There are several
factors influencing the rate of corrosion including diffusion, temperature, conductivity,
type of ions, pH value and electrochemical potential. The rate of corrosion can
be controlled or reduced by applying anti-corrosion coatings or corrosion
protection techniques including composite repair compounds, metal repair
putties with metal putty and reinforcement wrap. We shall explore the different factors
contributing to the corrosion rate here.
Diffusion
In the majority of cases, the
corrosion rates of metals are controlled by the diffusion of reactants to and
from the metal surface. Freshly exposed bare steel surfaces will corrode at a
greater rate than those covered with a compact layer of rust. The corrosion
rate is also heavily controlled by the diffusion of oxygen through the water to
the steel surface. In areas where oxygen diffusion is prevalent, corrosion
appears to occur at faster rates. High flow areas, such as in the vicinity of bell
mouths, will tend to exhibit higher corrosion rates because of the increased
oxygen levels, although erosion is also a factor. Areas covered by a thin,
conducting water moisture film will corrode faster than areas under immersion.
Temperature
As corrosion rates are determined by
diffusion, diffusion rates are also controlled by temperature. Steel and other
metals corrode at faster rates at higher temperatures than at lower
temperatures. For example, corrosion rates in the cargo tanks will also be
higher due to the increased temperature.
Conductivity
For corrosion to occur there must be a
conductive medium between the two parts of the corrosion reaction. Corrosion will
not occur in distilled water and the rate of corrosion will increase as the
conductivity increases due to the presence of more ions in the solution. The
corrosion rate of steel reaches a maximum close to the normal ionic content of
sea water. Fresh water corrodes steel to a lesser extent than brackish or
estuarine water, with sea water usually being the most corrosive to steel.
Type of ions
Some types of ions present in sea
water or in cargoes are more corrosive than others. Chloride ions are usually
the most destructive with sulfate and other sulfur containing ions also presenting
major problems. Chloride ions have a destructive effect on the protective
properties of any rusts produced by preventing the formation of the more
protective, densely packed oxides. Sulfur containing ions become involved in
additional electron generating reactions within the rust itself which in turn
forms a cyclic, self-regenerating process.
Acidity and alkalinity (pH)
pH is a measure of the acidity or
alkalinity on a scale of 1 to 14. pH 7 is neutral. In neutral sea water, the pH
is around 7.5 which mean that the hydrogen ions (acid) and hydroxyl ions
(alkali) are almost in balance. Under such circumstances, the reaction that
balances the iron dissolution is the reduction of dissolved oxygen to form
hydroxyl ions. If however the environment becomes more acidic and the pH falls
closer to 1, then there is a greater quantity of hydrogen ions than hydroxyl
ions present in the solution. The excess hydrogen ions can become involved in
the balancing (cathodic) reaction which results in the evolution of hydrogen
gas. As both the hydrogen ions and the hydrogen gas can diffuse very rapidly,
the steel can corrode faster. This is a common effect when carrying cargoes
such as pet-coke, sulphur and sour crude oils. Under alkaline conditions, where
there is an excess of hydroxyl ions and the pH levels tend towards 14, steel
cannot corrode and remains unaffected.
Electrochemical potential
Every metal takes up a specific
electrochemical potential when immersed in a conducting liquid. This potential
is called the half-cell potential as it can only be measured by comparing it to
another known reference potential produced by a reference electrode. Common
reference electrodes are the Saturated Calomel Electrode (SCE), silver/silver
chloride and copper/copper sulfate reference electrodes. The potential that a
metal takes up in a solution can determine if and how fast it will corrode. The
potential can be changed by connecting it to another dissimilar metal (as in
galvanic corrosion or by using sacrificial anodes) or by applying an external
potential.
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