3.

Corrosion and Corrosion

prevention

Table of content

Section Title Page

3.1 What is corrosion? 3.2

3.2 Why do some materials corrode faster than other ones? 3.4

3.3 What factors influence corrosion rate? 3.5

3.4 How can we protect against corrosion? 3.7

3.4.1 Factors to consider 3.7
3.4.2 Corrosion protection in general 3.9
3.4.3 Paints and coatings 3.10
3.4.4 Cathodic protection 3.10
3.4.5 Other corrosion protection methods 3.10

3.5 Forms of corrosion 3.11

3.5.1 Forms of corrosion on different materials 3.11
3.5.2 General (uniform) corrosion 3.12
3.5.3 Galvanic corrosion 3.13
3.5.4 Pitting corrosion 3.15
3.5.5 Crevice corrosion 3.16
3.5.6 Stress corrosion 3.16
3.5.7 Corrosion fatigue 3.17
3.5.8 Bacterial corrosion 3.18
3.5.9 Erosion corrosion 3.18
3.5.10 Dealloying corrosion 3.19

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3. Corrosion and corrosion prevention.

3.1 What is corrosion?

Corrosion is the breakdown of a material through a chemical reaction with the surrounding
environment.

For initiation and propagation of a corrosion attack a so called “corrosion cell” must be
established. A corrosion cell is an electrical circuit, with transport of electrons and ions
between two differently charged electrodes. A typical corrosion cell will consist of:

• Two different metals (Explained more detailed later)

• Two separate conductors
- Electrical contact between the two metals (Conductor 1).
- An electrolyte: liquid. (Conductor 2)
• Oxygen (Part of most corrosion processes)

Figure 3.1
A corrosion cell

Cathode:
Steel 2+ - Anode:
Zn = Zn + 2 e
Zinc
O2

½ O2 + H2 O + 2e - =
- 2OH -

The electrodes (metals) in a corrosion cell.

To have a corrosion cell we need a driving voltage. In most cases connecting two differently
charged electrodes (different metallic materials), as in a battery, creates the driving voltage.
As we will see later the electrodes can be two separate metallic phases of the same alloy, or
impurities in an alloy (see uniform corrosion). Also one piece of metal exposed to different
environments may serve as two different electrodes and give the same effect (see crevice
corrosion). In a corrosion cell, one of the metals will always be nobler than the other. The
positively charged metal surface is the anode. It is the anode that will suffer corrosion. The
cathode is negatively charged compared to the anode and will not corrode.

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Conductor 1: Electrical contact in a corrosion cell.
The first conductor in a corrosion cell is established when the anode is in metallic contact
with the cathode. This can be either by a direct metal-to-metal contact or via an external,
electrical conductor (Wire, bolt, deck support, suspension systems or similar). Metallic
contact enables transport of electrons (electrical current), from the anode to the cathode.

Conductor 2: The Electrolyte in a corrosion cell.

In most cases corrosion takes place in an aqueous environment, or at least in the presence
of humidity. Dry high-temperature corrosion only takes place under special conditions, for
example in engines and exhaust systems. Thus, the primary mechanism of most forms of
corrosion is of electrochemical nature. A prerequisite is the presence of an electrolyte
containing ions that can transport electrical current. The higher the concentration of ions
the better is the conductivity and the faster is the corrosion rate. An aqueous corrosion
process is often called “electrochemical corrosion” or “electrochemical reaction”.

When metals are immersed in a liquid (like seawater) the liquid itself will be the electrolyte.
An electrochemical reaction may also take place above the waterline as an electrolyte can
be formed by moisture in the atmosphere (high humidity, condensation or dew). Moisture
or water can easily collect impurities or salt from the steel surface or from the atmosphere,
and together they form a conductive electrolyte.

Oxygen to promote corrosion in a corrosion cell.

The above mentioned factors would be sufficient to give corrosion, but at a very low
corrosion rate. In many cases air is present, either as a part of the atmosphere or dissolved
in the liquid. The presence of air will speed up the corrosion rate as the oxygen in the air
reacts with the iron during the release of electrical energy. (See figure below).

Figure 3.2
The corrosion process on steel.
W ater
Steel
F e (O H ) 2
OH ¯ Fe 2+
C athode A node
e¯
C athode: A node:
O 2 + 2 H 2O + e ¯ → 4 OH ¯ Fe → Fe 2+ +e¯

W ater, Iron ions and H ydroxyl ions com bine

to give rust : F e (O H ) 2 , F e2O 3. n H 2O

As seen from the figure above the material dissolves when corrosion occurs. A large portion
or the resulting corrosion products will remain on the metal surface even though some of it
may be transported away by electrolytes with high flow velocities. Thus, in most cases we

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can actually see that a corrosion process is going on due to formation of voluminous
corrosion products on the metal surface. The most well-known corrosion product is rust.
Rust is the product we get when steel and iron goes through the corrosion process.

3.2 Why do some materials corrode faster than others?

It is a fact that some materials will corrode faster than others when exposed to a particular
environment. For example carbon steel will corrode rapidly in seawater, while gold is inert.
Why do they behave so differently?

The explanation is found by looking at the energy levels of the various materials. All
materials have a desire to be at a lowest possible energy level. For most metallic materials
this is as a mineral, oxide or similar and not in the form of the metal or alloy we use for
construction purposes. In nature only a few pure metals are found. These metals are called
“Noble metals” and do not need to go through energy consuming purification or a refining
process before taken into use. Thus, the energy level of the Noble metals is almost the
same as the level in their most stable form found in nature.

For Magnesium, Zinc, Aluminium, iron and steel the situation is quite different. These
metals (or their alloys) are not found free in nature. For example iron and steel are
extracted from iron ore in a blast furnace or electro oven where the iron ore together with
coal or coke is heated up to a very high temperature. To produce iron or steel large
amounts of energy is introduced. Thus, the energy levels of the materials we actually take
into use are much higher than the natural energy level of the metals found in nature.
Nature does not look upon the new energy level as very favourable and starts a process of
bringing the metals back to its’ origin. The metals will decompose (corrode) and energy will
be released; a corrosion process has started.

In a very simplified model you may say that the more energy required to produce a metal or
alloy the higher is the driving force to start a corrosion process. As seen later alloys can be
ranked to find out which one of them are stable and which ones are likely to corrode.

Figure 3.3
Energy levels of materials through a manufacturing process.
R e a c tio n b e tw e e n th e m a te r ia l a n d
th e s u r r o u n d in g e n v ir o n m e n t ta k e s p la c e
P la te s , p ip e s ,
p r o f ile s , e tc .
g W
g y r in at
e r c tu e
n
E u fa O r /h
xy u
an ge m i
M n d it
y
R a w m a t e r ia l
Iron ore R u st

T h e p r e s e n c e o f w a t e r / h u m id it y a n d O x y g e n
is a p r e - r e q u is it e f o r c o r r o s io n o f s t e e l
As mentioned above, the energy model is a simplification. Some materials can be much
more stable than one should expect. The main reason for this is usually one of the two
listed below (or a combination):

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Addition of alloying elements to give certain properties. For example stainless steels are
alloyed with Chromium, Nickel and Molybdenum. These materials will make the steel more
noble and will promote the formation of a strong, dense, protective oxide film on the metal
surface.
Formation of protective films on the metal surface which are more resistive than the base
material. (Usually oxide films: Stainless steels, Aluminium)

Also the opposite effect is frequently experienced: A material suffers corrosion where
inertness is expected. There are many reasons for these negative surprises. The most
occurring ones are:

Exposure environment is not as specified in the design.

(More severe conditions, e.g. chlorides / acid rain)
Unfavourable alloying elements have been used.
Impurities or contaminants introduced to the alloy.
Welding or machining have changed the microstructure of the alloy or the heat affected
zone.
An external energy source alters the electrochemical potential (Such as stray current,
welding etc.)

3.3 What factors influence corrosion rate ?

As we have seen above different materials show different behaviour in a given
environment. It is also a fact that a given material can be virtually inert in one type of liquid,
while it will suffer severe corrosion in another. For example, the corrosion rate of carbon
steel is very slow in pure, fresh water, while very high corrosion rates will be experienced in
an acid.

To predict the corrosion rate of a material is very difficult. The reason being that the
amount of influencing parameters and variables are enormous. Also, the rate of corrosion
may increase or diminish, depending on build up of corrosion products and how the
environment and operating conditions change with time.

It should also be noted that variable corrosiveness could be experienced for one type of
electrolyte. For example the corrosiveness of seawater varies to some degree from place to
place in the oceans. Important factors like salinity, temperature and microbiological
activity/growth will vary both with geographical location and season.

In general, corrosiveness in an environment increases, or varies with:

Temperature
Salinity
Oxygen content
Water velocity
Acidity (See below)
Type of electrolyte ( e.g. cargo or chemicals)
Content of contaminants / pollution that promotes corrosion
Micro-organisms.

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The salinity of seawater is one of the factors that determine corrosiveness. Salt makes the
water an electric conductor and promotes the process of electrochemical corrosion.

Acidity/pH: The pH scale (0-14) is used as a measure of acidity. The scale is based on the
concentration of hydrogen ions in a solution. A value of 1 refers to the highest acidity, while
14 is the most basic (alkaline) and 7 is neutral. In general corrosion will increase with
increasing acidity (low pH values), but high degree of alkalinity may also promote corrosion.
For example Aluminium is only passive in close to neutral solutions (pH 5-8).

The corrosiveness of the marine atmosphere usually increases with increasing.

• Humidity
• Temperature
• Content of salts
• Content of air pollution, including soot and dust particles

Figure 3.4
The corrosion rate will increase with increasing humidity

C o r ro sio n ra te

0 20 40 60 80 100
R ela tiv e H u m id ity , %

Finally, the exposure conditions are of great importance to the corrosion velocity. The
effect of rapid corrosion is often due to:

• Conditions that prevent wet metal surfaces from drying (poor ventilation, salts
that attract humidity, etc.)
• The increased conductivity of damp films on metal surfaces (from salts and acid
contaminants)
• Severe environmental stresses, like high pressure and temperature.
• Rapid changes in environmental conditions (e. g. Temperature: High/low
temperature giving thermal stresses of base material and protective systems and
condensation on surfaces)

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 • Mechanical stresses that destroy the protective systems or remove protective
films or layers formed on the metal surface.
• The breakdown of passive protective oxide layers on metal surfaces (e.g. oxide
films on stainless steel and aluminium and removal of copper oxides/hydroxides
at high flow rates).
• Galvanic coupling to a more noble material (Bi-metallic corrosion).

Corrosion can be measured as depth of attack in mm of even corrosion, in mm depth of

localised attack (pitting or crevice), in term of loss of weight (g/cm2) or as a rate (mm/year).

3.4. How can we protect against corrosion?

3.4.1 Factors to consider

Before an exact corrosion protection method, or combination of methods, can be decided

upon several aspects must be considered. Basically these aspects can be grouped in three:
A, B and C below:

A) Legislation, rules and requirements

Selection of a corrosion protection system must be seen in the context of the measures that
the authorities prescribe. These are in most cases of legislative character, requirements
from classification societies or national pollution authorities. Their objectives within
corrosion protection are:

To achieve a satisfactory level of safety for human life.

To protect the environment.

Typical examples are:

Safety:
DNV Rules for Classification of Ships.
The introduction of double hulls
Requirements for better access and more stringent inspection routines
Restrictions regarding Soft coats in ballast tanks.
The use of light coloured coatings in ballast tanks

Environment:
Oil Pollution Act of 1990, IMO Regulations
Restrictions on the use of Tar containing products and use of soft coats.
General requirements for protecting operators dealing with paint
Precautions regarding use of epoxies

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B) Owners philosophy

The owner of a structure always has a certain philosophy regarding corrosion protection.
Very often, the philosophy is separated in two phases: Construction stage and operation.
Actually it is important to think about the operation of the unit from the very beginning.
During the design phase of a newbuilding, attention should be paid to the corrosion
protection system that will be employed, in addition to inspection and maintenance
facilities. Regarded in relation to the high costs of subsequent maintenance, particularly if
steel has to be replaced, the correct strategy is to invest in optimal design and corrosion
protection at the newbuilding stage. The significance or criticality of a structure must be
evaluated along with its accessibility, operation and safety.

In many cases the corrosion protection philosophy is a mirror of the operation strategy of
the owner. For example: During production of oil there will be only one owner of the
platform. The design life of an offshore platform can be 25 years. The owner will seek to
reduce the total life time costs to a minimum, meaning that it can be a good investment to
spend money on an “expensive” protection system at the newbuilding stage instead of
carrying out extensive annual maintenance, starting only after a few years of operation. A
shipowner following a ship from “Cradle to grave” is more or less in the same situation,
while other ship owners and management companies who typically hold the ship for a short
period of time. Their prime interest is to keep all costs at a minimum for a given period of
time. The costs for necessary maintenance after the ship has been sold are considered as
irrelevant (but the second hand value is not). Thus, based on the over all operational
philosophy the corrosion protection philosophy is put up. Here are some of the factors to
consider:

Design life / period of ownership

Cost at newbuilding stage vs. extensive maintenance
Minimal out-of-service time / Minimal maintenance
Specification to back up philosophy
Easy inspection: Accessibility, light coloured paints, restriction on soft-coats
Acceptance criteria (When to do maintenance)
High degree of flexibility with regard to operation, trade, etc.
Satisfactory second-hand price
Implementation of philosophy: Suppliers to satisfy the requirements and operating
philosophy of the shipowner

C) Costs

As seen from above, the owner’s philosophy will be very closely connected to costs. In
addition it is worth while mentioning a general trend in the market: Owners are more and
more willing to base their cost estimates for a structure on a life time cost evaluation, LCC
(Life Cycle Cost). This is in contrast to what could be seen only a few years ago. Here, the

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costs were based on investment costs at the newbuilding / construction stage and minimal
attention was paid to the subsequent maintenance costs.

It is extremely important to closely evaluate the specifications for corrosion protection and
the acceptance criteria for cost, time involved, products used, standard of work performed,
safety, etc.

As coating lifetime is highly dependent on pre-treatment, the quality of the coating

products and the quality of application, these factors should be evaluated in the context of
a satisfactory inspection and maintenance programme.

3.4.2 Corrosion protection in general

Corrosion will always take place on steel and any other materials that are not completely
inert to the environment to which they are exposed. Even if it is always possible to prevent
corrosion it is virtually impossible to stop corrosion completely. For smaller, cheap units it
could be more expensive to protect against corrosion than simply to replace the unit when
it breaks down. However, in most cases we therefore talk about reducing the corrosion rate
to an acceptable level. For this reason, it is desirable to identify the best method and the
most cost-effective way of protecting the materials.

What is required to prevent iron and steel from rusting? We have seen that air (oxygen)
and an electrolyte / moisture is needed to initiate the corrosion process. If we can prevent
one of these factors from coming into contact with steel, or for that matter, both, we will
prevent rusting as we cut the electrical circuit in the “corrosion cell”. Experience has shown
that the most effective way of doing this is by applying an Organic coating (paint) to the
object. This is the most important and frequently used method of protecting against
corrosion.

Another frequently used method is the cathodic protection. This method actually reverses
the electrical current in the corrosion cell. Thus the dissolution of the metal is stopped,
while another metal introduced in the electrical circuit “sacrifices” itself. This metal (Zinc,
Aluminium or Magnesium) is called a sacrificial anode.

In spite of the fact that both paint and cathodic protection is described in separate sections
of this book a short introduction is given here.

3.4.3 Paints and coatings

Paints and coatings are the most important method of protecting tanks and holds. Coatings
prevent the steel from coming into contact with the corrosive environment. The quality,
and thus the useful life, of coatings depends primarily on the cleanness and pre-treatment
of steel surfaces, and on prevailing conditions while they are being applied. Other
important requirements concern coating quality, coating thickness and number of coats.

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There is no such thing as a universal product that can be regarded as the best coating under
all circumstances.

Coating can prevent corrosion via three main mechanisms:

• The barrier effect, which prevents seawater or other corrosive agents from
coming into contact with the surfaces that are to be protected. Example: epoxy
paints.
• The cathode effect: whereby the paint itself acts as a sacrificial anode. Example:
zinc-rich paints.
• Inhibiting / passivating, whereby the paint passivates the surface of the steel
(anodic effect). Example: Paints incorporate rust preventing pigments.

3.4.4. Cathodic protection

Sacrificial anodes or an impressed current system are used for cathodic protection of
various objects. Cathodic protection only works when both the anodes and the structures
they are to protect are immersed in water.

A combination of cathodic protection and other types of protection (particularly coatings)

can provide very good protection over a long period of time. All types of paint systems will
most likely suffer from mechanical damages or other imperfections that will reduce the
protective properties of a coating. Such areas will be protected by the cathodic protection
system. To combine paint and cathodic protection is also important because cathodic
protection does not protect structures above the water line. (Like upper regions of a tank).

3.4.5. Other corrosion protection methods

In addition to the methods mentioned above, corrosion can be reduced by the following
methods:

• Design (Corrosion traps, accessibility, maintainability)

• Optimal material selection
• Applying metallic coatings
• Using corrosion inhibitors in closed systems
• Changing the surrounding environment

Inhibitors

The addition of inhibitors (various types of chemicals) to closed pipe systems, ballast water
or cargo can reduce corrosion. The type of inhibitor to use depends on the fluid in the
system and on the type of materials to protect. An inhibitor will either passivate the surface

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of the metal or change the environment to be less aggressive. The problem with them is
often related to keeping a constant concentration and to achieve an evenly distribution in
the pipe system or on all parts of the structure. In practise this is difficult to achieve on
board a vessel at sea. Environmental considerations mean that it is not permitted to pump
contaminated water over board (Chromate, phosphates, etc.)

Inert gas

The primary function of inert gas is to prevent gas explosions, but it can also act as
corrosion protection. Nitrogen, carbon dioxide and ships’ exhaust gases are used as inert
gases. Exhaust gases include both combustion products from a ship’s engines and
hydrocarbon gases from its cargo. “Boil off” can be combusted to carbon dioxide. Exhaust
gases often contain a great deal of oxygen, water vapour, sulphur dioxide or similar and
may in fact increase corrosion. The composition of the exhaust gases must therefore be
checked before being used to reduce corrosion.

3.5. Forms of corrosion.

3.5.1 Forms of corrosion on different materials

All materials have their strong sides, but also their weaknesses. While some are very
corrosion resistant in one environment they can show a disastrous behaviour in another.
Different materials will be susceptible to different types of corrosion. When selecting a
material it is therefore important to know about the properties of the alternative materials.
The most frequently occurring corrosion forms for the most commonly used materials are
given in the table below.

Table 3.1
Common forms of corrosion on some materials

Carbon steel
- Uniform corrosion In most corrosive environments where electrolyte is stagnant.
- Uneven corrosion (deep pits) In most corrosive environments at high flow velocities.
- Galvanic corrosion In corrosive environments when coupled to a more noble
material.
- Stress corrosion cracking For high tensile steels. Combination of mechanical impact and
a corrosive environment.

Stainless steels
- Crevice corrosion Particularly in aqueous environments containing aggressive
ions like chlorides. Typical example: Seawater
- Pitting corrosion Particularly in aqueous environments containing aggressive
ions like chlorides. Typical example: Seawater
- Stress corrosion cracking Combination of mechanical impact and a corrosive
environment.
Aluminium
- Pitting corrosion Particularly in aqueous environments containing aggressive

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 ions like chlorides. Typical example: Seawater
- Galvanic corrosion In corrosive environments when coupled to a more noble
material.
Copper based alloys
- Erosion corrosion At flow velocities exceeding 2-2,5 m/s. Further aggravated in
the presence of pollution, particularly sulphides.
Titanium
- Hydrogen embrittlement Certain high tensile types exposed close to hydrogen source.
- Fatigue Generally good resistance. Has been experienced in heat
exchangers
Table 3.1. cont.

3.5.2 General corrosion.

The most common type of corrosion is the uniform or general corrosion. It is normally
characterised by a chemical or electrochemical reaction proceeding uniformly over the
entire surface or over a large area.

A piece of steel, greatly magnified, is found to be full of irregularities and pores. If we look
at steel through a microscope we can also see that the steel consists of different particles or
crystals. A steel plate will consist of a large number of microscopic electrical elements.
When a general type of corrosion attack takes place on a surface, both the anodic and the
cathodic processes are evenly distributed over the metal surface. The energy, which was
originally supplied to the steel during its extraction, is easily released. The steel reacts with
oxygen and moisture and forms rust. The cycle is complete and we are back to the original
lowest energy level in which iron and steel can exist.

A general corrosion attack leads to a reduction of the materials thickness linear with time.
The rate of corrosion can be calculated from corrosion data. For example a corrosion rate of
0.13 mm/year would result in a metal loss of 1.52 mm in a twelve-year period. A corrosion
allowance of 1.59 mm is often adequate to provide 12 years of service in process
exposures, perhaps 25 years in storage tanks. However, the world is rarely ideal and in most
cases an uneven corrosion must be expected. Hence, the corrosion attack can locally be up
to 10 times faster than the theoretical calculated average value.

Figure 3.5
General or uniform corrosion on a steel plate.

• A steel surface consists of noble and less noble areas Uniform corrosion is a corrosion attack
• This can be looked upon as small galvanic cells uniformly distributed over the entire surface
• The anodic parts will corrode
Corroded area
Rust

+
-
-
+ -
+ Steel
+ -
+ - +
+ + -
+ + Thickness after corrosion Original thickness
-

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3.5.3 Galvanic corrosion
Galvanic corrosion may occur when different metallic materials come into electrical contact
with each other or in contact with a conducting non-metal. (E.g. carbon or mill scale). As
seen earlier from the corrosion cell the metals also need to be exposed to a corrosive
environment (electrolyte).

When two materials are electrically coupled in seawater the more negative (active) material
in the couple will act as the anode, and will show an increased corrosion rate compared to
the unexposed state. The more positive (noble) component, the cathode, will have a
reduced corrosion rate.

Figure 3.6
Galvanic corrosion. The cathode is protected
while accelerated corrosion of the anode takes place.
The severity of the attack depends on:
• Conductivity of the electrolyte
• A node - Cathode area ratio

Electrolyte with good conductivity

W ide corrosion attack
Anode Cathode A node

Electrolyte with low conductivity

Anode Cathode Anode Attack close to cathode

Unpreferable area ratio

Cathode Anode Cathode Sm all anode w ill corrode rapidly

The degree of increased corrosion rate due to the galvanic coupling will vary from case to
case. Generally, the following factors will influence the galvanic corrosion process:

• The difference between the corrosion potentials of the uncoupled metals or alloys.
(See galvanic series below).
• The surface areas of the cathodic and anodic zones. When the surface area of the noble
metal (the cathode) is large compared to the more active member (the anode), an
unfavourable ratio exists. This will result in an accelerated corrosion of the anode. The
opposite area ratio (large anode and a smaller noble metal surface) produces only
slightly accelerated galvanic effects.
• The distance between the cathode and the anode. The shorter the distance the more
severe is the attack. This is shown in figure 10.5. The corrosion of the anode decreases
with increasing distance from the cathode, due to increased ohmic resistance.
• The electrical resistance of the galvanic circuit. A corrosion cell can be compared with
an electrical circuit. An increased resistance will reduce the electrical current and

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 thereby reduce the corrosion rate. Important factors are the conductivity of the metals
in the galvanic couple and the electrolyte. Thus, the benefit of applying a coating to
reduce the corrosion velocity is evident, as this will increase the electrical resistance in
the circuit.

The galvanic corrosion can of course be measured by immersion testing of the metals in the
environment of interest. In most cases, however, the galvanic corrosion is predicted by the
use of a galvanic series. In the galvanic series metals and alloys are ranked according to
their free corrosion potentials, measured as a volt signal in the electrolyte, e.g. seawater.
The potential difference between the materials is of decisive importance to the corrosion
velocities. If the potential difference is greater than 50 - 100 mV, the least noble material
may suffer accelerated corrosion.

It should be noted that the potential and range of potentials might differ considerably with
exposure condition, i.e. time, temperature, and still seawater versus high velocity
conditions.

Table 3.2
Galvanic series of metals and alloys in seawater at ambient temperatures relative to
different reference electrodes.

Ag/AgC1 : Silver/Silver-chloride/sea water electrode

Zn : Zinc electrode
Cu/CuSO4 : Copper/Copper-sulphate electrode

Reference electrodes
Material Ag/AgC1 Zn Cu/CuSO4
Graphite +0.25 +1.28 +0.17
Titanium 0 +1.03 -0.08
St. S (316) -0.05 +0.98 -0.13
Monel (400) -0.08 +0.95 -0.16
St. S 304) -0.08 +0.95 -0.16
Inconel (600) -0.15 +0.88 -0.23
Copper-nickel (90:10) -0.23 +0.80 -0.31
St. S (416) -0.28 +0.75 -0.36

Table 3.2. cont.

Reference electrodes
Material Ag/AgC1 Zn Cu/CuSO4
Admirality brass -0.30 +0.73 -0.38
Copper -0.33 +0.70 -0.41
Naval brass -0.34 +0.69 -0.42
Low alloy steel -0.61 +0.42 -0.69
Mild steel -0.66 +0.37 -0.74
Aluminium -0.80 +0.23 -0.88
Zinc -1.03 0 -1.11
Magnesium -1.60 -0.57 -1.68

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3.5.4 Pitting corrosion
Pitting is a form of local corrosion in which limited areas of the metal are attacked. This
form of corrosion is particularly likely to occur on passive metals such as stainless steel or
aluminium. Under normal conditions these materials are protected by an oxide film formed
on the metal surface by the oxygen in the air or in the electrolyte. Some times weak points
of the protective oxide film are penetrated by aggressive ions (like chlorides in the
seawater). Then the less noble base material is revealed and corrosion initiate locally at
these bare areas. Corrosion will subsequently progress deep into the material, and the rate
of attack may be very high. The holes created in the oxide film may be small or large in
diameter, but in most cases they are relatively small. As seen from the figure below a large
volume of the base material can be corroded away beneath a seemingly good, intact
surface. Consequently, pitting is one of the most insidious forms of corrosion. It causes
equipment to fail very rapidly and with only a small percent weight loss of the entire
structure. Factors such as alloying elements, temperature and flow conditions will influence
the pitting mechanism and the corrosion propagation rate.

Pits are sometimes isolated or they can be so close together that they seem to form a rough
surface. Generally, a pit may be described as a cavity or hole with a surface diameter about
the same as, or less than, the depth.

Figure 3.7
Pitting corrosion seen from above (left) and from the side (right).

Pitting corrosion Passive layer

Stainless steel

Seen from above Cross section

3.5.5 Crevice corrosion.

Crevice corrosion is a type of intense localised corrosion frequently occurring within narrow
gaps, crevices and under different types of deposits on metal surfaces exposed to corrosive
liquids. Particular attention must be paid to stainless steel under such conditions. The type
of attack is usually associated with small volumes of stagnant solution between overlapping
plates, under washers, gaskets, deposits and crevices under bolts where little oxygen is
available. However, it is not always necessary to have crevices to initiate such attacks. This
type of corrosion attack may also occur on a metal surface covered with spillage of paint,

Section 3 “Corrosion and corrosion prevention” Page 3. 15

Copyright© 2010 Jotun Paints South Africa (Pty.) Ltd. All rights reserved.
sand, mud or dirt. These deposits result in low oxygen contents underneath the deposit.
Thus, this form of corrosion is also called deposit corrosion.

The mechanism of crevice corrosion is complicated - but can be illustrated by low level
access of oxygen, needed in order to maintain the oxide film on passive materials. (See
“Pitting corrosion”). For crevice corrosion to occur the crevice must be wide enough to
permit entry of the corrosive liquid, but sufficiently narrow to maintain a stagnant zone of
solution within the crevice, limiting the transport of ions in and out of the crevice. Due to
this the environment inside the crevice will be different from the environment outside.
Corrosion will be initiated inside the crevice, as a more acidic environment compared with
the freely exposed surface will develop here. Solutions containing chloride ions are the
most aggressive environments with respect to causing crevice corrosion.

Figure 3.8
Crevice corrosion initiated on steel under panel and drop of paint.

Seaw ater
Ingress of seaw ater

Plate Paint

Stainless Steel

C orroded areas

3.5.6 Stress corrosion

Cracks may be formed in many construction materials. The main reason for initiation of a
crack is remaining internal stresses from manufacturing. Often a mechanical tensile stress is
also present, external deformations like bending, forming and welding, but at a level that in
itself is not harmful. However, this situation can change if the construction is exposed to a
corrosive environment. Stress corrosion cracking (SCC) is a combination of tensile forces
and a corrosion attack with a very rapid material failure as a result. The cracks formed by
this combined action are often difficult to detect and when allowed to grow they may lead
to sudden and catastrophic failures.

Well known materials that may show susceptibility to SCC in chloride environments are
austenitic stainless steels containing chromium and nickel and a number of aluminium
alloys. Generally the susceptibility to SCC increases with increasing temperature. For a

Section 3 “Corrosion and corrosion prevention” Page 3. 16

Copyright© 2010 Jotun Paints South Africa (Pty.) Ltd. All rights reserved.
number of alloy/environment combinations a safe temperature can be indicated, below
which the susceptibility to SCC is practically nil.

In the offshore industry a lot of the hot stainless steels tubes are blast-cleaned with a fine
non-metallic abrasive and then an epoxy coating is applied. This is done to minimise the
tendency of SCC, especially on insulated stainless steels with an operating temperature of
60 o C or higher.

3.5.7 Corrosion fatigue

As for SCC (see above), Corrosion fatigue is also a type of failure occurring as a consequence
of a combined effect of a corrosive environment and physical stresses. Here, the physical
stresses are in the form of cyclical variations. Corrosion fatigue is frequently found in
connection with deformations and vibrations caused when reduced material dimensions
with high-strength steel are used.

As shown by the figure below the safe area is above the dotted line. In this case the
material in question is capable of withstanding all combinations of loads and dynamic cycles
in a non-corrosive environment. However, when exposed to a corrosive environment the
same material will break after a certain number of dynamic cycles. This is indicated by the
curve entering the dangerous zone below the dotted line in the figure.

Figure 3.9
Corrosion fatigue may occur at a combination of dynamic loads and a corrosive
environment.

Load

Fatigue only No failure

above line

Corrosion fatigue

No. of dynamic cycles

3.5.8 Bacterial corrosion

In the sea, mud and soil different types of bacteria will always exist. Under certain
conditions they can take part in a corrosion process. The mechanisms behind this are
complicated and will not be dealt with here. Bacterial corrosion (microbiological, anaerobic,
etc.) is found in oil tanks, ballast tanks, and on structures/objects buried in marine muds
(for example a pipeline). Conditions that encourage bacterial corrosion are:

Section 3 “Corrosion and corrosion prevention” Page 3. 17

Copyright© 2010 Jotun Paints South Africa (Pty.) Ltd. All rights reserved.
 • Stagnant water
• Adequate nutrition for bacteria
• Sulphate (for sulphate-reducing bacteria - SRB)
• Suitable temperature (20 - 40 oC).

3.5.9 Erosion corrosion

Again, a result of two different factors combining to give a very common type of failure:
Erosion corrosion. A too high flow velocity of the flowing media causes the part of the
failure arising from erosion. This creates a turbulence that removes the protective layers or
the corrosion products from the metal surface. Then the bare base material will be
continuously exposed to the corrosive environment giving a very high, localised corrosion
velocity. Soft metals are particularly vulnerable to his form of attack, for example, copper,
brass, pure aluminium and lead, but most metals are susceptible to erosion corrosion in
particular flow situations.

Some factors, which are likely to cause erosion corrosion, are:

• Flow velocities exceeding the specified velocity.

• Sudden change in the bore or joint which introduces a discontinuity in the otherwise
smooth metal surface.
• A crevice which allows liquid to flow outside the main body of fluid.
• The presence of a corrosion product or other deposits which may disturb the laminar
flow

Figure 3.10
Erosion corrosion. Appearance by grooves, gullies, waves, rounded holes. Often the
pattern created is called horse-shoe attack.

Figure 3.11
Construction / design is decisive for the degree of erosion corrosion.
Design to the right is better than to the left.

Section 3 “Corrosion and corrosion prevention” Page 3. 18

Copyright© 2010 Jotun Paints South Africa (Pty.) Ltd. All rights reserved.
3.5.10 Dealloying corrosion

Dealloying corrosion, or selective corrosion, is actually a galvanic corrosion. Here, one

element, generally the most active one, is selectively removed from a solid alloy. As a result
the components of the alloy react in proportions which differ from a solid alloy. Apart from
the general term the process is often named after the removed element in the specific
cases, e.g. de-Zincification of brass, de-Aluminification of certain aluminium-bronzes.
However not in the case of graphitisation of grey irons (here the removed element is iron).

Perhaps the most well known example of de-alloying is de-Zincification of brass. This is
readily recognised as the alloy assumes a red copper colour, i.e. in contrast to the original
yellow. De-Zincificated zones are porous and mechanically weak and may result in a sudden
break when the alloy is exposed to physical impacts.

Section 3 “Corrosion and corrosion prevention” Page 3. 19

Copyright© 2010 Jotun Paints South Africa (Pty.) Ltd. All rights reserved.