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Chapter 17:
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?

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 THE COST OF CORROSION
• Corrosion:
-- the destructive
electrochemical
attack of a material.

© EHStock/iStockphoto
-- Ex: Rusting of
automobiles and
other equipment

• 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). 3
 ELECTROCHEMICAL CORROSION
Ex: consider the corrosion of zinc in an acid solution
• Two reactions are necessary:
-- oxidation reaction:
-- reduction reaction:
H+
Oxidation reaction
Zn Zn2+ H+
Adapted from Fig. 18.1,
Callister & Rethwisch 9e.

H+ Acid (From M. G. Fontana, Corrosion

Zinc flow of e- 2e- Engineering, 3rd edition. Copyright

in the metal H+ + solution © 1986 by McGraw-Hill Book

H Company. Reproduced with
H+ permission.)
H2(gas)
H+
reduction reaction

• Other reduction reactions in solutions with dissolved oxygen:

-- acidic solution -- neutral or basic solution

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ELECTROCHEMICAL REACTION

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ELECTROCHEMICAL CORROSION

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 STANDARD HYDROGEN ELECTRODE
• Two outcomes:
-- Corrosion -- Electrodeposition

e- e- e- e-
H2(gas) H+ 2e -
ne - 2e - ne -
H+

Platinum
Platinum Mn+

metal, M
Mn+ H+
metal, M

ions ions
H+
H2(gas)
25°C 25°C
1M Mn+ sol’n 1M H + sol’n 1M Mn+ sol’n 1M H+ sol’n
-- Metal is the anode (-) -- Metal is the cathode (+)
o
Vmetal <0 (relative to Pt)
o
Vmetal >0 (relative to Pt)
Adapted from Fig. 18.2,
Standard Electrode Potential Callister & Rethwisch 9e.

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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
more cathodic

Cu +0.340 o o
Pb - 0.126 VCd < V Ni  Cd corrodes
Sn - 0.136 - +
Ni - 0.250
Co - 0.277 DV o =
Cd - 0.403 0.153V
Fe - 0.440
more anodic

Cr - 0.744 Cd 25°C Ni
Zn - 0.763
Al - 1.662
1.0 M 1.0 M
Mg - 2.363
Cd 2+ solution Ni 2+ solution
Na - 2.714
Data based on Table 18.1, Adapted from Fig. 18.2,
K - 2.924 Callister 9e. Callister & Rethwisch 9e.

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CORROSION IN A GRAPEFRUIT
Cu (cathode) Zn (anode)
+ -
H+
H+ Zn 2+

reduction reactions 2e - oxidation reaction

H+
H+
Acid H+
H+ H+

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 EFFECT OF SOLUTION CONCENTRATION AND
TEMPERATURE
• Ex: Cd-Ni cell with • Ex: Cd-Ni cell with
standard 1 M solutions non-standard solutions

- + - +
n = #e-
per unit
oxid/red
Cd 25°C Ni Cd T Ni reaction
(= 2 here)
F=
1.0 M 1.0 M XM YM Faraday's
Cd 2+ solution Ni 2+ solution Cd 2+ solution Ni 2+ solution constant
• Reduce VNi - VCd by = 96,500
C/mol.
-- increasing X
-- decreasing Y
-- increasing T 10
 GALVANIC SERIES
• Ranking of the reactivity of metals/alloys in seawater
Platinum
more cathodic

Gold
Graphite
(inert)

Titanium
Silver
316 Stainless Steel (passive) Table 18.2, Callister &
Nickel (passive) Rethwisch 9e.
Source is M.G. Fontana, Corrosion
Copper Engineering, 3rd ed., McGraw-Hill
Book Company, 1986. Reprinted with
Nickel (active) permission)
Tin
more anodic

Lead
316 Stainless Steel (active)
(active)

Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
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 FORMS OF CORROSION
• Stress
• Uniform Attack corrosion ‫التآكل عند‬
Oxidation & reduction ‫مراكز اإلجهاد‬
reactions occur uniformly Corrosion at crack tips
• Erosion-corrosion ‫ل و التعرية‬
over surfaces. when a tensile stress Combined chemical attack and
is present. mechanical wear (e.g., pipe
• Selective Leaching elbows).
Preferred corrosion of • Pitting ‫تآكل التنقير‬
one element/constituent Forms Downward propagation
[e.g., Zn from brass (Cu-Zn)]. of small pits and holes.
of
Fig. 18.17, Callister &
corrosion Rethwisch 9e. (From M.G.
• Intergranular Fontana, Corrosion
Engineering, 3rd ed.,
‫تآكل بين الخاليا الحبيبية‬ McGraw-Hill Book
Company, 1986.)
Corrosion along
grain boundaries, • Galvanic ‫تآكل‬ • Crevice ‫ تآكل التصدع‬Narrow
and confined spaces.
often where precip. ‫الجلفاني‬
Rivet holes
particles form. g.b. Dissimilar metals are
prec.
physically joined in the
attacked
presence of an Fig. 18.15, Callister & Rethwisch 9e.
zones electrolyte. The (Courtesy LaQue Center for Corrosion
Technology, Inc.)
Fig. 18.18, Callister & more anodic metal 12
Rethwisch 9e.
 1) Uniform Attack Corrosion

Uniform attack is a form of electrochemical corrosion

that occurs with equivalent intensity over the entire
exposed surface and often leaves behind a scale or
deposit.

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2) Galvanic Corrosion

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3) Erosion–Corrosion

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 4) Stress Corrosion Cracking
The combined action of an applied tensile stress and a corrosive
environment; both influences are necessary.

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5) Crevice Corrosion

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5) Pitting Corrosion

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6) Intergranular Corrosion

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7)

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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
Metal oxide
- These metals form a thin, Metal (e.g., Al,
adhering oxide layer that stainless steel)
slows corrosion.

• Lower the temperature (reduces rates of oxidation and

reduction)

• Apply physical barriers -- e.g., films and coatings

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 CORROSION PREVENTION (ii)
• Add inhibitors ‫( مثبطات‬substances 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 Using a sacrificial anode
Adapted Zn 2+ Cu wire Adapted
from Fig. e- from Fig.
18.24, zinc zinc steel Mg Mg 2+ 18.23(a),
Callister &
Rethwisch 2e - 2e - pipe anode Callister &
Rethwisch
9e. steel Earth 9e.

e.g., zinc-coated nail e.g., Mg Anode

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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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 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

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