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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.

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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.

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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.

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.

 Faradays equation - The relationship that describes the


rate at which corrosion or plating occurs in an
electrochemical cell.

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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.

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:

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.
Example 22.2 SOLUTION
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 Faradays equation, where MCu = 63:54 g/mol and n = 2:

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Example 22.2 SOLUTION


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.
Example 22.3 SOLUTION
1. The total exposure time is:

From Faradays equation, using n = 2 and M = 55.847 g/mol:

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Example 22.3 SOLUTION


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.
Example 22.4 SOLUTION
1. The corrosion current is:

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

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Example 22.4 SOLUTION


3. The atomic mass of zinc is 65.38 g/mol. From Faradays
equation:

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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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Example 22.8 SOLUTION


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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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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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?
Example 22.5 SOLUTION
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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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, lowoxygen 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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2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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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2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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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2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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?
Example 22.6 SOLUTION
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?
Example 22.7 SOLUTION
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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2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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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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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2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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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2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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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2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

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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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.
Example 22.9 SOLUTION
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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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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