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?

Chapter 17 - 1

DESTRUCTIVE MECHANISM
In metal there is an actual loss either by dissolution
(corrosion) or by formation of non-metalic scale or film
(oxidation).
Ceramic material relatively resistant to deterioration,
usually occurs at elevated temperature or rather extreme
environments. Also called corrosion.
In polymer the term used is degradation. Polymer may
dissolve when exposed to a liquid solvent or they may
absorb the solvent and swell also electromagnetic radiation
(primarily ultraviolet) and heat may cause alterations in
their molecular structures
Chapter 17 - 2

THE COST OF CORROSION

Corrosion in metal:
- the destructive electrochemical attack on metal.
- ordinarlily begins at the surface
- -- Ex: Al Capone's
ship, Sapona,
off the coast
of Bimini.
Photos courtesy L.M. Maestas, Sandia
National Labs. Used with permission.

Cost:
-- 4 to 5% of the Gross National Product (GNP)* spend
in corrosion prevention, maintenance and replacement
-- 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).
Chapter 17 -

WHY CORROSION HAPPEN?

Because metals want to go back to
their stable states.
Usually, metals are stable when they
bind with others.
In the presence of a corrosive
environment, metals tend to reacts
with oxygen or other corrosive ions.
Chapter 17 - 4

CORROSION INGREDIENTS
Water
Oxygen
Electrolyte (ion transport in water) or
Electrical conductor
To prevent corrosion remove one of the
ingredient

Chapter 17 - 5

Corrosive Environments
All environments are corrosive to some degree.
Typical corrosive environments:
Humidity
Steam
Seawater
Alkalis
Acids

Chapter 17 - 6

Corrosive Environments
Include the atmosphere, aqueous solutions,
soils, acids, bases, inorganic solvents, molten
salts, liquid metals.
Atmospheric corrosion accounts for the
greatest losses.
Moisture contain dissolve oxygen, and other
compound such as sodium chloride.
Freshwater contained dissolve oxygen and
other minerals.
Sea water is more corrosive than freshwater.
Soil contain moisture, oxygen salt content,
alkalinity and acidity
Chapter 17 - 7

Effect of pH on Corrosion
Corrosion accelerated under acidic condition
Secondary reaction, prevent the oxide from
accumulating in the surface thus drive the
reaction into the product
Pitting cause the thermodynamic activity of
Fe further accelerating the corrosion process

Chapter 17 - 8

ELECTROCHEMICAL CORROSION
Ex: consider the corrosion of zinc in an acid solution

Two reactions are necessary:

-- oxidation reaction (give up electron) Zn Zn 2 2e

-- reduction reaction (receive electron)

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)
Chapter 17 - 9

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.

Chapter 17 - 10

STANDARD EMF (electromotive force) 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.
Chapter 17 - 11

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.)

Chapter 17 - 12

Corrosion Rates

Chapter 17 - 13

PASSIVITY
Some normally active metal and alloys under
particular environment; condition lose their chemical
reactivity and become extremely inert. Passivity
Results from the formation of a highly adherent and
very thin oxide form on metal surface which serve as
protective barrier to further corrosion.
Display by chromium, nickel, titanium, iron, stainless
steel, aluminum and their alloys.
Aluminum form a tough oxide Al2O3 which prevent
further oxidation
Unfortunately Fe2O3 is a flaky , not tough
However, a change in the character of the
environment may cause a passivated material to
Chapter 17 - 14
revert to an active state.

FORMS OF CORROSION
Stress corrosion
Corrosion at crack tips
Uniform Attack
when a tensile stress Erosion-corrosion
Oxidation & reduction
Combined chemical attack and
is present.
reactions occur uniformly
mechanical wear (e.g., pipe
over surfaces.
elbows).

Selective Leaching

Pitting

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

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

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.
Chapter 17 - 15

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

Chapter 17 - 16

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.

Chapter 17 - 17

CORROSION OF CERAMIC
MATERIALS
Extremely immune to corrosion by almost all
environments especially at room temperature.
Corrosion of ceramic materials generally
involve simple chemical dissolution in contact
to electrochemical process found in metals.
Frequently used because of their resistance to
corrosion.
Eg. glass is often used to contain liquids for
this reason.
Chapter 17 - 18

DEGRADATION OF POLYMERS
Whereas most metallic corrosions are
electrochemical, polymeric degradation is
physiochemical: that it involve physical as well as
chemical phenomena.
Polymers deteriorate by swelling and dissolution.
With swelling, the liquid or solute diffuses into and is
absorbed within the polymer: the small solute
molecules fit into and occupy positions among
polymer molecules thus the macromolecules are
forced apart. This increase in chain separation
results in a reduction of secondary intermolecular
bonding forces; as a consequences, the material
become softer and more ductile.
Chapter 17 - 19

DEGRADATION OF POLYMERS
Scission the severance or rupture of molecular chain bonds.This
courses a separation of chain segments at the point of scission and
a reduction in the molecular weight.
Bond rapture may result from exposure to radiation or to heat and
from chemical reaction.
Certain type of radiation possess sufficient energy to penetrate a
polymer specimen and interact with the constituent atoms or their
electrons.
Oxygen, ozone and other substances can causes or accelerate
chain scission as a result of chemical reaction
Thermal degradation corresponds to the scission of molecular chain
at elevated temperature; as a consequence some polymer undergo
chemical reactions in which gaseous species are produced.
Weathering when exposed outdoor condition deterioration is a
result of oxidation which initiated by ultraviolet radiation from the
sun and ,water absorption.
Chapter 17 - 20

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
Chapter 17 - 21

Quiz
a) Explain the differences between oxidation and reduction
electrochemical reaction
b)Which reaction occurs at the anode and which at the cathode

Chapter 17 - 22

Home work
a) Explain 5 different form of corrosion and in which
condition it will occur.
b) Explain three methods to prevent corrosion

Chapter 17 - 23

ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 17 - 24