ENME 665 Mechanical Behavior

of Materials
 Topic 9 – Hydrogen-Induced
Cracking and Corrosion Fatigue

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Environmentally-Induced Cracking
(EIC)
Environmentally-Induced Cracking (EIC) is a
general term for brittle mechanical failures
that occur when a susceptible alloy is under
tensile stress in a corrosive environment.

EIC generally includes Stress Corrosion

Cracking, Corrosion Fatigue and Hydrogen-
Induced Cracking.

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Hydrogen-Induced Cracking
Hydrogen-induced crack growth could
be a form of SCC in some
material/environment combinations.

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 Facts about hydrogen in
steel
General comments
– Before hydrogen can enter a metal, it must first adsorb
on the metal surface as atomic hydrogen. Thus, newly
created atomic hydrogen is necessary to enter into metal.
– Atomic hydrogen can diffuse through a metal lattice
because of its smaller size; molecules of hydrogen
cannot due to their lager size.
– Atomic hydrogen diffusing through a metal lattice can
combine to form molecular hydrogen within
structural defects such as voids, microcracks, or
discontinuities around inclusions.

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Facts about hydrogen in steel (cont.)
Solubility of hydrogen
– The solubility of hydrogen in metals is a function of
metal physical form (solid or liquid), crystalline lattice,
alloy content, temperature, and hydrogen partial-
pressure in the environment.
Rising temperature causes the increase in H solubility.
When α-Fe (body-centered cubic) transforms to γ-Fe (face-centered
cubic lattice), H solubility increases.
At melting point when liquid iron forms, the H solubility increases
significantly.
S = k p1/2, where p is the H partial pressure.
Steels with a lower solubility for hydrogen may have a greater
tendency for embrittlement.
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 Facts about hydrogen in steel (cont.)
Effects of hydrogen on mechanical properties of steel
– The effects of hydrogen on the mechanical behavior of
steels are generally controlled by:
The form of the hydrogen in the steel (atomic or molecular)
– Molecular H forming in steels create blisters, and does not
cause
embrittlement of the steel.
The strength level and stress-state of the steel
– In annealed steels stressed below their yielding point, the most
likely damage to occur from H charged into the steel is
blistering.
– Hardened, cold-rolled, or highly-stressed steels are more likely
to be mechanically embrittled or cracked as a result of
hydrogen entry.
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Hydrogen embrittlement
Hydrogen embrittlement
Sources of hydrogen in steel
Hydrogen ions can be “plated out” on the steel surface along with
the metallic cation during electroplating and enter the steel. This
phenomenon is particularly prevalent in chromium plating.
When steel is acid-pickled, hydrogen is liberated in the
corrosion reaction and may enter the steel. Electrolytic pickling
can also introduce hydrogen into the steel (cathodic charging).
Furnace atmospheres of hydrogen can result in hydrogen entry
during heat treatment of steel.
Hydrogen pickup in welding can lead to cracks in either the weld
metal or the heat-affected zones (HAZ). Moisture in coated
welding electrodes is a common source of such hydrogen.
Certain service environments can introduce hydrogen into steel:
(1) High-pressure hydrogen, (2) the reaction of steam with iron
at high temperature, and (3) corrosion of steel.
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Electroplating
Acid-pickled
Welding
Service environments-H2 pipe
Cathodic reaction of corrosion
Hydrogen entrance/diffusion
Hydrogen trapping
Hydrogen trapping
Hydrogen trapping case
Hydrogen trapping case
Hydrogen trapping case
Hydrogen trapping case
 Effects of hydrogen
Theoretically, once hydrogen has been
absorbed by a material, its effect, whether
from a gaseous (hydrogen gas) or
cathodic source (corrosion), is essentially
the same.

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Effects of hydrogen on metals
Hydrogen Degradation

HE

HIC
 High temperature case

Decarbonisation
– Diffusion of hydrogen into steels at high
temperature
– Reaction between H and C to form CH4
– CH4 close to the steel surface is released
– little effect
– CH4 in the bulk steel,
De-carburisation of carbide in pearlite to
cause loss of mechanical properties
Accumulation of methane in micro-pores to
initiate cracks
 Low temperature case
HIC, SWC

Internal hydrogen (bulk process)

– HIC
– Stepwise cracking (SWC)
– Stress oriented hydrogen induced
cracking (SOHIC)
– Blistering
Requirements
– Presence of pores or micro-
SOHIC
voids
– Presence of certain amount of
hydrogen
– The material remains ductile
beside the presence of
hydrogen
– Stress could be required or
not required.
 Internal hydrogen causing HIC,
SWC and SOHIC
H remained in steel Blistering
Mechanisms
– Accumulation
of hydrogen at
the defects HIC
– Increase of the
local pressure
– Cause mechanical SOHIC
rupture by
formation of cracks
and blisters. SWC
 External hydrogen causing
SSC and HSC
Hydrogen is produced by external sources (Corrosion/H2).
The presence of hydrogen permeating catalysers, such as
sulfides (H2S), increases the hydrogen entry into steels.
Strong perturbation of the crystallographic network, and
creation of local stress.
Mechanical load + local stress causes nucleation of cracks,
which
– start from the surface
– are perpendicular to the main stress axis
– are below the elasticity limit (yield stress)
Local stress
Local stress
Sensitive location for HIC
 Summary
• H can be introduced by external sources, or
remained after manufacturing.

• Specific microstructure can serve as H trapping sites

and preferential sites of cracking.

• H can influence mechanical property and cracking

behavior of a steel components, depending on
complicated factors.

• HE/HIC should be studied based on case-by-case

criteria.
 Corrosion Fatigue

Corrosion fatigue is the conjoint action of a

cyclic stress and a corrosive environment
to decrease the number of cycles to
failure.
– The basic role of the corrosive environment is
to decrease the life of the component.
– In comparison to the life when no corrosion is
present.

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 Cyclic stress: Amplitude
Types of stress for fatigue tests include:
– Axial (tension – compression)
– Flexural (bending)
– Torsional Mean stress    min
m  max
2

(twisting)
Stress amplitude  a   max  
min
2
Stress range  r   max  
min

 min
Stress ratio R 
 max

Generally, tensile stresses are positive and compressive stresses are negative.
 Cyclic stress: Shape
Examples of stress
cycles where
– (a) the stress in
compression and
tension
– (b) greater tensile
stress than
compressive stress
– (c) all of the stress
is tensile.
 S- N curves of metals
Strength, S

Fatigue fracture
strength

Number of
cycles, N

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Effect of corrosion on S-N curves

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 Features of fatigue failure

Fatigue is a surface initiated process in

that the fatigue cracks usually initiate on
the exposed surface of a smooth sample.

The crack initiation time may be from 25

to 50% of the number of cycles to
failure.

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Schematic diagram of the fatigue processes
D islo ca t io ns

1 11
1 11

Persistent Slip
Band

S urf a ce
S t age 1

Slip lines

S t age 11 25
Fatigue crack initiation – Stage 1

It is usually accompanied by plastic

deformation at 450 to the applied stress
axis. These are called persistant
dislocation slip bands.

The crack length in stage 1 is usually very

small.

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Fatigue crack propagation – Stage 11
At the end of stage 1, the crack macroscopically
propagates at 900 to the stress axis in stage 11 of the
process. At this point multiple slip processes are
occurring which lead to blunting of the crack tip and the
formation of striations on the fracture surface.
The striations are at 450 to the crack growth directions and
look like waves on the ocean surface in form. The
striations represent one burst of crack growth but may take
more than one cycle to form. Striations are characteristic
of the fatigue process.
The time from initiation until the last cycle is taken up
by crack growth in stager 11 of fatigue, so it may take
from 75 to 50% of the fatigue life.
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Fatigue crack propagation – Stage 111
Stage 111 follows stage 11 and operates when the
remaining cross section of material is too small
to withstand the applied stress and tensile shear
overload failure occurs forming a final shear lip at
450 to the surface.
The shear lip size depends on the strength of the
material and the range of the applied stress.
The features on the surface in stage 111 consists of
tensile shear dimples.

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Features of corrosion fatigue failure

The effect of a corrosive environment

in addition to the cyclic stressing
will be felt in stage 1 and 11 of the
fatigue process.
– Stage 111 is usually a mechanical
fracture process.

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 Effects of corrosion on Stage 1

In the absence of a corrosive environment,

the localized plastic deformation in the
form of persistent dislocation slip bands
(PSB's) will initiate cracks.
The role of a corrosive environment is to
reduce the crack initiation stage by
inducing additional initiation mechanisms.
(make it faster)

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Effects of corrosion on Stage 1 (cont.)

Additional initiation mechanisms include:

– Dissolution of metal after mechanical disruption
of passive films by PSB's.
– Metal preferential dissolution simply due to
active sites in PSB's.
– Dissolution of grain boundary regions due to
compositional effects, for example
sensitized steels.
– Pitting corrosion.

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Effects of corrosion on Stage 11
The effects on stage 11 fatigue can be
separated out by using pre-cracked
samples to conduct test.
– The data can be plotted as the crack
propagation rate per cycle against the log of
the stress intensity range.
– Corrosion fatigue cracks are usually of the
transgranular type although a few exceptions
do exist. The general role of the corrosive
environment at the crack tip is to accelerate the
crack growth rate.
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 Mechanisms for Stage 11 crack
propagation
One mechanism that may be involved is the
general corrosion of the crack tip in
extending the crack length at all times in
addition to the increase in crack length from
the mechanical stressing. The crack tip can
then be considered to be extending with an
increase in the crack growth rate.

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Fatigue crack growth rate during
fatigue process
stress intensity range

where σ is the applied stress, a is the crack

size, and Y is a dimensionless geometry
factor that is dependent on the geometry
of the crack, the geometry of the part, and
the loading configuration

The values Y and a are dependent on

geometry, so for a specified crack and
part geometry, the stress intensity
factor is proportional to applied
stress
 Determination of fatigue crack growth
rate and stress intensity factor
A fluctuating stress intensity drives the crack to grow at some
rate. When a stress intensity range ΔK is applied to a material
for some number of cycles ΔN, this drives the crack to grow in
length by a specific amount Δa. The growth rate of the crack at a
specific stress intensity range is then given by the ratio Δa/ΔN. In
continuous form, the crack growth rate is given by the
derivative da/dN.

A stress intensity range can be calculated

from the stress intensity equations if the stress
range, crack length and sample geometry are
either measured or known.
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Typical fatigue crack growth rate

with
corrosion
log (da/dn)

Stage 11 Crack
Propagation
Region

Kt
h log
K
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 Prevention method
Choose materials with low fatigue crack propagation rates.
– Materials can withstand fatigue by two methods. The first is to resist
initiation but have a rapid growth rate. The second is to allow easy
crack initiation but have a slow crack growth rate. For corrosion
fatigue resistance the second is the better material as in corrosion
fatigue crack initiation is accelerated by pitting etc.
Reduce stress by thicker sections, design changes.
Induce compressive stresses.
Inhibitors stop corrosive action.
Cathodic protection.
Coatings, both organic (paints) and inorganic (zinc, chrome
plates etc).

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