Corrosion Fundamentals

Corrosion is a natural process that seeks to reduce the binding

energy in metals. The end result of corrosion involves a metal
atom M being oxidized, whereby it loses one or more electrons
and leaves the bulk metal,
M   Mm+ + m e-
The lost electrons are conducted through the bulk metal to
another site where they reduce (i.e. combine with) a non-
metallic element N or another metallic ion G+ that is in contact
with the bulk metal,
N + n e-   Nn-
Gm+ + m e-   G
In corrosion parlance, the site where metal atoms lose electrons
is called the anode, and the site where electrons are transfered
to the reducing species is called the cathode. These sites can be
located close to each other on the metal's surface, or far apart
depending on the circumstances.
Anode/cathode pairs, known as corrosion cells, come in a
variety of forms including composition cells (also known as
Galvanic Cells), stress cells, and concentration cells.

Electrolytes and the Corrosion Circuit

Corrosion is essentially an electric circuit, since there is a flow of

current between the cathode and anode sites. In order for a
current to flow, Kirchoff's circuit laws require that a circuit be
closed and that there exists a driving potential (or voltage).
Part of the corrosion circuit is the base metal itself; the rest of
the circuit exists in an external conductive solution (i.e. an
electrolyte) that must be in contact with the metal. This
electrolyte serves to take away the oxidized metal ions from the
anode and provide reduction species (either nonmetalic atoms or
metallic ions) to the cathode. Both the cathode and anode sites
must be immersed in the same electrolyte for the corrosion
circuit to be complete. The most common electrolyte associated
with corrosion is ordinary water.
What provides the potential that drives the corrosion circuit? In
most cases, the differences in the atom binding energies within a
metal provide the driving potential (e.g. composition cells, stress
cells). Ion concentration gradients in the electrolyte can also
provide a potential (concentration cells).
Note that inside the metal, the charge carriers are electrons;
outside the metal, the charge carriers are ions dissolved in the
electrolyte.
Composition Cells

Composition cells (also known as Galvanic cells) arise when two metals with
dissimilar compositions or microstructures come into contact in the presence of
an electrolyte. The two most common examples follow:

Formed by two single-phase metals in contact, such as

iron and zinc, or nickel and gold. The metal that is higher
on the Electrochemical Series will be the cathode. The
other metal will suffer anodic reactions and will corrode.
Dissimilar Incidentally, dissimilar metal contact (while bathed in a
metals suitable electrolyte) is the technology behind the
construction of batteries. The voltage of a battery directly
follows from the natural electrode potential of the
corrosion reactions present inside the battery. Hence,
controlled corrosion is a good thing!

Formed by a metal alloy composed of multiple phases,

Multi- such as a stainless steel, a cast iron, or an aluminum
phase alloy. The individual phases possess different electrode
alloy potentials, resulting in one phase acting as an anode and
subject to corrosion.

Stress Cells

Stress cells can exist in a single piece of metal where a portion of the metal's
microstructure possesses more stored strain energy than the rest of the metal.
Metal atoms are at their lowest strain energy state when situated in a regular
crystal array. Deviations from this lowest-strain state follow:

By definition, metal atoms situated along grain

boundaries are not located in a regular cystal array (i.e. a
Grain grain). Their increased strain energy translates into an
boundaries electrode potential that is anodic to the metal in the
grains proper. Thus, corrosion can selectively occur along
grain boundaries.

Regions within a metal subject to a high local stress will

High
contain metal atoms at a higher strain energy state. As a
localized
result, high-stress regions will be anodic to low-stress
stress
regions and can corrode selectively.
 For example, bolts under load are subject to more
corrosion than similar bolts that are unloaded. A good
rule of thumb is to select fasteners that are cathodic (i.e.
higher on the Electrochemical Series) to the metal being
fastened in order to prevent fastener corrosion.

Regions within a metal subjected to cold-work contain a

higher concentration of dislocations, and as a result will
be anodic to non-cold-worked regions. Thus, cold-worked
Cold sections of a metal will corrode faster.
worked
For example, nails that are bent will often corrode at the
bend, or at their head where they were worked by the
hammer.

Concentration Cells

Concentration cells can arise when the concentration of one of the species
participating in a corrosion reaction varies within the electrolyte. Two examples
will be given:

Consider a metal bathed in an electrolyte containing

its own ions. The basic corrosion reaction where a
metal atom losses an electron and enters the
electrolyte as an ion can proceed both forward and
backwards, and will eventually reach equilibrium.

If a region of the electrolyte (adjacent to the metal)

Electrolyte were to exhibit a decreased concentration of metal
concentration ions, this region would become anodic to the other
portions of the metal surface. As a result, this portion
of the metal would corrode faster in order to increase
the local ion concentration.

The net affect is that local corrosion rates are

modulated in order to homogenize reduction ion
concentrations within the electrolyte.

Oxidation Perhaps the most common concentration cell affecting

concentration engineered structures is that of oxygen gas. When
oxygen has access to a moist metal surface, corrosion
is promoted. However, it is promoted the most where
the oxygen concentration is the least (for the reasons
described in the above box).

As a result, sections of a metal that are covered by

dirt or scale will often corrode faster, since the flow of
oxygen to these sections is restricted. An increased
corrosion rate will lead to increased residue, further
restricting the oxygen flow to worsen the situation.
Pitting often results from this "runaway" reaction.
Interrupt the Corrosion Circuit

Strategies for breaking the corrosion circuit involve adding a non-conductor into
the loop or removing the electrolyte.

Applying a nonconductive paint or polymer coating to

Nonconductive
a metal will prevent the conductive electrolyte from
coating:
touching the metal, thereby preventing the flow of
Artificial
current.

Stainless steels, aluminum, and titanium already

Nonconductive have nonconductive coatings provided by their
coating: durable oxide layers, and can thereby resist corrosion
Natural provided they avoid oxygen-poor (i.e. highly
reducing) environments.

Another approach to breaking the corrosion circuit is

Electrolyte to remove electrolytes from the metal's surroundings.
removal However, this can be quite a challenge given the
ubiquitous presence of water in our environment.

Reduce the Driving Potential

Strategies for minimizing the electrode potential is to either add a battery into the
corrosion circuit or to swing the potential in favor of purposely corroding a
sacrificial metal. Such techniques are commonly called Galvanic Protection.

Since all corrosion circuits exhibit a potential (i.e. voltage)

difference between the corroding anode and the reducing
cathode, one technique to minimize this potential is to
place a battery in the circuit that attempts to reverse the
voltage difference. In effect, the battery pushes electrons
Applied back into the anode, whose original intent was to donote
voltage electrons to the cathode and corrode.
(Impressed
Current) An application that uses this technique to reduce corrosion
is in the protection of underground pipelines. Typically, by
saving the pipeline metal the corrosion is shifted to one of
the terminals of the battery. However, this is not so bad
since a localized battery can be maintained easier than
miles of pipeline.
 In order to save the anodic corrosion-intent metal in a
corrosion circuit, another metal than is more anodic (i.e.
lower on the Electrochemical Series) can be brought into
contact with the original metal. Now, a composition cell is
set up between the original metal and the new more active
metal, promoting the corrosion of the new metal. In effect,
the new metal acts as a sacfrificial anode, since any
Sacrificial
corrosion that was to occur will shift to this metal.
anode
Applications include the protection of ship hulls and water
tanks (e.g. adding a block of zinc to a steel hull). Also
included are parts made from galvanized steel, where a
steel component is plated with zinc. If the coating suffers a
scratch, the zinc will corrode more readily than the
underlying steel, thereby protecting the steel.