8 Forms of Corrosion:

• Uniform
• Pitting
• Crevice Corrosion or Concentration Cell
• Galvanic or Two-Metal
• Stress Corrosion Cracking
• Intergranular
• Dealloying
• Erosion Corrosion
 Uniform corrosion
• This type of corrosion includes the
commonly recognized rusting of iron and
other metals.
Uniform Corrosion
Example of Uniform Corrosion
 Localised corrosion
• A range of corrosion processes
• Selective attack
• Environment (CO2, CCl-, pH, Flow rate)
• Material
– Occur at heterogeneous site of the metal
(segregation, inclusions, different phases, grain
boundaries)
• Mechanical
– Stress (static or fluctuating)
 Pitting
Localised corrosion which selectively attacks area
of a metal surface where there is:
– A surface scratch
– An emerging dislocation
– A compositional heterogeneity

The result is the formation of a hole

One of the most insidious form of corrosion
Weight loss is very small but grave
consequences
 O2 OH- O2 OH-

M n+

1-Inside the growing pit the hydrolysis of Mn+ lowers the pH and breaks
down the passive film. The cathodic oxygen reduction reaction
continues outside the pit.
2-The presence of chloride is important, as it allows a pH of about 1 to be
achieved (HCl is a strong acid, and does not associate) and the metal
chlorides are very soluble.
3-Other anions (e.g. OH- and SO42-) can inhibit pitting, either by buffering
the pH in the pit or by causing the precipitation of a salt film.
 Pitting
• Pitting is distinguishable from crevice corrosion in the
initiation phase.
• The alloy is passive
– pitting requires a passive external surface that can
provide a high potential to cause the current to flow
into the pit; if the external surface is active, this driving
force is not available
– thus carbon steel will only pit if the solution tends to
passivate it (e.g. alkaline solutions), it won’t pit if it is
corroding generally (e.g. neutral salt solutions)
 Pitting
• pits become more stable as they become larger
– for very small pits the acidity will be neutralised by
diffusion into the bulk solution very easily
– as the pits get larger the diffusion distances increase,
and it gets harder for the acidity to diffuse away
• pitting becomes more likely as the potential becomes
more positive
– this provides a greater driving force for the corrosion
process, and helps to stabilise the metastable pits
 Pitting
• Pit growth tends to follow a law of the form
depth = constant x timen
where n is between 0.3 and 0.5
• Pitting is a statistical process, and can be
modelled by extreme value statistics
 Crevice corrosion
• Intensive localised corrosion frequently
occurs with crevices and other shielded
areas of metal surface exposed to
electrolyte.
• Can occur even under non metallic
contacts, e.g. rubber gaskets
• Liquid entry but stagnant
• Rate of crevice is higher than on bulk
• Mainly the case of passivate alloy, e.g.SS
CREVICE CORROSION
First stage
 M n+

Crevice corrosion M
anodic

O2 OH-
Cathodic

M n+ O2 M n+
O2 OH- OH-

M M

1 – anodic and cathodic reactions occur over the entire surface

 M n+

Crevice corrosion M
anodic

O2 OH-
Cathodic

M n+ M n+ M n+
O2 OH- O2 OH-

M M
M

2 – Depletion of oxygen inside the crevice

3 - Metal dissolution takes place inside the crevice
 Crevice corrosion
M n + + nCl − + nH 2O → M (OH )n + nHCl

Cl-

M n+
O2 OH- O2 OH-
M n+
M n+
M
M
M

4 – Attraction of Cl- inside the crevice (charge balance)

5 – pH decreases inside the crevice (more acid) – enhance dissolution
 Crevice corrosion
Cl-

Cl-
O2 OH- O2 OH- M n+
M n+
M n+
H+
M
M
M

6 – The crevice formation is an auto-catalytic process

 Summary
• Auto catalytic process
• A small area anodic inside the crevice
• A large cathodic aerated area outside

• Dangerous
 Galvanic Corrosion:
• Possibility when two dissimilar metals are electrically
connected in an electrolyte
• Results from a difference in oxidation potentials of
metallic ions between two or more metals.
The greater the difference in oxidation potential, the
greater the galvanic corrosion.
• The less noble metal will corrode (i.e. will act as the
anode) and the more noble metal will not corrode (acts
as cathode).
• More base metal act as mainly the anode
• The driving force is the difference in electrode potential
 Important points
• Relative areas of anode and cathode.
At Icorr
Ia=Ic , Aa ia=Ac ic
• Difference in potential between anode and cathode
– Galvanic series
• Anode may passivate
• Effects of environment
– Zinc and steel (inversion of anode and cathode at
100°C
• Distance effects
– Depends on the conductivity of the solution
• Beneficial applications
– Dry battery, galvanisation
GALVANIC SERIES
Galvanic Series in Seawater Tendency to be protected from corrosion, cathodic, more
noble end

Mercury
Platinum
Gold
Zirconium Graphite
Titanium
Hastelloy C Monel
Stainless Steel (316-passive)
Stainless Steel (304-passive)
Stainless Steel (400-passive)
Nickel (passive oxide)
Silver
Hastelloy 62Ni, 17Cr
Note, positions of
Silver solder
Inconel 61Ni, 17Cr
SS and AL
Aluminum (passive AI203)
70/30 copper-nickel
90/10 copper-nickel
Bronze (copper/tin)
Copper
Brass (copper/zinc)
Alum Bronze Admiralty Brass
Nickel
Naval Brass Tin
Lead-tin
Lead
Hastelloy A
Stainless Steel (active)
316 404 430 410
Lead Tin Solder
Cast iron
Low-carbon steel (mild steel)
Manganese Uranium
Aluminum Alloys
Cadmium
Aluminum Zinc
Beryllium
Magnesium
 Galvanic Corrosion
Table 1 Standard emf series Table 2 Galvanic Series in Seawater
Reaction Eo at 25oC,
(V vs NHE)
Au-Au3+ +1.498  Platinum
2+
Pt-Ptgalvanic series.
•The +1.2 Noble or •The emf,
Goldor electrochemical series.
+
Ag-Ag
•Ordered +0.799 Silver
by observed behaviour incathodic •Ordered by standard equilibrium potential
2+
Hg-Hg2
service +0.788 18-8activity
•Assumes Mo stainless steel (passive)
of solution species is one
2+
Cu-Cu for corrosion products
•Allows +0.337 Nickel
•Does not (passive)
allow for protective corrosion
•Note that some alloys can appear
•Can be defined for alloys Cupronickels
products (60-90 Cu, 40-10 Ni)
twice according
+ to whether they are
H -H
•Different 0.000
for every environment •CannotCopper
be defined for alloys
active
2
or passive
Nickel (active)
Ni-Ni2+ -0.250 18-8 Mo stainless steel (active)
Fe-Fe2+ -0.440 Steel or iron
3+
Cr-Cr -0.744 2024 aluminium (4.5 Cu, 1.5 Mg, 0.6 Mn)
2+
Zn-Zn -0.763 Cadmium
Al-Al3+ -1.662 Active or Commercially pure aluminium (1100)
2+
Mg-Mg -2.363 anodic Zinc

+
Na-Na -2.714 Magnesium and magnesium alloys
After de Bethune and Loud from INCO test results
Galvanic Series:

Questions:
1. Worst combination?
2. Aluminum and steel?
3. Titanium and Zinc?
4. Stainless Steel and
Copper?
5. Mild steel and cast
iron?
GALVANIC CORROSION
DEZINKIFICATION BRASS
 Galvanic Corrosion
Potentials:

Figure 1 illustrates the idea of an electro-chemical

reaction. If a metal is placed in a conducting solution
like salt water, it dissociates into ions, releasing
electrons, as the iron is shown doing in the figure, via
the ionization reaction
Fe  Fe++ + 2e-
The electrons accumulate on the iron giving it a
negative charge that grows until the electrostatic
attraction starts to pull the Fe++ ions back onto the
Figure 1. A bi-metal corrosion cell. The
metal surface, stifling further dissociation. At this point corrosion potential is the potential to
the iron has a potential (relative to a standard, the which the metal falls relative to a
hydrogen standard) of –0.44 volts. Each metal has its hydrogen standard.

own characteristic corrosion potential (called the

standard reduction potential), as plotted in Figure 2.
If two metals are connected together in a cell, like
the iron and copper samples in Figure 1, a potential
difference equal to their separation on Figure 2 appears
between them. The corrosion potential of iron, -0.44,
differs from that of copper, +0.34 , by 0.78 volts, so if Figure 2. Standard reduction
no current flows in the connection the voltmeter will potentials of metals.
register this
 Liquid Cell Battery:

Dry cell is a galvanic electrochemical cell with a pasty low-

moisture electrolyte. A wet cell, on the other hand, is a cell with a
liquid electrolyte, such as the lead-acid batteries in most cars
 Dry Cell - Zinc-carbon battery

Zn(s) → Zn2+(aq) + 2 e- - oxidation reaction that happens at zinc = anode

2MnO2(s) + 2 H+(aq) + 2 e- → Mn2O3(s) + H2O(l) - reduction reaction at

carbon rod = cathode
Design for Galvanic Corrosion?
• Material Selection: Do not connect
dissimilar metals! Or if you can’t avoid it:
– Try to electrically isolate one from the other
(rubber gasket).
– Make the anode large and the cathode small
• Bad situation: Steel siding with aluminum fasteners
• Better: Aluminum siding with steel fasteners
• Eliminate electrolyte
• Galvanic of anodic protection
Design for Galvanic Corrosion?
• Galvanic severity depends on:
– NOT
• Not amount of contact
• Not volume
• Not mass
– Amount of separation in the galvanic series
– Relative surface areas of the two. Severe
corrosion if anode area (area eaten away) is
smaller than the cathode area. Example: dry
cell battery
 Galvanic corrosion in alloys
• Galvanic corrosion can occur between
different phases in an alloy
• This is especially important when one of the
phases is much more active as a cathode,
e.g.:
– Cu-containing precipitates in aluminium alloys –
initiate pitting corrosion
– Fe and Cu impurities in commercial zinc
– cause a large increase in corrosion rate
compared to pure zinc
 Quiz
• Which is better

Brass bolt in a steel structure Steel bolt in a brass structure

 Quiz
• Which is better

Brass bolt in a steel structure Steel bolt in a brass structure

Small brass cathode will Small steel anode will

cause small increase in suffer large increase in
corrosion of steel corrosion due to
structure. Bolt will be coupling with brass
protected from corrosion structure.
by coupling to steel
 Stress Corrosion Cracking:
• Spontaneous corrosion induced cracking of a
material under static (or residual) tensile stress.
• I.e parts that have residual stress – SCC +
stress concentration.
• Environmentally assisted cracking (EAC), other
forms:
– Hydrogen embrittlement
– Caustic embrittlement
– Liquid metal corrosion
 Stress-Corrosion Cracking
• Cracking of a metal under the combined
effects of a static stress and a specific
corrosive environment
• Several possible mechanisms, still not fully
understood
• Cause of major industrial costs and safety
hazards
 Stages of Stress-Corrosion Cracking

SCC has two general stages – initiation and propagation

Initiation of SCC
The initiation stage of SCC involves a series of events
These events are as follows:
(1) localized breakdown of the passive oxide film due to
mechanical damage or to chemical attack by
aggressive ions, such as Cl–,
(2) formation of a corrosion pit after the oxide film has been
broken, and
(3) initiation and growth of a stress-corrosion crack
 Propagation of SCC

The stress-corrosion cracks propagate and grow due to the combined effects of
the applied stress and the corrosive conditions within the crack arising from
acidification of the crack electrolyte.
 Mechanisms of SCC
– Anodic dissolution
– Hydrogen embrittlement
– Film-induced cleavage
 Anodic Dissolution

1 The walls and tip of the crack are passive

2 The passive film at the crack tip is ruptured by the plastic
strain, and active corrosion occurs

3 The crack tip repassivates

4 Go back to 1
 Film-Induced Cleavage

1 The walls and tip of the crack are covered by a brittle film
(either an oxide film or a de-alloyed layer)

2 The film at the crack tip is ruptured by the plastic strain

3 The brittle crack continues into the metal
4 The crack is blunted by plastic strain
 Hydrogen Embrittlement

H H H H
H HH
H

1 Hydrogen produced by the cathodic reaction

2 Hydrogen diffuses to region of tri-axial tensile stress
ahead of the crack

3 Hydrogen causes brittle fracture

4 Crack blunts by plastic deformation as it runs out of
hydrogen
Hydrogen Embrittlement
• sources of hydrogen
– welding
– electroplating
– contact with gaseous hydrogen
– corrosion, especially in the presence of
sulphides
• higher strength materials are more
susceptible to hydrogen embrittlement
 Stress Corrosion Cracking Systems

• Brass and ammonia (often in local

atmospheres).
• Austenitic stainless steels and chloride
solutions (70oC).
• Carbon steels in caustic, carbonate/
bicarbonate, nitrate and phosphate.
• High strength aluminium alloys in water or
water vapour.
 Hydrogen Induced Cracking
• Internal cracking of lower strength steels
(e.g. pipeline steels) due to high pressure
hydrogen collecting at inclusions.
• Internal cracking of steels at higher
temperatures due to reaction of dissolved
hydrogen with carbon to form methane
HIC
 Stress-Corrosion Testing
Constant Load Testing

Stress

Threshold stress

log(Time to Failure)
 Stress-Corrosion Testing
• Slow strain-rate testing (or constant
extension rate testing)
• Extend a plain or pre-cracked specimen at
a slow constant rate
• Then assess by
– fracture surface
– change in elongation or reduction in area
– time to failure
 Stress-Corrosion Testing
• Fracture mechanics testing
– apply a constant load to a pre-cracked
specimen
– measure crack growth rate as a function of
stress intensity factor (K)

A measure of the severity of the

stress state at the crack tip

K =  a
Fracture Mechanics Testing

log (crack growth rate)

Fast fracture starting to occur
as K approaches KIc
Plateau crack velocity
typical range of values 1011 to
10–3 m/s
Threshold stress intensity
factor, KIscc

Stress Intensity Factor

 Control of Stress-Corrosion
• Remove stress (often difficult, especially
for residual stresses)
• Avoid the necessary environment
• Apply electrochemical protection where
possible
• Use a different material
• Live with it
Liquid Metal Embrittlement
• Liquid metals can permeate down grain
boundaries and cause intergranular
cracking:
– mercury on brass and aluminium alloys
– liquid zinc on stainless steel
 Factors:
• Must consider metal and environment. What to
watch for:
– Stainless steels at elevated temperature in
chloride solutions.
– Steels in caustic solutions
– Aluminum in chloride solutions
• 3 Requirements for SCC:
1. Susceptible alloy
2. Corrosive environment
3. High tensile stress or residual stress
 Design for Stress Corrosion
Cracking:
• Material selection for a given environment
• Reduce applied or residual stress - Stress
relieve to eliminate residual stress (i.e.
stress relieve after heat treat).
• Introduce residual compressive stress in
the service.
• Use corrosion alloy inhibitors.
• Apply protective coatings.
SCC
Corrosion Fatigue
• Metal fatigue results in crack propagation
due to a cyclic stress
• Corrosion makes both crack initiation and
propagation easier
Corrosion Fatigue - S-N Curve
Stress Amplitude

Air

Corrosion

log (cycles to failure, Nf)

Corrosion Fatigue - Crack
Growth

log (Crack Growth Rate, da/dN)

Log (Stress Intensity Factor Range, K

 Intergranular Attack:
• Corrosion which occurs preferentially at
grain boundries.
• Why at grain boundries?
– Higher energy areas which may be more
anodic than the grains.
– The alloy chemistry might make the grain
boundries dissimilar to the grains. The grain
can act as the cathode and material
surrounding it the anode.
INTERGRANULAR Corrosion
 Intergranular Attack:
• How to recognize it?
– Near surface
– Corrosion only at grain boundries (note if only
a few gb are attacked probably pitting)
– Corrosion normally at uniform depth for all
grains.
 Intergranular
• Metal consists of grains
• Under some circumstances they corrode
preferentially
• The material is said to be sensitised
• Most significant problem
– Weld decay of austenitic SS
– Metal becomes susceptible to I/a corrosion
– Depletion of Cr, precipitates as Cr23C6.
 Cr23C6

Concentration of Cr
decreases near the
precipitates

Grain boundaries will be depleted in Cr and will corrode

 Solution of weld decay
• Use a low carbon grade of stainless steel
• Use a stabilised grade of steel, which
includes a strong carbide-forming element
(Nb or Ti) to lock up the carbon
• For existing components that have been
sensitised, heat treat to re-dissolve the
carbides (but this is very difficult in
practice)
 Dealloying
• Selective etching
– Net removal of one element from an alloy
– Whole of exposed surface may be attacked
– Leaving the overall geometry unchanged
• Prime cause of dealloying or demetallification
– Galvanic effect
• Alloy containing one noble element and one
base element (Brass)
• Base element can dissolve leaving a matrix of
the noble element
• Prob. reduces by addition of Tin
Example 1: Intergranular Attack:
• Sensitization of stainless steels:
– Heating up of austenitic stainless steel (750 to
1600 F) causes chromuim carbide to form in
the grains. Chromuim is therefore depleted
near the grain boundries causing the material
in this area to essentially act like a low-alloy
steel which is anodic to the chromium rich
grains.
– Preferential Intergranular Corrosion will occur
parallel to the grain boundary – eventually
grain boundary will simply fall out!!
 Design for Intergranular Attack:
• Watch welding of stainless steels (causes
sensitization). Always anneal at 1900 – 2000 F
after welding to redistribute Cr.
• Use low carbon grade stainless to eliminate
sensitization (304L or 316L).
• Add alloy stabilizers like titanium which ties up
the carbon atoms and prevents chromium
depletion.
Example 2: Intergranular Attack:
• Exfoliation of high strength Aluminum
alloys.
– Corrosion that preferentially attacts the
elongated grains of rolled aluminum.
– Corroded grains usually near surface
– Grain swells due to increase in volume which
causes drastic separation to occur in a
pealing fashion.
 Dealloying:
• Danger!
– The alloy may not appear damaged
– May be no dimensional variations
– Material generally becomes weak – hidden to
inspection!
 Dealloying:
• Two common types:
– Dezincification – preferential removal of zinc in brass
• Try to limit Zinc to 15% or less and add 1% tin.
• Cathodic protection

– Graphitization – preferential removal of Fe in

Cast Iron leaving graphite (C).