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Corrosion and Degradation of

Materials
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?

ELECTROCHEMICAL CORROSION
Ex: consider the corrosion of zinc in an acid solution
Two reactions are necessary:
Zn Zn2 2e
-- oxidation reaction:
-- reduction reaction:

2H 2e H2 (gas)

H+
Oxidation reaction
Zn Zn2+
H+

Zinc

flow of e
2ein the metal

H+

H+ +
H
H+
H2(gas)
H+
reduction reaction

Acid
solution

Adapted from Fig. 17.1,


Callister & Rethwisch 8e.
(Fig. 17.1 is from M.G.
Fontana, Corrosion
Engineering, 3rd ed., McGrawHill Book Company, 1986.)

Other reduction reactions in solutions with dissolved oxygen:


-- acidic solution
O2 4H 4e 2H2O

-- neutral or basic solution


O2 2H2O 4e 4(OH)
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STANDARD HYDROGEN ELECTRODE


Two outcomes:
-- Electrodeposition

H2(gas)

Mn+ H+
ions
H+

e-

25C

e-

ne -

2e -

metal, M

metal, M

ne -

e-

Platinum

e-

Mn+
ions

H+ 2e H+

H2(gas)

Platinum

-- Corrosion

25C

1M Mn+ soln 1M H + soln

1M Mn+ soln 1M H+ soln

-- Metal is the anode (-)

-- Metal is the cathode (+)

o
Vmetal
0 (relative to Pt)

o
Vmetal
0 (relative to Pt)

Standard Electrode Potential

Adapted from Fig. 17.2,


Callister & Rethwisch 8e.
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STANDARD EMF SERIES

more anodic

more cathodic

EMF series
metal
Au
Cu
Pb
Sn
Ni
Co
Cd
Fe
Cr
Zn
Al
Mg
Na
K

o
Vmetal

Metal with smaller


o
Vmetal
corrodes.

+1.420 V
Ex: Cd-Ni cell
+0.340
o
o
V
<
V
Cd corrodes
Ni
Cd
- 0.126
- 0.136
+
- 0.250
DV o =
- 0.277
0.153V
- 0.403
- 0.440
Cd
Ni
25C
- 0.744
- 0.763
- 1.662
1.0 M
1.0 M
- 2.363
Cd 2 + solution Ni 2+ solution
- 2.714
Adapted from Fig. 17.2,
Data based on Table 17.1,
Callister & Rethwisch 8e.
- 2.924 Callister 8e.
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EFFECT OF SOLUTION CONCENTRATION AND


TEMPERATURE
Ex: Cd-Ni cell with
standard 1 M solutions

V V 0.153 V
o
Ni

o
Cd

Cd

25C

Ni

1.0 M
1.0 M
Cd 2+ solution Ni 2+ solution

Refer Ex prob 17.1 (pg


681)

Ex: Cd-Ni cell with


non-standard solutions

VNi VCd

Cd

RT X
V V
ln
nF Y
o
Ni

o
Cd

Ni

XM
YM
Cd 2 + solution Ni 2+ solution

Reduce VNi - VCd by


-- increasing X
-- decreasing Y
-- increasing T

n = #eper unit
oxid/red
reaction
(= 2 here)
F=
Faraday's
constant
= 96,500
C/mol.

GALVANIC SERIES

more anodic
(active)

more cathodic
(inert)

Ranking of the reactivity of metals/alloys in seawater


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

Based on Table 17.2, Callister &


Rethwisch 8e. (Source of Table
17.2 is M.G. Fontana, Corrosion
Engineering, 3rd ed., McGrawHill Book Company, 1986.)

FORMS OF CORROSION
Stress corrosion

Uniform Attack
Oxidation & reduction
reactions occur uniformly
over surfaces.

Combined action of
stress & corrosive
environment

Selective Leaching

Corrosion along
grain boundaries,
often where precip.
particles form.
g.b.
prec.
attacked
zones
Fig. 17.18, Callister &
Rethwisch 8e.

Combined chemical attack and


mechanical wear (e.g., pipe
elbows).

Pitting

Preferred corrosion of
one element/constituent
[e.g., Zn from brass (Cu-Zn)].

Intergranular

Erosion-corrosion

Forms
of
corrosion

Galvanic

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.)

Crevice Narrow and

Dissimilar metals are confined spaces.


Rivet holes
physically joined in the
presence of an
electrolyte. The
Fig. 17.15, Callister & Rethwisch 8e. (Fig. 17.15
more anodic metal
is courtesy LaQue Center for Corrosion
Technology, Inc.)
corrodes.
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CORROSION PREVENTION (i)


Materials Selection
-- Use metals that are relatively unreactive in the
corrosion environment -- e.g., Ni in basic solutions
-- Use metals that passivate
- These metals form a thin,
adhering oxide layer that
slows corrosion.

Metal oxide
Metal (e.g., Al,
stainless steel)

Lower the temperature (reduces rates of oxidation and


reduction)
Apply physical barriers -- e.g., films and coatings

CORROSION PREVENTION (ii)


Add inhibitors (substances added to solution that decrease
its reactivity)
-- Slow oxidation/reduction reactions by removing reactants
(e.g., remove O2 gas by reacting it w/an inhibitor).
-- Slow oxidation reaction by attaching species to
the surface.

Cathodic (or sacrificial) protection


-- Attach a more anodic material to the one to be protected.
Galvanized Steel
Adapted
from Fig.
17.23,
Callister &
Rethwisch
8e.

Using a sacrificial anode

Zn 2+

zinc

zinc
2e - 2e steel

e.g., zinc-coated nail

steel
pipe

e-

Cu wire
Mg Mg 2+
anode
Earth

e.g., Mg Anode

Adapted
from Fig.
17.22(a),
Callister &
Rethwisch
8e.

CORROSION RATE

Answer : Questions 17.11 & 17.12

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PREDICTION OF CORROSION
RATES
Polarization = displacement of electrode
potential from its equilibrium value
2 types of polarization : activation or
concentration
Magnitude displacement = Overvoltage ()

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Activation Polarization

12

Concentration Polarization
Under what conditions is concentration
polarizing rate controlling?
the reaction rate is high and/or
the concentration of active species in the
liquid solution is low.

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SUMMARY
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
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