
residual) resulting in ladder-like crack array linking
(sometimes small) pre-existing HIC cracks.
They usually appear in the base metal adjacent to the
weld heat affected zones where they initiate from HIC
damage or other cracks or defects including sulfide
stress cracks.

Stress-oriented hydrogen-induced cracking

(SOHIC)

Factors Affecting SOHIC

Steel composition and condition: SOHIC can occur in carbon steels,
in low sulphur carbon steels, in HIC resistant steels and in ultra low
sulphur advanced steels. SOHIC is relatively uncommon
phenomenon usually associated with low strength ferritic pipeline
and pressure vessel steels.
Post weld heat treatment, as applied to carbon steels for pressure
vessels, reduces residual stresses and hardness differences across
weld zones, thereby reducing the risk of SOHIC.
Environment: Hydrogen up-take in the steel is required for SOHIC to
occur. The degree of SOHIC is related to the hydrogen concentration
in the steel (which is dependent on partial pressure of H2S, pH and
temperature) and the stress state.
Stresses: External tensile stresses (residual and/or applied) are
required to induce SOHIC.

Morphology
SOHIC: Arrays of cracks aligned nearly perpendicular
to the applied stress, which are formed by the link up
of small HIC cracks in the steel. SOHIC is commonly
observed in the base metal adjacent to the HAZ of a
weld and is oriented in the through-thickness
direction. SOHIC may also be produced in susceptible
steels at other high stress points such as from the tip
of mechanical cracks and defects and from the
interaction between HIC on different planes in the
steel.

Sulphide stress corrosion

cracking
Cracking of metal under the combined action or
residual and/or applied tensile stress and corrosion in
the presence of water and hydrogen sulphide.
Sulphide stress cracking (SSC) involves hydrogen
embrittlement of the metal by atomic hydrogen that is
produced by the sulphide corrosion process on the
metal surface.
The atomic hydrogen can diffuse into the metal and
produce embrittlement, drastically reducing ductility
and deformability and increasing the likelihood of
cracking.

Schematic showing morphology of sulfide stress cracking in a hard heat affected zone.

Factors affecting SSC

Metal composition and condition: SSC can occur in carbon steels,
low-alloy steels, stainless steels and non-ferrous metals like Nibased, Co-based, Al, Cu and Ti alloys.
The tendency for SSC is increased by the presence of hard
microstructures such as untempered or partly tempered
transformation products (martensite), particularly in the heat
affected zones of welds.
pH: Susceptibility to SSC decreases with increasing pH.
Stress: SSC is controlled by the applied stress and by residual
stresses from working, forming or welding operations.

Examples
SSC is most likely found in hard weld and heat
affected zones and in high strength components
including bolts, relief valve springs, compressor
shafts, sleeves and springs.

Prevention
SSC can generally be prevented by limiting the
hardness of welds and heat affected zones
through preheat, PWHT, weld procedures and
control of carbon equivalents.
PWHT is beneficial in reducing the hardness and
residual stresses that render steel susceptible to
SSC.

Hydrogen Embrittlement
When electrochemically generated, hydrogen dissolves at the metal surface
then it migrates to stressed locations.
Hydrogen entry into high strength steels or steels with a hardness can result
in hydrogen embrittlement. A material can fail in a brittle manner at stresses
well below its yield strength.
Hydrogen embrittlement is normally limited to high strength materials due to
the fact that these materials reach tensile strengths high enough to initiate
the failure mechanism.
The susceptibility to hydrogen embrittlement increases with increasing
strength and hardness.
Even though a steel contains hydrogen, no permanent damage occurs unless
sufficient stress is applied to cause the steel to crack.

Prevention of hydrogen embrittlement

Annealing alloy (softening)

Baking component to remove dissolved hydrogen
Select more resistant alloy
Use inhibitor to minimize corrosion
Change design, avoid sharp corners and eliminate sites
for crevice corrosion

Fretting corrosion
Fretting is a phenomenon of wear which occurs between two
mating surfaces subjected to cycling relative motion of
extremely small amplitude of vibrations.
Fretting appears as pits or grooves surrounded by the corrosion
products.
The deterioration of materials by the conjoin action of fretting
and corrosion is called fretting corrosion.

Fretting is usually accompanied by corrosion in corrosive

environments.
Wear corrosion or friction oxidation are terms that have been
applied to this kind of damage.

Examples of fretting

Fretting of blade roots of tube blades

Fretting bolted parts, e.g. suspension springs
Fretting of engine components
Fretting damage of riveted joints
Loosing the wheels from axles

Factors affecting fretting

1- Contact load: wear is a linear function of load and fretting would,
therefore increase with increased load.
2- Number of cycles: the degree of fretting increases with number of
cycles.

3- Temperature: The effect of temperature depends on the type of

produced oxide. If a compact oxide is formed can prevents metal to
metal contact, fretting wear is decreased.
4- Relative humidity: The effect of humidity of fretting is opposite site to
the effect of general corrosion where an increase in humidity causes
a decrease in corrosion rate.

Mechanism of fretting corrosion

Adhesion : Contact between two surfaces. The surfaces must be in
close contact with each other. The contact occurs at few sites, called
asperities. The asperities are bonded together at adhesion sites created
by the relative slip of the surfaces.

Oxidation and debris generation: The material removed from the metal
surface due to fretting is called debris. The composition of the debris
differs from one metal another. The debris produced by low carbon steel
consists of mainly ferric oxide.
Crack initiation : Cracks grow in a direction perpendicular to the applies
stress at the fretting area. Some of cracks may not propagate at low
stress. The stage of crack initiation is called fretting fatigue. Crack
propagation at higher stress lead to failure. The crack originates at the
boundary of a fretted zone and propagates. During propagation, if a
corrosion medium contacts the crack, corrosion fatigue also contributes
to the crack propagation.

Figure 7.13

Mechanism of fretting corrosion

Prevention of fretting corrosion

Use low viscosity lubricating oils.
Use gaskets to absorb vibration.
Increase the hardness of the two contacting
metals using shot- peening.
Combination of a soft metal with a hard metal
Design of contacting surface to avoid slip.
Use materials to resist ferreting corrosion