Lecture 3

Types of Corrosion
The Eight Forms of Corrosion
1. Uniform attack (general corrosion)
2. Galvanic corrosion
3. Crevice corrosion
4. Pitting
5. Intergraular attack (IGA)
6. Selective leaching
7. Flow-Accelerated Corrosion
8. Stress corrosion cracking (SCC)
UNIFORM ATTACK or GENERAL
CORROSION
This is the most common form of corrosion.
A chemical reaction (or electrochemical reaction)
occurs over entire exposed surface (or large areas)
more or less uniformly.
Metal thins fails.
Not usually serious and is typically predictable from
simple tests (e.g., coupon or specimen immersion)
Can be designed around by specifying an adequate
CORROSION ALLOWANCE for the expected
lifetime of the component.
Uniform attack minimized by:
specifying proper materials
correctly applying coatings
using corrosion inhibition
protecting cathodically.


1800-year-old Roman nail shows
how iron and steel can withstand
burial underground.

Note: Environment is crucial!
ATMOSPHERIC CORROSION
Usually uniform.
Dry, damp or wet conditions have profound effect on
corrosion.
Dry atmospheres:
at ambient temperatures, most metals corrode very
slowly
atmospheric oxygen promotes a protective oxide film ...
such films are defect-free (sort of!), non-porous (more
or less!) and self-healing
passivity of metals like SS, Ti, Cr depends on
protective oxide films (but such passivity extends to
other environments, e.g., aqueous).

EXAMPLE:
Ag & Cu tarnish in dry air with traces of H
2
S
(undesirable - aesthetically, technically - affects
electrical contacts, etc.).
The S
2-
incorporation in the normally-protective
oxides creates lattice defects which destroy
protective nature of films tarnishing.
Moisture not required for tarnishing, it can
actually retard tarnishing of Cu in presence of
traces of H
2
S.
Damp atmospheres:
corrosion increases with moisture content;
at critical moisture level (~ 70% RH), an
invisible, thin film of moisture forms on (metal)
surface, provides electrolyte for current
(critical RH depends on surface condition:
cleanliness, presence of oxide or scale, presence
of salts or other contaminants that may be
hygroscopic).
Wet atmospheres:
promote puddles, pockets, visible water layers
(from dew, sea spray, rain, etc.)
crevices, condensation traps, etc., create water
pools, and lead to wet atmospheric corrosion
even when rest of surface dry
Corroded weathering steel I-beam. Note how
corrosion has thinned the bottom of the vertical
web where corrosion products have fallen and
formed a moist corrosive deposit. soluble
corrosion products increase wet corrosion
(dissolved ions increase conductivity, sustain
higher electrical currents)
insoluble corrosion products may retain moisture
during alternate wet and dry conditions, lead to
continuous wet corrosion.
Corroded weathering
steel I-beam.
Note how corrosion
has thinned the bottom
of the vertical web
where corrosion
products have fallen
and formed a moist
corrosive deposit.
Corroded steel framework on the ceiling of a parking
garage. The seams in this corrugated structure act as
condensation traps and lead to wet atmospheric
corrosion.

Rusting of iron and steel, formation of patina on
copper, Examples of damp wet corrosion.









Corroded regions of a painted highway bridge
Corroded weathering steel highway bridge girder
ATMOSPHERIC CONTAMINANTS

Wet atmospheric corrosion is often governed by level
of contaminants.
e.g., marine salts vary drastically with distance from
the sea:
steel at 25 m from the sea will corrode 12x faster than
same steel 250 m away.
Industrial atmospheres are generally more corrosive
than rural, mainly because of sulfur compounds
produced by burning fuels.
SO
2
selectively adsorbs on metals under humid
conditions metal oxide corrosion products catalyze
oxidation to SO
3
:
SO
2
+ 1/2 O
2
SO
3
(with a catalyst)
H
2
O + SO
3
H
2
SO
4

Small additions ( ~ 0.2%) of Cu, Ni or Cr increase
resistance of steel to sulfur pollution by enhancing the
formation of a tighter, more protective rust film.

NOTE: longevity of ancient Fe probably due to SO
2
-

free environments rather than high degree of corrosion
resistance.
Nitrogen compounds promote atmospheric
corrosion - from fuel burning (NOx as well as
SOx), as well as by thunderstorms.

N
2
+ x O
2
2 NOx

nitrogen-based fertilizers (from NH
3
) increase
nitrogen pollutants in atmosphere.
H
2
S promotes atmospheric corrosion (e.g., Ag, Cu
tarnishing)
from industry (oil & gas, pulp and paper , etc.);
from decomposition of organic S compounds;
from sulfate-reducing bacteria (SRB) in polluted
rivers etc.

H
2
O
SRB + SO
4
2-
H
2
S
Dust particles detrimental (stick to metal surfaces,
absorb water, H
2
SO
4
etc., may contain Cl
-
WHI CH
I S BAD since it breaks down protective oxide films).
CO
2
dissolution in water can give pH ~ 5.6 (in
equilibrium with normal atmosphere containing CO
2
)
BUT CO
2
is not significant in atmospheric
corrosion, in fact sometimes can inhibit it (if SO
2
is
present).
Surface temperature very important - as T rises,
corrosion rate rises - though damp and wet
corrosion stop when moisture driven off;
Metal surfaces that retain moisture generally
corrode faster than rain-washed surfaces; rain
flushes impurities off surfaces, removes particles,
etc. that promote differential aeration, etc.
Winter exposure generally more severe (more
combustion products in atmosphere, temperature
inversions, etc.), though summer gives higher
surface temperatures.
Relative humidity very important: for clean Fe,
critical RH ~ 60%
above this, rust begins to form slowly from
deposited water film. At 75 - 80% RH,
corrosion rate increases rapidly (probably
because of capillary condensation within the
rust layer).
if corrosion product rust is microporous,
moisture will condense at different RHs
depending on pore size:
1.5 nm - diameter pore (capillary)
condenses water at 50% RH;
36 nm - diameter pore at 98% RH.
Note: dust, particles, etc. on surfaces create
crevices that can condense moisture at various
RHs.
Salt or soluble corrosion products will form
electrolytes in condensed moisture - lower critical
RH, also increase corrosion.
Damp and wet corrosion are described in terms of
ELECTROCHEMI STRY.

We have seen how a metal dissolution, such as:

Zn + 2 HCl ZnCl
2
+ H
2

can be regarded as two reactions:
Zn Zn
2+
+ 2 e- (oxidation - an ANODIC process)

2H
+
+ 2e H
2
(reduction - a CATHODIC process)

BOTH REACTIONS OCCUR SIMULTANEOUSLY AND
AT THE SAME RATE.







It follows, that during metallic corrosion
THE RATE OF OXI DATI ON EQUALS THE RATE OF
REDUCTI ON.
Electrochemical reactions
occurring during corrosion
of zinc in air-free
hydrochloric acid
Implies that a corroding surface has anodic and
cathodic areas for UNIFORM CORROSION
These must be distributed evenly over the surface
and in fact must move around.
Some anodic half reactions for corrosion:
Zn Zn
2+
+ 2 e
-
Na Na
+
+ e
-
Fe Fe
2+
+ 2 e
-
Cu Cu
2+
+ 2 e
-
etc.

Anodic half reaction must be balanced by cathodic
half reactions:
Primary cathodic half reactions include:

hydrogen evolution 2 H
+
+ 2 e
-
H
2


oxygen reduction O
2
+ 4 H
+
+ 4 e
-
2 H
2
O
(acid solution)

oxygen reduction O
2
+ 2 H
2
O + 4 e
-
4 OH
-
(neutral or basic solution)

More cathodic half reactions:
metal ion reduction M
3+
+ e
-
M
2+

(e.g. Fe
3+
+ e- Fe
2+
)

metal deposition (e.g. Cu
+
+ e
-
Cu)

Note that the flow of charge (i.e., electrons) is a
measure of the reaction rate (metal dissolution or
corrosion rate).
Thus, if the corrosion current can be measured, the
corrosion rate is directly evaluated through Faradays
Law

F n
t I M
m
wt

=
m = mass deposited/released (g);
M
wt
= atomic or molecular weight (g/mol);
I = current passed (Amps);
t = time current/potential applied (seconds);
n = electrons transferred in the half-cell reaction;
F = Faraday constant (96485 C/mol).
this is the number of charges that must be passed to
reduce or oxidise one mole of a compound
Say the I
measured
= 10
-5
amps/cm
2
Using Faradays Law the corrosion rate is calculated
as:



Or in a more useable unit (divide by the density
7.86 g/cm
3
for iron; convert cm to mm and seconds to
years)

( ) ( )
( )
s cm g 10 9 . 2
mol C 96485 2
cm A 10 mol g 56
CR m
2 9
2 5

= =
yr / mm 12 . 0 yr / m 116 CR = =