Corrosion

Dr. Rahul Khandagale

Ph.D (IIT-Bombay)

Corrosion : The deterioration of a material

resulting from chemical attack by its
environment.
Caused by: Chemical reaction
Temp. Concentration of
reactent and product .

Other factors: Mechanical stress, erosion

Electrochemical corrosion of metals

Reaction of hydrochloric
acid with zinc to produce
hydrogen gas

Galvanic cells created by differences

in composition, structure, and stress

Sources of Localized Corrosion

Environment

oxygen concentration
chloride ion concentration
pH
flow rate

Sources of Localized Corrosion

Material

segregation
inclusions
different phases
grain boundaries

Sources of Localized Corrosion

Mechanical
static stress
fluctuating stress

Galvanic Corrosion
Conventional
current

Electrons

2+ 2+
FeFe

Fe
O2

O2

Cu

Galvanic Corrosion

Important factors in galvanic corrosion

relative areas of anode and cathode
difference in potential between anode and
cathode
effect of anodic polarization on anode (some
may passivate)

Galvanic Corrosion

Table 1

Standard emf series

Eo at 25oC,
(V vs NHE)
Au-Au3+
+1.498

2+
The
Pt-Pt galvanic series.+1.2 Noble or
Ag-Ag+
+0.799 cathodic
Ordered
by observed
2+
Note
that some alloys
Hg-Hg
+0.788 can
2
behaviour
in service
2+
Cu-Cu
+0.337 to
appear twice according

Table 2

Galvanic Series in Seawater

Reaction

Platinum
TheGold
emf, or electrochemical series.
Silver by standard equilibrium
Ordered
18-8 Mo stainless steel (passive)
potential
Nickel (passive)
Allows for corrosion
Assumes
activity
of solution
Cupronickels
(60-90 Cu,
40-10 Ni)
whether
they
are
active
or
+
H2-H
0.000
Copper
products
species
is one
passive
Nickel (active)
2+ be defined for alloys
Can
Does
not
for (active)
protective
Ni-Ni
-0.250
18-8
Mo allow
stainless steel
Fe-Fe2+
Steel orproducts
iron
Different
for every-0.440
corrosion
3+
Cr-Cr
-0.744
2024 aluminium
(4.5 Cu,
1.5alloys
Mg, 0.6 Mn)
environment
Cannot
be
defined
for
Zn-Zn2+
-0.763
Cadmium
3+
Al-Al
-1.662 Active or
Commercially pure aluminium (1100)
2+
Mg-Mg
-2.363
Zinc
anodic
Na-Na+
-2.714
Magnesium and magnesium alloys

After de Bethune and Loud

from INCO test results

Which is better?

Brass bolt in a steel structure

Steel bolt in a brass structure

Small brass cathode will

cause small increase in
corrosion of steel
structure. Bolt will be
protected from corrosion
by coupling to steel

Small steel anode will

suffer large increase in
corrosion due to
coupling with brass
structure.

What should we paint?

A milk cooler has an
inner liner of stainless
steel, and an outer casing
of mild steel. Chilled
brine is used between the
steel and stainless steel to
cool the milk.
This
would of
bethe
a very
Corrosion
mildbad idea
as
anyispin-holes
the paint
steel
occurringin- would
would
as idea
the anode,
it be aact
good
to paintwith the
full
of of
thethe
stainless
thearea
inside
mild steel as
the
cathode.
steel
casing?

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

Differential Aeration
Conventional
current

Fe2+
Fe2+
O2

Fe

Fe2+
O2

Fe

Potential

Electrons

2.0
1.6 Aerated
Deaerated
1.2 alkaline
pH goes
by pH goes acid by
Fe3+
+
O0.8
Fe2+ + H2O FeOH+ + H+
2 + 2H2O + 4e 4OH
0.4
Fe oxides
Steel passivates
Steel corrodes
stable
0.0
actively
-0.4 Fe2+ stable
-0.8
Fe metal stable
-1.2
-1.6
0
7
14
pH

Crevice Corrosion
O2

Metal

Cr3+ is a reaction with

OCr2 3+Hydrolysis

water, in this case

+
2Cr3+ corrosion
+ 6H2O isCr
O
+
6H
Active
corrosion
2 3
Oxygen is consumed in crevice
by in
slow
occurring
thepassive
absencecorrosion
of an
oxide film
Passive corrosion continues, and pH falls by Cr3+ hydrolysis
Metal

1
2
3

Passive film breaks down in acid and rapid active corrosion

starts

The active corrosion causes even stronger acidification and

stabilises the crevice corrosion

Crevice Corrosion

Pitting corrosion
on freecorrosion
surface
Crevice
under washers

Pitting
Cl-

Cl-

O2

O2

Cr3+ Cr3+

- and
2The presence
Other
Inside
anions
the growing
(e.g.
of chloride
OH
pit the
is
hydrolysis
SO
important,
of as
Cr3+
it
4 ) can
inhibit pitting,
lowers
allows
athe
pHpH
ofeither
and
about
breaks
by
1 to
buffering
be
down
achieved
the passive
pH(HCl
in
thea pit
film.
is
strong
The
or cathodic
byacid,
causing
and
oxygen
the
does
precipitation
reduction
not associate)
of a
salt film
reaction
and
the metal
continues
chlorides
outside
arethe
very
pitsoluble

Characteristics of Pitting Corrosion

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
wont pit if it is corroding generally (e.g.
neutral salt solutions)

Characteristics of Pitting Corrosion

passivity broken down locally, usually by

chloride
the cause of the initiation of pitting corrosion is
still not entirely clear, but it involves a very
small pit nucleus that grows over periods of
the order of seconds

Characteristics of Pitting Corrosion

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

Characteristics of Pitting Corrosion

small pits are often stabilised by a film of

oxide or metal that partially covers the
entrance
this allows pits that would not otherwise be
stable to continue growing (these are known as
metastable pits)

Characteristics of Pitting Corrosion

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

Management of Pitting

Stainless steels
Pitting breakdown potential (that potential
above which the anodic current starts to
increase); lower pitting potential implies
greater susceptibility
Critical pitting temperature (CPT, temperature
at which pitting is observed in aggressive
conditions); lower CPT implies greater
susceptibility
Pitting Resistance Equivalent (formula based
on composition e.g. Cr + 3Mo + 30 N) gives
ranking of alloys

Management of 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

Dealloying
Alloy containing one noble element and
one base element (e.g. brass, Cu + Zn)
Base element can dissolve leaving a matrix
of the noble element

dezincification of brass
graphitization of grey cast iron

Causes loss of mechanical strength without

obvious change in shape

Dealloying

Plug-type dealloying of a brass tube

Intergranular When
Corrosion
stainless steel is heated to about
650oC, Cr carbides form at the grain
boundaries

Cr Cr
Cr
Cr
C

C
C

Because of its high diffusion rate,

the grain
boundary
concentration
carbon canIfdiffuse
a long
way to Cr
form
falls
low enough
(belowcan
about
then
However,
chromium
only9%),
diffuse
a
the precipitate
it will
nodistance,
longer remain
passive,
and
short
and this
reduces
the
grain
boundary
corrosion
will occur at
matrix
concentration
of chromium
the grain boundary

Intergranular Corrosion
When grain boundary chromium carbide
precipitation has occurred, the stainless
steel is said to be sensitised.
Sensitisation frequently occurs in the heataffected zone during welding, and the
resultant corrosion is called weld decay.

Intergranular Corrosion
- Weld Decay of Stainless Steel

Solving 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)

Flow Effects

Flow can
increase transport of oxygen to the metal
surface (may help to passivate)
increase the rate of dissolution of corrosion
product films
mechanically remove oxides

Terminology is poorly-defined, and often

contradictory

Erosion Corrosion
Corrosion accelerated by impact by solid
particles
These may remove metal, or they may just
remove oxide and allow metal to corrode
more quickly

Impingement
Corrosion rate increased by the impact of
turbulent eddies on the metal surface
These locally remove the corrosion product
by rapid dissolution, and allow rapid active
corrosion
Characterised by horseshoe-shaped pits

Cavitation
High velocity flow leads to pressure falling
below zero at points of highest flow
Vapour bubbles form in these regions as
the liquid is pulled apart
When the pressure increases again the
collapse of the vapour bubbles creates an
intense shockwave that removes metal or
oxide from the surface

Flow Effects

THANK YOU
&
GOOD LUCK