UNIT II At ordinary temp generally all the metals are slightly attacked.

However,
alkali metals – Li, Na, K, Rb etc. and alkaline earth metals – Be, Ca, Sr
CORROSION AND ITS CONTROL etc. are attacked very rapidly and get oxidized readily.
Corrosion – causes of corrosion – principles of chemical corrosion –
Pilling–Bedworth rule – principles of electrochemical corrosion –
differences between chemical and electrochemical corrosion –
factors influencing corrosion – types of corrosion – galvanic
corrosion, differential aeration corrosion, pitting corrosion,
waterline corrosion, stress corrosion – Impacts of corrosion on
power plants
Mechanism:
Corrosion control and prevention – selection of materials and
(i) Oxidation takes place at the surface of the metal.
proper designing - cathodic protection – sacrificial anode –
M M2++2e-
protective coatings – anodization, galvanization, anti-corrosive
(ii) Atmospheric O2 is converted to oxide ion (O2-) due to the
agents – molybdates and phosphates.
transfer of electrons from metal.
I) Explain the classification or theories of corrosion. ½ O2+2e- O2-
(iii) Oxide ion react with the metal ions to form metal oxide
film
Based on the environment, corrosion is classified into
M2++O2- M2+O2- = MO
(i) Dry or Chemical Corrosion
(ii) Wet or Electrochemical Corrosion
DRY OR CHEMICAL CORROSION:
This form of corrosion is primarily caused by the direct attack of
atmospheric gases like O2, halogens, H2S, SO2, N2, or anhydrous
inorganic liquids on the metal surface with which they come into
contact.
Types of chemical corrosion
1) Corrosion by oxygen (or) oxidation corrosion.
2) Corrosion by hydrogen
3) Corrosion by other gases like SO2, CO2, H2S and F2 etc.
4) Liquid metal corrosion.
Corrosion by oxygen (or) oxidation corrosion
Oxidation corrosion occurs when metals are exposed to oxygen at low or
high temperatures, typically in the absence of moisture. Nature of oxide film:
All metals, except for noble metals like silver (Ag), gold (Au), and Nature of oxide film decides further corrosion. The oxide layer
platinum (Pt), are susceptible to oxidation at high temperatures. formed may be
a) Stable oxide layer
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 b) Unstable oxide layer d)Porous Layer:
c) Volatile oxide layer This layer contains pores and cracks. In such a case the atmospheric
d) Porous layer oxygen has access to the underlying surface of the metal through the
pores or cracks of the layer, there by corrosion continues until the entire
a) Stable oxide layer: metal is converted to its oxide. E.g.: Iron when attacked by H2S at high
A stable layer has a fine grain structure and can bind to the parent metal temperature forms a porous FeS layer.
surface tightly. Since such a layer is impervious in nature, it acts as a
protective coating, protecting the metal surface. As a result, further
oxidation corrosion is prevented.
E.g.: Al, Sn. Pb, Cu, etc. form stable oxide layers on the surface thus
preventing further oxidation.

Pilling - Bedworth Rule:

The rule states that
(a) If the volume of the metal oxide formed is greater than the
volume of the metal reacted, then the oxide layer is protective or
non-porous.
b) Unstable layer:
Example: oxides of heavy metals such as Al, Sn, Pb, Cu, etc.
The metal oxide formed will not be stable so it decomposes back into its
(b)If the volume of the metal oxide formed is lesser than the volume
metal and oxygen. E.g. Au, Ag
of the metal reacted, then the oxide layer is non-protective or
porous.
Example: oxides of alkali and alkaline earth metals such as Li, Na, Mg,
Ca, etc.
c)Volatile Layer: Pilling - Bedworth Ratio
The oxide layer formed is volatile in nature and evaporates as soon as it It is the ratio of the volume of the metal oxide formed to the
is formed, there by leaving the underlying metal surface exposed for volume of the metal reacted.
further attack. This causes rapid continuous corrosion, leading to
excessive corrosion. E.g. Molybdenum oxide (MoO3).
Significance of P-B Ratio:
P-B ratio ≥ 1: A non-porous, protective film forms, which prevents
further corrosion

P-B ratio < 1: A porous, non-protective film forms, which allows

corrosion to occur faster.

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2) Corrosion by hydrogen: The nature of film (protective or non-protective films) decides further
Hydrogen Embrittlement: corrosion.
Hydrogen Embrittlement occurs when metal comes into contact with 4. Liquid metal corrosion:
H2S, resulting in the formation of atomic hydrogen at room temperature. It occurs due to the chemical action of flowing liquid metal on solid
This atomic hydrogen readily diffuses through the metal and collects in metal or alloy at high temp.
the voids, where it combines to form molecular hydrogen H2. The This corrosion involves either
collection of these gases in the voids creates extremely high pressure, a) Dissolution of solid metal by a liquid metal
which causes metal cracks and blisters. This is known as hydrogen b) Internal penetration of the liquid metal into the solid
embrittlement. metal. E.g. Nuclear devices.

WET or ELECTROCHEMICAL CORROSION:

This type of corrosion occurs when
(a) Two dissimilar metals or alloys are in contact with each other in
presence of aqueous solution or moisture.
(b) The same metal is exposed to different concentrations of O2 or
electrolyte.

Corrosion occurs due to the existence of separate anodic and cathodic

areas or parts (electrochemical cell) between which current flows
through the conducting solution.
In two dissimilar metals (galvanic corrosion), the metal having higher
value in electrochemical series acts as a cathode while the other acts as
an anode. In the same metal electrochemical cell forms due to localized
Decarburisation: stress or due to exposure to a solution of varying concentration or
Thermal dissociation of molecular H2 produces atomic hydrogen at high varying aeration.
temperatures. As steel is exposed to this environment, atomic hydrogen Mechanism of wet corrosion:
reacts with the steel's carbon to form methane gas. Decarburization Under the condition (a) or (b) one part of the metal becomes anode and
refers to the method of lowering the carbon content of steel. another becomes cathode.
At anode: oxidation or dissolution of metal occurs.
M Mn++ ne-
At cathode: Reduction occurs. But the reaction depends on the
The process of decrease in carbon content in steel is known as corrosive environment.
decarburization. 1. If the corrosive environment is acidic, hydrogen gas is
3. Corrosion by other gases: This is due to the direct chemical action evolved.
of metals with atmospheric gases like SO2, CO2, Cl2, NOx and HCl etc. 2H++ 2e- H2
2. If the corrosive environment is neutral or slightly
alkaline, hydroxide ion is formed.
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 ½ O2 + 2e- + H2O 2OH-  If the rust film develops cracks, the exposed metal acts as an
Based on mechanism, there are two types in wet or electrochemical anode, while the covered part of the metal becomes the cathode.
corrosion.  The anode areas are much smaller than the cathode areas, leading
1. Hydrogen evolution type corrosion (Acidic environment): to localized corrosion.

 It occurs in the acidic environment.

 Displacement of hydrogen ions from the acidic solution by the
metal ions.
 All metals above hydrogen in the electrochemical series have
a tendency to get dissolved in acidic solution with
simultaneous evolution of hydrogen.
 The anodic area is very large whereas the cathode area is small.

Salient Features of Electrochemical corrosion:

i. Formation of anodic and cathodic areas or parts in contact with each
other
ii. Presence of conducting medium
iii. Corrosion occurs at anodic areas only
iv. Formation of corrosion product between anode and cathode
v. Some times more than one reduction reactions i.e., both evolution of
hydrogen and reduction of oxygen take place. If two types of reduction
reaction take place, the corrosion is severe
E.g.: When zinc is dipped in aerated acid.

2.Write the differences between chemical and

2. Absorption of oxygen (or) formation of hydroxide ion type electrochemical corrosion.
corrosion (Basic or Neutral environment): S.No Chemical Corrosion Electrochemical Corrosion
 Electrochemical corrosion occurs when base metals are in 1 It occurs only in dry condition Occurs in presence of moisture or
contact with neutral solutions like water, NaCl, or moisture electrolyte
with dissolved oxygen. 2 Chemical corrosion Electrochemical corrosion
 The best example is rusting of iron. occurs due to a direct occurs due to electrochemical
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 chemical reaction between a reactions between a metal and its 0.33V, when a small amount of impurity like CuSO4 is added. This
metal and its environment environment, where an electric results in the increased rate of corrosion of zinc metal due to the
without the involvement of an current is generated. formation of galvanic cell.
electrical current. iii) Hydrogen overvoltage: Rate of corrosion can be reduced by
3 Even a homogeneous metal increasing the hydrogen overvoltage. On the other hand, reduction of
surface Heterogeneous surface or hydrogen overvoltage by addition of foreign ions accelerates the
bimetallic contact gets corrosion of metal/alloy. E.g. The addition of few drops of CuSO4 to
corroded. acidic solution where Zn is placed.
4 Corrosion products Corrosion occurs at the anode iv) Purity of metal: Impurity of a metal generally causes heterogeneity
accumulate at the place where while corrosion product forms and forms minute electrochemical cells and the anodic part gets
corrosion occurs. elsewhere. corroded. For e.g. Zn metal containing impurity such as Pb (or) Fe
5 Self-controlled Continuous process undergoes corrosion. The rate and extent of corrosion increases with
6 Follow absorption mechanism Electrochemical Reaction extent of impurities. Even a trace amount of impurity causes galvanic
7 Eg: Formation of mild scale Eg: Rusting of iron in a moist corrosion.
on iron When exposed to atm. atm. Higher the % of impurity faster the rate of corrosion. Eg. Al metal
containing impurity.
3.Explain the various factors influencing corrosion.

The rate and extent of corrosion depends on

1. Nature of metal(substrate)
2. Nature of corroding environment v) Physical state of metals: The smaller the grain- size of metal or
alloy, the greater will be its solubility and greater will be its corrosion.
1. NATURE OF METALS (SUBSTRATE) Even in a pure metal, areas under stress tend to be anodic and lead to
i) Position in the emf (or) galvanic series: Extent of corrosion corrosion.
depends on the position of metal in emf or galvanic series. The metal vi) Nature of the surface film:
higher in series is more active and suffers corrosion. The rate and extent When metals are exposed to the atmosphere, practically all metals get
of corrosion is directly proportional to electrode potential difference covered with a thin surface film of metal oxide. The ratio of the volume
between them. of metal oxide to the metal is known as specific volume ratio. Greater
The more active metal (or higher up in the series) suffers corrosion when the specific volume ratio, lesser is the oxidation corrosion rate. For eg:
two metals or alloys are in electrical contact. (galvanic corrosion). The the specific volume ratio of Ni, Cr, W are 1.6, 2.0 and 3.6 respectively.
greater is the difference in their position, the faster is the corrosion of Consequently, the rate of oxidation corrosion is least for tungsten (W).
anodic metal/alloy. The potential difference between the anode and vii) Passive character of the metal:
cathode is the driving force of an electrochemical reaction. Metals like Ti, Al, Cr, Mg, Ni and Co are passive due to the formation of
ii) Over voltage: highly protective, thin film of oxide on the metal or alloy surface. They
The overvoltage of metal is inversely propositional to corrosion rate. exhibit much higher resistance than expected from their position in
Example: When zinc metal is placed in dilute sulphuric acid, the galvanic series.
hydrogen overvoltage is 0.7V. But hydrogen over voltage is decreased to
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Oxide film on Cr has self-healing nature, if broken it repairs itself on re- iv) Presence of suspended particle: If the suspended particles are
exposure to oxidizing condition. chemically active in nature, they may absorb moisture and act as strong
Corrosion resistance of stainless steel is due to the passive and self- electrolytes. [ex. NaCl, (NH4)2SO4].
healing character of Cr present in it. Even the chemically inactive suspended particles absorb the impurities
viii) Nature of the corrosion product: present in the air and become active and slowly enhance the corrosion
a) Solubility of corrosion product: rate.
If the corrosion product is soluble in the corrosive medium, corrosion v) Effect of pH: Generally acidic media are more corrosive than
proceeds at a faster rate. If the corrosion product is insoluble or forms alkaline and neutral media. Hence metals may be virtually classified
another insoluble product by interaction with the medium, the corrosion according to pH range in which they will be affected (or) resistant.
product functions as a physical barrier, thus by suppressing further Amphoteric metals like Al, Zn, Pb dissolve in acidic and alkaline
corrosion. PbSO4 formation in case of Pb in H2SO4. medium and form complex ion but they have greatest stability at some
b) Volatility of corrosion product intermediate pH range, like 6-7 and above 11.5. If metal oxide is
If the corrosion product is volatile, it evaporates as soon as it is formed, insoluble at any pH, its corrosion rate is independent of pH. Metal is
there by leaving the underlying metal surface exposed for further attack. readily attacked by even weak acid in presence of oxygen.
This causes rapid and continuous corrosion. For eg: Mo forms MoO3 vi) Polarization (Back emf): The potential difference between the
volatile oxide anode and cathode is the driving force of an electrochemical reaction
2. NATURE OF THE CORRODING ENVIRONMENT: like corrosion. When metal undergoes corrosion, corrosion takes place at
i) Temperature With increase of temperature, the corrosion rate also the anode while H2 evolution occurs at the cathode. The corrosion
increases because the reaction as well as diffusion rate of ions in the products formed as a result of corrosion get accumulated around the
corrosion medium increases. electrode and change the concentration around the electrodes or polarize
ii) Humidity: The higher the humidity of the atmosphere the greater is the electrode which develops opposing emf or back emf.
rate and extent of corrosion. If atmosphere air contains CO2, O2 etc. the Polarization is a process wherein, there is a variation of electrode pot.
moisture furnishes electrolyte and forms electrochemical cells. due to conc gradient at the electrode due to slow diffusion of ions.
If oxide film on the metal is hygroscopic it absorbs moisture and makes Because of back emf potential, higher than the theoretical potential is
electrochemical cell. needed to carry out the anodic reaction (corrosion) and cathodic reaction
For eg: atmospheric corrosion of iron is slow in dry air compound to (H2 evolution).
moist air. The potential difference between the theoretical and actual value is
Iron combines with O2 and water to form ferrous hydroxide which called over voltage. corrosion is quite slow because of over voltage. The
combines with atmospheric CO2 to form ferrous bicarbonate. corrosion can be reduced by adding certain additives (inhibitors) to the
2Fe + O2 + 2H2O -------> 2Fe(OH)2 corroding environment by polarization.
Fe(OH)2 + CO2 ------> Fe(HCO3)2
iii) Impurities present in the atmosphere: Atmosphere vicinity of 4.Explain the types of electrochemical corrosion.
industrial areas contains corrosive gases like CO2, H2S, SO2, fumes of The principle of electrochemical corrosion is involved in the following
HCl, H2SO4 etc. These gases increase the acidity of the liquid, electrical types of corrosion
conductivity and corrosion current. In marine atm the presence of Na 1. Galvanic corrosion
and other chlorides increase the conductivity of the sea water and
thereby corrosion is speeded up.
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2. Differential aeration corrosion The area with the higher oxygen concentration becomes the cathode.
3. Stress corrosion The area with the lower oxygen concentration becomes the anode.
4. Pitting corrosion Consequently, the portion of the metal that has the lower oxygen
5. Waterline corrosion concentration is the portion subject to corrosion.
Eg. i) Corrosion of metals partially immersed in solution just below the
1.Galvanic Corrosion: water line.
When two dissimilar metals are in contact (joined by riveting or ii) Corrosion of iron under drops of water.
welding) and jointly exposed to an electrolyte, the metal higher in the When the metallic surface is partially immersed in an electrolyte and
electrochemical series undergoes corrosion. The metal lower in the partially exposed to air, the poor oxygenated metallic part becomes
electrochemical series becomes cathode and it is protected from the anodic and undergoes oxidation.
attack.

Oxygen rich metallic part becomes cathodic. At the cathode, O2 takes up

electrons to form OH- ions.

The Zn2+ and 2OH- ions interact to give Zn(OH)2.

Example: Steel screw in a brass marine hardware easily undergoes

corrosion. Iron has E0 = -0.44V. For Cu E0 = +0.34 V. Iron corrodes in
preference to Cu.
Mechanism:
At Anode: Corrosion occurs.
At Cathode: In acidic solution hydrogen evolution is the cathodic
reaction while in neutral or slightly alkaline solution oxygen absorption
takes place. General facts about differential aeration corrosion:
Galvanic corrosion can be avoided by 1. Corrosion may be accelerated in apparently inaccessible places.
i. Fixing an insulation material between the two metals. 2. Corrosion may be accelerated under accumulation of dirt, sand, scale
ii. Making the cathode metal smaller than anode metal or other.
iii. Coupling metals close in the emf series or galvanic series 3. Metals exposed to aqueous media corrode under blocks of wood or
piles of glass, which screen that portion of the metal from oxygen
2.Differential aeration corrosion: access.
Differential aeration corrosion is a type of corrosion that occurs when Different Types of Differential Aeration Corrosion:
oxygen concentrations vary across a metal's surface. The varying i) Waterline Corrosion: Maximum corrosion takes place along the line
concentration of oxygen creates an anode and a cathode on the metal's just beneath the level of water meniscus.
surface.
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 v) Corrosion on wire fence: The areas where the wire-cross are less
aerated than the rest of the fence and hence corrosion occurs at wire
crossing which are anodic.
ii) Pitting corrosion: Metal area covered by a drop of water and sand, vi) Caustic Embrittlement: Because of conc gradient of NaOH, conc
dust, scale etc. cell corrosion takes place in the boiler.

3.Stress corrosion:
Stress corrosion, also known as stress corrosion cracking, is a type of
corrosion that occurs due to the simultaneous action of a corrodent and a
sustained tensile stress. This mechanism is characterized by corrosion in
the microscopic granular composition of a metal's surface. The
introduction of stresses (either applied or residual) causes the boundaries
to open, introducing fine cracks on the metal's surface.
iii) Crevice Corrosion: If a crevice between different metallic objects
or between metal and non-metallic material is in contact with liquid, the
crevice becomes the anodic region and suffers corrosion.

iv) Pipeline corrosion: Differential aeration corrosion may also occur at The interface where the grains of a metal contact each other is known as
the different parts of the pipeline. Buried pipelines or cables passing the grain boundary. When metals are melted, either due to the
from one type of soil to another, from clay (less aerated) to sandy (more manufacturing process or during welding, impurities tend to accumulate
aerated) sand. and segregate the grain boundaries. This segregation and increased
impurity concentration make passivation of these areas less effective,
thus making these areas less corrosion resistant than the rest of the
surface.
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Due to minimized passivation, corrosion occurs at these vulnerable In pitting corrosion, a pit is formed when the protective coating on the
areas, creating points of weaknesses. Applied or induced stresses then metal surface breaks, a micro pit (anode) formed on the metal surface.
cause cracks to open up at these locations, while the rest of the metal's Once the pit is formed the process of corrosion becomes very fast due to
surface remains relatively unaffected. the different amount of oxygen in contact with the metal surface. The
Stress corrosion is typically classified as a severe type of corrosion portion (pit) with lower concentration of oxygen becomes anode and
because brittle failure can occur with little to no warning. This condition portion with higher concentration of oxygen becomes cathode.
can be avoided by controlling hardness and stress levels, introducing
compressive stresses (e.g., shot peening) and using protective coatings to The most common pitting corrosion causes are:
prevent corrosion. i. Cracks in protective coating
ii. Scratches, scuffs and small chips
4.Pitting corrosion: iii. Non-uniform stress
Pitting corrosion is a localized form of corrosion by which cavities or iv. Defective metal substrate
"holes" are produced in the material. v. Turbulent fluid flow
vi. Non-uniform protective coating
vii. Chemical attack on protective coating.

5.Waterline corrosion:
Waterline corrosion is a type of oxidation process that can happen to
materials in contact with water. Waterline corrosion occurs when one
portion of a base material is submerged in the water and another portion
is in contact with the air. This creates a differential of the amount of
oxygen in contact with the material's surface above and below the
waterline and results in a corrosive reaction.

Pitting is considered to be more dangerous than uniform corrosion

damage because it is more difficult to detect, predict and design against. When water is stored in the steel tank, then corrosion starts, along the
Corrosion products often cover the pits. A small, narrow pit with line beneath the level of water meniscus. As we know that beneath the
minimal overall metal loss can lead to the failure of an entire water level concentration of oxygen is very low therefore metal part
engineering system. below. The water level acts as anode and metal part above the water
level have higher concentration of oxygen therefore this region acts as
cathode.
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 • Unexpected equipment failures due to corrosion lead to
unplanned outages.
• Power generation capacity is reduced, leading to financial losses
from downtime.
5. Safety Hazards:
• Corrosion in pressure vessels, steam pipes, and other high-stress
components increases the risk of leaks, explosions, or chemical
spills.
• These safety hazards endanger plant workers, maintenance staff,
and surrounding communities.
6. Environmental Impact:
5. Explain the Impacts of Corrosion on Power Plants. • Corrosion in pipes or storage tanks can cause hazardous material
Corrosion is a major concern in power plants, as it affects the efficiency, leaks or spills.
reliability, safety, and longevity of critical equipment and infrastructure. • Environmental contamination and violations of regulatory
The impacts of corrosion in power plants can be both direct and indirect, standards may occur.
with significant consequences for plant performance, environmental 7. Corrosion Fatigue:
safety, and maintenance costs. • Repeated mechanical stress combined with corrosion accelerates
1. Reduced Efficiency and Performance: material degradation.
• Corrosion decreases the effectiveness of heat exchangers, boilers, • This can lead to fatigue failures in cyclically loaded components,
and turbines. such as turbines and piping systems.
• Insulating layers like rust and scale form, reducing heat transfer. 8. Regulatory Non-Compliance:
• More fuel is required to produce the same amount of power, • Corrosion-induced failures may result in plant shutdowns or
increasing operational costs. regulatory fines if environmental or safety standards are violated.
2. Increased Maintenance Costs: • Non-compliance can affect plant reputation and long-term
• Corroded components require more frequent repairs or viability.
replacements. 9. Increased Operational Costs:
• Regular inspections and replacement of corroded parts escalate • Corrosion can lead to higher energy consumption and
the maintenance budget. inefficiency.
• Proactive monitoring systems are needed to detect early • Increased maintenance, repair costs, and energy inefficiencies
corrosion. strain the plant’s financial resources.
3. Equipment Failures: Mitigation Strategies:
• Corrosion leads to structural weakness, resulting in failures like • Implementing corrosion monitoring systems.
cracks or ruptures in boilers, pressure vessels, and piping. • Using corrosion-resistant materials and coatings.
• Failure of critical components can cause unplanned shutdowns • Conducting regular maintenance and inspections.
and operational disruptions. • Applying corrosion inhibitors and preventive measures.
4. Downtime and Production Losses:

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6. Explain the various corrosion control techniques (f) As far as possible, crevices (gap or crack) should be avoided between
and its prevention. adjacent parts of a structure.
(g) Bolts and rivets should be replaced by proper welding.
Corrosion of metals is a vital concern for the materials scientist. This
natural phenomenon causes substantial financial losses in various sectors
and requires extensive efforts to limit its impact. Therefore, there is a
need to innovate an effective and economically viable technique for
producing and also applying intelligent/smart coatings to minimize
corrosion.

Methods:
There are some methods to control corrosion.
1. Proper designing
2. Cathodic protection (h) Metal washers should be replaced by rubber or plastic washers as
3. Protective coatings they do not adsorb water. They also act as insulation.
4. Anti corrosive agents (i) Corrosion in pipelines can be prevented by using smooth bends.
1. Proper designing: Sharp corners and recesses should be avoided, because they favour the
The design of the material should be such that "corrosion, even if it formation of stagnant areas and accumulation of solids etc.
occurs, is uniform and does not result in intense and localized
corrosion". Important design principles are:
(a) Avoid the contact of dissimilar metals in the presence of corroding
solution:
If this principle is not followed, then corrosion is localized on the more
active metal (in the immediate vicinity of contact) while the less active
metal remains protected. (j) Heat treatment like annealing minimizes the stress corrosion.
(b) When two dissimilar metals are to be in contacts the anodic material (k)A good design of water storage container is the one from which water
should have and large area as possible; whereas the cathodic metal can be drained and cleaned easily. Such a design avoids accumulation of
should have as much smaller area as possible. dirt etc.
(c)If two dissimilar metals in contact have to be used, they should be as (k) Whenever possible, the equipment should be supported on legs to
close as possible to each other in the electrochemical series. allow free circulation of air and prevent the formation of stagnant pools
(d) Whenever the direct joining of dissimilar metal is unavoidable, an or damp areas.
insulating fitting may be applied in between them to avoid direct metal
electrical contact.
(e) The anodic metal should not be painted or coated, when in contact
with a dissimilar cathodic metal, because any break in coating would
lead to rapid localized corrosion.

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Uniform flow of corrosion liquid is desirable. Since both stagnant areas 1. Sacrificial Anodes are used to protect the hulls of ships, water heaters,
and highly turbulent flow and high velocities can cause accelerated pipelines, distribution systems, above-ground tanks, underground tanks,
corrosion. So, highly impingement conditions of flowing liquid should and refineries.
be avoided as much as practically possible. Advantages:
1. No external electrical power is required.
2.Cathodic protection: 2. Anodes are relatively fool – proof and little maintenance is required.
The reduction or prevention of corrosion by making metallic structure as 3. Anodes are easy to install.
cathode in the electrolytic cell is called cathodic protection. Since there 4. Hull protection is provided at all times until the anode is completely
will not be any anodic area on the metal, corrosion does not occur. There consumed.
are two methods of applying cathodic protection to metallic structures. Disadvantages:
a) Sacrificial anodic protection (galvanic protection) 1. Periodic replacement of anode is necessary.
b) Impressed current cathodic protection. 2. Increased noise level from the anodes
a. Sacrificial anodic protection (galvanic protection): 3. High starting current is required.
In this method, the metallic structure to be protected is made cathode by 4. Uncoated parts cannot be protected.
connection it with more active metal (anodic metal). Hence, all the 5. It possesses limited driving potential, hence, it’s not applicable for
corrosion will concentrate only on the active metal. The parent structure large objects.
is thus protected. The more active metal so employed is called sacrificial 6. Periodic replacement costs, especially in ships since they must be dry
anode. The corroded sacrificial anode block is replaced by a fresh one. docked
Metals commonly employed as sacrificial anodes are magnesium, zinc, b) Impressed current cathodic protection:
aluminium and their alloys. Magnesium has the most negative potential In this method, an impressed current is applied in opposite direction to
and can provide highest current output and hence is widely used in high nullify the corrosion current and convert the corroding metal from anode
resistivity electrolytes like soil. to cathode.

Usually, the impressed current is derived from a direct current source

(like battery or rectifier on AC line) with an insoluble, inert anode (like
graphite, scrap iron, stainless steel, platinum or high silica iron). A
sufficient DC current is applied to an inert anode, buried in the soil (or
Applications: immersed in the corroding medium) and connected to the metallic
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structure to be protected. The anode is, usually, a back fill, composed of metal to form a thick oxide layer. The thickness of the oxide layer
coke breeze or gypsum, so as to increase the electrical contact with the depends on factors such as voltage, temperature, and time.
surrounding soil. Coloring (Optional): After anodizing, the oxide layer is porous,
Applications: allowing for dyeing with various colours. This step is optional but is
1. This method is applied to protect the structures like tanks, pipelines, often used for aesthetic purposes, especially for items like architectural
transmission line towers, underground water pipelines, oil pipelines, elements, consumer products, or military parts.
ships etc. Sealing: After anodizing (and optional colouring), the oxide layer is
Advantages: sealed to close the pores and enhance the durability of the finish. This
1. The amount of current generated from ICCP is ranges from 20 V to can be done by immersing the anodized part in hot water or steam, or
100 V. It is much greater than that of any galvanic system. using chemical sealing agents, which helps increase corrosion resistance
2. The anode metal has longer life than sacrificial anodic method. and stabilize the colour.
Disadvantages:
1. This method needs more maintenance.
2. The operating cost is high.
3. It may cause interferences on other structures.

3.Protective coatings:
Anodization:
Anodization is an electrochemical process used to increase the thickness
of the natural oxide layer on the surface of metal parts like aluminium,
titanium, and magnesium. This process improves corrosion resistance,
wear resistance, and enhances the aesthetic appearance of the metal.
Steps involved in the Anodizing Process:
Cleaning: The metal surface must be cleaned thoroughly to remove dirt,
oils, or oxidation. Chemical cleaners or abrasive methods can be used to
ensure a smooth, clean surface. Types of Anodizing:
Etching: Etching process is used to further clean and roughen the Sulfuric Acid Anodizing
surface. This can improve the adhesion of the anodized layer and Hard Anodizing
enhance the final appearance. Chromic Acid Anodizing
Electrolytic Bath: The metal piece is submerged in an electrolytic Phosphoric Acid Anodizing
solution, often sulfuric acid or other acidic solutions, and connected to Titanium Anodizing
the positive terminal of a DC (Direct Current) power supply. The bath is Magnesium Anodizing
also connected to a cathode. Ceramic Anodizing
Anodizing (Electrochemical Reaction): When current flows through Aluminium Anodizing:
the solution, the metal undergoes an oxidation reaction at the surface. Aluminium alloys are anodized to increase corrosion resistance and to
The metal dissolves at the anode (the workpiece) , and oxygen is allow dyeing (colouring), improved lubricants , or improved adhesion.
released from the electrolyte. The oxygen reacts with the surface of the
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Anodizing an aluminium part is a multiple-step process aimed at Customizing the anodized aluminium components by introducing colors
improving the part’s properties, such as hardness, corrosion resistance, during or after the anodizing process is possible. This involves
and aesthetics. introducing dyes or pigments into its microscopic grooves created by the
The stepwise procedure is given below: electrochemical process.
Cleaning Coloring anodized aluminium is achieved by:
The aluminium surface is cleaned using a mild detergent to remove Electrolytic coloring
contaminants like dirt, grease, or oils. Proper cleaning will improve the Dip coloring
adhesion of the anodic coating to the aluminium and ensure a quality Integral coloring
coating. Interference coloring
Pre-treatment
Pre-treatment will allow to remove surface impurities not removed by Key Benefits of Anodizing:
the cleaning step, surface irregularities, and excess alloying elements. Enhanced Corrosion Resistance: The anodized layer is much thicker
Etching can clean and remove surface irregularities while de-smutting and harder than the natural oxide, providing superior resistance to
can remove smuts (thin layers of alloying elements) on the aluminium corrosion, especially in harsh environments.
components. Durability: Anodized aluminium is more wear-resistant, scratch-
Anodizing resistant, and can withstand a variety of environmental conditions.
The aluminium component is immersed in an electrolytic system with a Aesthetic Appeal: Anodizing can enhance the appearance of aluminium
bath containing an acid (chromic or sulfuric acid, depending on the type with a wide range of colors and a glossy or matte finish, making it
of anodizing), the aluminium part as the anode (aluminium anode), and popular for consumer goods and architectural finishes.
an inert material like stainless steel as the cathode. The direct current Environmentally Friendly: The process does not involve toxic or
(DC) is passed through the electrolytic solution which releases oxygen hazardous chemicals and is generally considered eco-friendly compared
ions. At the same time, the aluminium anode goes into the solution and to other metal finishing methods.
becomes aluminium ions. The oxygen ion and the aluminium ions react Advantages:
to form the layer of aluminium oxide (Al2O3) coating deposited on the  It's easy to maintain; it can be cleaned with water and mild
part surface. detergents to restore the original lustre.
At anode:  It is UV stable and will not peel or flake.
Oxidation of the aluminium atoms occurs at the anode  It Protects the base metal to offer a deeper, richer metallic
2Al(s)+3H2O(aq)→Al2O3(s) + 6H+(aq) + 6e- appearance.
At the cathode: Dis Advantages:
Reduction occurs at the cathode  Only specific grades of aluminium can be used for this process,
6H+(aq) + 6e- → 3H2(g)  It cannot be used on Stainless Steel, which is durable to mortar,
The complete electrochemical reaction is: salt, chlorine and marine environments,
2Al(s)+3H2O(aq) → Al2O3(s) + 3H2(g)  This method draws from the base metal so it can be subject to
The oxide coating depends on the acid anodizing type, voltage, and colour variations.
duration. Furthermore, thicker coatings ensure better corrosion
resistance and higher surface hardness. Galvanization:
Coloring
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Galvanization is the process of coating a metal (typically steel or iron) Preparation: The steel surface is cleaned using methods like acid
with a protective layer of zinc to prevent corrosion. The purpose of cleaning, pickling, or abrasive blasting.
galvanization is to improve the metal's resistance to rust and Electroplating: The steel is immersed in a zinc-containing electrolyte
environmental degradation, thus extending its lifespan. The most solution, and an electric current is passed through it, causing the zinc
common method of galvanization is hot-dip galvanizing, but there are ions to migrate and coat the surface of the steel.
other methods, such as electrogalvanizing, as well. Here’s a breakdown Finishing: After the electroplating process, the galvanized steel is rinsed
of the galvanization process: and dried. Electrogalvanized coatings tend to be thinner than hot-dip
1. Hot-Dip Galvanizing (The Most Common Method) coatings but can still provide a degree of corrosion resistance.
In hot-dip galvanizing, steel or iron parts are immersed in a bath of
molten zinc. The process creates a metallurgical bond between the zinc
and the steel, forming a coating that protects the steel from corrosion.
Steps in Hot-Dip Galvanizing:
Cleaning: The metal surface is cleaned to remove any rust, oil, dirt, or
mill scale. This is typically done through a series of cleaning processes,
such as:
Pickling: Immersing the metal in a dilute acid solution (usually
hydrochloric or sulfuric acid) to remove scale and rust.
Fluxing: The cleaned metal is dipped into a flux solution (usually zinc
ammonium chloride) to prepare the surface for better adhesion of the
zinc.
Dipping in Molten Zinc: After cleaning, the steel or iron part is dipped
into a bath of molten zinc (at about 450°C or 840°F). This creates a
metallurgically bonded layer of zinc on the steel surface.
Cooling: The part is removed from the molten zinc and allowed to cool. 3. Mechanical Galvanizing (Dry Process):
As it cools, the zinc forms a protective layer, which is typically Mechanical galvanizing is a process where zinc powder is applied to
composed of several layers of zinc alloy bonded to the surface of the steel using mechanical tumbling. This method doesn't involve molten
steel. zinc or electroplating but instead uses a combination of mechanical
Inspection and Quality Control: The galvanized metal is inspected for energy, zinc powder, and small steel beads to create a coating.
coating thickness and quality. If needed, additional treatments like Steps in Mechanical Galvanizing:
passivation or chromate conversion can be applied to improve the Preparation: Steel parts are cleaned and then placed into a rotating
coating’s durability. drum with zinc powder and steel shot.
2. Electrogalvanizing (Electroplating) Tumbling: The drum is rotated, and the steel shot impacts the zinc
In electrogalvanizing, zinc is applied to the surface of steel through an powder, causing it to bond to the surface of the steel through mechanical
electrochemical process, where zinc ions from a zinc salt solution are energy.
deposited onto the steel surface using electric current. This method is Curing: After coating, the parts are heated in an oven to cure the zinc
often used for smaller parts or when a thinner zinc coating is desired. coating, making it durable and corrosion-resistant.
Steps in Electrogalvanizing:
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Benefits of Galvanization: Aesthetic Concerns: While galvanized coatings are functional, they
Corrosion Protection: Zinc acts as a sacrificial anode, meaning it often have a rough texture and a dull gray appearance, which may not be
corrodes first before the steel does, protecting the steel from rust and desirable for aesthetic applications. This can be mitigated with post-
deterioration. Even if the coating is scratched or damaged, the exposed galvanizing treatments like painting or powder coating.
steel is still protected by the surrounding zinc.
Durability: Galvanized coatings are extremely durable and can last for 4.Anti-corrosive agents:
many years, even in harsh environments, making galvanized materials Corrosion can harm materials' strength, look, and usefulness,
suitable for outdoor or industrial applications. particularly in industries like manufacturing, transportation, and
Low Maintenance: Galvanized materials require minimal maintenance construction.
compared to untreated steel or iron. The coating is tough and resistant to Anti-corrosive agents prevent or reduce corrosion, a common and often
wear and tear. dangerous chemical reaction between metals and their environment.
Cost-Effectiveness: While the initial cost of galvanizing can be higher, These materials work by altering the chemical environment, forming a
it reduces the need for frequent maintenance or replacement, making it protective coating on the metal surface, or directly stopping the chemical
cost-effective over the long term. reactions that lead to corrosion. They are widely utilized in automotive,
Environmental Resistance: Galvanized steel is resistant to many maritime, and oil and gas sectors where exposure to harsh conditions
environmental factors, including exposure to moisture, salt, and accelerates corrosion.
chemicals. Molybdates as Anti-Corrosive Agents
Applications of Galvanization: Molybdates are compounds containing the molybdate ion
Construction: Used in steel framing, roof panels, bridges, and outdoor (MoO₄²⁻), which act as anodic inhibitors. They work by forming a
structures where corrosion resistance is critical. protective oxide layer on the metal surface, preventing further oxidation
Automotive: Galvanized steel is used in car bodies, chassis, and parts and reducing the rate of corrosion.
exposed to weather to prevent rust and extend the life of vehicles. 1. Metal Surface Interaction:
Agriculture: Galvanized metal is used in equipment like fences, A clean metal surface is shown reacting with molybdate ions.
irrigation systems, and silos because of its resistance to the elements. Molybdate ions are deposited onto the metal, reacting with oxidized
Pipes and Infrastructure: Galvanized steel pipes are used for water metal ions.
supply, sewage, and other infrastructure systems due to their durability 2. Formation of a Protective Layer:
and corrosion resistance. The interaction forms a stable metal-molybdate complex. Over
Electrical Equipment: Galvanized steel is often used in electrical time, a passivating oxide layer develops, preventing oxygen and chloride
enclosures and hardware, which need to resist rust and corrosion. ions from contacting the metal.
Limitations of Galvanization: 3. Environment Protection:
Thickness of Coating: While galvanization provides excellent corrosion The outer layer blocks corrosive agents like water, oxygen, and
resistance, the coating thickness can sometimes be too much for delicate salts.
parts or intricate shapes. Hot-dip galvanizing is not suitable for very thin Applications of Molybdates as Anti-Corrosive Agents:
metals or complex parts with small features. 1.Water Treatment:
Brittleness: In certain environments or if the coating is not applied Molybdates are used in cooling water systems to prevent corrosion in
correctly, the zinc coating can become brittle over time, especially under pipes and heat exchangers.
mechanical stress. 2.Metal Coatings:
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Used in primers and coatings for industrial equipment, bridges, and The effectiveness of molybdates depends on achieving an optimal
vehicles to protect against corrosion in harsh environments. concentration, which requires precise control and monitoring.
3.Oil and Gas Industry: 5.Slow Formation of Protective Layer:
Protect pipelines, tanks, and other equipment exposed to corrosive The molybdate-induced protective layer takes time to develop, which
chemicals and high moisture levels. may be a limitation in rapidly corrosive environments.
4.Electronics:
Applied in corrosion-resistant coatings for electrical contacts and circuit Phosphates as Anti-Corrosive Agents:
boards. Phosphates protect metals by forming an insoluble phosphate
5.Marine Applications: layer on the surface. This layer acts as a barrier, preventing oxygen and
Molybdates are used in coatings for ships and marine structures to water from reaching the underlying metal.
prevent damage from saltwater exposure. 1.Interaction with Metal Surface:
Advantages of Molybdates: Phosphate ions interact with the exposed metal surface, reacting
1.Effective Corrosion Inhibition: with metal cations released during initial oxidation. This interaction
Forms a stable, passivating layer on metal surfaces, reducing the rate of often occurs in environments where phosphates are present in coatings,
corrosion significantly. paints, or water treatments.
2.Compatibility: 2.Formation of Metal-Phosphate Complex:
Suitable for various metals, including steel, copper, and aluminum. The phosphate ions chemically bond with the metal ions to form
3.Non-Toxic Alternatives: a stable metal-phosphate complex. This complex acts as an intermediate
Less toxic than traditional chromates, making molybdates a safer option protective barrier, adhering tightly to the surface.
for both humans and the environment. 3.Development of Protective Layer:
4.Eco-Friendly Options: Over time, the metal-phosphate complex reacts further with
Can be formulated in compliance with environmental regulations, environmental components (oxygen and water) to form a dense, passive
reducing ecological impact. oxide-phosphate layer. This protective layer prevents corrosive agents
5.Thermal Stability: such as oxygen, water, and chloride ions from penetrating and damaging
Performs well under high-temperature conditions, making them ideal for the metal surface.
industrial applications.
Disadvantages of Molybdates: Applications
1.Cost: •Industrial Coatings:
Molybdates are more expensive compared to some other inhibitors, such Phosphate-based primers are commonly applied to metals before
as phosphates. painting, especially in automotive and marine industries, to enhance
2.Limited Effectiveness in Acidic Conditions: corrosion resistance.
They perform best in neutral to alkaline environments and may be less •Water Treatment:
effective in highly acidic conditions. Phosphates are used in boiler water systems to minimize scale formation
3.Potential for Overuse: and prevent corrosion in pipes and tanks.
Excessive use in water treatment systems can lead to environmental •Pipeline Protection:
concerns and increased operational costs. Phosphate treatments in oil and gas pipelines reduce pitting corrosion
4.Dependent on Concentration: caused by harsh environments.
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Advantages: 3.What is corrosion engineering? Mention its importance.
Cost-effective and efficient in forming a durable protective layer. The branch of Engineering that deals with the study of corrosion
Environmentally friendly options (e.g., plant-based phosphates) are mechanisms and to prevent or control it economically and safely is
being developed. known as Corrosion Engineering.
Limitations: Corrosion Engineering helps in designing materials and protective
May require a specific pH range to work effectively. coatings that extend the lifespan of infrastructure and reduce
Overusing phosphates in water systems can lead to environmental maintenance costs.
concerns such as eutrophication.
4.Mention the adverse effects of corrosion.
Part-A 1. Damage to airplanes: Corrosion can lead to in-flight issues and
1. What is corrosion? What are its types? potential safety risks.
2. Damage to oil pipelines: Corrosion may cause ruptures, leading
Corrosion is the progressive destruction or oxidation of metals or to expensive and hazardous environmental damage.
alloys as a result of a chemical or electrochemical reaction with their 3. Damage to bridges: Corrosion of bridge supports can lead to
environment. bridge failure.
Examples: 4. Cost of repairs: Corrosion increases the cost of fixing or
i) Rusting of iron – when iron is exposed to the atmospheric replacing household equipment.
conditions, a layer of reddish scale and powder of Fe3O4 is 5. Loss of efficiency: Corrosion reduces the performance of
formed. materials and systems.
ii) Formation of green film of basic carbonate- [CuCO3 +
Cu(OH)2] on the surface of copper when exposed to moist air 5.What happens when a metallic rod is partially buried under
containing CO2. earth?
Based on the environment, corrosion is classified into
(i) Dry or chemical corrosion and When metallic rod is partially buried under earth, corrosion is
(ii) Wet or electrochemical corrosion accelerated by the accumulation of dirt, sand, scale or other serial
contamination. These restrict the access of oxygen and hence act as
anode which promotes differential aeration corrosion. The result is
2.Mention the importance of corrosion studies.
localized corrosion due to non-uniform attack.
(i)Economic Importance:
It reduces material losses due to sudden failures of piping, tanks,
6.Why are zinc and magnesium frequently used as sacrificial
machines, ships, and other metal structures.
anodes?
(ii)Conservation Importance:
It helps to preserve limited metal resources and reduces wastage, saving
Metals like Zn and Mg are higher up in electrochemical series and they
energy and water used in metal production and fabrication.
undergo oxidation very easily. Hence these are used as sacrificial anode
(iii)Safety Importance:
which dissolves due to oxidation and the cathode metal is protected.
It protects critical infrastructure like bridges, pipelines, and pressure
vessels from corrosion, reducing the risk of accidents and failures.

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7.An iron rod partly immersed in water under goes corrosion near non-protective, allowing oxygen to reach the fresh metal
water line? Give the reason. surface and causing continued corrosion
The area above the water line (highly oxygenated) acts as the cathode
and is completely unaffected by corrosion and the area under the water 13. What is pilling bedworth ratio? Mention its significance.
line acts as anode and is affected by corrosion. Hence, a corrosion It is the ratio of the volume of the metal oxide formed to the volume of
product forms near the water line. the metal reacted.

8.Bolt and nut made of the same metal is usually preferred in

practice. Why? Significance of P-B Ratio:
It is preferred in practice because galvanic corrosion is avoided due to P-B ratio ≥ 1: A non-porous, protective film forms, which prevents
homogeneous metals. further corrosion
9.Corrosion of a metal is the highest at the metal junction in a P-B ratio < 1: A porous, non-protective film forms, which allows
galvanic couple. Account the reason. corrosion to occur faster.
Metal junction, where air cannot diffuse easily, is less aerated and
becomes anodic; the remaining parts are more aerated and become
cathodic. So, the corrosion concentrates at the metal junction in a
galvanic couple.

10.Iron is corroded faster than aluminium even though iron is

placed below Al, in electrochemical series. Why?
Al forms a thin, non-porous, tightly adhering protective film of Al2O3 on
its surface and this film does not allow Al to undergo further corrosion.
Hence Fe is corroded faster than aluminium.

11.Small anodic area results in intense corrosion. Why?

Rate of corrosion is more rapid and intense, if the anodic area is smaller
and the cathodic area is larger. When the cathodic area is larger, the
demand for electrons will be more and this results in an increased rate of
corrosion of metals at anodic area.

12. Define pilling bedworth rule.

1. Protective Oxide Layer: The oxide layer is protective, if its
volume is at least equal to or greater than the volume of the
metal from which it formed.
2. Non-Protective Oxide Layer: If the oxide layer’s volume is
smaller than the metal’s volume, it becomes porous and
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