Environment Assisted Cracking

ME 472: Corrosion Engineering

Dr. Zuhair M. Gasem

ME Department
King Fahd University of Petroleum and
Minerals
Dhahran Saudi Arabia
 Environment Assisted Cracking
Dr. Z. Gasem
ME 472-061 2
KFUPM

A metal in a corrosive environment and under

mechanical loading can fail due to one of three
cracking modes depending on the nature of the
environment and the applied stresses:
Under static Stress
Stress Corrosion Cracking
In Hydrogen containing environments
Hydrogen Induced Cracking (HIC)
Hydrogen Embitterment (HE)
Hydrogen Blistering
Under cyclic loading:
Corrosion Fatigue
 Types of Fracture
Dr. Z. Gasem
ME 472-061 3
KFUPM

A metal breaks or
fractures in two ways:
Ductile fracture (high
resistant to crack growth; ductile
intense deformation before
fracture)
Brittle fracture (low
resistance to crack growth;
little deformation and
sudden fracture) Brittle

Two types of brittle crack

path:
Intergranular (crack
travels between grains)
Transgranular (crack cuts
through grains)
Dr. Z. Gasem
ME 472-061
KFUPM
Stress Corrosion Cracking (SCC) 4

SCC: a brittle cracking process

resulting from the simultaneous Stress
action of a tensile stress and a
specific corrosion environment.
The metal is ductile if tested Tested in
in other environments. environment
The metal is brittle if tested in causing SCC
the specific environment
SCC is hazardous because: Tested in
brittle fracture occurs rapidly environment not
and suddenly (no prior causing SCC
warning) which can lead to brittle
catastrophic failure (before
Strain
damage can be inspected)
Ductile
 SCC
Dr. Z. Gasem
ME 472-061 5
KFUPM

Stress Corrosion Cracking is

caused by the combined action
of a tensile stress plus a
specific corrosive
environment and
temperature on a susceptible
alloy.
The static stresses may be due
to:
residual stresses
welding
fabrication or repair
applied (the working load)
SCC always starts at stress
raisers such as notched and
sharp corners which elevate
the applied stresses.
 SCC
Dr. Z. Gasem
ME 472-061 6
KFUPM

Three components of SCC:

1. a tensile stress
2. a specific environment
3. a susceptible
alloy/microstructure
Eliminating any one of these
components will prevent
SCC
Example: SCC in a pressure
vessel made out of Ti alloy
and exposed to N2O4
Fracture took place in 34 h.
 SCC
Dr. Z. Gasem
ME 472-061 7
KFUPM

SCC occurs in specific

combination of
alloy/environment
Carbon steel in caustics (NaOH
or KOH) (pH>10)
Carbon steel will not SCC in
acidic solution
Stainless steels in chloride
solutions (Cl-)
Copper alloys in ammonia
(NH3)
Aluminum alloys in hot pure
water or steam
Example: 304 SS HE tubes
carrying chloride-containing
environment at 120 C.
The crack grew from inside the
tube to the outer diameter.
Dr. Z. Gasem
8
ME 472-061
KFUPM
Metal/environment Combination Exhibiting SCC
Dr. Z. Gasem
9
ME 472-061
KFUPM Metal/environment Combination Exhibiting SCC
 SCC
Dr. Z. Gasem
ME 472-061 10
KFUPM

Features of SCC:
Multiple cracks and
branching
TG
The longest crack grow
normal to tensile stresses
the stress causing SCC is
elastic (lower than the
yield strength of the alloy)
Alloys are more susceptible
than pure metals
little metal loss by general
IG
corrosion
Cracks can be
intergranular (IG) or
transgranular (TG)
 Industries Suffering from SCC
Dr. Z. Gasem
ME 472-061 11
KFUPM

Chemical industries: a study

showed that 1/3 of all
corrosion failures were due to
SCC
Petroleum industries: high
strength steel pipes in deep
high pressure wells containing
H2S
A serious problem in nuclear
power plants (Stainless steel
tubes)
A major problem in aircraft
industries (aluminum
alloys/seawater) Example: aircraft fuselage
made out of high strength
aluminum failed by SCC
 SCC of Pipelines
Dr. Z. Gasem
ME 472-061 12
KFUPM

SCC presented a major cause of

failure of older pipelines (>20 y).
The cracking is referred to as
carbonate and bicarbonate
cracking.
This is due to increased pH at the
external surface of the steel pipe
when carbonate (CO3-2 ) or
bicarbonates (HCO3-) react with
acids:
HCO3- + H+CO2 + H2O
Coating damage or tape wrap
disbondment expose the pipe
external surfaces to high
alkalinity soils.
Oxygen reduction further
increases the pH to high
alkalinity
Carbon steel shows SCC in
carbonate/bicarbonate soils
Many old lines are now being
recoated to reduce the risk of
failures.
 Case Study#1: Chloride SCC
Dr. Z. Gasem
ME 472-061 13
KFUPM

SCC of SS in chlorides is
called chloride SCC
After 13 years of use, the
roof of an indoor
swimming-pool collapsed.
Twelve people died on
1985 in Switzerland.
Chloride induced SCC of
SS.
The chloride possibly
came from the pool via
water evaporation.
Dr. Z. Gasem
14
ME 472-061
KFUPM Case Study#2: Caustic SCC in Steel

SCC of carbon steels in

alkaline solution is called
caustic SCC
A section from 4 carbon
steel steam line transports
steam to the boiler feed
water deaerator showed
numerous cracks and had
to be replaced after 10
years in service. The
steam temperature and
pressure were reported to
be 250 F and 5 psig.
 Thermal Power Plant
Dr. Z. Gasem
ME 472-061 15
KFUPM

1. Boiler
2. A drum
3. HP turbine
4. MP turbine
5. LP turbine
6. Condenser
7. Re-heater
8. Feed-water
pump
9. Burner
 Observations
Dr. Z. Gasem
ME 472-061 16
KFUPM

Several cracks at the

weld metal were
observed from the
outside using
magnetic particle
inspection
 Observations
Dr. Z. Gasem
ME 472-061 17
KFUPM

numerous cracks
observed on the
internal surface of the
line
root toe cracks

cracks growing normal

to the weld emanating
from the root weld
 Observations
Dr. Z. Gasem
ME 472-061 18
KFUPM

Excessive crack
growth and branching
A metallographic cross
section of a growing
crack was taken
The crack path is
predominately
intergranular
 Observations
Dr. Z. Gasem
ME 472-061 19
KFUPM

Excessive branching and the intergranular crack paths

suggest that the observed cracks are primarily due to
stress corrosion cracking phenomena.
Carbon steel is generally immune to SSC in pure steam
water but susceptible to SCC in steams containing caustic
(NaOH).
Caustic is intentionally injected in small amounts to boiler
feed water to control the water pH.
Steam born NaOH can be trapped and accumulated at
flow discontinuities such as root weld toes
A localized highly concentrated caustic can develop near
the root welds and, if there is sufficient residual tensile
stresses, SCC would be inevitable.
 Conclusions
Dr. Z. Gasem
ME 472-061 20
KFUPM

The failed section of the steam line cracked

due to caustic stress corrosion cracking
resulting in excessive root weld metal cracking
and branching.
Stress relieve welds by post weld heat
treatment.
Improve the root pass weld to minimize flow
discontinuities.
The amount of caustic injected to the steam
should be minimized as possible.
 Sources of Tensile Stresses
Dr. Z. Gasem
ME 472-061 21
KFUPM

Loading stresses
Residual Stresses:
compressive stresses do not cause cracking
(shot peening is used to mitigate SCC).
tensile stresses resulting from fabrication techniques (welding,
press fitting, deep drawing, rolling of tubes, riveting, and
quenching with no subsequent stress relief treatment) can
produce high residual tensile stresses which may lead to SCC.
corrosion products from general corrosion may build up in
constricted regions and generate high stresses.
Post-fabrication stress relieving (Post Weld Heat
Treatment, PWHT) is a method to reduce residual
stresses.
 Two types of SCC
Dr. Z. Gasem
ME 472-061 22
KFUPM

Cracking modes:
a: crack without
environmental
effect
B: TG SCC
C: IG SCC
Transgranular SCC
Active metal path
dissolution
(chloride SCC in
austenitic SS)
Intergranular SCC
differences in
composition due to
segregation
Caustic SCC of C-
steel in caustic
 Stages of SCC
Dr. Z. Gasem
ME 472-061 23
KFUPM

SC cracking occurs by initiation and growth.

environmental cracks are microscopic in their
early stages of development and cant be
detected by visual examination. SC cracks can
initiate from stable pits in some
alloy/environment system. Crack can take some
time to initiate (induction period).
SC cracks grow and penetrates further in the
susceptible material and may lead to sudden
fracture.
 Mechanisms of SCC Initiation
Dr. Z. Gasem
ME 472-061 24
KFUPM

Cracks can be generated by

pits formation and growth in passivating metals and
alloys
Crevice corrosion under thermal insulations (can be
detected by infrared scan detecting cold spots)
Deformation slip steps at surfaces are precursor for
cracks in non passivating metals
Initiation stage can be neglected due to the presence
of fabrication defects:
Weld defects = 0.1 to 0.5 mm
Critical crack size in SCC of SS/NaCl vary from 0.01 to 0.2
mm
 SCC in Steel Alloys
Dr. Z. Gasem
ME 472-061 25
KFUPM

carbon steels are susceptible to SCC in

caustic solutions
SCC of carbon steels occur commonly in
crevices between rivets and bolt heads in
water boilers with added NaOH to control the
pH.
SCC observed on the external surfaces of
buried carbon and low-alloy steel pipeline
used to transport petroleum and natural gas.
 Methods to Control SCC
Dr. Z. Gasem
ME 472-061 26
KFUPM

Stress Corrosion Cracking Control

Mechanical Metallurgical Environmental

Avoid Stress Concentrations Change alloy microstructure Modify Environment

Relieve fabrication stresses Use metallic coatings Apply cathodic protection

Reduce applied stresses Change alloy composition Add inhibitor

Introduce compressive stresses Use organic coatings

Dr. Z. Gasem
27
ME 472-061
KFUPM
NACE Guide for Alloy/Electrolyte Susceptible to SCC
Dr. Z. Gasem
ME 472-061
KFUPM SCC Evaluation for Smooth Specimens 28

Evaluation of the total

SCC life which includes
initiation and
propagation.
Smooth specimens may
be tested under
constant extension
(constant strain):
U-bend specimen
C-ring specimen
constant load
 Hydrogen Damage
Dr. Z. Gasem
ME 472-061 29
KFUPM

Hydrogen damage: failure of

metals and alloys due to the
presence of hydrogen.
Occur most frequently in
carbon steels, low alloy steels,
and high strength steels.
Hydrogen is available in
aqueous solutions and in moist
air.
H atom is very small and can
diffuse easily in metals even at
room temperature.
 Types of Hydrogen Damage
Dr. Z. Gasem
ME 472-061 30
KFUPM

At room temperature:
Hydrogen embrittlement (high strength steels
yield strength>90 Ksi (620 MPa))
Hydrogen blistering (intermediate strength
steels)
Hydrogen Induced cracking
At high temperatures:
Hydrogen attack
Hydride formation (in Fe, Ni, Ti, and Zr)
 1. Hydrogen Embrittlement
Dr. Z. Gasem
ME 472-061 31
KFUPM

Hydrogen embrittlement occurs

when hydrogen atoms diffuse into
a metal and cause a loss of tensile
ductility.
Example: high strength steels
(quenched and tempered)
containing small amount of
dissolved hydrogen (few parts per
million ) suffer loss of ductility and
may fail in a sudden brittle fracture
under high tensile loading.
Sources of hydrogen can be: acid
pickling, electroplating, rain,
cathodic protection, welding,
atmospheric corrosion, and
aqueous corrosion.
A major catastrophic failure was
the collapse of a large canopy over
the entrance of the Berlin
Congress Hall due to HE of high
strength steel structures.
 1. Hydrogen Embrittlement
Dr. Z. Gasem
ME 472-061 32
KFUPM

atmospheric corrosion
can generate
sufficient atomic
hydrogen to embrittle
high tensile fasteners
and cause failures.
The figure shows a
high strength steel
bolt failed due to HE
after 10 years in
service.
 1. Hydrogen Embrittlement
Dr. Z. Gasem
ME 472-061 33
KFUPM

Pre-tensioned high strength steel beams in

bridges suffer from HE.
Hydrogen is produced during welding of moist
steel surfaces.
Hydrogen generated in arc welding from the
welding flux dissolves in the liquid weld metal as
atomic hydrogen.
After the weld metal solidifies, atomic hydrogen
diffuse into the heat affected zone where higher
stresses may lead to failure due to hydrogen
embrittlement.
 2. Hydrogen Blistering
Dr. Z. Gasem
ME 472-061 34
KFUPM

Occur in low strength steels exposed to

hydrogen atmospheres for long time
Reduction of hydrogen ions in acidic
solutions produces atomic hydrogen
H+ + H+ + 2e- = H2 (gas evolution; no
harm)
Certain environments prevent H
combination and produce H atoms (H2S)
H+ + H+ + 2e- = H + H (adsorbed
hydrogen atoms)
H atoms diffuse into the metal
H atoms will combine and form H2 at
internal voids and inclusions (MnS) near
the surface and build up high pressure
(can go up to 300 atm) and may rupture
the voids
Blisters (1mm-10mm in diameter) act as
internal cracks
Dr. Z. Gasem
ME 472-061
KFUPM
2. Hydrogen Blistering 35

Steel pipeline transmitting wet

sour gases (gas containing H2S)
and sour crude frequently suffer
from H blistering.
H2S prevents combination of H
atoms at the surface to form H2
allowing high concentration of
free H atoms on the surface
which consequently enter the
metal.
Good quality steels clean steels
with minimum inclusions (mainly
MnS) are required for oil filed
equipment used in sour gases
and crude transmissions.
Steels are tested against
hydrogen blistering before using
in sour applications.
 3. Hydrogen Induced Cracking
Dr. Z. Gasem
ME 472-061 36
KFUPM

The hydrogen gas molecules trapped at the defect can lead to

hydrogen induced cracking (HIC) and stepwise cracking
(SWC) in steel containing large inclusions. The process requires:
high internal hydrogen pressure to form blisters
local stresses cause adjacent small blisters to link up
HIC link up along adjacent blisters by a ductile tearing to form
stepwise cracking.

HIC SWC
SWC in pipeline steel
Dr. Z. Gasem
ME 472-061
KFUPM
Prevention of Hydrogen Damage 37

Selection of resistant materials to HD

Lower strength materials are more resistant to HD
Coatings and linings
Compressive residual stresses

Lowering the stress

Remove any hydrogen combination poisons

Bake-out treatment to remove internal hydrogen

from steel (heat at 175 C for three hours)
 Corrosion Fatigue
Dr. Z. Gasem
ME 472-061 38
KFUPM

Corrosion Fatigue: accelerated initiation and

propagation cracking under the combined action
of a cyclic stress and a corrosive environment.
Fatigue resistance to initiation and propagation
are reduced in a corrosive environment as can
be seen in the S-N curves.
All metals and alloys are sensitive to corrosion
fatigue in any corrosive environment
Common parts fail by corrosion fatigue: ship
propeller shafts, wire cable in wet environments,
pipes cracking from thermal cycling.
 Corrosion Fatigue
Dr. Z. Gasem
ME 472-061 39
KFUPM

Metal components under fatigue

loading are selected according to
their fatigue strengths (the stress
below which no failure take place).
The fatigue strengths of steels in
air are about 50% of their tensile
strengths.
In corrosive environments, fatigue
strengths are around 10-20% of
their tensile strengths.
Example: an Al alloy under fatigue
load of 150 MPa:
fail after 2x106 cycles in air
fail after 2x105 cycles in tap water
 Corrosion Fatigue
Dr. Z. Gasem
ME 472-061 40
KFUPM

Notched
Notches reduce fatigue Smooth
strengths further. specimens specimens

In smooth components:
Endurance limit for smooth
steel alloy in air = 400 MPa
Endurance limit for smooth
steel alloy in distilled water =
300 MPa
Endurance limit for smooth
steel alloy in seawater = 120
MPa
In notched components:
Endurance limit for smooth
steel alloy in air = 150 MPa
Endurance limit for smooth
steel alloy in distilled water =
100 MPa
Endurance limit for smooth
steel alloy in seawater = 60
MPa
 Corrosion Fatigue in Oil Field
Dr. Z. Gasem
ME 472-061 41
KFUPM

In oil wells, a pump is used to lift

the oil in the reservoir.
The most common pump is
known as a sucker rod pump.
The up-and-down movement of
the sucker rods drives the oil up
the tubing to the surface
This reciprocating movement
subject the rod to fatigue loading
due to its weight.
Crude oil includes salt water and
is extremely corrosive Sucker rod
The rod commonly fails by
corrosion fatigue (2/3 of the
wells will have corrosion fatigue
failure of sucker rods every year)
 Features of Corrosion Fatigue
Dr. Z. Gasem
ME 472-061 42
KFUPM

Crack growth is
perpendicular to loading
with no branching (as
opposed to SCC)
Cracks usually start at
corrosion pits at the
surface
Cracks usually are
transgranular
Beach marks are usually
observed in steel alloys
failed by fatigue
Dr. Z. Gasem
ME 472-061
KFUPM
Corrosion Fatigue Variables 43
Dr. Z. Gasem
ME 472-061
KFUPM
Sources of cyclic stresses 44

Cyclic stress could be due

to:
Rotating shafts
Vibration induced fatigue
Changes in pressure in
tubes and pressure vessels
Take off and landing in
aircraft
An example: corrosion
fatigue failure of boiler
tubes due to fluctuation in
internal pressure.
Dr. Z. Gasem
ME 472-061
KFUPM Prevention of Corrosion Fatigue 45

Reduce design stresses and remove

residual tensile stresses
Shot peening to introduce compressive
stresses
Use of inhibitors is effective in reducing
corrosion fatigue cracking
Cathodic protection

Avoid stress raisers such as notches

Coatings with continuous maintenance