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Hull Corrosion
The term corrosion refers to the destruction of a metal or alloy by chemical or
electrochemical reaction. Corrosion of a ship's metal hull below the waterline is
predominantly electrochemical. Corrosion occurs when the conditions are present to
form an electrochemical corrosion cell. These conditions are always present on the
underwater portion of a ship's metal hull. This is illustrated in the following drawing.
Variations in the chemistry of metal, both within the same hull metal and between
dissimilar hull metals, lead to electro-potential differences. Seawater, acting as the
electrolyte, links these areas of differing electro-potential, forming a corrosion cell.
The areas of the hull that are consumed electrochemically in the corrosion cell
(releasing electrons to the seawater) are said to be anodic, and the areas of the hull
where current reenters the hull are said to be cathodic. Hull corrosion occurs in those
areas that are anodic.
The rate at which the corrosion of a metal occurs depends to a large extent on the
relative electro-potentials of the two areas of metal linked in the corrosion cell. Within
a given metal this difference is minimal. For dissimilar metals it is much greater. A
measure of the electro-potential differences between dissimilar metals is given in the
Galvanic Series. In a corrosion cell, the metal with the greater negative electrical
potential acts as the anode and will corrode.
A galvanic series has been drawn up below for metals and alloys in seawater, which
shows their relative nobility. The series is based on corrosion potential measurements
in seawater. The relative position of the materials can change in other environments.
The further apart the materials are in this series, the higher the risk of galvanic
corrosion.
Chemistry of Corrosion
Common structural metals are obtained from their ores or naturally-occurring
compounds by the expenditure of large amounts of energy. These metals can therefore
be regarded as being in a metastable state and will tend to lose their energy by
reverting to compounds more or less similar to their original states. Since most
metallic compounds, and especially corrosion products, have little mechanical
strength a severely corroded piece of metal is quite useless for its original purpose.
Virtually all corrosion reactions are electrochemical in nature, at anodic sites on the
surface the iron goes into solution as ferrous ions, this constituting the anodic
reaction. As iron atoms undergo oxidation to ions they release electrons whose
negative charge would quickly build up in the metal and prevent further anodic
reaction, or corrosion. Thus this dissolution will only continue if the electrons
released can pass to a site on the metal surface where a cathodic reaction is possible.
At a cathodic site the electrons react with some reducible component of the electrolyte
and are themselves removed from the metal. The rates of the anodic and cathodic
reactions must be equivalent according to Faraday’s Laws, being determined by the
total flow of electrons from anodes to cathodes which is called the “corrosion
current”, Icor. Since the corrosion current must also flow through the electrolyte by
ionic conduction the conductivity of the electrolyte will influence the way in which
corrosion cells operate.
Or,
Reaction 2a is most common in acids and in the pH range 6.5 – 8.5 the most important
reaction is oxygen reduction 2b. In this latter case corrosion is usually accompanied
by the formation of solid corrosion debris from the reaction between the anodic and
cathodic products.
Pure iron (II) hydroxide is white but the material initially produced by corrosion is
normally a greenish colour due to partial oxidation in air.
Further hydration and oxidation reactions can occur and the reddish rust that
eventually forms is a complex mixture whose exact constitution will depend on other
trace elements which are present. Because the rust is precipitated as a result of
secondary reactions it is porous and absorbent and tends to act as a sort of harmful
poultice which encourages further corrosion. For other metals or different
environments different types of anodic and cathodic reactions may occur. If solid
corrosion products are produced directly on the surface as the first result of anodic
oxidation these may provide a highly protective surface film which retards further
corrosion, the surface is then said to be “passive”. An example of such a process
would be the production of an oxide film on iron in water, a reaction which is
encouraged by oxidizing conditions or elevated temperatures.
Types of Corrosion
There are a number of types of corrosion at sea and there is a need to know these
various mechanisms of corrosion, so that appropriate measures can be taken to
counteract their detrimental effects. The types of corrosion encountered are described
below:
o Galvanic corrosion occurs when two different metals are placed in contact
with each other and is caused by the greater willingness of one to give up
electrons than the other. Three special features of this mechanism need to
operate for corrosion to occur:
The metals need to be in contact electrically
One metal needs to be significantly better at giving up electrons
than the other
An additional path for ion and electron movement is necessary.
Prevention of this problem is based on ensuring that one or more of the three
features do not exist. Break the electrical contact using plastic insulators or
coatings between the metals. Select metals close together in the galvanic
series. Prevent ion movement by coating the junction with an impermeable
material, or ensure environment is dry and liquids cannot be trapped.
o Selective attack occurs in alloys such as brass when one component or phase
is more susceptible to attack than another and corrodes preferentially leaving a
porous material that crumbles. It is best avoided by selection of a resistant
material but other means can be effective such as:
Corrosion Prevention
By retarding either the anodic or cathodic reactions the rate of corrosion can be
reduced. This can be achieved in several ways:
o Conditioning the Metal: This can be sub-divided into two main groups:
o Electrochemical Control:
Using the amplified D.C. signal from the controller the reactor rectifier supplies
larger current from ship’s A.C. power source.
Although the first cost is considerable, the savings on hull maintenance over the
life of the ship is considerable.