Stress Corrosion Cracking,

Hydrogen Embrittlement
Corrosion Fatigue
STRESS CORROSION CRACKING
• Stress corrosion cracking (SCC) refers
to the cracking caused by the
simultaneous presence of tensile
stress and a specific corrosive
medium.
• During SCC the metal or alloy is
virtually unattacked over most of its
surface, while fine cracks progress
through it.
• Serious consequences since it can
occur at stresses within the range of
typical design stress.
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• Two classic cases: “season cracking” of brass, and
the “caustic embrittlement” of steel; both
obsolete terms.
• Season cracking refers to failure of brass cartridge
cases. Cracks observed in brass cartridge during
heavy rainfall especially in tropics, at the point
where the case was crimped to the bullet;
Ammonia resulting from decomposition of
organic matter caused cracking of the cartridge.
• Explosions of riveted boilers occurred in early
steam locomotives, at the riveted holes. These
areas were cold worked during riveting. Caustic
or Sodium hydroxide was found near the hole,
which caused the embrittlement at the holes.
(hence called ‘caustic embrittlement’).
• Not all metal-environment combinations are susceptible to cracking.
E.g. SS cracks in NaCl but not in ammonia, whereas, brass cracks in
ammonia but not in chlorides.
• SS do not crack in sulfuric acid, nitric acid, acetic acid, or pure water,
but crack in chloride and caustic.
• Important variables in SCC are:
– Temperature
– Solution composition
– Metal composition
– Stress
– Metal structure

Crack morphology
• SC cracks give the appearance of brittle mechanical fracture; Although
SCC is not strictly a mechanical process, it is still called a crack.
• Intergranular and transgranular SCC are observed.
• Intergranular cracking proceeds along grain boundaries, while
transgranular cracking advances without apparent preference for
boundaries.

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Stress Effects
• Increasing stress decreases the
time before cracking occurs.
• The minimum stress depends on
tem, alloy composition, and
environment composition.
• In some cases 10% of the yield
stress, whereas in other cases
70% of Y.S.
• For each alloy-environment
combination there is an effective
minimum, or threshold stress
which may change by changing
environmental condition during
operation.
• The stresses may be due to any
source; applied, residual,
thermal, or welding.

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Time to cracking
• Time in SCC is important since the major physical damage occurs during
the later stages. As the SC crack penetrates the material, the x-section is
decreased and the final cracking failure results entirely from mechanical
action.

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Environmental Factors
• SCC well known in various aqueous mediums, but also in liquid metals, fused salts,
and non-aqueous inorganic liquids.
• Oxidizers often have a pronounced effect on cracking tendencies.

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SCC is accelerated with temp
• In some systems room temp is enough whereas in other systems, cracking
occurs at boiling conditions.
• Most alloys begin to crack at as low as 100˚C.

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 Mechanism of SCC
• A pit, trench or other discontinuity on the surface of the metal acts as
stress raiser.
• Stress conc. at the tip of the notch increases tremendously as the radius of
the notch decreases. Stress corrosion cracks are often observed to start at
the base of the pit.
• Once crack initiates, the tip of crack has a small radius and the stress conc.
is great. A mechanical step or jump can occur during crack propagation.
• Crack propagation stops in the absence of corrosive environment.
• Plastic deformation of an alloy can occur in the region immediately
preceding the crack tip because of high stresses. If the alloy is a
metastable, a phase transformation could occur (e.g. austenite to
martensite in Ni-base SS). The newly formed phase could have different
strength, susceptibility to hydrogen, or reactivity.
• Two basic models for a general mechanism of SCC have been postulated:
– The dissolution model wherein anodic dissolution occurs at the crack tip because
strain ruptures the passive film at the tip
– The mechanical model, wherein specific species adsorb and interact with strained
metal bonds and reduce bond strength.
– The first seems more universal than the second. 9
Metallurgical Factors
The susceptibility of SCC is affected by:
– Average chemical composition
– Preferential orientation of grains
– Composition and distribution of precipitates
– Dislocation interactions
– Progress of phase transformation
SCC Prevention
• SCC may be reduced or prevented by application of one or more of
the following methods:
– Lowering the stress
– Eliminating the critical environmental species e.g. degassification,
demineralization, or distillation etc.
– Changing the alloy
– Applying cathodic protection
– Adding inhibitors
– Coatings
– Shot-peening

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 HYDROGEN DAMAGE
• A general term which refers to mechanical damage of a metal
caused by the presence of, or interaction with hydrogen.
• May be classified into four distinct types:
– Hydrogen blistering
– Hydrogen embrittlement
– Decarburization
– Hydrogen attack
• Hydrogen blistering results from the penetration of hydrogen
into a metal. May cause local deformation or, in some cases,
complete destruction of vessel wall.
• Hydrogen embrittlement also caused by penetration of
hydrogen into metal, resulting in loss of ductility and tensile
strength.
• Decarburization or removal of Carbon from steel is often
caused by hydrogen.
• Hydrogen attack refers to the interaction between hydrogen
and a component .
 Environmental Factors
• Atomic hydrogen is the only species capable of diffusing through
steel or other metals. The molecular form does not diffuse through
metals.
• Various sources of nascent hydrogen are:
– High temp moist atmosphere
– Corrosion processes
– Electrolysis
• Reduction of hydrogen ions causes production of hydrogen atoms
and subsequently forming hydrogen molecules.
• Hence, corrosion, application of cathodic protection, electroplating
and other processes are major source of hydrogen in metals.
• Certain substances such as sulfide ions, phosphorous and arsenic
compounds reduce the rate of hydrogen ion reduction; These
substances function by decreasing the rate at which hydrogen
combines to form molecules.
• In the presence of such substances there is a greater concentration
of atomic hydrogen on the metal surface.
 Hydrogen Blistering
• X-section of a wall of tank; inner
surface contains acid electrolyte
and outer exposed to atmosphere.
• Hydrogen evolution occurs on the
inner surface as a result of a
corrosion reaction on cathodic
protection.
• At any time some of the hydrogen
atoms diffuse into the metal rather
than combining into molecules.
• Much of the hydrogen diffuses
through the steel and combines to
form hydrogen molecules on the
exterior surface.
• If hydrogen atom diffuse into a
void (a common defect in rimmed
steel) they combine into molecular
hydrogen.
• Since molecular hydrogen cannot diffuse, the
concentration and pressure of the hydrogen gas
within the void increases.
• The equilibrium pressure of molecular hydrogen
in contact with the atomic hydrogen is several
hundred thousand atmospheres, which is
sufficient to rupture any known engineering
material.
• Hydrogen blistering is most prevalent in
petroleum industry. It occurs in storage tanks and
refining processes.
• One method to control is to add inhibitor, such as
polysulfide ions.
 Hydrogen Embrittlement
• Exact mechanism not known; but the initial cause is
the same.
• For Ti and other strong hydride forming metals,
dissolved hydrogen reacts to form brittle hydride
compounds.
• In other materials such as iron and steel, the
interaction between dissolved hydrogen atoms and
the metal is not completely known.
• Most of the mechanisms that have proposed for
hydrogen embrittlement are based on slip
interference by dissolved hydrogen. This slip
interference may be due to the accumulation of
hydrogen near dislocation sites or microvoids, but
the precise mechanism is still in doubt.
• Hydrogen embrittlement is distinguished from SCC generally by
interactions with applied currents.
• Cases where applied current makes the specimen more anodic and
accelerates cracking, are considered to be stress corrosion cracking,
with anodic dissolution process contributing to the progress of
cracking.
• On the other hand, cases where cracking is accentuated by current
in opposite direction, which accelerates the hydrogen evolution
reaction, are considered to be hydrogen embrittlement.
• A few ppm of absorbed gas cause cracking.
• Hydrogen cracking tendency decreases with increasing temp and
significant change occurs above about 70C.
• Hydrogen cracking is usually not a problem with steels having yield
strengths below 1000 MPa, when corrosion reactions other than HF
and H2S. For these acids the limit drops to about 550 MPa.
 Prevention
Hydrogen blistering can be prevented by:
• Using “clean” steel;
– Rimmed steels tend to cause problems.
– Killed steel may be used.
• Using coatings.
– Metallic, inorganic and organic coatings and liners are often used.
– Steel clad with austenitic SS or nickel is often used for this purpose.
– Rubber, plastic or brick lining may be used.
• Using inhibitors;
– used in closed systems.
• Removing poisons;
– Corrosive mediums containing hydrogen-evolution poisons such as sulfides, arsenic
compounds, cyanides, and phosphorous containing ions are sources for hydrogen
embrittlement.
– Many of these are encountered in petroleum industry.
• Substituting alloys;
– Ni-containing steels and Ni-base alloys have very low hydrogen diffusion rates and
are often used to prevent hydrogen blistering.
Hydrogen embrittlement can be prevented by:
• Prevention for Hydrogen embrittlement may be
different from hydrogen blistering
– e.g. use of clean steel helps in prevention of hydrogen
blistering but has relatively little influence on hydrogen
embrittlement.
• Reducing corrosion rate:
– Vigorous hydrogen evolution takes place during pickling
operations; use of inhibitors may retard the corrosion rate
and hence hydrogen embrittlement.
• Altering plating conditions:
– Baking: This removes hydrogen from the steel if heated at
relatively low temps (200-300F).
• Substituting alloys:
– Alloys with Ni or Mo reduce the susceptibility.
• Practicing proper welding:
– Low-hydrogen welding rods should be used.
 CORROSION FATIGUE
• Fatigue is defined as the tendency of a metal to fracture under
repeated cyclic stressing.
• Corrosion fatigue is defined as the reduction of fatigue resistance
due to the presence of a corrosive medium. Thus corrosion
fatigue is defined in terms of mechanical properties and not the
appearance of the fracture.
• There is a large area covered with corrosion products and a
smaller roughened area resulting from the final brittle fracture.
• Corrosion fatigue is probably a special case of SCC, however, the
mode of fracture and preventive measures differ.
• Crack initiation and crack growth respond differently to
environmental factors.
Environmental Factors
• Corrosion fatigue resistance is markedly affected by the
stress-cycle frequency, unlike ordinary fatigue which
has negligible influence of the frequency of cyclic
stressing.
• Corrosion fatigue is more pronounced at low stress
frequencies; low frequency cycle result in greater
contact between the metal and the corrosive.
• Also influenced by type of corrosive to which the metal
is exposed.
• E.g. Iron, steel, SS and Al-bronzes possess good
corrosion fatigue resistance in water. In seawater, Al-
bronzes and austenitic SS retain only 70-80% of their
normal fatigue resistance. High Cr-alloys retain only 30-
40% of their normal fatigue life.
Mechanism
• Corrosion fatigue seems to be most prevalent in medium that produce
pitting attack. Corrosion pits act as stress raisers and initiate cracks.
• It is most likely that the corrosion is most intense at the crack tip and as a
consequence there is no stable pit radius.
• A corrosion fatigue failure is usually transgranular and does not show the
branching that is characteristic of many SCC.
• Final stages of the corrosion fatigue are identical to those occurring during
ordinary fatigue; final fracture is purely mechanical and does not require
the presence of corrosive.
Prevention
• Increase in Tensile Strength improves ordinary
resistance but is detrimental to corrosion fatigue. Since
once crack is initiated in high TS material it usually
progresses more rapidly than a low strength material.
Crack is readily initiated in corrosion fatigue due to
corrosive action in high TS material and the materials
fails quickly
• Corrosion fatigue may be reduced by reducing the
stress on the component; this can be done by
– altering the design,
– stress-relieve Heat Treatment, or
– shot-peening the surface to induce compressive stresses.
• Corrosion inhibitors are also effective.
• Coatings also may help in preventing corrosion fatigue,
using techniques which do not produce TS in the
coatings/plating, or charge hydrogen in the metal.