Corrosion Types 472 192 Comp Webct

ME 472
(Corrosion Engineering)
Corrosion Types/Follow these slides and class

discussions/notes
ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

Objectives;
Understanding different corrosion types and their

mechanisms
=>What and how it looks like (how to recognize?

=>Why? and where?
=>Monitoring?/Testing?
=>Control

Different Forms of Corrosion (identification 2)

Distribution of Corrosion Failures by Major Category

What is uniform corrosion?
Corrosion which occurs uniformly over the entire exposed surfaces of the material
General thinning of the material takes place
Uniform corrosion is relatively easily measured and predicted, making disastrous
failures relatively rare.
In many cases, it is objectionable only from an appearance standpoint.

What is uniform corrosion? Measurement
Specimen preparation
 Exposure to environment
 Specimen cleaning
 Measurement of change in specimen weight.
• Corrosion rate expressions.

- mm/y : mm penetration per year.
- gmd : grams/m2 day
- ipy : inches penetration per year
- mpy : milli-inches per year
- mdd : mg per square decimeter per day.

What is uniform corrosion? Measurement
Corrosion Coupons for weight loss measurement

What is uniform corrosion? Its control
This type of corrosion can be controlled by;
=>Organic coatings
=>by providing corrosion allowance
=>Using inhibitors
=> Cathodic protection
=>Better corrosion resistant materials (weathering steels)

What is Galvanic Corrosion?
• A Galvanic cell is formed when two dissimilar

metals are connected electrically while both are
immersed in a corrosive solution.
•The more active metals or alloys of the two is

corroded preferentially by galvanic corrosion.

What is Galvanic Corrosion? Important considerations
For galvanic corrosion to occur, three conditions must be present:

Electrochemically dissimilar metals must be present
These metals must be in electrical contact, and
The metals must be exposed to an electrolyte
And the severity of galvanic corrosion depends on:

 Relative potential difference b/w the metals (galvanic series)
 Area ratio of anode to cathode
Conductivity of the electrolyte

What is Galvanic Corrosion? Galvanic series vs. EMF series
•Galvanic series is a list of measured

Ecorr for various metals and alloys for
a given environment.
• EMF series arranged by standard

equilibrium potentials (half cell
potentials) under standard conditions
and only for pure metals
.

What is Galvanic Corrosion? Kinetics 1
Galvanic coupling Zn to Pt;

i ) shifts the corrosion potential of Zn from Ecorr to Ecouple.
ii ) increases the corrosion rate from icorr(Zn) to icorr(Zn-Pt).

What is Galvanic Corrosion? Kinetics 2
Effect of i0 by comparison of Zn-Pt and Zn-Au galvanic couples.
E°Au3+/Au = 1.498 V io,H2(Au) = 10-6 A/cm2

E°Pt2+/Pt = 1.2 V io,H2(Pt) = 10-3 A/cm2
icorr(Zn-Pt) > icorr(Zn-Au) > icorr(Zn)
Ecorr(Zn-Pt) > Ecorr(Zn-Au)

What is Galvanic Corrosion? Area effect example 1

What is Galvanic Corrosion? Galvanizing
Corrosion of a galvanic couple between two corroding metals
Zn - Fe couple in a deaerated acid solution
What is happening?

What is Galvanic Corrosion? Some conclusions
1) If two corroding metals are galvanically coupled, the corrosion rate of more active
metal( i.e. with more active corrosion potential) is accelerated, and that of the other
metal is retarded.
2) The polarity of electrode for galvanic couple should be defined on the basis of
corrosion potential.
3) Galvanic corrosion behavior can not be predicted accurately on the basis of EMF
series. Use galvanic series to predict corrosion behavior of galvanic couple.

What is Galvanic Corrosion? How to avoid?
1) Select combinations of metals as close together as possible in the galvanic series.

2) Avoid the unfavorable effect of a small anode and large cathode.
3) Insulate the components from each other.
4) Apply coatings with caution.
5) Add inhibitors into solution.
6) Install a third metal that is anodic to both metal in the galvanic series.

What is Intergranular Corrosion (IGC)?
GBS are considered more reactive than the matrix, however the
difference of the reactivity is not very high, so usually GB effects
are neglected
 However in few alloy systems, GBs can cause very severe

corrosion problem.
So IGC is
Localized attack at and adjacent to grain boundaries, with

relatively little corrosion of the grains.
The alloy, sensitive to IGC, disintegrates and/or loses its

strength when exposed to environments.

Causes of intergranular corrosion:
A. Segregation of impurities at the grain boundary

ex) Fe in Al alloys.
B. Enrichment of one of the alloying elements or depletion of one of these

elements in the grain boundary areas.

Intergranular Corrosion of stainless steels and nickel base alloys
Exposed temperature : 425 oC to 815 oC
Sensitization
This results from the preferential attack of

Cr_ depleted zone due to precipitation of
Cr23C6 at grain boundary.


Intergranular Corrosion (IGC) => Effect of C
304 (%C<0.08)
304L (%C<0.03)
 Resistance to IGC
TTS curves for type 304 and 304L SS obtained using the Strauss test.

Intergranular Corrosion (IGC) => How to avoid IGC?
(1) Metallurgical measures :

a) Solution annealing : heating the alloy to 1050 C where all Cr-carbides are dissolved,
followed by rapid cooling.
b) Low-carbon alloy modifications : lower the carbon content to below 0.03% for
austenitic stainless steels (304L, 316L) or to below 50 ppm for ferritic stainless steels.
c) Stabilization treatment : add strong carbide former (Ti, Nb) in melt
:Types 347 and 321 stainless steels.
(2) Environmental measures :
Lower acidity and less oxidizing conditions will generally reduce the susceptibility to
IGC.

Intergranular Corrosion (IGC) => How to avoid IGC?

What is IGC? Measurement=> Oxalic acid test?)
Polishing of specimen  Etch the specimen for 1.5 min. at 1.0 A/cm2 in oxalic
acid  Determine the type of surface morphology :
 Ditch
 Step
 Dual

Localized corrosion (Corrosion of active
passive metals)

What is localized corrosion ?
Localized corrosion forms by

severe anodic current concentrated
at small anode that is separated from
large cathode by relatively large
distance.
Localized attack that can penetrate
a metallic component even though
there is little uniform corrosion.
This is one of the most destructive
forms of corrosion

What is localized corrosion ?
This type of corrosion is common for passive metals
(active-passive)
Stable pit forms above pitting potentials in these metals

What is localized corrosion ? Mechanism
• - Autocatalytic Nature of Pitting Corrosion
• Pitting corrosion occurs by the breakdown of passive

film (mechanically or by Cl- , which is detrimental in
breaking the passive film, paint failure, deposits).
• Mixing electrolytes in the pit with bulk solution is

highly restricted ; major concentration difference is
built up; low pH and high [Cl-].
• Large cathode area(external surface) and small

anode area(pit).
• External surface is generally passivated due to high

O2 + high pH or cathodically protected.

What is localized corrosion ? Pitting control
Control the environment (reduce Cl- content)

Use suitable alloy grade for particular environment (Temp. an
d Cl ion content)
Lower acidity of solution, lower O2
Shot peen the surface to reduce the stresses
Keep the passive metals clean
Avoid stagnation
Proper design

What is localized corrosion ? Pitting control
 PRE = % Cr + 3.3 (% Mo + 1/2 % W)

+ 16~30 % N
Cr, Mo,N, W,
Epit
Cr, Mo,
W
Epp
Cr
Cr, W,
Mo
ip Ic

What is Crevice Corrosion ?
A localized corrosion occurs in

crevices due to different environmental
conditions.
Crevice corrosion usually occurs within

narrow fissures between metal/metal or
metal/non metal joints such as flanges,
gaskets, bolts, or even under deposits,
due to:
limitation of the
diffusion and migration of solution
species to and from the bulk (outside)
electrolyte through the small crevice
gap.

What is Crevice Corrosion ?
• Effect of oxygen (differential aeration cell)
Chemical reaction in low O2 compartment:
Anodic dissolution : Fe  Fe2+ + 2e-

Hydrolysis reaction : Fe2+ + 2H2O  Fe(OH)2 + 2H+  pH .
Low pH  prevent passivation and undergoes severe corrosion
Chemical reaction in High O2 compartment

Oxygen reduction : O2 + 2H2O + 4e-  4OH-  pH 
High pH favors the formation of passive film

What is Crevice Corrosion ? Mechanism?
Consider a riveted plated section of metal M immersed in aerated sea water.
High O2
Low O2

What is Crevice Corrosion ? Mechanism summary?
• Anodic reaction :
M  M+ + e-
• Cathodic reaction :
O2 + 2H2O + 4e- 4OH-
• Electromigration of Cl- into crevice
• Hydrolysis reaction of metal ion in

crevice :
M+Cl- + H2O  MOH  + H+ Cl-
•Low pH, high [Cl-], depassivation and

IR drop lead to an accelerating or
autocatalytic corrosion in the crevice.

What is Crevice Corrosion ? Control
Pitting and crevice corrosion problems are similar, only
difference is the initiation process, so
Controlling strategies are similar

What is Stress Corrosion Cracking?
“ A brittle failure of a metal/alloy caused by the simultaneous action of a
tensile stress and a specific corrosion environment”
“ Almost all materials are susceptible to SCC BUT only when it is under a well
defined SCC criteria”

What is Stress Corrosion Cracking?

What is Stress Corrosion Cracking? Sources of stress
Stresses due to:

Fabrication (deep drawing, punching, rolling, riveting, welding, spinning)
If not annealed, will remain in the structure (stress relieve annealing)
=>almost impossible for large systems/structures
Cooling rates/non-uniform cooling
Due to corrosion products (volume expansion as compared to parent

metal)

What is Stress Corrosion Cracking? Types
Chloride SCC:
In austenitic stainless steels under tensile stress in the presence of
oxygen, chloride and high temperature.
Caustic SCC:
Cracking of steels in caustic environments where hydrogen
concentration is high (Inconel tubes in alkaline solutions )
Sulfide SCC:
Occurs in hydrogen sulphide environments (oil drilling industry)
Seasonal Cracking:
SCC of brass in ammonia environments (refrigeration plant)

What is Stress Corrosion Cracking? Environment
 SCC immune alloy systems?
Not complete immunity

Induction period (of crack nucleation and growth)
Depends on environment (different alloys are SCC
Susceptible in different environments)

What is Stress Corrosion Cracking? Environment
“SCC environmental criteria for different industrial materials based on long
term experimental data”

What is Stress Corrosion Cracking?mechanism
 SCC of austenitic stainless steels is:
Transgranular ->non-sensitized specimens
Intergranular if alloy is sensitized
Chloride SCC MECHANISM (Film rupture and slip dissolution model)
Film breakdown by Cl-

attack or emergency of
slip steps
Formation of Pit
Crack initiation &

propagation

What is Stress Corrosion Cracking? Its control
 Change of material: Use crack resistant material based on

previous track record
 Change of environment: remove Cl, caustic, temp. , remove
O2, change pH, add inhibitors,
 Barrier coatings
 Cathodic protection
 Stress relief annelaing (to minimize residual stresses
 Shot peening to induce compressive stresses
 Good design to minimize crevice issues

Hydrogen Induced corrosion
 Although corrosion is an electrochemical reaction between metal surface and

the surrounding environment, it can cause the inside of metal to be damaged by
hydrogen produced by cathodic reaction of corrosion.
The hydrogen readily dissolves and diffuses in metal crystals and can have
detrimental effects on mechanical strength and ductility.
Mechanical damages of a metal caused by the presence of, or interaction with,

hydrogen are as follows :
• Hydrogen embrittlement
• Hydrogen blistering
• Hydrogen attack
• Hydride formation

Atomic hydrogen, and not the molecule, is the smallest atom of the periodic table
and as such it is small enough to diffuse readily through a metallic structure.
When the crystal lattice is in contact or is saturated with atomic hydrogen, the
mechanical properties of many metals and alloys are diminished.
If the formation of molecular hydrogen is suppressed, nascent atomic hydrogen

may diffuse into the interstices of the metal instead of being harmlessly evolved as a
gaseous reaction product.
There are many chemical species which poison this recombination (e.g., cyanides,
arsenic, antimony, or selenium compounds). However, the most commonly
encountered species is hydrogen sulfide (H2S), which is formed in many natural
decompositions, and in many petrochemical processes].

Source of Hydrogen:
1) Gas phase : H2, H2O, CH4, H2S, and NH3.
2) Cathodic reaction in corrosion, electroplating and pickling.
2H+ + 2e- H2 or 2H2O + 2e-  H2 + 2OH-
3) Melting and Welding
• Hydrogen dissolved in steel during melting can lead to flakes or bursts in

forging or rolling processes.
• Hydrogen pickup in welding can lead to cracks in either the weld metal or
the heat affected zone.

Mechanism of hydrogen entry in steels

Cracks occur under humid environment containing hydrogen sulfide.
Mechanisms for such cracks are classified into the following two categories.
(1) Sulfide stress corrosion cracking (SSC)

It occurs when external stress (working stress, residual stress) is working on steel,
and propagates to the vertical direction to axial stress. It is also called Sulfide
Stress Cracking (SC).
(2) Hydrogen induced cracking (HIC)

It occurs under a condition without external stress. The cracking is parallel to the
plate surface and propagates stepwise to the thickness direction with time.
(3) Blistering
Surface swelling due to occurrence of cracks on the surface or immediately
beneath the surface is called blistering.

Blistering is a special case of

hydrogen damage and occurs
when hydrogen atoms diffuse
into the steel, and hydrogen
gas nucleates at internal
defects and inclusions, forming
voids which eventually generate
enough pressure to locally
rupture the metal.


What is Flow Accelerated Corrosion?
Corrosion due to combined action of a corrosive
fluid and fluid flow
EROSION CORROSION
FAC IMPINGEMENT CORROSION
CAVITATION
The fluid can be aqueous or gaseous, single or multiphase

What is Flow Accelerated Corrosion?
Due to fluid flow protective film may be removed mechanically and then
bare metal corrosion by flowing fluid
Oxygen supply to metal surface is increased [it will result enhanced

corrosion of active metals and passivation of passive metals]
Fluid may also remove the corrosion products and thus exposing bare
metal surface to corrosive fluid
 Increased supply of ions to metal surface

What is Flow Accelerated Corrosion? EROSION
Solid particles in the fluid cause abrasive wear of the material and
cause metal loss.
Erosion is mainly mechanical effect.
Occurs in metals in contact with high-velocity fluid carrying solid

particles.

Erosion in steel tube-

inserts in fire tube boiler
(heat source inside of the
tubes and water to be
heated is outside)
Fluid: hot flue gases
containing ashes
2 months in service

Sources of mechanical forces involved in erosion:

Turbulent flow, fluctuating shear stresses and pressure impacts
Impact of suspended solid particles
Impact of suspended liquid droplets in high speed gas flow
Impact of suspended gas bubbles in aqueous flow
Violent collapse of vapor bubbles following cavitation

What is Flow Accelerated Corrosion? EROSION-Corrosion
Erosion corrosion occurs when metal is in contact with high velocity flow
electrolyte
Electrolyte with solid particles
Solid particles may remove metal mechanically
 Electrolyte without solid particles
In turbulent flow, hydrodynamic shear forces may remove oxide and
allow metal to corrode quickly

E-C is a problem with any part

in contact with a moving fluid:
 Piping systems especially

elbows, tees, and bends where
there is change in flow direction
or increase in turbulence
 pumps, valves, heat

exchangers, nozzles, impellers,
and turbine blades
At any surface discontinuities
causing flow turbulence

E-C looks like grooves,

elongated pits, and rounded
holes which indicate the flow
pattern
E-C failures usually occur in
short time periods (few months)
Horseshoe-shaped depressions on the internal surface of a

brass heat exchanger tube caused by erosion-corrosion.
Source: Nalco Chemical Company

Important Factors:
Soundness of protective
films
Fluid velocity / Limiting
velocity
As velocity increases, it will
increase the supply of oxygen,
chloride and other ions to
metal surface
Also higher velocity prevents
deposits and concentrations;
so will it be useful then?

What is Flow Accelerated Corrosion?Prevention
Proper material selection (use high E-C resistant alloys (SSs vs CS)
Proper design:
Increase pipe dia to reduce flow velocity and enhance laminar flow
Increase thickness at bends and tees
Remove flow discontinuities
Avoid impingement flow
Control the environment
Filters to remove abrasive particles
Add inhibitors
 Coatings
CP

What is Flow Accelerated Corrosion? Impingement attack
Localized E-C caused by impinging flow (fluid flow is normal to metal
surface)
Usually in two phase flow (Vapor liquid, Liquid-solid)
 Occurs in pumps, impellers, valves, heat exchangers tubes, turbine
blades, elbow etc.
Corrosion rate increased by the impact of particles normal to the metals
surface

What is Flow Accelerated Corrosion? Impingement attack

What is Flow Accelerated Corrosion? Impingement attack control
Proper materials election
Separate different flowing phases

Filtering out unwanted solids
Installing water traps in steam lines
 installation of wear plates and baffles in tanks and vessels
Design for replacement sections

Flow Induced Corrosion
 Cavitation is a special form of erosion corrosion,
which is caused by water bubbles produced by
high speed impeller, which collapse at metal
surface and cause corrosion.
Pressure variations in a liquid can form

countless small cavities to form and implode on
metal surface
Cavities fill with liquid vapor and gases present

in the liquid. Liquid will begin to boil locally due to
pressure reduction below vapor pressure.
When pressure rises above the vapor pressure,

vapor bubbles will implode causing high pressure
shock waves with pressures up to 400MPa and can
damage any metal

Flow Induced Corrosion=> Cavitation control
Proper design to minimize hydrodynamic pressure differences
Use harder and more corrosion resistant alloys

Alloys containing high levels of Ni, Cr, Co, and W
For some pump rubber coating/plastic that absorb cavitation energy
Specify smooth finish at critical metal surfaces
Avoid clogging/stoppage of upstream filters

 In some cases, inhibitors have been used successfully to limit cavitation
corrosion, as in the water side of diesel engine cylinder liners.
Cavitation is a problem with ship propellers, hydraulic pumps and turbines, valves,
orifice plates, and all places where the static pressure varies very abruptly

What is Corrosion Fatigue?
Fatigue is the failure of a metal by cracking when it is subjected to cyclic

stress.
The usual case involves rapidly fluctuating stresses that may be well
below the tensile strength.
As stress is increased, the number of cycles required to cause fracture

decreases.
 For steels, there is usually a stress level below which no failure will
occur, even with an infinite number of cycles, and this is called the
endurance limit.

When a metal is subjected to cyclic stress in a corrosive environment, the
number of cycles required to cause failure at a given stress may be reduced
well below the dotted line obtained for the same metal in air

Fatigue fracture usually occurs at stresses below the yield point but
after many cyclic applications of stress

During corrosion fatigue, “low cycle” stresses are more damaging than
high frequency stresses (HFS are important in normal fatigue)
Environment is also very important, for example in seawater:
=>Al bronze and type 300 series stainless steels lose 20~30% of
normal fatigue resistance, while high Cr alloys lose 60~70% resistance.

An infamous example of corrosion fatigue occurred in 1988 on an airliner flying

between the Hawaiian Islands. This disaster, which cost one life, prompted the
airlines to look at their airplanes and inspect for corrosion fatigue

The "beach marks" on the propeller shown below mark the progression of
fatigue on this surface.
Similar beach marks are shown on the aerospace part. The high magnification
scanning electron microscope image on the right shows striations (individual crack
progression marks).

What is Corrosion Fatigue? Control?
Control of corrosion fatigue can be accomplished by either:

=> changing the design to reduce stresses and/or cycling
=> Reduce stresses by heat treatment (for residual stresses), shot

peening (to change surface residual stresses to compressive)
=>Use corrosion inhibitors
=>use coatings (electrodeposited, such as Zn, Cr, Ni etc.) and

nitrided layers

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ME 472

Corrosion Types/Follow these slides and class

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

Understanding different corrosion types and their

=>What and how it looks like (how to recognize?

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

• Corrosion rate expressions.

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

Corrosion Coupons for weight loss measurement

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

This type of corrosion can be controlled by;

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

• A Galvanic cell is formed when two dissimilar

•The more active metals or alloys of the two is

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

For galvanic corrosion to occur, three conditions must be present:

And the severity of galvanic corrosion depends on:

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

•Galvanic series is a list of measured

• EMF series arranged by standard

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

Galvanic coupling Zn to Pt;

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

Effect of i0 by comparison of Zn-Pt and Zn-Au galvanic couples.

E°Au3+/Au = 1.498 V io,H2(Au) = 10-6 A/cm2

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

1) Select combinations of metals as close together as possible in the galvanic series.

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

 However in few alloy systems, GBs can cause very severe

Localized attack at and adjacent to grain boundaries, with

The alloy, sensitive to IGC, disintegrates and/or loses its

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

Causes of intergranular corrosion:

A. Segregation of impurities at the grain boundary

B. Enrichment of one of the alloying elements or depletion of one of these

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

Intergranular Corrosion of stainless steels and nickel base alloys

Exposed temperature : 425 oC to 815 oC

This results from the preferential attack of

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

(1) Metallurgical measures :

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

Localized corrosion forms by

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

• Pitting corrosion occurs by the breakdown of passive

• Mixing electrolytes in the pit with bulk solution is

• Large cathode area(external surface) and small

• External surface is generally passivated due to high

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

Control the environment (reduce Cl- content)

ME472: CORROSION ENGINEERING Dr. Ihsan-ul-Haq Toor

 PRE = % Cr + 3.3 (% Mo + 1/2 % W)