Naval Architecture & Ship Construction MA3022

Section: Hull Corrosion

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.  

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Naval Architecture & Ship Construction MA3022
Section: Hull Corrosion

Galvanic Series in Sea Water

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Naval Architecture & Ship Construction MA3022
Section: Hull 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.

The corroding piece of metal is described as a “mixed electrode” since simultaneous

anodic and cathodic reactions are proceeding on its surface. The mixed electrode is a
complete electrochemical cell on one metal surface. The most common and important
electrochemical reactions in the corrosion of iron are thus,

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.

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TNC/KC/August’04
Naval Architecture & Ship Construction MA3022
Section: Hull Corrosion

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 Uniform corrosion (generally attributed to 30% of corrosion-based

failures), as the name suggests, occurs over the majority of the surface of a
metal at a steady and often predictable rate. Although it is unsightly its
predictability facilitates easy control, the most basic method being to make the
material thick enough to function for the lifetime of the component. Uniform
corrosion can be slowed or stopped by using the following;
(1) Slow down or stop the movement of electrons
(a) Coat the surface with a non-conducting medium such as
paint, lacquer or oil
(b) Reduce the conductivity of the solution in contact with the
metal an extreme case being to keep it dry. Wash away
conductive pollutants regularly.
(c) Apply a current to the material (see cathodic protection).
(2) Slow down or stop oxygen from reaching the surface. Difficult to
do completely but coatings can help.
(3) Prevent the metal from giving up electrons by using a more
corrosion resistant metal higher in the electrochemical series. Use a
sacrificial coating which gives up its electrons more easily than the
metal being protected. Apply cathodic protection. Use inhibitors.
(4) Select a metal that forms an oxide that is protective and stops the
reaction. Control and consideration of environmental and thermal
factors is also essential.

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Naval Architecture & Ship Construction MA3022
Section: Hull Corrosion

o Localized corrosion (generally attributed to 70% of corrosion-based

failures), can be a great deal more severe than uniform corrosion as the failure
occurs without warning and after a surprisingly short period of use or
exposure. These are difficult to detect and check lists and survey guidelines
are produced based on actual experience to deter such occurrences.

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 Pitting corrosion occurs in materials that have a protective film such as a

corrosion product or when a coating breaks down. The exposed metal gives up
electrons easily and the reaction initiates tiny pits with localized chemistry
supporting rapid attack. Control can be ensured by:

 Selecting a resistant material

 Ensuring a high enough flow velocity of fluids in contact with
the material or frequent washing
 Control of the chemistry of fluids and use of inhibitors
 Use of a protective coating
 Maintaining the material’s own protective film.

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:

 Coating the material

 Reducing the aggressiveness of the environment
 Use of cathodic protection

o Microbial corrosion covers the degradation of materials by bacteria, moulds

and fungi or their by-products. It can occur by a range of actions such as:

 Attack of the metal or protective coating by acid by-products,

sulphur, hydrogen sulphide or ammonia
 Direct interaction between the microbes and metal which
sustains attack.

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Naval Architecture & Ship Construction MA3022
Section: Hull Corrosion

Prevention can be achieved by:

 Selection of resistant materials

 Frequent cleaning
 Control of chemistry of surrounding media and removal of
nutrients
 Use of biocides
 Cathodic protection.

o Intergranular corrosion is preferential attack of the grain boundaries of the

crystals that form the metal. It is caused by the physical and chemical
differences between the centres and edges of the grain. It can be avoided by:

 Selection of stabilised materials

 Control of heat treatments and processing to avoid susceptible
temperature range.

o Crevice corrosion happens when two areas of a component in close proximity

differ in the amount of reactive constituent available the reaction in one of the
areas is speeded up. An example of this is crevice corrosion which occurs
when oxygen cannot penetrate a crevice and a differential aeration cell is set
up. Corrosion occurs rapidly in the area with less oxygen. The potential for
crevice corrosion can be reduced by:

 Avoiding sharp corners and designing out stagnant areas

 Use of sealants
 Use welds instead of bolts or rivets
 Selection of resistant materials

o Corrosion fatigue: The combined action of cyclic stresses and a corrosive

environment reduce the life of components below that expected by the action
of fatigue alone. This can be reduced or prevented by:

 Coating the material

 Good design that reduces stress concentration
 Avoiding sudden changes of section
 Removing or isolating sources of cyclic stress

o Fretting corrosion: Relative motion between two surfaces in contact by a stick-

slip action causes breakdown of protective films or welding of the contact
areas allowing other corrosion mechanisms to operate. Prevention is possible
by:

 Designing out vibrations

 Lubrication of metal surfaces
 Increasing the load between the surfaces to stop the motion
 Surface treatments to reduce wear and increase friction
coefficient

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Naval Architecture & Ship Construction MA3022
Section: Hull Corrosion

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:

 Coating the metal, in order to interpose a corrosion resistant

coating between metal and environment. The coating may
consist of:
 another metal, e.g. zinc or tin coatings on steel,
 a protective coating derived from the metal itself, e.g.
aluminium oxide on “anodised” aluminium,
 organic coatings, such as resins, plastics, paints, enamel,
oils and greases.
The action of protective coatings is often more complex than
simply providing a barrier between metal and environment.
Paints may contain a corrosion inhibitor zinc coating in iron or
steel confers cathodic protection.
 Alloying the metal to produce a more corrosion resistant alloy,
e.g. stainless steel, in which ordinary steel is alloyed with
chromium and nickel. Stainless steel is protected by an
invisibly thin, naturally formed film of chromium sesquioxide
Cr O .
2 3

o Conditioning the Corrosive Environment:

 Removal of Oxygen. By the removal of oxygen from water

systems in the pH range 6.5-8.5 one of the components required
for corrosion would be absent. The removal of oxygen could be
achieved by the use of strong reducing agents e.g. sulphite.
However, for open evaporative cooling systems this approach
to corrosion prevention is not practical since fresh oxygen from
the atmosphere will have continual access.
 Corrosion Inhibitors. A corrosion inhibitor is a chemical
additive, which, when added to a corrosive aqueous
environment, reduces the rate of metal wastage. It can function
in one of the following ways:
 anodic inhibitors – as the name implies an anodic
inhibitor interferes with the anodic process.
Fe → Fe++ + 2e
If an anodic inhibitor is not present at a concentration
level sufficient to block off all the anodic sites, localised
attack such as pitting corrosion can become a serious
problem due to the oxidising nature of the inhibitor
which raises the metal potential and encourages the
anodic reaction (shown above). Anodic inhibitors are
thus classified as “dangerous inhibitors”. Other

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Naval Architecture & Ship Construction MA3022
Section: Hull Corrosion

examples of anodic inhibitors include orthophosphate,

nitrite, ferricyanide and silicates.
 cathodic inhibitors – the major cathodic reaction in
cooling systems is the reduction of oxygen.
½O2 + H2O + 2e → 2OH
There are other cathodic reactions and additives that
suppress these reactions called cathodic inhibitors. They
function by reducing the available area for the cathodic
reaction. This is often achieved by precipitating an
insoluble species onto the cathodic sites. Zinc ions are
used as cathodic inhibitors because of the precipitation
of Zn(OH)2 at cathodic sites as a consequence of the
localised high pH. (See reaction above). Cathodic
inhibitors are classed as safe because they do not cause
localised corrosion.
 Other inhibitor used are i) adsorption type corrosion
inhibitors, ii) mixed inhibitors.

o Electrochemical Control:

Since corrosion is an electrochemical process its progress may be studied by

measuring the changes which occur in metal potential with time or with
applied electrical currents. Conversely, the rate of corrosion reactions may be
controlled by passing anodic or cathodic currents into the metal. If, for
example, electrons are passed into the metal and reach the metal/electrolyte
interface (a cathodic current) the anodic reaction will be stifled while the
cathodic reaction rate increases. This process is called cathodic protection and
can only be applied if there is a suitable conducting medium such as sea water
through which a current can flow to the metal to be protected. In sea water
corrosion of steel is prevented if the potential of the metal surface is lowered
by 300 or 400 mV. Cathodic protection may be achieved by using a DC power
supply (impressed current) or by obtaining electrons from the anodic
dissolution of a metal low in the galvanic series such as aluminium, zinc or
magnesium (sacrificial anodes). Similar protection is obtained when steel is
coated with a layer of zinc. Even at scratches or cut edges where some bare
metal is exposed the zinc is able to pass protective current through the thin
layer of surface moisture. In certain chemical environments it is sometimes
possible to achieve anodic protection, passing a current which takes electrons
out of the metal and raises its potential. Initially this stimulates anodic
corrosion, but in favourable circumstances this will be followed by the
formation of a protective oxidised passive surface film.

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Naval Architecture & Ship Construction MA3022
Section: Hull Corrosion

The principle of impressed current systems is that

 Voltage difference is maintained between HULL  ANODES, which protect
the hull against corrosion.

 Anodes are made of non-consumable lead/silver, platinum/palladium alloys or

platinized titanium.

 The amount of current is monitored and controlled by the controller. Otherwise,

there will be overprotection with wastage of current.

 Reference cells (made of silver/silver chloride) detects the voltage between

HULL  REFERENCE CELL

 An amplifier controller is used to amplify the micro-range reference cell current

and it compares this with the preset protective potential value, which is to be
maintained.

 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.

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