Module 4: CORROSION AND ITS CONTROL

Pre- requisites : corrosion , corrosion product, corrosive and non corrosive metals. Galvanic
series and electrochemical series.

Mechanism of corrosion - Chemical and Electrochemical corrosion.

Types of corrosion: Galvanic corrosion, Differential aeration corrosion, Pitting corrosion,

Intergranular corrosion, Waterline corrosion, Stress corrosion.

Factors Affecting Corrosion Rate: - (i) Nature of metal, (ii) Nature of environment.
Methods of Corrosion Control : Material selection, Design, Cathodic protection

Protective Coatings: Metallic coatings - anodic coating (galvanizing) and cathodic coating
(Tinning)

Methods of Applying Metallic Coatings - Hot dipping, Metal Spraying, Electroplating and
Diffusion coating

 Organic coatings – Paints

Corrosion with an example

Corrosion can be defined as any process of destruction and consequent loss of solid metal through
an unwanted chemical or electro chemical attack by its environment starting at the surface.

Corrosion can be considered as a process reverse of extraction of metals.

Example: rusting of iron.
It can be noted that corrosion is associated with metal where as erosion is associated with non
metal (wood, paper etc).

Wet or electrochemical theory of corrosion

It is a common type of corrosion of metal in aqueous corrosive environment. This type of
corrosion occurs when the metal comes in contact with a conducting liquid or when two
dissimilar metals are immersed or dipped partly in a solution. According to this theory, there is
the formation of a galvanic cell on the surface of metals. Some parts of the metal surface act as
anode and rest act as cathode.
The chemical in the environment and humidity acts as an electrolyte. Oxidation of anodic part
takes place and it results in corrosion at anode, while reduction takes place at cathode. The
corrosion product is formed on the surface of the metal between anode and cathode.
To understand the wet corrosion, let us take the example of corrosion of iron. Oxidation of metal
takes place at anode while the reduction process takes place at cathode. By taking rusting of iron
as an example, the reaction can be explained as that it may occur in two ways: (i) evolution of
hydrogen (acidic medium) and (ii) absorption of oxygen (Neutral or alkaline medium).

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 At anode: oxidation occurs. Fe → Fe++ + 2e-

At cathode:
Case I: Evolution of H2

The hydrogen ions (H +) are formed due to the acidic environment and the following
reaction occurs in the absence of oxygen
2H+ + 2e - = H2 ↑ (reduction)
The overall reaction is Fe + 2H+ = Fe+2 + H2

In this case, metals react in the acidic environment and are dissolved (undergo
corrosion) to release H2 gas. All metals above hydrogen in electrochemical series can
show this type of corrosion.

Case II: Absorption of O2

This type of corrosion takes place in neutral or basic medium in the presence of oxygen.
The following chemical reactions occur at anode and cathode.

At anode Fe = Fe+2 + 2e¯ (oxidation)

n the presence of sufficient amount of dissolved oxygen ferrous hydroxide is oxidized to

ferric hydroxide. Ferric hydroxide is actually hydrated ferric oxide, Fe2O3.H2O, which is
yellowish rust.

Galvanic corrosion
Galvanic corrosion: This type of electrochemical corrosion is also called bimetallic corrosion.
When two dissimilar metals are connected and exposed to an electrolyte, they will form a
galvanic cell. The anodic metal will be oxidized and it will undergo corrosion.

Zinc (Zn) and copper (Cu) metals connected with each other in an electrolyte medium form
a galvanic cell. Zinc acts as anode and undergoes corrosion while cathode will be
unaffected.

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 At anode: Zn = Zn++ + 2e– [Oxidation] corrosion
At cathode: Cu++ + 2e– = Cu [Reduction] unaffected
In acidic medium, the corrosion takes place by evolution of hydrogen while in neutral or
slightly alkaline medium, corrosion occurs by oxygen absorption method.

Example of galvanic corrosion:

1. Steel screws in brass marine hardware,
2. Steel pipe connected to copper plumbing,
3. Steel propeller shaft in bronze bearing,
4. Zinc coating on mild steel
5. lead–tin solder around copper wires.

Concentration cell corrosion

Concentration cell corrosion occurs either due to varying concentration of electrolyte in contact
with a metal or due to difference in concentration of air or oxygen over the metal surface. Due to
this a potential difference is developed between two areas resulting in corrosion. Differential
aeration corrosion is most common.
Example: If a metal rod is dipped in an electrolyte, the portion dipped in water is poor in oxygen
concentration and works as anode which gets corroded and the portion above water acts as
cathode which is protected. The system will act as a concentration cell and the chemical
reactions for zinc dipped in water are given as:

Zn(OH)2 appears as corrosion products.

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 Mechanism of differential aeration attack caused by partial immersion of a metal

Pitting corrosion
Ans) Pitting corrosion is an extremely intense localized corrosion. Due to crack on the surface of
a metal, local straining of metal, sliding under load, chemical attack, there is formation of a
local galvanic cell. The crack portion acts as anode and rest of the metal surface acts as
cathode. It is the anodic area which will be corroded and the formation of a pit is observed.
This type of corrosion is thus called pitting corrosion. Presence of external impurities such
as sand, dust, scale embedded on the surface of metals lead to pitting. For example,
stainless steel and aluminium show pitting in chloride solution.

Waterline corrosion

When water is stored in a metallic tank for a long time undisturbed, it is observed that the metal
below the waterline gets corroded. It is because of the formation of differential aeration cell. As
we know that beneath the water level concentration of oxygen is very low therefore metal part
below the water level acts as anode and metal part above the water level have higher
concentration of oxygen therefore this region act as cathode. Hence corrosion of metal below
the waterline takes place. The reaction involve are as follows:

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Intergranular corrosion

This type of attack results from local differences in composition such as coring commonly
encountered in alloy castings. This corrosion is observed in case of alloys. The corrosion product
is observed at the boundaries of grains. Externally, it is not seen. There is a sudden failure of
material due to this corrosion. For example, Grain boundary precipitation, notably chromium
carbides in stainless steels, is a well-recognized and accepted mechanism of intergranular
corrosion. During the welding of stainless steel (an alloy of Fe, C, Cr), chromium carbide is
precipitated at the grain boundaries and the region adjacent to grain boundaries becomes
depleted of chromium composition and is made anodic with respect to solid solution within the
grains richer in chromium. Rapid quenching after heat treatment of a metal is the remedy of
inter-granular corrosion.

Inter granular corrosion can be prevented through:

 Use low carbon grade of stainless steels

 Use stabilized grades alloyed with titanium or niobium . Titanium and niobium are strong
carbide- formers. They react with the carbon to form the corresponding carbides thereby
preventing chromium depletion.

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  Use post-weld heat treatment.

Stress corrosion
Stress corrosion is observed in alloys under specific corrosive environment. It happens when
there is tensile stress in alloys and is exposed to aggressive corrosive environment, both the
conditions are essential. The portion under stress will act as anode and rest part of the structure
will act as cathode. It is now a galvanic system and hence anodic part which is small in area will
corrode more.

Examples: 1.mild steel exposed to chloride environment.

2. Brasses in ammonia environment.
3. Caustic embrittlement.

Factors influencing the rate of corrosion

Since corrosion is a process of destruction of metal surface by its environment, the two factors
that govern the corrosion process are: (i) Nature of metal and
(ii) Nature of environment

(i) Nature of metal:

(a) Position of metal in galvanic series: It decides the corrosion rate. A metal having higher
position in galvanic series undergoes corrosion when connected to another metal below it.
Also, more difference in the position of galvanic series will cause faster corrosion at anodic
metal.

(b) Over voltage: The reduction in over voltage of corroding metal or alloy accelerates the
rate of corrosion. Hence hydrogen over voltage governs the process of corrosion.
Over Voltage: It has been observed experimentally that the actual voltage required for
electrolysis is greater than that calculated from standard potentials. This additional voltage
required is called over voltage. This is require because the rate of transfer of electrons at
the interface of electrode and solution for both the half cell reaction is slow.

(c) Purity of metal: Pure metal resists corrosion, while impurities in a metal form a local
galvanic cell (metal as anode and impurity as cathode) and result in the corrosion of metal.
Rate of corrosion increases due to more exposure of impurities. For alloys the system is a
homogeneous solid solution, hence no local action and no corrosion.

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(d) Relative areas of anode and cathode: Smaller the area of anode compared to cathode
will lead to faster corrosion of anode. It is because the corrosion current at anode and at
cathode will be same. But for small anodic area the current density will be large at anode
and larger cathodic area will demand more electrons which will be fulfilled by fast reaction
at anode (oxidation), i.e. rapid corrosion.
(e) Physical state of the metal: Small granular metal will corrode faster than the larger one.
Also the type of structure formed by a metal will have effect on the corrosion rate. A bent
metal (stress) is rapidly corroded due to stress.

(f) Nature of oxide film: An oxide film is formed by the reaction between metal and
oxygen. If this oxide film is porous and oxygen can be diffused through it, more corrosion
is expected (already shown in dry or chemical corrosion). Also, if volume of metal oxide is
more than the volume of metal (The specific volume ratios of Ni, Cl, W are 1.6, 2.0 and
3.6) least corrosion or no further corrosion occurs.

(g) Nature of corrosion product: If the corrosion product is volatile or soluble with
surrounding medium, then rate of corrosion will increase. For example; SnCl4 are volatile,
so faster is corrosion of Sn in chlorine atmosphere. In case of soluble corrosion product, it
will be enhanced by water and metal surface will be exposed for further corrosion.

(h) Passivity of the metal: Metals like Al, Cr, Ti etc are passive and they exhibit higher
corrosion resistance than expected from their position in their galvanic series due to the
formation of highly protective, thin film of oxide. This film formed is self-healing in
nature, if broken, repairs itself on re exposure to oxidizing conditions.

(ii) Effect of environment

The role of environment in the corrosion of a metal is very important. Environmental
parameters like temperature, humidity, pH, etc. play important role. The effect is discussed
here.

(a) Temperature: The rate of diffusion increases by rise in temperature; hence the rate of
corrosion is also increased. At higher temperature, passive metals also become active and
undergo corrosion. But higher temperature reduces the concentration of oxygen and hence
corrosion is reduced (in case of water where oxygen is dissolved).

(b) Humidity: In humidity, gases like CO2, SO2, NOx are dissolved which form
electrolytes. It will cause galvanic corrosion. Some oxides are water soluble, humidity
washes away the corrosion products and metal surface is further corroded. Other soluble
corrosion products can also be washed away by humidity, causing further corrosion.

(c) Impurity of atmosphere: Pollutants like H2S, SO2, CO2 and acid vapors cause more
pollution where they dissolve. In sea water (salty in nature which acts as an electrolyte) the
corrosion rate increases. Some suspended particles are dissolved in humidity and form
electrolyte which helps in corrosion.

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 (d) pH value: pH value means concentration of H+ (acidic nature). In acidic medium (pH
less than 7), corrosion is faster. Also, in basic medium pH > 7, some metals such as Pb, Zn,
Al, etc. form complexes and hence they corrode. Example: Zn corrodes minimum at pH
11, but at higher pH (more than 11) it corrodes faster. At pH 5.5, Al corrodes minimum.

(e) Nature of ions present: Cu++ ions present in the vicinity of Fe, accelerate corrosion,
while silicates present in the vicinity resist corrosion.

(f) Conductance effect: Due to presence of salts and water in earth, it is of conducting
nature. More conductance leads to more stray current and hence fast corrosion. Dry sandy
soil is less conducting and hence less corrosion, while mineralized clay soil is more
conducting hence more corrosion occurs.

(g) Oxygen concentration and oxygen concentration cell: Oxygen is one of the important
element responsible for corrosion. It forms oxides and hydroxides (in presence of H 2O) on
the surface of metal as corrosion product. Oxygen concentration cell is formed on the
surface of metal due to difference in oxygen concentration (iron rod half dipped in water
corrodes due to this effect). Dipped portion will be anode and outer portion will be
cathode.

Methods of Corrosion Control

Material selection for corrosion control

The choice of the metal is not only based on cost but also on the chemical properties and its
environment.
1. Avoid dissimilar metals from coming in direct contact with each other.
2. If it is unavoidable to choose dissimilar metals, then anodic metal should have large
surface area as compared to cathodic area.
3. If two dissimilar metals are to be used, an insulator can be used to cut off the direct
contact between metals.
4. The metals selected should close to each other in the galvanic series.
5. The anodic metal should not be painted or coated.
6. Corrosion resistance can be improved by alloying.
7. Heat treatments like annealing reduce internal stresses.
8. Corrosion can be prevented by maintaining suitable pH.

Designing for corrosion control

The design should be such that corrosion if occurs should be uniform and non localized.
1. Proper design should avoid the presence of crevices between adjacent parts. Thus
the use of nuts and bolts is to be avoided and should be replaced by welding.
2. The design should allow adequate cleaning and flushing of critical parts. Thus
sharp corners and recesses should be avoided

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 3. Whenever possible, the equipment should be supported on legs to allow free
circulation of air.

Cathodic protection method

The principle involved in the process is to force the metal to be protected to behave like cathode
and thereby corrosion does not occur. They are of two types:
1. Sacrificial cathodic protection method. (galvanic protection method)

In this method, a more active metal like Zn, Mg is connected to the structure to be
protected. The corrosion is concentrated at the more active metal and thus saving the
metal structure from corrosion. The more active metal employed is called sacrificial
anode. The corroded block can be replaced.
Important applications of cathodic protection include:
(1) Protection from soil corrosion of underground cables and pipelines.
(2) Protection from marine corrosion of cables, ship hulls ,piers etc.
This method is used normally to protect pipelines carrying water or industrial wastes and
which are normally embedded under the soil thereby facing the conditions of soil
corrosion as well as microbiological corrosion. This is the method of choice where there
is no source of electricity and when a completely underground system is desirable .This is
most economical method for short term protection because the capital investment is low.

2. Impressed current cathodic protection:

In this method, an impressed current from external source is applied in opposite direction
to neutralize the corrosion current, and convert the corroding metal from anode to
cathode. Thus the anodic corroding metal becomes cathodic and protected from
corrosion. The impressed current is deriving from the external DC source. The negative
terminal of DC source is connected with metal to be protected whereas the positive
terminal of DC is connected to the anode. Here anode may be graphite, stainless steel
scrap iron etc. The impressed current protection method is used for water tanks, water &
oil pipe lines, transmission line towers etc.

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 Applications of impressed current cathodic protection:
This type of protection has been applied to buried structures such as tanks and pipelines,
transmission line towers, marined piers; laid up ships, open water box coolers etc.

Protective Coatings: Metallic coatings - anodic coating and cathodic coating

In order to protect base metal form corrosion metal coating process has been adopted. The
coating of metal can be achieved by following processes.

i) Anodic metal coating (Galvanization):

Metal coating which is anodic to base metal, known as anodic metal coating. In order to protect a
metal from corrosion, any metal (anodic in nature) which is higher in the galvanic series like Zn
is coated on the surface of metal (base metal/ cathodic in nature).

The best example of anodic metal coating is Galvanization. Galvanization is a process in which
coating of base metal (to be protected) takes place by dipping the base metal (cathodic in nature)
into the molten zinc (anodic in nature).

ii) Cathodic metal coating (Tinning):

Metal coating which is cathodic to base metal, known as cathodic metal coating. In order to
protect a metal from corrosion, any metal (cathodic in nature) which is lower in the galvanic
series like Sn, Cu, Ni etc, are coated on the surface of metal (base metal/ anodic in nature).

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The best example of cathodic metal coating is Tinning. Tinning is a process in
which coating of base metal (to be protected) takes place by dipping the base metal
(anodic in nature) into the molten Tin (cathodic in nature).

Anodic coating (galvanizing) Cathodic coating (Tinning)

1. Coating metal is anodic with respect 1. Coating metal is cathodic with respect
to base metal. to base metal.
2. Electrode potential of the coating 2. Electrode potential of the coating metal
metal is lower than the base metal. is higher than the base metal.
3. Coating of Zn on Fe. 3. Coating of Sn (Tin) on Fe.
4. Coating will protect the base metal 4. Coating will protect the base metal only
even if it is non uniform. when it is uniform.

Methods of Applying Metallic Coatings

1. Hot dipping
2. Metal spraying
3. Electroplating
4. Diffusion coating (Cementation)

1. Hot dipping

In hot dipping process, the metal to be coated is immersed in a bath of molten coating metal. The
molten coating metal is covered by a molten flux layer which prevents oxidation of molten
coating metal and cleans the surface of the base metal. It is used for producing a coat of low
melting metal such as zinc , tin, lead, aluminium etc. on iron, steel and copper which have
relatively higher melting points. The four steps involved in hot dipping are: Pickling, Fluxing,
Dipping and Wiping.
Two most widely applied hot dipping processes are

(a) Galvanizing: it is the process of coating iron or steel sheets with a thin coat of zinc to
prevent them from rusting. In this process the iron or steel article is first cleaned by
pickling with dilute HCl or dilute sulphuric acid solution for 15-20 minutes at 60-
90oC. this treatment helps in removing scale, rust and other impurities. The pickled
article is washed with water and dried. The article is dipped in a bath of molten zinc
maintained at 425-430oC. The surface of the bath is covered with a flux of
ammonium chloride to prevent oxide formation. (because clean metal surface

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 immediately tends to form oxide by reacting with atmospheric oxygen). The article of
sheet leaving the zinc bath gets coated with a thin layer of zinc metal. The surface of
the metal initially forms an alloy with zinc. On the alloy, zinc then gets deposited.
The coated sheet pass through a pair of hot rollers which removes excess zinc
deposited and makes the coating uniform and adhering. Finally the sheet is annealed
at a temperature of 650oC and cooled slowly. As zinc is anodic to iron, galvanizing is
the example of anodic coating.

Uses: Galvanizing is most widely used to protect roofing sheets wires, nails, bolts, screws,
buckets, tubes etc. from atmospheric corrosion. An important application of galvanization has
been the cathodic protection of aluminium and its alloys by zinc when subjected to sea water
spray and intermittent immersion in sea water.

Galvanized utensils should not be used for storing and cooking foods, especially acidic ones
because zinc dissolves in dilute acids to form highly toxic and even poisonous compounds.

(b) Tinning: it is another important hot dipping process in which iron and steel articles are
coated with tin. The process consists in treating steel sheet in dilute sulphuric acid (pickling) at
about 75oC for 3-5 minutes to remove any oxide films. After this, sheet is passed through a bath
of ZnCl2 flux which helps in adhering molten metal to the metal sheet. The sheet is passed
through a tank of molten tin. The sheet covered with molten tin passes through the series of
rollers immersed in palm oil bath. The palm oil protects the hot tin coated surface from
oxidation. The rollers remove any excess of tin and produce a thin film of uniform thickness on
the sheet. Palm oil is removed from the surface by absorption in bran saw dust etc. which in turn
are removed by brushing and finally sheets are polished with dry flannel rollers.

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Uses: Due to non toxic nature and resistance to atmospheric corrosion, tinning is widely used for
coating steel, copper and brass sheets. They are used for manufacturing containers for storing
foodstuffs, ghee, oils, kerosene and packing food materials. Tinned copper sheets are employed
for making cooking utensils and refrigeration equipments.

2. Metal or thermal spraying

Metal or thermal spraying (sometimes known as metallizing) basically involves the projection of
molten or heated particles from a suitably designed torch onto a prepared surface. The metal can
be in the form of a wire or powder and the heat can be supplied by either a gas flame or an
electric arc. In wire flame spraying, the oldest spray process, heat from combustion of oxy-
acetylene melts the wire and particles are stripped off by means of a stream of compressed air.
This atomises the material and propels it onto the work piece. The materials or metals with low
melting point can be used, which includes zinc and aluminium, so the process is widely used. It
is portable, easy to use and reasonably inexpensive but coatings exhibit lower bond strengths,
higher porosity and tend to heat the substrate more than other methods.
However, it is slow so a very expensive process. Metal spraying cannot be used for coating
cavities and other difficult areas and would not be economical for treating large, open structures
such as mesh, because of the large loss of metal that would result.

3. Electroplating.

In electroplating, electro-deposition of metal (anode) by means electrolysis over surface of

metals and alloys (cathode or base metal). The two electrodes are dipped in the electrolyte
solution which contains the metal ions to be deposited on the base metal. When a direct current is
passed from an external source, the coating metal ions migrate towards cathode and get
deposited over the surface of base metal in the form of a thin layer. In electroplating metal like
Au, Ag, Zn, Sn, Cr, Ni etc. can be placed on the surface of base metal (Cathode).

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4. Diffusion coating (Cementation)
Diffusion coatings or Cementation coatings are obtained by heating the base metal in a revolving
drum containing a powder of the coating metal. Coating metal diffuses into the base metal
resulting in the formation of layers of alloy of varying composition. The coating thickness is
controlled by varying the time of treatment and temperature. The process is suitable (for coating
small articles of uneven surfaces and intricate shapes (like bolt, screw, valves, gauge tools).

Sheradizing: This process consists in cementation of iron articles with zinc powder. The cleaned
ironed article is packed with zinc dust in a drum which is rotated slowly for 2-3 hours at a
temperature of 350-370oC. During this process, zinc diffuses into iron resulting in the formation
of iron zinc alloy at the surface.
It is used for protecting small articles like bolts, screws, nuts, washers etc. against atmospheric
corrosion. The main advantage of Sheradizing is that it imparts quite uniform coating, even if the
surface has crevices or depression.

Chromizing : it is carried out using a mixture of powdered chromium(55-60%)and alumina (40-

45%)at about 1300-1400oC for 3-4 hours. The use of alumina prevents coalescence of chromium
particles. Chromizing is extensively used for protecting turbine blades.

Calorizing : calorizing is carried out by first sand blasting the metal objects and heating them in
a tightly packed drum with a mixture of aluminium powder and aluminium oxide together with a
trace of ammonium chloride as a flux. Calorizing is used for protecting furnace parts, screws
and thread bolts. Calorized steel has also been used for making retorts, condensers, valves etc. in
petroleum refining and also in tubes of heaters, radiant steams super heaters etc.for heating
ferrous alloys.

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Organic coatings – Paints
Paint is defined as a mechanical dispersion of mixture of one or more pigment in a vehicle. The
medium or vehicle consists of non-volatile film forming materials like drying oils and resins in a
suitable volatile solvents called thinner. When a paint is applied to a properly treated metal
surface, the thinner evaporates leaving behind the film forming the materials and the pigments on
the surface. The mixture gradually dies into a solid film. Driers like metallic soaps (salts of fatty
acids with metals like lead, manganese, cobalt, zinc etc.) are added in case of drying oil to
accelerate film formation.

Requirements of a good paint:

1. It should form a good, impervious and uniform film on the metal surface so that
effective protection from corrosion is achieved.
2. It should have a high covering power.
3. The film should not crack on drying.
4. It should have a good resistance to the atmospheric conditions in which it is used.
5. It should have the required consistency for the required purpose so that it can be
spread on the metal surface easily.
6. It should have a glossy film.
7. It should give a stable and descent color on the metal surface.
8. The film produced should be washable.

Constituents of paints and their functions:

1.Pigments:
 It is the principal constituent.
 Gives opacity, colour and strength.
 Protects the paint from harmful UV rays.
Example: may be natural (clay, chalk, mica) or synthetic (ZnO, TiO 2)

2. Fillers or extenders:
 Acts as carriers for pigment colour.
 Reduce the cost of paint.
 Reduces the cracking and improves durability.
Example: talc, clay, asbestos.

3. Vehicle:
 Holds the pigment.
 Improves water repellency, durability, toughness.
 Improves adhesion.
Example: drying oils (dehydrated castor oil, linseed oil) or semidrying oils (soya bean oil, fish
oil)

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 4. Thinners:
 Suspends the pigment.
 Increases the elasticity.
 Helps in drying of the film.
Example: turpentine, kerosene.

5. Driers:
 Oxygen carriers.
 Catalyst for accelerating the drying of oil by oxidation and polymerization.
Examples: borates, linoleates, naphthenates of Pb, Co, Zn, Mn

6. Plasticizers:
 Provides elasticity.
 Prevents cracking of the film.
Example: Tertiary amyl alcohol, triphenyl phosphate, triglyceryl phosphate

7. Anti-skinning agents:
 Prevents the gelling and skinning of the paint.
Example: polyhydroxy phenols, guaiacol etc.

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