Module 8, Objective 2

(part 3/3)
Types of Corrosion, pg. 21-27

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Objectives
• Identify the corrosion mechanisms for given conditions.

1) General or Uniform
2) Galvanic*
3) Crevice and Pitting*
4) Temperature gradient
5) Velocity gradient
6) Cavitation
7) Fretting
8) Atmospheric (dry, damp, wet)
9) Stray current
12) Stress corrosion cracking (SCC)*
10) Biological
11) Intergranular (IGC), Exfoliation
13) Hydrogen induced cracking (HIC)*
12) Stress corrosion cracking (SCC)*
13) Hydrogen induced (HIC/SSC)*, Hydrogen blistering
14) Corrosion fatigue
14) Corrosion fatigue cracking
15) Selective leaching
15) Selective leaching
16) Graphitization 16) Graphitization
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12) Stress Corrosion Cracking (SCC)*
• Stress corrosion cracking (SCC) is one of the most serious corrosion problems in
industry
• Very difficult to detect
• Usually no measurable metal loss, bulging or yielding of the metal
• Cracking grows 90° into the surface in otherwise safe environments
• Catastrophic failure may occur without warning

SCC occurs only when two factors are present:

1. Stress (tensile stress specifically)
• May be below the yield point
• Stress may be internal residual stress (e.g. work hardening, quench hardening, thermal
stresses) or external tensile stress (e.g. load bearing, high pressure pipe)
2. Environment/material combination
• Each material will experience SCC in different environments
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Environment/Material Combinations

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Story Time!
A leak was detected along
the pipeline right-of-way

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Engineering Technologists
were sent to the scene to
determine the cause…

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The orientation of the
crack is strange.

Typically most of the

stress in a pipeline is
hoop stress, so most
cracking occurs
longitudinal to the
pipe.

This crack is
transverse. What
stresses must have
been acting on this
location?

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A closer look…
Is the large crack the only
crack present?

“Colonies” of cracking is
typical of SCC.

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 The Fracture Surface
You haven’t been trained in fractography (yet), but what do you see here?
The light grey to the sides is likely from cutting this failure out.
What can you tell from the darker region? How did this failure progress?

The darker black colour would be the corrosion products.

• SCC progressed from the surface through the majority of the pipe’s wall thickness.
The remaining material failed when there was only about ¼ of the material remaining.
• The darker grey region looks like overload failure (once the applied stress > UTS) 10
12) Stress Corrosion Cracking (SCC)
All types of SCC require the same two factors:
➢ Stress + Environment/material combination
• Stress opens up the cracks, pulling the bad environment down into
the cracked region
• The environment gets down to the crack tip, reacting with the metal
there and allowing the crack to propagate further
The science behind what causes SCC is poorly understood, but the three
basic mechanisms we will discuss are:
a. active path corrosion,
b. film induced cleavage, and
c. caustic embrittlement.
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12a) SCC – Active Path Corrosion
• Active path corrosion is the rapid corrosion/cracking along a path that has
a high reactivity compared to the rest of the material.
• The most common active path is the grain boundary
• Segregation of impurity elements can make it more difficult for passivation to occur
(e.g., sensitized austenitic stainless steel).
• Like intergranular corrosion (IGC), but the applied stress
increases the rate by opening up cracks
• Opened crack allows easier diffusion of the environment to
and away from the crack tip
• Cracking also means a little metal loss results in a large wall
thickness loss!

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12b) SCC – Film Induced Cleavage
• Film-induced cleavage occurs when the surface film cracks
• The bare metal is a very small anode and the remaining oxide film is the cathode.
• Cracking will follow the crystal plane into the grain (transgranular) until it hits the
next grain where it will change direction following the new crystal plane.

• Chloride SCC in austenitic stainless steels is an

example of film-induced cleavage.
• The presence of chlorine will prevent the slipped
region from forming a passive oxide surface.
• These steels, which are normally ductile, will now crack
in a brittle manner.

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12c) SCC – Caustic Embrittlement “Caustic” in this case
means “strongly basic”

• Caustic embrittlement is another form of SCC which has historically been

responsible for some of the most catastrophic boiler explosions.
• In order to protect boiler steel from aqueous corrosion, it is standard
practice to raise the boiler water to a pH between 9 and 11.5
• Carbon and low alloy steels are
not typically corroded by basic
solutions, but strong basic or
caustic solutions can cause
SCC.

• Too high pH is bad, but a

slightly higher pH helps to
prevent corrosion.
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How High pH Helps Boilers
1. Presence of some base (OH-) ensures no acid (H+) is present
• Neutralization: OH- + H+ → H2O
• Acid would increase the corrosion rate dramatically

2. Formation of a passive iron oxide layer

• Magnetite (Fe3O4), also called “black oxide”
• Naturally occurring magnetic iron oxide, “lodestone”
• Adherent to the surface, protecting the metal beneath
• Forms at high temperature, low oxygen content, pH 5-12
• Below pH 5 or above pH 12, the magnetite coating becomes soluble in water

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• Too high pH (>12) causes
“caustic corrosion”

• Magnetite exists
between pH 5-12

• High pH >12 causes

dissolution of the
protective magnetite
layer (black oxide)

➢Increases corrosion rate

at higher pH
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12c) SCC – Caustic Embrittlement
So we are intentionally making our boiler water basic (pH 9 to 11.5), but
basic solutions aren’t a problem until pH > 12… How does that happen?
“Wick Boiling”, AKA “Caustic Wicking”
• Wick boiling causes the basic solution to become more concentrated in
local cracks, crevices and porous deposits in high heat areas.
• As the water boils, the hydroxide is left behind which raises the pH (>14).
• Iron under stress (pressure) will crack in a strong caustic environment
• SCC initiates at these crevices, eventually causing a catastrophic failure.
• Boilers used to be riveted, and frequently failed in the crevice between the
joined metal. Now most boilers are welded to eliminate this problem.

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13) Hydrogen Induced Cracking (HIC)*
• Hydrogen induced cracking (HIC) or hydrogen embrittlement
occurs when hydrogen dissolves into a metal.

Three Steps
1. Creation of monoatomic hydrogen
2. Hydrogen embrittlement
3. Diffusion to hydrogen sinks, formation of H2 gas

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13) HIC – Step 1: Monoatomic Hydrogen
• Hydrogen typically exists as a diatomic molecule, H2 gas
• H2 is too large to fit into the iron’s crystal structure, so will never diffuse into
the steel
• Only monoatomic hydrogen (H) will dissolve into the metal
• H is very small, so fits into interstitial sites between the metal atoms
• Small size also allows H to diffuse very rapidly, even at room temperature
• How does monoatomic hydrogen (H) form?
• Electric arc welding
• Any water or hydrocarbons will ionize in the arc (H2O → 2H+ + O2-)
• Electrolysis
• Ex: chrome plating, where the voltage used to plate the metal can cause water to ionize
• Certain types of corrosion
• Most commonly in the presence of sour gas, H2S
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13) HIC – Step 2: Hydrogen Embrittlement
• Once hydrogen has dissolved into the metal, it exists as an
interstitial solid solution
• Hydrogen in the interstitial sites distorts the crystal structure
• Loss of ductility (ex: elongation might drop from 42% to 7%)
• Loss of impact toughness
• This is known as “hydrogen embrittlement”
• Ferrite alone is quite ductile, so will retain some ductility
• Usually relatively safe from hydrogen induced cracking (HIC)
• Martensite is a bigger problem
• Any martensite present will be even less ductile than usual
• Severe risk of hydrogen induced cracking (HIC)
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13) HIC – Step 3: Hydrogen Sinks
• Hydrogen diffuses through the metal until it finds a precipitate, void or defect
• These act as “hydrogen sinks”, collecting H which combines to form H2 gas.
• H2 has a volume approximately four times larger than single hydrogen atoms,
which creates pressures in excess of 23 ksi.
• Huge internal pressure will cause fracture in brittle metals.
• Too bad hydrogen also causes our metal to become brittle…

Embrittlement + Pressure (H2 gas) = Cracking

• Both mechanisms work together to cause a sudden brittle fracture.

• Crack growth rates are rapid, causing the steel to fail with little warning!

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HIC Initiation - “Fish Eyes”
• H2 gas builds up at hydrogen sinks
(often precipitates), causing a
brittle fracture due to pressure

• Initial failure radiates out from the

hydrogen sink in all directions,
creating a “fish eye”

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13) HIC Prevention
Contributing Factors:
• Presence of hydrogen
• Monoatomic H only forms from certain processes.
• Diffusion rate is high enough that most of the hydrogen diffuses out of the metal within the first 48 hours, even at room temperature.
• Presence of martensite
• Best to keep hardness HRC < 22. At this hardness, the steel should not contain any martensite.
• Tensile stress
• External stress or internal residual stress (ex: plastic deformation, thermal stress from welding, etc) will work to open any cracks.
• Low temperature
• At higher temperatures, the susceptibility to cracking is reduced.
• The diffusion rate of hydrogen is high enough at high temperature (>150°C) that it passes through the vessel wall without forming H2.
• Welds are often post-weld heat treated for this reason (up to ~650°C), allowing the hydrogen to escape in a matter of hours.
• The shape of precipitates or inclusions in the steel.
• Hydrogen will collect at any inclusion, but flat, sharp inclusions will initiate cracking more easily than round inclusions.
• MnS is a large concern because it tends to become flattened during rolling.
• The number of precipitates or inclusions in the steel.
• Removing all inclusions will prevent the hydrogen from collecting to form H2, so it will diffuse without causing cracking.
• On the other hand, a large number of fine, round precipitates will cause the hydrogen to spread out more evenly and fail to initiate
cracking. However, the precipitates will also decrease ductility.

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13b) Sulphide Stress Cracking (SSC) Note: SSC is different from SCC!

• Sulphide Stress Cracking (SSC) is known by a number of different names:

• Hydrogen sulphide cracking, sulphide cracking, sulphide stress corrosion cracking, sulphide corrosion cracking

• SSC is a form of HIC in the presence of hydrogen sulphide (sour gas, H2S).
H2S + Fe → FeS +2H Does not form H2 gas! The presence of H2S “poisons” the
reaction to form H2, creating monoatomic hydrogen instead
Yellow corrosion product (good clue!)

• Not only is the H2S corroding our iron directly, it is also causing HIC!
• The monoatomic hydrogen causes cracking as discussed previously:
1. Diffuses into the metal
2. Embrittles the iron-iron bonds (interstitial H)
3. Collects at sinks (to form H2 gas)

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13b) SSC Prevention
Contributing Factors:
• Hydrogen sulphide must be present.
• The time for failure to occur decreases as the H2S concentration increases.
• Failures can occur at concentrations as low as 0.1 ppm in water.
• Water (electrolyte) must be present.
• The H2S cannot react with Fe unless there is at least trace amounts of H2O present.
• High strength steel must be involved.
• Cracking increases as the hardness increases.
• NACE standard for sour gas service requires HRC < 22 HRC (no martensite present).
• Low pH (acidic environment) promotes cracking
• Keeping pH > 9 ensures excess OH- is present, neutralizing any H+ that is released.
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13c) Hydrogen Blistering
• Hydrogen blistering is a special case of HIC that occurs when:
• The steel has been rolled (usually hot rolled)
• The steel is ductile (often ferrite, martensite is not necessary)
• A large amount of hydrogen is present
A steel plate showing hydrogen blistering
• Rolled steel will have “segregation bands”
with large numbers of inclusions.
• Hydrogen enters the steel, forming H2 gas at
multiple inclusions along the segregation
band.
• Cracking jumps from inclusion to inclusion.
• Join together to form one extremely large crack
along the centerline: a “blister”
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14) Corrosion Fatigue Cracking
• Cyclic stress causes fatigue (load/unload/load/unload, etc.)
• Cyclic stress in a corrosive environment will make fatigue worse

• Once a crack is started, it will open and close repeatedly

➢Each time the crack opens, corrosion reagents are replenished at
the crack tip

• Corrosion leads to greater crack propagation per cycle than with cyclic
stress on its own.
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15) Selective Leaching, AKA “Dealloying”
• Caused by the galvanic difference between elements in an alloy
• “Leaching” means dissolving something, leaving everything else behind.

Example: Brass
• Zinc is far more reactive than copper
• Dezincification in brass occurs when
zinc is preferentially corroded which
leaves red porous copper

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Dezincification of admiralty brass
16) Graphitization
• Occurs when steel is heated (>500°C) for long periods of time.

• The carbon transforms from iron carbide (Fe3C) into graphite

➢ Lower strength
➢ Increased corrosion rate
• Graphite is much less reactive than iron, so acts as a cathode to
the iron anode

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 Exercise 2 (pg. 28,29)
6. Stress corrosion cracking requires external or residual ___________
and a _______________________ environment.
7. Hydrogen blistering is caused by _____________ hydrogen joining together into
__________________ hydrogen within the metal.
8. Boiler metal is normally protected from corrosion by a coating of __________
which dissolves below a pH of ___ or above a pH of ____.
9. Caustic embrittlement is a type of _____________________.
19. Corrosion tends to _________________ as the pH decreases.
27. Identify the likely cause of failure for the following: The shank on a cast Copper
Nickel (alloy C71000) seawater valve was worn away by erosion. It was repaired by
welding 60/40 brass onto the valve shank to build it back up. Later buildup metal
material became porous, turned dark red and some of it broke off.
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 Bonus Questions
You are overseeing the welding of a pipeline joint on a rainy day.
What is your biggest concern?

Give a step-by-step explanation of how hydrogen can cause

cracking in steel.

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 Bonus Questions
You are overseeing the welding of a pipeline joint on a rainy day. What
is your biggest concern?
• Hydrogen induced cracking (the welding arc will ionize the water,
allowing monoatomic hydrogen to enter your steel)

Give a step-by-step explanation of how hydrogen can cause cracking in

steel.
1. Creation of monoatomic hydrogen, which diffuses into the steel
2. Hydrogen embrittlement due to H present at interstitial sites
3. Diffusion to hydrogen sinks, formation of H2 gas, build up of
pressure
Embrittlement + Pressure = Cracking
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