The Science and Engineering of Materials, 4 Ed: Chapter 22 - Corrosion and Wear

The Science and Engineering
of Materials, 4th ed
Donald R. Askeland – Pradeep P. Phulé
Chapter 22 – Corrosion and Wear
1 1
Objectives of Chapter 22
 To introduce the principles and mechanisms
by which corrosion and wear occur under
different conditions. This includes the
aqueous corrosion of metals, the oxidation
of metals, the corrosion of ceramics, and
the degradation of polymers.
 To give summary of different technologies
that are used to prevent or minimize
corrosion and associated problems.
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2
Chapter Outline
 22.1 Chemical Corrosion
 22.2 Electrochemical Corrosion
 22.3 The Electrode Potential in
Electrochemical Cells
 22.4 The Corrosion Current and Polarization
 22.5 Types of Electrochemical Corrosion
 22.6 Protection Against Electrochemical
Corrosion
 22.7 Microbial Degradation and
Biodegradable Polymers
 22.8 Oxidation and Other Gas Reactions
 22.9 Wear and Erosion
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Section 22.1
Chemical Corrosion
 Chemical corrosion - Removal of atoms from a material
by virtue of the solubility or chemical reaction between
the material and the surrounding liquid.
 Dezincification - A special chemical corrosion process by
which both zinc and copper atoms are removed from
brass, but the copper is replated back onto the metal.
 Graphitic corrosion - A special chemical corrosion process
by which iron is leached from cast iron, leaving behind a
weak, spongy mass of graphite.
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.
Figure 22.1 Molten lead is held

in thick steel pots during
refining. In this case, the
molten lead has attacked a weld
in a steel plate and cracks have
developed. Eventually, the
cracks propagate through the
steel, and molten lead leaks
from the pot.
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5
Figure 22.2 Photomicrograph of a copper deposit in brass,

showing the effect of dezincification (x50).
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Section 22.2
Electrochemical Corrosion
 Electrochemical corrosion - Corrosion produced by the
development of a current in an electrochemical cell that
removes ions from the material.
 Electrochemical cell - A cell in which electrons and ions
can flow by separate paths between two materials,
producing a current which, in turn, leads to corrosion or
plating.
 Oxidation reaction - The anode reaction by which
electrons are given up to the electrochemical cell.
 Reduction reaction - The cathode reaction by which
electrons are accepted from the electrochemical cell.
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Figure 22.3 The components in an electrochemical cell: (a) a

simple electrochemical cell and (b) a corrosion cell between a
steel water pipe and a copper fitting.
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Figure 22.4 The anode and cathode reactions in typical

electrolytic corrosion cells: (a) the hydrogen electrode, (b) the
oxygen electrode, and (c) the water electrode.
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Section 22.3
The Electrode Potential in
Electrochemical Cells
 Electrode potential - Related to the tendency of a
material to corrode. The potential is the voltage
produced between the material and a standard
electrode.
 emf series - The arrangement of elements according to
their electrode potential, or their tendency to corrode.
 Nernst equation - The relationship that describes the
effect of electrolyte concentration on the electrode
potential in an electrochemical cell.
 Faraday’s equation - The relationship that describes the
rate at which corrosion or plating occurs in an
electrochemical cell.
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10
Figure 22.5 The half-cell

used to measured the
electrode potential of
copper under standard
conditions. The electrode
potential of copper is the
potential difference
between it and the
standard hydrogen
electrode in an open
circuit. Since E0 is great
than zero, copper is
cathodic compared with
the hydrogen electrode.
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Example 22.1
Half-Cell Potential for Copper
Suppose 1 g of copper as Cu2+ is dissolved in 1000 g of water
to produce an electrolyte. Calculate the electrode potential of
the copper half-cell in this electrolyte.
Example 22.1 SOLUTION
From chemistry, we know that a standard 1-M solution of Cu2+
is obtained when we add 1 mol of Cu2+ (an amount equal to the
atomic mass of copper) to 1000 g of water. The atomic mass of
copper is 63.54 g/mol. The concentration of the solution when
only 1 g of copper is added must be:
From the Nernst equation, with n = 2 and E0 = +0.34 V:
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Example 22.2
Design of a Copper Plating Process
Design a process to electroplate a 0.1-cm-thick layer of copper
onto a 1 cm  1 cm cathode surface.
In order for us to produce a 0.1-cm-thick layer on a 1 cm2
surface area, the weight of copper must be:
From Faraday’s equation, where MCu = 63:54 g/mol and n = 2:
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14
Therefore, we might use several different combinations of

current and time to produce the copper plate:
Our choice of the exact combination of current and time

might be made on the basis of the rate of production and
quality of the copper plate.
A current of ~ 1 A and a time of ~ 45 minutes are
not uncommon in electroplating operations.
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Example 22.3
Corrosion of Iron
An iron container 10 cm  10 cm at its base is filled to a height
of 20 cm with a corrosive liquid. A current is produced as a
result of an electrolytic cell, and after 4 weeks, the container
has decreased in weight by 70 g. Calculate (1) the current and
(2) the current density involved in the corrosion of the iron.
1. The total exposure time is:
From Faraday’s equation, using n = 2 and M = 55.847 g/mol:
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2. The total surface area of iron in contact with the
corrosive liquid and the current density are:
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Example 22.4
Copper-Zinc Corrosion Cell
Suppose that in a corrosion cell composed of copper and zinc,
the current density at the copper cathode is 0.05 A/cm2. The
area of both the copper and zinc electrodes is 100 cm2.
Calculate (1) the corrosion current, (2) the current density at
the zinc anode, and (3) the zinc loss per hour.
1. The corrosion current is:
2. The current in the cell is the same everywhere. Thus:
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3. The atomic mass of zinc is 65.38 g/mol. From Faraday’s

equation:
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Section 22.4
The Corrosion Current and
Polarization
 Polarization - Changing the voltage between the anode
and cathode to reduce the rate of corrosion.
– Activation polarization is related to the energy
required to cause the anode or cathode reaction
– Concentration polarization is related to changes in the
composition of the electrolyte
– Resistance polarization is related to the electrical
resistivity of the electrolyte.
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Section 22.5
Types of Electrochemical Corrosion
 Intergranular corrosion - Corrosion at grain boundaries
because grain boundary segregation or precipitation
produces local galvanic cells.
 Stress corrosion - Deterioration of a material in which an
applied stress accelerates the rate of corrosion.
 Oxygen starvation - In the concentration cell, low-
oxygen regions of the electrolyte cause the underlying
material to behave as the anode and to corrode.
 Crevice corrosion - A special concentration cell in which
corrosion occurs in crevices because of the low
concentration of oxygen.
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Example 22.5
Corrosion of a Soldered Brass Fitting
A brass fitting used in a marine application is joined by
soldering with lead-tin solder. Will the brass or the solder
corrode?
From the galvanic series, we find that all of the copper-based
alloys are more cathodic than a 50% Pb-50% Sn solder. Thus,
the solder is the anode and corrodes. In a similar manner, the
corrosion of solder can contaminate water in freshwater
plumbing systems with lead.
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Figure 22.6 Example of microgalvanic cells in two-phase alloys:

(a) In steel, ferrite is anodic to cementite. (b) In austenitic
stainless steel, precipitation of chromium carbide makes the low
Cr austenite in the grain boundaries anodic.
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Figure 22.7 Photomicrograph of intergranular corrosion in a

zinc die casting. Segregation of impurities to the grain
boundaries produces microgalvanic corrosion cells (x50).
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Figure 22.8 Examples of stress cells. (a) Cold work required to

bend a steel bar introduces high residual stresses at the bend,
which then is anodic and corrodes. (b) Because grain
boundaries have a high energy, they are anodic and corrode.
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Example 22.6
Corrosion of Cold-Drawn Steel
A cold-drawn steel wire is formed into a nail by additional
deformation, producing the point at one end and the head at
the other. Where will the most severe corrosion of the nail
occur?
Since the head and point have been cold-worked an additional
amount compared with the shank of the nail, the head and
point serve as anodes and corrode most rapidly.
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.
Figure 22.9 Concentration cells: (a) Corrosion occurs beneath a

water droplet on a steel plate due to low oxygen concentration
in the water. (b) Corrosion occurs at the tip of a crevice
because of limited access to oxygen.
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Example 22.7
Corrosion of Crimped Steel
Two pieces of steel are joined mechanically by crimping
the edges. Why would this be a bad idea if the steel is
then exposed to water? If the water contains salt, would
corrosion be affected?
By crimping the steel edges, we produce a crevice. The
region in the crevice is exposed to less air and moisture,
so it behaves as the anode in a concentration cell. The
steel in the crevice corrodes.
Salt in the water increases the conductivity of the
water, permitting electrical charge to be transferred at a
more rapid rate. This causes a higher current density and,
thus, faster corrosion due to less resistance polarization.
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Figure 22.10 (a) Bacterial

cells growing in a colony
(x2700). (b) Formation of
a tubercule and a pit
under a biological colony.
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Section 22.6
Protection Against Electrochemical
Corrosion
 Inhibitors - Additions to the electrolyte that preferentially
migrate to the anode or cathode, cause polarization, and
reduce the rate of corrosion.
 Sacrificial anode - Cathodic protection by which a more
anodic material is connected electrically to the material
to be protected. The anode corrodes to protect the
desired material.
 Passivation - Producing strong anodic polarization by
causing a protective coating to form on the anode
surface and to thereby interrupt the electric circuit.
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Example 22.8
Effect of Areas on Corrosion Rate for
Copper-Zinc Couple
Consider a copper-zinc corrosion couple. If the current
density at the copper cathode is 0.05 A/cm2, calculate the
weight loss of zinc per hour if (1) the copper cathode area
is 100 cm2 and the zinc anode area is 1 cm2 and (2) the
copper cathode area is 1 cm2 and the zinc anode area is
100 cm2.
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Figure 22.11 Alternative methods for joining two pieces of

steel: (a) Fasteners may produce a concentration cell, (b)
brazing or soldering may produce a composition cell, and (c)
welding with a filler metal that matches the base metal may
avoid the formation of galvanic cells (for Example 22.8)
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1. For the small zinc anode area:
2. For the large zinc anode area:
The rate of corrosion of the zinc is reduced significantly

when the zinc anode is much larger than the cathode.
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34
Figure 22.12 Zinc-plated steel and tin-plated steel are

protected differently. Zinc protects steel even when the
coating is scratched, since zinc is anodic to steel. Tin does
not protect steel when the coating is disrupted, since steel is
anodic with respect to tin.
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Figure 22.13 Cathodic protection of a buried steel pipeline:

(a) A sacrificial magnesium anode assures that the galvanic
cell makes the pipeline the cathode. (b) An impressed voltage
between a scrap iron auxiliary anode and the pipeline assures
that the pipeline is the cathode.
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36
Figure 22.14 (a) Intergranular
corrosion takes place in austenitic
stainless steel. (b) Slow cooling
permits chromium carbides to
precipitate at grain boundaries.
(c) A quench anneal to dissolve
the carbides may prevent
intergranular corrosion.
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Example 22.9
Design of a Corrosion Protection System
Steel troughs are located in a field to provide drinking water
for a herd of cattle. The troughs frequently rust through and
must be replaced. Design a system to prevent or delay this
problem.
We might, for example, fabricate the trough using stainless
steel or aluminum. Either would provide better corrosion
resistance than the plain carbon steel, but both are
considerably more expensive than the current material.
We might suggest using cathodic protection; a small
magnesium anode could be attached to the inside of the
trough. The anode corrodes sacrificially and prevents
corrosion of the steel.
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38
Example 22.9 SOLUTION (Continued)
Another approach would be to protect the steel trough
using a suitable coating. Painting the steel (that is, introducing
a protective polymer coating) and, using a tin-plated steel,
provides protection as long as the coating is not disrupted.
The most likely approach is to use a galvanized
steel, taking advantage of the protective coating and the
sacrificial behavior of the zinc. Corrosion is very slow due
to the large anode area, even if the coating is disrupted.
Furthermore, the galvanized steel is relatively inexpensive,
readily available, and does not require frequent inspection.
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Example 22.10
Design of a Stainless-Steel Weldment
A piping system used to transport a corrosive liquid is
fabricated from 304 stainless steel. Welding of the pipes is
required to assemble the system. Unfortunately, corrosion
occurs and the corrosive liquid leaks from the pipes near
the weld. Identify the problem and design a system to
prevent corrosion in the future.
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Figure 22.15 The

peak temperature
surrounding a
stainless-steel weld
and the sensitized
structure produced
when the weld
slowly cools (for
Example 22.10)
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A portion of the pipe in the HAZ heats into the sensitization
temperature range, permitting chromium carbides to
precipitate. If the cooling rate of the weld is very slow, the
fusion zone and other areas of the heat-affected zone may also
be affected. Sensitization of the weld area, therefore, is the
likely reason for corrosion of the pipe in the region of the weld.
We might use a welding process that provides very
rapid rates of heat input, causing the weld to heat and cool
very quickly.
We might heat treat the assembly after the weld is
made. By performing a quench anneal, any precipitated
carbides are re-dissolved during the anneal and do not re-form
during quenching.
Perhaps our best design is to use a stainless steel that
is not subject to sensitization.
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Section 22.7
Microbial Degradation and
Biodegradable Polymers
 Simple polymers (such as polyethylene, polypropylene,
and polystyrene), high-molecular-weight polymers,
crystalline polymers, and thermosets are relatively
immune to attack.
 However, certain polymers—including polyesters,
polyurethanes, cellulosics, and plasticized polyvinyl
chloride (which contains additives that reduce the degree
of polymerization)—are particularly vulnerable to
microbial degradation.
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Section 22.8
Oxidation and Other Gas Reactions
 Oxidation - Reaction of a metal with oxygen to produce a
metallic oxide. This normally occurs most rapidly at high
temperatures.
 Pilling-Bedworth ratio - Describes the type of oxide film
that forms on a metal surface during oxidation.
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45
Figure 22.16 The standard free energy of formation of

selected oxides as a function of temperature. A large
negative free energy indicates a more stable oxide.
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Example 22.11
Chromium-Based Steel Alloys
Explain why we should not add alloying elements such as

chromium to pig iron before the pig iron is converted to
steel in a basic oxygen furnace at 1700oC.
In a basic oxygen furnace, we lower the carbon content of
the metal from about 4% to much less than 1% by
blowing pure oxygen through the molten metal. If
chromium were already present before the steel making
began, chromium would oxidize before the carbon (Figure
22.16), since chromium oxide has a lower free energy of
formation (or is more stable) than carbon dioxide (CO2).
Thus, any expensive chromium added would be lost
before the carbon was removed from the pig iron.
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Figure 22.17 Three

types of oxides may
form, depending on the
volume ratio between
the metal and the oxide:
(a) magnesium produces
a porous oxide film, 9b)
aluminum forms a
protective, adherent,
nonporous oxide film,
and (c) iron forms an
oxide film that spills off
the surface and provides
poor protection.
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Example 22.12
Pilling-Bedworth Ratio
The density of aluminum is 2.7 g/cm3 and that of Al2O3 is
about 4 g/cm3. Describe the characteristics of the
aluminum-oxide film. Compare with the oxide film that
forms on tungsten. The density of tungsten is 19.254
g/cm3 and that of WO3 is 7.3 g/cm3.
For 2Al + 3/2O2  Al2O3, the molecular weight of Al2O3 is
101.96 and that of aluminum is 26.981.
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For tungsten, W+ 3/2O2  WO3. The molecular weight of
WO3 is 231.85 and that of tungsten is 183.85:
Since P-B ~ 1 for aluminum, the Al2O3 film is

nonporous and adherent, providing protection to the
underlying aluminum. However, P-B > 2 for tungsten,
so the WO3 should be nonadherent and nonprotective.
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Example 22.13
Parabolic Oxidation Curve for Nickel
At 1000oC, pure nickel follows a parabolic oxidation curve
given by the constant k = 3.9  10-12 cm2/s in an oxygen
atmosphere. If this relationship is not affected by the
thickness of the oxide .lm, calculate the time required for
a 0.1-cm nickel sheet to oxidize completely.
Assuming that the sheet oxidizes from both sides:
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Section 22.9
Wear and Erosion
 Adhesive wear - Removal of material from surfaces of
moving equipment by momentary local bonding, then
bond fracture, at the surfaces.
 Abrasive wear - Removal of material from surfaces by
the cutting action of particles.
 Cavitation - Erosion of a material surface by the
pressures produced when a gas bubble collapses within a
moving liquid.
 Liquid impingement - Erosion of a material caused by the
impact of liquid droplets carried by a gas stream.
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Figure 22.18 The

asperities on two rough
surfaces may initially be
bonded. A sufficient force
breaks the bonds and the
surfaces slide. As they
slide, asperities may be
fractured, wearing away
the surfaces and
producing debris.
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Figure 22.19 Abrasive wear, caused by either trapped or free-

flying abrasives, produces troughs in the material, piling up
asperities that may fracture into debris.
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Figure 22.20 Two steel sheets joined by an

aluminum rivet (for Problem 22.25).
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Figure 22.21 Cross-section through an integrated circuit

showing the external lead connection to the chip (for
Problem 22.26).
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The Science and Engineering

Chapter 22 – Corrosion and Wear

Figure 22.1 Molten lead is held

Figure 22.2 Photomicrograph of a copper deposit in brass,

Figure 22.3 The components in an electrochemical cell: (a) a

Figure 22.4 The anode and cathode reactions in typical

Figure 22.5 The half-cell

From the Nernst equation, with n = 2 and E0 = +0.34 V:

From Faraday’s equation, where MCu = 63:54 g/mol and n = 2:

Therefore, we might use several different combinations of

Our choice of the exact combination of current and time

From Faraday’s equation, using n = 2 and M = 55.847 g/mol:

2. The current in the cell is the same everywhere. Thus:

3. The atomic mass of zinc is 65.38 g/mol. From Faraday’s

Figure 22.6 Example of microgalvanic cells in two-phase alloys:

Figure 22.7 Photomicrograph of intergranular corrosion in a

Figure 22.8 Examples of stress cells. (a) Cold work required to

Figure 22.9 Concentration cells: (a) Corrosion occurs beneath a

Figure 22.10 (a) Bacterial

Figure 22.11 Alternative methods for joining two pieces of

2. For the large zinc anode area:

The rate of corrosion of the zinc is reduced significantly

Figure 22.12 Zinc-plated steel and tin-plated steel are

Figure 22.13 Cathodic protection of a buried steel pipeline:

Figure 22.15 The

Figure 22.16 The standard free energy of formation of

Explain why we should not add alloying elements such as

Figure 22.17 Three

Since P-B ~ 1 for aluminum, the Al2O3 film is

Figure 22.18 The

Figure 22.19 Abrasive wear, caused by either trapped or free-

Figure 22.20 Two steel sheets joined by an

Figure 22.21 Cross-section through an integrated circuit

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