Prepared by : Sayeed Biswas

Lecturer (Mechanical Engineering)

AE-181,Engineering materials
Corrosion
Corrosion can be defined as the deterioration of materials by chemical processes. Of these, the
most important by far is electrochemical corrosion of metals, in which the oxidation process
M → M+ + e– is facilitated by the presence of a suitable electron acceptor, sometimes referred to
in corrosion science as a depolarizer.

Corrosion cells and reactions

The special characteristic of most corrosion processes is that the oxidation and reduction steps
occur at separate locations on the metal. This is possible because metals are conductive, so the
electrons can flow through the metal from the anodic to the cathodic regions. The presence of
water is necessary in order to transport ions to and from the metal, but a thin film of adsorbed
moisture can be sufficient.

A corrosion system can be regarded as a short-circuited electrochemical cell in which the anodic
process is something like

Fe(s) → Fe2+(aq) + 2 e–

and the cathodic steps can be any of

O2 + 2 H2O + 4e– → 4 OH–

H+ + e– → ½ H 2(g)

M2+ + 2 e– → M(s)

where M is a metal.
Prepared by : Sayeed Biswas
Lecturer (Mechanical Engineering)
AE-181,Engineering materials
Electrochemical corrosion of zinc in acid solution
The fact that corrosion consists of at least one oxidation and one reduction reaction is not always
as obvious as it is in batteries. The two reactions are often combined on a single piece of metal as
illustrated schematically here for a piece of steel and in the following Figure for a piece of zinc
immersed in an acidic solution.

Electrochemical reactions occurring during the corrosion of zinc in air-free hydrochloric

acid

In this Figure, a piece of zinc immersed in hydrochloric acid solution is undergoing corrosion. At
some point on the surface, zinc is transformed to zinc ions, according to equation. This reaction
produces electrons and these pass through the solid conducting metal to other sites on the metal
surface where hydrogen ions are reduced to hydrogen gas according to equation.

These equations illustrate the nature of an electrochemical reaction for zinc. During such a
reaction, electrons are transferred, or, viewing it another way, an oxidation process occurs
together with a reduction process. The overall corrosion processes are summarized in the
following equation:
Prepared by : Sayeed Biswas
Lecturer (Mechanical Engineering)
AE-181,Engineering materials

General Attack Corrosion:

Also known as uniform attack corrosion, general attack corrosion is the most common type of
corrosion and is caused by a chemical or electrochemical reaction that results in the deterioration
of the entire exposed surface of a metal. Ultimately, the metal deteriorates to the point of failure.

General attack corrosion accounts for the greatest amount of metal destruction by corrosion, but
is considered as a safe form of corrosion, due to the fact that it is predictable, manageable and
often preventable.

Pitting Corrosion
Pitting is one of the most destructive forms of corrosion as it will potential cause equipment
failures due to perforation / penetration. pitting generally occurs on metal surfaces protected by
oxide film such as Stainless steel, aluminum, etc. Typically for boiler and feed water system,
pitting corrosion rate increase dramatically with the increase of oxygen content in the fluid.

Lets look at figure below, oxygen rich fluid in contact with metal surface (at the top of the pit)
will becomes the cathode. At the bottom of the pit, low in oxygen level becomes the anode. this
will form a complete circuit where metal at the pit (FE) will be ionized to release electron (e) and
form ion Ferum (FE2+), this electron will travel to the top of pit to react with Oxygen (O2) (and
water, H2O) to form ion hydroxides (OH-). Ion Ferum (FE2+) will react with ion hydroxides
(OH-) to form Ferum Oxide (Fe2O3) which typically a brown rust. Deeper the pit leeser the
oxygen content and higher the potential and pitting corrosion rate.
Prepared by : Sayeed Biswas
Lecturer (Mechanical Engineering)
AE-181,Engineering materials

Preventive measures
There are several preventive approah to avoid pitting. There are :

 Proper material selection e.g. molydenum having higher pitting resistance.

 Use higher alloys for increased resistance to pitting corrosion
 Control oxygen level by injecting oxygen scavenger in boiler water system.
 Cathodic protection and/or Anodic Protection.
 Agitation of stagnant fluid.

Cavitation corrosion
Cavitation erosion is the process of surface deterioration and surface material loss due to the
generation of vapor or gas pockets inside the flow of liquid. These pockets are formed due to low
pressure well below the saturation vapor pressure of the liquid and erosion caused by the
bombardment of vapor bubbles on the surface.
Cavitation erosion usually involves an attack on the surface by gas or vapor bubbles, creating a
sudden collapse due to a change in pressure near the surface. Low pressure (below the saturated
vapor pressure) is generated hydrodynamically, due to various flow parameters, such as liquid
viscosity, temperature, pressure and nature of flow. This deterioration is initiated by a sudden
surge of bubbles hammering the surface, resulting in deformation, as well as pitting.

Cavitation erosion can occur on the surfaces of metals and nonmetals. It may produce
undesirable noise levels and reduce the useful life of very valuable property. Noise created due to
cavitation erosion in submarines increases the risk of enemy detection during wartime.

Cavitation erosion can damage and destroy critical and valuable equipment, such as
industrial/military/power station equipment and parts, such as pump impellers, delicately
balanced high-speed propellers and turbine blades, causing failures leading to potential risk of
life and injury for workers and others; loss of revenue, due to equipment downtime and the extra
costs of failure analysis, repair and replacement.
Prepared by : Sayeed Biswas
Lecturer (Mechanical Engineering)
AE-181,Engineering materials

Fig: Cavitation corrosion

Season Cracking

Season cracking occurs in copper-based alloys subjected to a residual or applied tensile stress
and exposed to a specific environment, such as moist air containing traces of ammonia.Season
cracking is also known as stress corrosion cracking or environmental cracking.

Season cracking occurs most often in copper alloys containing more than 15% zinc. This
cracking occurs due to a reaction between ammonia and copper, forming the cuprammonium ion,
a chemical complex which is water-soluble, and hence washed from the growing cracks. Such
cracking can also occur in copper and any other copper alloy, such as bronze.

Season cracking is characterized by deep, brittle cracks which penetrate into affected
components. If the cracks reach a critical size, the component can suddenly fracture, sometimes
with disastrous results. If the concentration of ammonia is high, then the attack is much more
severe, and all exposed surfaces are subject to cracking.
Prepared by : Sayeed Biswas
Lecturer (Mechanical Engineering)
AE-181,Engineering materials
Season cracking results from the conjoint action of three components:

 Susceptible material (copper and its alloys)

 Specific chemical species (ammonia)

 Tensile stress (residual)

Season cracking prevention

 Stress relief
 Annealing
 Avoiding ammonia
 Use of materials known not to crack in the specified environment

Stress corrosion cracking or "season cracking" occurs only in the simultaneous presence of a
sufficiently high tensile stress and a specific corrosive environment.

Galvanic Corrosion

Galvanic corrosion, or dissimiliar metal corrosion, occurs when two different metals are located
together in a corrosive electrolyte. A galvanic couple forms between the two metals, where one
metal becomes the anode and the other the cathode. The anode, or sacrificial metal, corrodes and
Prepared by : Sayeed Biswas
Lecturer (Mechanical Engineering)
AE-181,Engineering materials
deteriorates faster than it would alone, while the cathode deteriorates more slowly than it would
otherwise.

Three conditions must exist for galvanic corrosion to occur:

 Electrochemically dissimilar metals must be present

 The metals must be in electrical contact, and
 The metals must be exposed to an electrolyte

Fretting corrosion:

Fretting corrosion occurs as a result of repeated wearing, weight and/or vibration on an uneven,
rough surface. Corrosion, resulting in pits and grooves, occurs on the surface. Fretting corrosion
is often found in rotation and impact machinery, bolted assemblies and bearings, as well as to
surfaces exposed to vibration during transportation.
Prepared by : Sayeed Biswas
Lecturer (Mechanical Engineering)
AE-181,Engineering materials
Intergranular corrosion

Intergranular corrosion is a chemical or electrochemical attack on the grain boundaries of a

metal. This often occurs due to impurities in the metal, which tend to be present in higher
contents near grain boundaries. These boundaries can be more vulnerable to corrosion than the
bulk of the metal.

Several methods have been used to control or minimize the intergranular corrosion of susceptible
alloys, particularly of the austenitic stainless steels. For example, a high-temperature solution
heat treatment, commonly termed solution-annealing, quench-annealing or solution-quenching,
has been used. The alloy is heated to a temperature of about 1,060° to 1,120 °C and then water
quenched. This method is generally unsuitable for treating large assemblies, and also ineffective
where welding is subsequently used for making repairs or for attaching other structures.

Another control technique for preventing intergranular corrosion involves incorporating strong
carbide formers or stabilizing elements such as niobium or titanium in the stainless steels. Such
elements have a much greater affinity for carbon than does chromium; carbide formation with
these elements reduces the carbon available in the alloy for formation of chromium carbides.

Crevice corrosion

Page-592,593

Introduction to physical metallurgy by SHIDNEY H AVNER

Corrosion protection method/Methods of combating corrosion

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Introduction to physical metallurgy by SHIDNEY H AVNER