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Chapter 17 - 1

ISSUES TO ADDRESS...
How does corrosion occur?
Which metals are most likely to corrode?
What environmental parameters affect
corrosion rate?
How do we prevent or control corrosion?

Corrosion and Degradation of
Materials
Chapter 17 - 2
Deteriorative mechanisms are different for the three material
types:

1. Metals actual material loss either by dissolution
(corrosion) or by the formation of nonmetallic scale or film
(oxidation).

2. Ceramics resistant to deterioration which usually occurs
at elevated temperatures or in extreme environments,
also called corrosion.

3. Polymers may dissolve when exposed to a liquid
solvent, electromagnetic radiation (ultraviolet) and heat :
degradation.

Chapter 17 - 3
Corrosion:
-- the destructive electrochemical attack of a material.
-- Ex: Al Capone's
ship, Sapona,
off the coast
of Bimini.
Cost:
-- 4 to 5% of the Gross National Product (GNP)*
-- in the U.S. this amounts to just over $400 billion/yr**
* H.H. Uhlig and W.R. Revie, Corrosion and Corrosion Control: An Introduction
to Corrosion Science and Engineering, 3rd ed., John Wiley and Sons, Inc.,
1985.
**Economic Report of the President (1998).
Photos courtesy L.M. Maestas, Sandia
National Labs. Used with permission.
THE COST OF CORROSION
Chapter 17 - 4
Corrosion is defined as the destructive and unintentional attack
of a metal electrochemical and begins at the surface.

Electrochemical a chemical reaction in which there is
transfer of electrons from one chemical species to another.

Metal atoms characteristically lose or give up electrons
oxidation reaction. The oxidation takes place is called anode.
Oxidation sometimes called anodic reaction.

The electrons generated from the metal atom must be
transferred to another chemical species reduction reaction.
The location at which reduction occurs is called the cathode.
Reduction also called as cathodic reaction.




Chapter 17 - 5
Two reactions are necessary:
-- oxidation reaction:
-- reduction reaction:


Zn Zn
2+
+ 2e



2H
+
+2e

H
2
(gas)
Other reduction reactions in solutions with dissolved oxygen:
-- acidic solution -- neutral or basic solution


O
2
+4H
+
+4e

2H
2
O


O
2
+2H
2
O+4e

4(OH)

Adapted from Fig. 17.1,


Callister & Rethwisch 8e.
(Fig. 17.1 is from M.G.
Fontana, Corrosion
Engineering, 3rd ed., McGraw-
Hill Book Company, 1986.)
ELECTROCHEMICAL CORROSION
Zinc
Oxidation reaction
Zn
Zn
2+
2e
-
Acid
solution
reduction reaction
H
+
H
+
H
2
(gas)
H
+
H
+
H
+
H
+
H
+
flow of e
-

in the metal
Ex: consider the corrosion of zinc in an acid solution
Chapter 17 - 6
STANDARD HYDROGEN ELECTRODE
Two outcomes:
0
o
metal
< V (relative to Pt)
Standard Electrode Potential
Adapted from Fig. 17.2,
Callister & Rethwisch 8e.
-- Corrosion
-- Metal is the anode (-)
P
l
a
t
i
n
u
m



m
e
t
a
l
,

M



M
n+

ions
ne
-
H
2
(gas)
25C
1M M
n+
soln 1M H
+
soln
2e
-
e
-
e
-
H
+

H
+

-- Electrodeposition
-- Metal is the cathode (+)
M
n+

ions
ne
-
e
-
e
-
25C
1M M
n+
soln 1M H
+
soln
P
l
a
t
i
n
u
m

m
e
t
a
l
,

M

H
+
H
+
2e
-
0
o
metal
> V (relative to Pt)
H
2
(gas)
Chapter 17 - 7
STANDARD EMF SERIES
metal
o
Metal with smaller
V corrodes.
EMF series
Au
Cu
Pb
Sn
Ni
Co
Cd
Fe
Cr
Zn
Al
Mg
Na
K
+1.420 V
+0.340
- 0.126
- 0.136
- 0.250
- 0.277
- 0.403
- 0.440
- 0.744
- 0.763
- 1.662
- 2.363
- 2.714
- 2.924
metal
V
metal
o
Data based on Table 17.1,
Callister 8e.
m
o
r
e

a
n
o
d
i
c

m
o
r
e

c
a
t
h
o
d
i
c

AV =
0.153V
o
Adapted from Fig. 17.2,
Callister & Rethwisch 8e.
-
1.0 M
Ni
2+
solution
1.0 M
Cd
2 +
solution
+
25C Ni Cd
Cd
o
Ni
o
Ex: Cd-Ni cell
V < V Cd corrodes
Chapter 17 - 8
EFFECT OF SOLUTION CONCENTRATION AND
TEMPERATURE
Ex: Cd-Ni cell with
standard 1 M solutions


V
Ni
o
V
Cd
o
= 0.153 V
-
Ni
1.0 M
Ni
2+
solution
1.0 M
Cd
2 +
solution
+
Cd 25C
Ex: Cd-Ni cell with
non-standard solutions
Y
X
ln
nF
RT
V V V V =
o
Cd
o
Ni Cd Ni
n = #e
-

per unit
oxid/red
reaction
(= 2 here)
F =
Faraday's
constant
= 96,500
C/mol.
Reduce V
Ni
- V
Cd
by
-- increasing X
-- decreasing Y
-- increasing T
-
+
Ni
Y M
Ni
2+
solution
X M
Cd
2 +
solution
Cd
T
Chapter 17 - 9
GALVANIC SERIES
Ranking of the reactivity of metals/alloys in seawater
Based on Table 17.2, Callister &
Rethwisch 8e. (Source of Table
17.2 is M.G. Fontana, Corrosion
Engineering, 3rd ed., McGraw-
Hill Book Company, 1986.)
Platinum
Gold
Graphite
Titanium
Silver
316 Stainless Steel (passive)
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
316 Stainless Steel (active)
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
m
o
r
e

a
n
o
d
i
c

(
a
c
t
i
v
e
)

m
o
r
e

c
a
t
h
o
d
i
c

(
i
n
e
r
t
)

Chapter 17 - 10
Uniform Attack
Oxidation & reduction
reactions occur uniformly
over surfaces.
Selective Leaching
Preferred corrosion of
one element/constituent
[e.g., Zn from brass (Cu-Zn)].
Stress corrosion
Corrosion at crack tips
when a tensile stress
is present.
Galvanic
Dissimilar metals are
physically joined in the
presence of an
electrolyte. The
more anodic metal
corrodes.
Erosion-corrosion
Combined chemical attack and
mechanical wear (e.g., pipe
elbows).
FORMS OF CORROSION
Forms
of
corrosion
Crevice Narrow and
confined spaces.
Fig. 17.15, Callister & Rethwisch 8e. (Fig. 17.15
is courtesy LaQue Center for Corrosion
Technology, Inc.)
Rivet holes
Intergranular
Corrosion along
grain boundaries,
often where precip.
particles form.
Fig. 17.18, Callister &
Rethwisch 8e.
attacked
zones
g.b.
prec.
Pitting
Downward propagation
of small pits and holes.

Fig. 17.17, Callister &
Rethwisch 8e. (Fig. 17.17
from M.G. Fontana,
Corrosion Engineering,
3rd ed., McGraw-Hill Book
Company, 1986.)
Chapter 17 - 11
-- Use metals that passivate
- These metals form a thin,
adhering oxide layer that
slows corrosion.
Lower the temperature (reduces rates of oxidation and
reduction)
CORROSION PREVENTION (i)
Metal (e.g., Al,
stainless steel)
Metal oxide
Apply physical barriers -- e.g., films and coatings
Materials Selection
-- Use metals that are relatively unreactive in the
corrosion environment -- e.g., Ni in basic solutions
Chapter 17 - 12
Add inhibitors (substances added to solution that decrease
its reactivity)
-- Slow oxidation/reduction reactions by removing reactants
(e.g., remove O
2
gas by reacting it w/an inhibitor).
-- Slow oxidation reaction by attaching species to
the surface.
CORROSION PREVENTION (ii)
Adapted
from Fig.
17.22(a),
Callister &
Rethwisch
8e.
Using a sacrificial anode
steel
pipe
Mg
anode
Cu wire
e
-
Earth
Mg
2+
Cathodic (or sacrificial) protection
-- Attach a more anodic material to the one to be protected.
Adapted
from Fig.
17.23,
Callister &
Rethwisch
8e.
steel
zinc zinc
Zn
2+
2e
-
2e
-
e.g., zinc-coated nail
Galvanized Steel
e.g., Mg Anode
Chapter 17 - 13
Metallic corrosion involves electrochemical reactions
-- electrons are given up by metals in an oxidation reaction
-- these electrons are consumed in a reduction reaction
Metals and alloys are ranked according to their
corrosiveness in standard emf and galvanic series.
Temperature and solution composition affect corrosion
rates.
Forms of corrosion are classified according to mechanism
Corrosion may be prevented or controlled by:
-- materials selection
-- reducing the temperature
-- applying physical barriers
-- adding inhibitors
-- cathodic protection
SUMMARY