CHAPTER 17:

CORROSION AND DEGRADATION

ISSUES TO ADDRESS...
• Why does corrosion occur?
• What metals are most likely to corrode?
• How do temperature and environment affect
corrosion rate?
• How do we suppress corrosion?

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 THE COST OF CORROSION
• Corrosion:
--the destructive electrochemical attack of a materi
--Al Capone's
ship, Sapona,
off the coast
of Bimini.

• Cost:
--4 to 5% of the Gross National Product (GNP)*
--this amounts to just over $400 billion/yr**

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For metallic materials, the corrosion process is normally
electrochemical in nature, i.e., a chemical reaction in which
there is transfer of electrons from one chemical species to
another.
Metals atoms lose or give up electrons in an oxidation
reaction.
n 
Eg: M M  ne
2 
Fe  Fe  2e
3 
Al  Al  3e
The site at which oxidation takes place is called the anode.
The electrons generated from the oxidation become part of
another chemical species in a reduction reaction.
For example metals undergo corrosion in acid solutions,
which have a high concentration of Hydrogen (H+) ions;
the H+ ions are reduced as follows:

 
2H  2e  H 2
 CORROSION OF ZINC IN ACID

• Two reactions are necessary:

-- oxidation reaction: Zn  Zn2  2e
-- reduction reaction:
2H  2e  H2 (gas )
• Other reduction reactions:

-- in an acid solution

 
O2  4H  4e  2H2O

-- in a neutral or base solution

 
O2  2H2O  4e  4(OH)
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The location at which reduction occurs is called Cathode.
It is possible for two or more of the reduction reactions
above to occur simultaneously.
An overall electrochemical reaction must consist of at least
one oxidation and one reduction reaction. The individual
oxidation and reduction reactions are called half-reactions.
Electrode Potentials:
Some metals oxidise more easily than others.
Standard half cell: A pure metal electrode immersed
in a 1 M solution of its ions and at 250 C.
Galvanic couple: Two metals electrically connected in a
liquid electrolyte .
 STANDARD HYDROGEN (EMF) TEST
• Two outcomes:
--Metal sample mass --Metal sample mass

--Metal is the anode (-) --Metal is the cathode (+)

o o
Vmetal  0 (relative to Pt) Vmetal  0 (relative to Pt)

Standard Electrode Potential

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 STANDARD EMF SERIES
• EMF series o
• Metal with smaller
metal Vmetal o
Vmetal corrodes.
Au +1.420 V • Ex: Cd-Ni cell
Cu +0.340
Pb - 0.126
Sn - 0.136
Ni - 0.250 DVo =
Co - 0.277 0.153V
Cd - 0.403
Fe - 0.440
Cr - 0.744
Zn - 0.763
Al - 1.662
Mg - 2.262
Na - 2.714
K - 2.924 5
EFFECT OF SOLUTION CONCENTRATION
• Ex: Cd-Ni cell with • Ex: Cd-Ni cell with
standard 1M solutions non-standard solutions
o o RT X
VNi  VCd  0.153 o
VNi  VCd  VNi o
 VCd  ln
- nF Y
+
n = #e-
per unit
oxid/red
Cd T Ni reaction
(=2 here)
F=
XM YM Faraday's
Cd2+ solution Ni2+ solution constant
• Reduce VNi - VCd by =96,500
C/mol.
--increasing X
--decreasing Y
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 GALVANIC SERIES
• Ranks the reactivity of metals/alloys in seawater
Platinum
Gold
Graphite
Titanium
Silver
316 Stainless Steel
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
316 Stainless Steel
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium 8
Corrosion Rates:
The half cell potentials listed earlier are thermodynamic
parameters that relate to systems at equilibrium (zero
current).
Real corroding systems are not at equilibrium, i.e., there
will be flow of current from anode to cathode.
Also half-cell potentials give the tendency for a reaction,
they do not say anything about the rate (recall info given
by phase diagram).
The corrosion penetration rate is used to give an idea
about the rate of corrosion:

KW
CPR 
At
W = weight loss in mg after exposure time t (hours)
 density in g/cm3; A = Exposed area in square inches
K = constant (534 or 87.6 )
CPR is in milli-inch/year or mm/year
The corrosion rate can also be given in terms of the electric
current density associated with electrochemical corrosion
reactions.

i
r
nf

r is in mol/m2-s
The potential of the electrodes will not be at the equilibrium
value
 The displacement of the potential of each electrode
from its equilibrium value is called polarization and the
magnitude of this displacement is called overvoltage
represented by h.

There are two types of polarizations: Activation and

Concentration : they control the rate of corrosion
Activation Polarization:
All electrochemical reactions consist of a
sequence of steps that occur in series at the interface
between the metal electrode and the electrolyte.
Activation polarization refers to the condition
wherein the reaction rate is controlled by the one step in
the series which occurs at the slowest rate. The term
Activation is associated with this step since an activation
barrier is associated with this rate-determining step.
Example:
Reaction Steps:
•Adsorption of H+ ions from the solution onto the Zinc
surface.
•Electron transfer from the Zinc to form a Hydrogen atom,

 
H e  H
• Combining of two Hydrogen atoms to form a molecule of
Hydrogen,
•The coalescence of many Hydrogen molecules to form a
bubble.
The slowest of these steps determines the rate of the
overall reaction.
For activation polarization, the relationship between
overvoltage ha and current density i is:

i
h    log
io
Here  and io are constants for the particular half-cell. The
parameter io is the exchange current density and it is
magnitude of the current at equilibrium.
 FORMS OF CORROSION
• Stress corrosion
Stress & corrosion
• Uniform Attack work together • Erosion-corrosion
Oxidation & reduction at crack tips. Break down of passivating
occur uniformly over layer by erosion (pipe
surface. elbows).
• Selective Leaching • Pitting
Preferred corrosion of Downward propagation
one element/constituent of small pits & holes.
(e.g., Zn from brass (Cu-Zn)).
• Intergranular
Corrosion along
grain boundaries, • Galvanic
often where special Dissimilar metals are
• Crevice Between two
phases exist. pieces of the same metal.
physically joined. The
Rivet holes
more anodic one
corrodes.(see Table
17.2) Zn & Mg
Fig. 17.6, Callister 6e. (Fig. 17.6 is
very anodic. courtesy LaQue Center for Corrosion
Technology, Inc.) 9
Fig. 17.9, Callister 6e.
 CONTROLLING CORROSION
• Self-protecting metals!
--Metal ions combine with O
to form a thin, adhering oxide layer that slows corrosion.
• Reduce T (slows kinetics of oxidation and reduction)
• Add inhibitors
--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 (e.g., paint it!).
• Cathodic (or sacrificial) protection
--Attach a more anodic material to the one to be protected.

Adapted Adapted from Fig. 17.13(a),

from Fig. Callister 6e. (Fig. 17.13(a) is
17.14, from M.G. Fontana, Corrosion
Callister Engineering, 3rd ed., McGraw-
6e. Hill Book Co., 1986.)
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 SUMMARY
• Corrosion occurs due to:
--the natural tendency of metals to give up electrons.
--electrons are given up by an oxidation reaction.
--these electrons then are part of a reduction reaction.
• Metals with a more negative Standard Electrode
Potential are more likely to corrode relative to
other metals.
• The Galvanic Series ranks the reactivity of metals in
seawater.
• Increasing T speeds up oxidation/reduction reactions.
• Corrosion may be controlled by:
-- using metals which form -- adding inhibitors
a protective oxide layer -- painting
-- reducing T --using cathodic protection.

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 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems: