Chapter 18:

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?

1
• 01 Introduction
• 02 Electrochemical Considerations
• 03 Corrosion Rates
• 04 Prediction of Corrosion Rates
• 05 Passivity
• 06 Environmental Effects
• 07 Forms of Corrosion
• 08 Corrosion Environments
• 09 Corrosion Prevention
• 10 Oxidation
• 11 Swelling and Dissolution
• 12 Bond Rupture
• 13 Weathering

2
 THE COST OF CORROSION
• Corrosion:
-- the destructive
electrochemical
attack of a material.
-- Ex: Rusting of

© EHStock/iStockphoto
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**
Figun_18_p638a
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+
H+ Acid
Zinc flow of e- 2e-
in the metal H+ + solution
H
H+
H2(gas)
H+
reduction reaction

• Other reduction reactions in solutions with dissolved oxygen:

-- acidic solution -- neutral or basic solution

4
An electrochemical cell
consisting of iron and copper
Electrodes Anode Cathode

Iron corrodes
(Oxidation)

Copper electrodeposits
(Reduction)

Fig_18_02
An electrochemical cell
consisting of iron and zinc
Electrodes Cathode Anode

Zinc corrodes

Iron electrodeposits

Fig_18_03
 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) V o
metal >0 (relative to Pt)

Standard Electrode Potential

7
The standard hydrogen reference half-cell

Fig_18_04
 STANDARD ElectoMotive Force (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,
K - 2.924 Callister 9e.
9
Table_18_01
CORROSION IN A GRAPEFRUIT
Cu (cathode) Zn (anode)
+ -
H+
H+ Zn 2+

reduction reactions 2e - oxidation reaction

H+
H+
Acid H+
H+ H+

11
 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 12
 GALVANIC SERIES
• Ranking of the reactivity of metals/alloys in seawater
Platinum
more cathodic

Gold
Graphite
(inert)

Titanium
Silver
316 Stainless Steel (passive)
Nickel (passive)
Copper
Nickel (active)
Tin
more anodic

Lead
316 Stainless Steel (active)
(active)

Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
13
 The Galvanic Series:
The relative reactivities in seawater

Table_18_02
14
• 01 Introduction
• 02 Electrochemical Considerations
• 03 Corrosion Rates
• 04 Prediction of Corrosion Rates
• 05 Passivity
• 06 Environmental Effects
• 07 Forms of Corrosion
• 08 Corrosion Environments
• 09 Corrosion Prevention
• 10 Oxidation
• 11 Swelling and Dissolution
• 12 Bond Rupture
• 13 Weathering

1
Electrochemical cell consisting of standard zinc and hydrogen
electrodes that has been sort-circuited

Fig_18_05
Schematic representation of possible steps in the hydrogen
reduction process, controlled by activation polarization.

Fig_18_06
 Corrosion rate
• Corrosion penetration rate—as a function of
specimen weight loss, density, area, and time
of exposure
– CPR = KW/ρAt
• Expression relating corrosion rate and current
density
– r = I /nF

18
 Passivity
• A number of metals and alloys
passivate, or lose their
chemical reactivity, under
some environmental
circumstances.
– involve the formation of a
thin protective oxide film
– Stainless steels and
aluminum alloys
• The active-to-passive behavior
may be explained by the alloy's
S-shaped electrochemical
potential-versus-log current
density curve
Fig_18_12

19
• 01 Introduction
• 02 Electrochemical Considerations
• 03 Corrosion Rates
• 04 Prediction of Corrosion Rates
• 05 Passivity
• 06 Environmental Effects
• 07 Forms of Corrosion
• 08 Corrosion Environments
• 09 Corrosion Prevention
• 10 Oxidation
• 11 Swelling and Dissolution
• 12 Bond Rupture
• 13 Weathering

2
 FORMS OF CORROSION
• Stress corrosion • Hydrogen embritlement
• Uniform Attack Corrosion at crack tips a significant reduction
Oxidation & reduction when a tensile stress in ductility that accompanies
reactions occur uniformly is present. the penetration of atomic
over surfaces.
hydrogen into a metal/alloy
• Selective Leaching • Erosion-corrosion • Pitting
Preferred corrosion of Combined chemical Downward propagation
one element/constituent attack and mechanical of small pits and holes.
[e.g., Zn from brass (Cu-Zn)]. wear (e.g., pipe
elbows).
• Intergranular
Corrosion along
grain boundaries,
often where precip. • Galvanic
particles form. Dissimilar metals are • Crevice Narrow and
g.b.
physically joined in the confined spaces.
prec. presence of an Rivet holes
electrolyte. The
attacked more anodic metal
zones
corrodes. 21
Fig_18_14
Immersed in seawater, crevice corrosion has occurred
at the regions that were covered by washers.

Fig_18_15
Mechanism of crevice corrosion

Fig_18_16
Fig_18_17
Fig_18_18
Fig_18_19
Fig_18_20
Fig_18_21
Fig_18_22
 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

31
 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 Using a sacrificial anode
Adapted Zn 2+ Cu wire
from Fig. e-
18.24, zinc zinc steel Mg Mg 2+
Callister &
Rethwisch 2e - 2e - pipe anode
9e. steel Earth
e.g., zinc-coated nail e.g., Mg Anode 32
Fig_18_23
Fig_18_24
• 01 Introduction
• 02 Electrochemical Considerations
• 03 Corrosion Rates
• 04 Prediction of Corrosion Rates
• 05 Passivity
• 06 Environmental Effects
• 07 Forms of Corrosion
• 08 Corrosion Environments
• 09 Corrosion Prevention
• 10 Oxidation
• 11 Swelling and Dissolution
• 12 Bond Rupture
• 13 Weathering

3
 Oxidation
• Oxidation of metallic
materials by electrochemical
action is also possible in dry,
gaseous atmospheres
• An oxide film forms on the
surface that may act as a
barrier to further oxidation if
the volumes of metal and
oxide film are similar
• The kinetics of film formation
may follow parabolic, linear,
or logarithmic rate laws. Fig_18_25

36
Table_18_03
 Corrosion of ceramics
• Ceramic materials, being compounds of
metallic and nonmetallic elements, may be
though of as having already been corroded
• Ceramic materials, being inherently corrosion
resistant, are frequently used at elevated
temperatures and/or in extremely corrosive
environments.

38
• 01 Introduction
• 02 Electrochemical Considerations
• 03 Corrosion Rates
• 04 Prediction of Corrosion Rates
• 05 Passivity
• 06 Environmental Effects
• 07 Forms of Corrosion
• 08 Corrosion Environments
• 09 Corrosion Prevention
• 10 Oxidation
• 11 Swelling and Dissolution
• 12 Bond Rupture
• 13 Weathering

3
 Degradation of polymers
• Polymeric materials deteriorate by noncorrosive processes.
• Upon exposure to liquids, they may experience degradation
by swelling or dissolution.
– With swelling, solute molecules actually fit into the molecular
structure.
– Dissolution may occur when the polymer is completely soluble in the
liquid.
• Scission, or the severance of molecular chain bonds, may
be induced by radiation, chemical reactions, or heat.
– This results in a reduction of molecular weight and a deterioration of
the physical and chemical properties of the polymer.
• Weathering: any resultant degradation caused by exposure
to outdoor conditions

40
 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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