Corrosion in very simple terms may be defined as a pervasive process of deterioration or destruction of

metals and alloys or a physiochemical interaction between metal and its environment.

Almost 1/5th of the annual steel production throughout the world is consumed by replacing the damaged
steel parts / components. The problem becomes even worse, when working in marine environment,
wherein, if the correct corrosion prevention practices are not included at every step of fabrication /
installation / repairs / maintenance process, it could be a costly affair in terms of ship’s / its equipment’s
service life span.

It is a fact that the biggest nightmare of any marine engineer would be failure of platform / equipment
when at sea. In order to prevent / arrest the corrosion menace, one must understand the corrosion, its
various types, how does it propagate and what could be done to minimize the same.

Corrosion may be broadly classified in following three categories, we can talk in detail further, how these
three main categories can be further subdivided for a better and clear understanding of issue: -

• Chemical and electrochemical

• High temperature and low temperature
• Wet corrosion and dry corrosion.

Chemical or Electrochemical Corrosion is a process of an electrical exchange between electrons in metal

and ions in a conducting electrolyte. It could be better understood by the rusting process of Iron in presence
of water and oxygen.

A general relation between the rate of corrosion, corrosivity of the environment and corrosion resistance
of materials can be expounded as follows

Corrosivity of environment
Rate of Corrosive Attack =
Corrosion resistance of metal

The first step in the rusting process involves the dissolution of solid iron into solution.
Fe(s) → Fe2+(aq) + 2e-

The electrons produced by this reaction combine with hydrogen ions in the water and dissolved oxygen to
produce water
4e- + 4H+(aq) + O2(aq) → 2H2O

The consumption of hydrogen ions that occurs as iron dissolves leaves hydroxide (OH-) ions in the water.
The iron ions react with them to form green rust or Hydrated Iron Oxide
Fe2+(aq) + 2OH-(aq) → Fe (OH)2(s)
These iron ions also combine with hydrogen and oxygen in the water to produce iron ions, responsible for
the formation of the reddish deposit that gradually eats holes into the metal
4Fe2+(aq) + 4H+(aq) + O2(aq) → 4Fe3+(aq) + 2H2O

Which further combine with the extra hydroxide ions to form iron hydroxide, which dehydrates to
become Fe2O3.H2O, which is also the chemical formula for rust.
Fe3+(aq) + 3OH-(aq) → Fe (OH)3

OR in more simpler terms

Fe + O2 +H2O = Fe2(OH)3

Types of Corrosion

Uniform corrosion: is the corrosion process, where the surface is corroded / removed almost evenly. This
happens mostly on unprotected carbon steel and on zinc-coated steel under atmospheric conditions. In
practicality, there would be few areas which will corrode faster than others leading to a rough surface with
an irregular covering of corrosion

Control Remedies: The easiest form of protection would be protective coating with a suitable
coating / paint scheme, which would act as a barrier between the Metal, Oxygen and Water.

Shallow Pitting corrosion: is the corrosion which is found in localized areas that leads to the creation of
small holes or “pits”. It happens generally in all passive metals such as aluminum, titanium and stainless
steel. The passive metals offer corrosion resistance due to a thin oxide layer on the surface which has a
thickness of few nanometers.

The corrosion process starts with a local break-down of this passive layer. Unlike uniform corrosion which
can be seen clearly on the surface, pitting corrosion can be quite problematic, which appears only as small
pinholes on the surface. The amount of material removed below the pinholes is generally unknown, as
hidden cavities may form, making pitting corrosion more difficult to detect and predict.

This type of corrosion could be an incubator for more severe forms of corrosion such as stress corrosion
cracking
 Control Remedies: Technically, there is no reasonable way to control pitting corrosion. This form
of corrosion must be excluded right from the start through design considerations and use of the
right material.

Crevice corrosion: As the name itself suggests, this type of corrosion occurs within crevices and other
shielded areas on metallic surfaces that are exposed to a corrosive environment.

Typically, crevices can develop a local chemistry that is different from that of the bulk fluid, especially when
stagnant solutions can remain in these crevices. The contact area of metallic and non-metallic surfaces may
be attacked by this form of corrosion. The most common occurrences of this type of corrosion is under
washers or gaskets

Galvanic effects can also play a role in crevice degradation. Some of the phenomena occurring within the
crevice may be somewhat reminiscent of galvanic corrosion:

Galvanic corrosion
Two connected metals + Single environment
Crevice corrosion
One metal part + Two connected environments

Control Remedies: in crevice corrosion, the size and shape of the crevice and the nature of the
concentration process leading to the development of the differential local chemistry are the prime
factors deciding extent of damage or corrosion. The extreme and often unexpected local chemistry
conditions inside the crevice also need to be considered for a remedial / preventive action. Thus,
great care must be taken towards usage of similar material in nut, bolt and washers in any
arrangement. Additionally, the metal to metal contact must always be avoided by means of non-
absorbent washers and usage of higher alloys that more strongly resist crevice corrosion

Galvanic Corrosion: takes place when at least two dissimilar metals or alloys must be electronically
connected in general electrolyte. In galvanic corrosion, metal that oxidises / corrodes is always lower in
galvanic series to another metal. The mode of action is like that of a battery cell. Thus, the higher, the
current that flows in the system, the severer the corrosion.
 Control Remedies: Material combinations that will not / least affected by galvanic corrosion must
be accepted. Alternatively, usage of sacrificial anodes in areas, where usage of different type of
material cannot be avoided. For eg. Zinc is the less noble metal which actively protects steel by
being corroded itself and Zinc anodes are being widely used in marine industry.

Stress Corrosion Cracking (SCC) is corrosion that is induced due to presence of tensile stresses (mechanical),
and corrosive medium (electrolyte), wherein due to electrochemical process the corrosion especially at
elevated temperature results in cracking of certain materials.

Stresses present in material during fabrication / assembly stage could commence cracking. Stress corrosion
cracking is not simply an overlapping of corrosion and mechanical stresses, but can be understood as an
autocatalytic, self-accelerating process leading to high metal dissolution rates (anodic reaction). Initially, a
small pit is formed and develops into a crack due to applied or residual stress in the material. This leads to
further crack propagation and again to the exposure of new highly active metal surfaces in the crack. Metal
dissolution in the crack will advance rapidly until mechanical failure occurs and can lead to unexpected
sudden brittle failure of normally ductile metals subjected to stress levels well below their yield strength

Control Remedies: Proper annealing / surface heat treatments could help relive the material of
stresses and could be a major remedy to avoid stress induced cracking

Environmental stress cracking (ESC) The premature initiation of cracking of a plastic due to the
simultaneous action of stress and strain and contact with specific chemical environments causes
unexpected brittle failure of thermoplastic (especially amorphous) polymers. The source of stress is often
that which is unavoidably processed in during moldings and therefore, applied stress for this type of
cracking is not a prerequisite for environmental stress cracking. The underlying principle is different from
typical corrosion processes occurring in metals and is also not applicable to FRP boats (wherein the FRP
boats, the polymer molecules are chemically bonded to each other, although a thermoplastic, Once
crosslinking due to chemical bonding has occurred, a thermoset plastic does not soften, melt, or flow when
heated)
Selective Leeching: Selective leeching or dealloying is the selective corrosion of one or more components
of an alloy. It is also called parting, selective leaching or selective attack. Common dealloying examples
are decarburization, decobaltification, denickelification, dezincification, and graphitic corrosion due to
reaction with one or more chemical substances in a medium that contacts the surface.

Control Remedies Dealloying, selective leaching and graphitic corrosion can be prevented by
selecting metals/alloys that are more resistant to dealloying and or controlling the environment to
minimize the selective leaching. Based on existing requirements, the usage of sacrificial anode
cathodic protection or impressed current cathodic protection may also be explored, if necessary.

Hydrogen-assisted cracking is caused by the diffusion of hydrogen atoms into the metal during its
manufacturing stage. The presence of hydrogen weakens the mechanical integrity of the metal and leads
to crack growth and brittle fracture at stress levels below the yield strength. Like stress corrosion cracking,
it can lead to sudden failure of metal parts without any detectable warning signs. It can be divided into 4
types according to the failure appearance:
• Hydrogen blistering
• Hydrogen embrittlement
• Decarburization (removal of carbon)
• Hydrogen attack (T>200 °C)

In common applications, hydrogen damage is usually only relevant for high-strength steel with a tensile
strength of approximately 1000 N/mm2 or higher.

Hydrogen Blistering
 Hydrogen Embrittlement

Decarburization (removal of carbon)

Decarburization occurs when metals are subjected to high temperatures, and the carbon present on the
surface reacts with oxygen or hydrogen and diffuses. Carbon from the interior will then diffuse towards the
surface, that is, carbon diffuses from a region of high concentration to a region of low concentration to
continue the decarburization process and establish the maximum depth of decarburization (MAD).

Hydrogen Attack

High-temperature Hydrogen Attack (HTHA) refers to the loss of strength and ductility of steel by high-
temperature reaction of absorbed hydrogen with carbides in the steel, resulting in decarburization and
internal fissuring. High-temperature hydrogen attack is also referred to as hot hydrogen attack or
decarburization.

Erosion corrosion: In this form of corrosion is because of mechanical action between the corrosive fluid
and the metallic surface often by impinging liquid, abrasion by a slurry, particles suspended in fast flowing
liquid or gas, bubbles or droplets, cavitation etc. The corrosion manifests as grooves, waves, rounded holes,
etc. exhibiting usually a directional pattern. In passive alloys the mechanical abrasion wears off the
protective layer that inhibits corrosion.
 https://www.sciencedirect.com/topics/engineering/erosion-corrosion

Control Remedies: Erosion corrosion can be prevented through streamlining the flow of liquids
through openings to reduce turbulence, control fluid velocity, usage of more resistant materials
and using corrosion inhibitors or cathodic protection to minimize its effects.

Intracrystalline (intergranular) corrosion: Metals and alloys, like other elements, have micro-structures that
can be described as grains. Metals can contain multiple grains, and these are separated by a grain boundary.
Intergranular corrosion is a localized corrosion, where the corrosive attack takes place in a quite narrow
path preferentially along the grain boundaries in the metal structure resulting in loss of ductility of metal.

In stainless steels the problem occurs after the metal is heated to between 425°C and 870°C. During the
heating, the chromium in the stainless steel reacts with carbon in the steel and forms particles of chromium
carbide at the grain boundaries. The regions near the grain boundaries become depleted in chromium
resulting in regions around the grain boundaries are no longer protected by the chromium passivation, and
therefore are susceptible to intergranular corrosion, and this is also termed as weld decay.

https://ars.els-cdn.com/content/image/1-s2.0-S0925838816338257-fx1_lrg.jpg

Control Remedies: low carbon base and filler metal may be used in welding application to reduce
or eliminate carbon during the process. However, the same may not be always practical as carbon
is a vital alloying ingredient in some applications. Minimize the time the weld and heat affected
zone spend at temperatures conducive to sensitization could be one another alternative. Usage of
filler metals with special alloying ingredients to prevent the formation of chromium carbides, for
 instance, titanium and niobium can be alloyed into the filler metal and help prevent reactions
between chromium and carbon and last but not the least is post weld heat treatment.

Microbiologically Infused Corrosion is caused by electrochemical reactions created by those

microorganisms that form ‘biofilms’ on immersed steel structures. Fungi are closely associated to this
process. However, bacteria are the main component of the biofilms, and contribute most to MIC and the
formation and transformation of corrosion products. The metabolic activities of bacterial communities
within the biofilms interact with environmental factors, such as dissolved oxygen, pH, organic, and
inorganic compounds, to influence the electrochemical state of the metal and influence the rate of
corrosion. Diverse bacterial populations can coexist in biofilms and often form synergistic communities
which contribute to the electrochemical processes via cooperative metabolic processes what is interesting
is that bacteria not only cause corrosion but can also inhibit or protect against corrosion

Marine biofouling is an undesirable settlement and accumulation of marine microorganisms, plants and
animals on submerged surfaces of materials. Although the marine biofouling as well as microbiologically
infused corrosion both commence on submerged steel surfaces from the formation of an absorbed film
created by marine microorganisms on its surface. However, they both differ to each other since
microbiologically induced corrosion is a process occurring at micro level, whereas the biofouling is a
settlement and accumulation process occurring at macro level. Also, there are biological difference in type
of organisms attacking in both the process.
The marine biofouling of ship’s hull increases vessel weight & underwater hull roughness resulting in
increase in frictional resistance, which directly affects the fuel consumption and in some cases is the prime
cause of excessive vibration propagation during vessel movement. It also initiates or accelerates the
corrosion of metal and concrete structures. Biofouling attaches itself to underwater equipment thereby
decreasing the efficiency of cathodic protection and other underwater equipment. The last but not the
least, bio-fouling organisms on ship vessels will migrate to different oceans where they do not naturally
belong to and disturb the ecological system. Of late the classification and regulation societies are going
more and more stringent towards finding more viable solutions to protect the marine environments.
Control Remedies Although a lot of research in ongoing on to eliminate the ever present
biologically induced growth on underwater surfaces. Corrosion prevention by protective coatings
has a greater role to play in curbing this menace. Although periodical physical Hull cleaning and
application of self-polishing paint barrier between Hull and marine growth, which are designed to
wear down smoothly, while maintaining bio-active interface between the coating and water are
being widely used throughout marine industry. Sol-gel based protective layers equipped with active
functionalities as pre-treatment or conversion layers using recent developments in
nanotechnology to improve the properties of coatings to have multifunctional capabilities also
need to be explored.