Factors influencing Rate of Corrosion

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Introduction

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 and reinforcement wrap. We shall explore the different factors contributing to the corrosion rate here.

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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 moisture film will corrode faster than areas under immersion. Therefore the hullage space at the top of ballast tanks and at the top of double bottom tanks where air has become trapped tends to corrode more quickly than deeply submerged areas where there is a lower availability of oxygen.

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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. As a result, under-deck areas and regions adjacent to the engine room, or to heated cargo tanks, will tend to corrode faster or preferentially. One of the features of the modern double hulled tanker with fully segregated ballast tanks is that when the cargo tanks are fully loaded, the empty ballast tanks act as a vacuum flask or thermos-bottle and retain the heat in the cargo for significantly longer periods than the single hull design. This increase in temperature of the cargo/ ballast bulkhead combined with the cooler outer shell bulkhead (in the underwater regions) produces a complex set of corrosion conditions and results in an increase in the corrosion rate of the steel in the ballast tanks. Corrosion rates in the cargo tanks themselves will also be higher due to the increased temperature.

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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.

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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. This can produce intensive pitting on the inner bottoms of cargo tanks in oil and product carriers. The sulfur can originate from both the inert gas system and from cargoes containing sulfur, such as sour crude oil.

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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. Many of the blisters which are found in ballast tanks, particularly in the double bottoms, are filled with a high pH fluid. When the blister caps are removed, the steel is bright underneath. However, it will begin to corrode once the cap is removed, so once one or two of a group of blisters have been checked and the liquid found to be alkaline, the remainder of the blisters should be left intact.

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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, as occurs with an active cathodic protection system of the type employed on the external hull.

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