MODULE 4: CORROSION

Definition: Destruction or deterioration or disintegration of a metal by chemical or

electrochemical reaction with its environment is called corrosion.

Corrosion Metallic compound

(oxidation) Metal

Metallurgy (reduction)
A state of higher energy A state of lower energy
Type of environment:
The environment could be of any type such as atmosphere, water, sea water, acids, steam gases,
soils, liquid metals etc.
Examples of corrosion:
1. The most familiar examples of corrosion are rusting of iron when exposed to the atmospheric
conditions. During this a layer of reddish scale & powder of oxide (Fe3O4) is formed & the
iron becomes weak.
2. Another example is formation of green film of basic carbonate [CuCO3 + Cu(OH)2] the
surface of copper when exposed to moist air containing CO 2.

Basic requirement for corrosion:

For corrosion to proceed there must be an anode, a cathode and an electrolyte.

Atmospheric corrosion (Dry or Direct chemical corrosion)

Definition:
The surface of metals is directly attacked by the atmospheric gases such as O 2, CO2, H2S,
halogens of the medium & gets coated with corresponding compounds like oxides, carbonates,
sulphides, etc. Such type of corrosion which is brought about by the atmospheric conditions is
called atmospheric corrosion or direct corrosion.

There are three main type of chemical corrosion.

a) Corrosion due to oxygen.
Hydrogen
b) Corrosion due to other gases
Chlorine

c) Liquid metal corrosion.

a)Corrosion due to oxygen ( Oxidation corrosion) :-

1
Oxygen present in the medium directly attacks the metal surface at low or high temperature.

2M + O2 2MO {Metal + O2 + Metal Oxide}

The extent of corrosion depends upon the type of oxide film formed by metals.
Oxide films formed are classified into three categories,

Stable Unstable Volatile

Porous oxide film Non porous oxide film

(Non protective) (Protective)

1) Stable Oxide film:

A stable oxide film consists of fine grains in its structure & it can get adhered tightly to the metal
surface.

Metal + O2 further
Of air Metal attack through pores /
cracks continues
Fig: - Porous Oxide layer
Porous oxide film (Non protective) It
is of two types
Non porous oxide film (Protective)

The protective & non protective nature of the oxide layer depends mainly upon the “pilling
Bedworth Rule”.

Pilling Bedworth rule:

According to this rule, an oxide is protective or non porous if, the volume of oxide (film) is
at least as great as the volume of metal from which it is formed.
If the volume of oxide is less than the volume of metal from which it is formed, it will be
nonprotective as it cannot prevent the diffusion/access of oxygen to the fresh metal surface
below.

E.g: Porous oxide film.

Alkali metals such as Li, Na, K or alkaline earth metal such as Ca, Mg react with oxygen,
forming oxide such as Na2O, K2O, CaO, MgO etc.

2
E.g: Non- Porous oxide film. Metals like Al, Cr etc. form this oxide such as Al 2O3, Cr2O3 etc. 2)
Unstable Oxide film: - Where the oxide film formed is unstable & it decomposes back into
metal & oxygen.

Metal + Oxygen Metal oxide Metal + Oxygen

unstable

e.g. Oxides of metals like Gold, Silver, and Platinum etc. Hence metal forming unstable oxide
film does not get covered.

3) Volatile oxide film:-

When the oxide film formed is volatile it vaporizes as soon as it is formed, the underlying metal
surface is exposed for further attack of oxygen & thus causes continue & excessive corrosion.
e.g. Molybdenum metal form its oxide MoO3, which is volatile

Exposed surface porous metal oxide

Further attack
Metal Through
Metal Pores/ cracks
Continues.

Porous oxide layer

e.g. Molybdenum metal form its oxide MoO3, which is volatile.

b) Corrosion due to other gases:

Among the other dry gases which cause corrosion on metals are F2, Cl2, H2S, SO2 etc. The extent
of corrosion depends upon the chemical affinity between the metal & gas involved. The rate of
further corrosion depends upon the volume of the corrosion film & volume of the metal. e.g.
2Ag + Cl2 2AgCl

Sn + 2Cl2 SnCl4

Here the film of silver chloride is protective (non porous), hence the rate of further corrosion
reduces while that of stannic chloride is volatile in nature, hence rate of corrosion is enhanced.

i) Corrosion by hydrogen (hydrogen embrittlement):

This attacks the metals like Fe as

Fe + H2S FeS + 2H (atomic hydrogen).

3
The atomic hydrogen thus formed, penetrates the voids in metal by diffusion & gets
accumulated there & recombines to form molecules hydrogen.

H+H H2 (Molecular hydrogen)

The molecule hydrogen is trapped in voids & as in concentration increases, it causes blisters &
fissures in the metal, considerably lowering the strength & ductility of the metal. This is known
as hydrogen embrittlement.

ii) Hydrogen attack: At high temperature hydrogen attack is due to diffusion of atomic
hydrogen into metal. But atomic hydrogen is formed by the thermal dissociation of the
molecule hydrogen.

H2 heat H + H (Thermal dissociation)

The atomic hydrogen is chemically very active at high temperature & readily combines with C,
S, O and N usually present in small amount in metals. e.g. atomic hydrogen readily combines
with C in steel at high temperature with the formation of high pressure methane gas (CH 4) which
causes intergranular cracking fissuring or blistering in the metal.

C + 4H CH4↑

This is known as decarburization& is considerably reduces the strength of steel & causes
brittleness.

C) Liquids metal corrosion: (Corrosion due to other liquids)

If any liquid metal comes in contact with solid metal, a chemical action occur thereby dissolving
solid metal into liquid metal or liquid metal penetrates the solid metal. By both the actions the
solid metals get weakened & become brittle. Such type of corrosion has been found to occur in
devices used for nuclear power.
e.g: 1) liquid metal mercury dissolves some of the metals , forming amalgams, thereby corroding
them.
2) A coolent (Na metal) leads to corrosion of cadmium in nuclear reactor.

2. Immersed corrosion. (Wet or Electro chemical corrosion)

(Electrochemical Theory)
This type of corrosion occurs: I) when a conducting liquid is in contact with a single metal. II)
when two dissimilar metals/ alloys are either immersed or partially dipped in a solution.

Definition:

4
The corrosion which is brought about through ionic reaction in presence of moisture or solution
as a conducting medium is called electrochemical corrosion or immersed corrosion as it occurs
where they are immersed in the solution.

Essential are:-
i) The formation of anodic & cathodic part ii)
Presence of a conducting medium. iii)
Corrosion of anodic part only.
iv) Cathodic reaction can take place in two ways, I) By H2 evolution II) By O2 absorption v)
Formation of corrosion product between anode and cathode.

Mechanism of electrochemical corrosion

i) Evolution of Hydrogen :-
• This type of corrosion will take place if the medium is acidic.
E.g. A steel tank containing acidic industrial waste and a small piece of copper scrap in
contact with the steel.
Hydrogen Evolution Mechanism

- - - - - - - - H2- - - - - - - - - steel tank

- Fe++- H+- - - - --H+ - - - -
Fe- - Fe++ 2e-
+ ---------- acidic water
----- - -Fe++- - ------ -----

anode Small copper anode

(Cathode)
• Iron from steel forms Anode and undergo oxidation as follows, Anodic reaction: Fe
→ Fe2+ + 2e- (oxidation)
• Fe2+ is released in acidic water and electrons travel from anode to cathode.
• At cathode hydrogen ion from the acidic undergo reduction as follows,
Cathodic reaction: 2H+ + 2e- → H2 ↑ ( reduction)
• In hydrogen evolution type of corrosion cathode are small areas &anodes are usually
large areas, hence extent of corrosion is less.

ii) Absorption of Oxygen:

5
 • This type of corrosion will take place if the medium contains oxygen.
• E.g. rusting of iron.
• The surface of iron is generally coated with a thin film of iron oxide. However if this iron
oxide film develops some cracks, anodic areas are created on the surface of the exposed
iron metal while the rest metal surface forms the cathode & neutral aqueous solution like
NaCl acts as an electrolyte.
• At anode iron undergoes oxidation as follows,
Anodic reaction: Fe → Fe+2 + 2e- ( oxidation)
2+
• Fe is released in aqueous medium and electrons travel from anode to cathode. Dissolved
oxygen from electrolyte undergoes reduction as follows.
Cathodic reaction: H2O + 1/2O2 + 2e- → 2(OH) - (Reduction)

• The Fe+2 ions at anode & OH- ions at cathode combine to form compound
Fe++ + 2 OH- → Fe(OH)2 (brown rust)
If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide
2 Fe(OH)2 +1/2 O2 + H2O → 2Fe(OH)3↓
Yellow Rust
• If supply oxygen is limited the corrosion product is black anhydrous magnetite (Fe 3O4)
• Here the anodic area is smaller than the cathodic area thus the rate of corrosion is faster
as large cathodic areas demand more electrons and small anodic areas undergo corrosion
to greater extent.

Distinguish between Atmospheric corrosion and electrochemical corrosion.

Atmospheric corrosion/chemical corrosion Electrochemical corrosion

1 It occurs in dry condition. 1 It occurs in presence of aqueous solution

or electrolyte.
2 It involves the direct chemical attack on 2 It occurs through large number of galvanic
the metal by environment. cells.

6
3 It can be explained by absorption 3 It can be explained by electrochemical
mechanism. reaction mechanism.
4 Corrosion products accumulate at the 4 Corrosion products accumulate at the
same spot where corrosion starts. cathodic area. Hence, further corrosion
Hence, further corrosion is prevented. occurs.
5 It is a slow process. 5 It is a rapid process.
6 It occurs on both homogenous and 6 It occurs on heterogeneous surfaces.
heterogeneous surfaces.
7 Corrosion is uniform. 6 Corrosion is not uniform.

Different Types of corrosion

1. Galvanic Corrosion (Bimetallic corrosion):- Definition:

When two metallic materials (dissimilar metals) are electrically connected and exposed to an
electrolyte, the metal occupying higher position in electrochemical/galvanic series undergoes
corrosion, is called ‘galvanic corrosion’. Explanation:
When two dissimilar metals as Zn & Cu are electrically connected & exposed to electrolyte. Zinc
which is higher in electrochemical series forms the anode & undergoes corrosion (attacked & get
dissolved) while copper which is lower in electrochemical series acts as the cathode and is
protected from corrosion. This type of corrosion is known as galvanic corrosion. It is wet or
electrochemical corrosion.

Zn Zn++ + 2e- (oxidation)

Examples:
1. Copper sheet joined by iron nails.
Steel screw in marine brass hardware.
Role of metallic impurities in Galvanic Corrosion:
• The metal in pure state corrodes to a very small extent. But when the metal contains metallic
impurities, the degree of corrosion is very high.

7
• The corrosion of metals in presence of other metallic impurity depends upon their position in
electrochemical series. The metal which is anodic will get corroded while cathodic metal will
remain unaffected.
• E.g: If a plate of zinc is placed in dilute acid solution, it will not corrode, while if zinc
contains iron as impurity, zinc corrodes to larger extents, since iron is cathodic to zinc. Thus
presence of cathodic impurities increases the rate of corrosion of metals. If the metal contains
more active metal as an impurity (anodic), then the corrosion of the metal can be prevented.

2. Concentration cell corrosion (Differential aeration corrosion.)

• This type of corrosion occurs when one single metal is exposed to different concentration of
electrolyte or air.
•
• Differential aeration: It is the most important type of concentration cell corrosion which
occurs when one part of a metal is exposed to a different air concentration from the other part
of the metal.
• As a result, difference in the potential takes place between differently aerated areas. It has
been found experimentally that poor oxygenated (poorly aerated) parts of metals are
anodic and highly oxygenated (highly aerated) parts of metal are cathodic.
• Example:

• If a piece of metal say Zinc is partially immersed in dilute solution of a salt NaCl & the
solution is not mixed properly, the parts above & closely adjacent to the water line are most
strongly aerated because of the easy access of oxygen to this area & hence become cathodic.
• On the other hand, parts immersed to greater depth have less access of oxygen & so they are
poorly aerated i.e. they show a smaller oxygen concentration & thus become anodic.
• As a result difference of potential is created which is responsible for the flow of current
between two differently aerated areas of same metal Zinc.
• Zinc will dissolve at the anodic area & oxygen will take up electrons at the cathodic area to
form hydroxyl ions.
• The reactions involved are as follows,

Zn → Zn++ + 2e- (Oxidation)

8
 ½ O2 + H2O + 2e- → 2OH- (reduction)

• The circuit is completed by migration of ions, through the electrolyte & flow of electrons
through the metal from anode to cathode.

Pitting corrosion:
• Pits are holes or cavities that are developed on the metal surface when the protective oxide
film breaks.
• Around such pits, small anodic and cathodic areas are formed. Due to this corrosion is
accelerated in localized area known as pitting corrosion.
• Pits may also be formed due to surface roughness, scratches, sliding under the load, action of
some chemicals etc.
• When such pits are covered by a drop of water or impurity (dust, dirt, scale), anodic and
cathodic areas are formed. The part under the drop of water acts as an anode as it is poorly
oxygenated, while the remaining portion of the surface forms cathode.
• Eg. Iron rod under drop of water/ dust/ sand/ scale.

• At anode iron undergoes oxidation as follows,

Anodic reaction: Fe → Fe+2 + 2e- ( oxidation)
2+
• Fe is released in aqueous medium and electrons travel from anode to cathode. Dissolved
oxygen from electrolyte undergoes reduction as follows.
Cathodic reaction: H2O + 1/2O2 + 2e- → 2(OH) - (Reduction)

• The Fe+2 ions at anode & OH- ions at cathode combine to form compound
Fe++ + 2 OH- → Fe(OH)2 (brown rust)
If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide
2 Fe(OH)2 +1/2 O2 + H2O → 2Fe(OH)3↓
Yellow Rust
• If supply oxygen is limited the corrosion product is black anhydrous magnetite (Fe 3O4)

9
 Waterline corrosion:

• It is observed in a steel tank containing stagnant(unmoving) water for a long time.

• The area above the waterline is highly oxygenated, hence behaves as cathode. While the area
just below the water meniscus is poorly oxygenated hence behaves as an anode.

• Maximum corrosion of the part just below the waterline takes place as follows:
• At anode iron undergoes oxidation as follows,
Anodic reaction: Fe → Fe+2 + 2e- ( oxidation)
• Fe2+ is released in aqueous medium and electrons travel from anode to cathode. Dissolved
oxygen from electrolyte undergoes reduction as follows.
Cathodic reaction: H2O + 1/2O2 + 2e- → 2(OH) - (Reduction)

• The Fe+2 ions at anode & OH- ions at cathode combine to form compound
Fe++ + 2 OH- → Fe(OH)2 (brown rust)
If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide
2 Fe(OH)2 +1/2 O2 + H2O → 2Fe(OH)3↓
Yellow Rust
• If supply oxygen is limited the corrosion product is black anhydrous magnetite (Fe 3O4)

• The rust is deposited at waterline hence the corrosion is called waterline corrosion.

• This corrosion is a serious problem of ocean going ships which can be prevented by painting
the sides of ships by special antifouling paint.

3. Intergranular Corrosion

• Smaller subunit of an alloy or metal is called as grains.

10
 • Each grain consists of all the constituents of the alloy.
• All the grains of a given metal/alloy have identical arrangement of atoms.
• This type of corrosion occurs along the grain boundaries where the material is sensitive
to corrosion attack (anodic) as compare to that at the centre in particular corrosion
medium. .

• Example: During welding of stainless steel (which is the alloys of iron, chromium,
carbon)
• Chromium Carbide gets precipitated at the grain boundaries.

Cr + C → CrC
• Thus the concentration of chromium at the grain boundary decreases therefore becomes
more anodic to the grain centre & also to the precipitated chromium carbide.
• Hence corrosion takes place at grain boundary.
• The grain boundary corrosion is a microscopic attack without any apparent external
signs.
• Hence in most of the cases without any pre warning sudden failure of material occurs as
cohesion between the grains is lost during corrosion.
• This type of corrosion can be avoided or controlled to a greater extent by proper heat
treatment during the formation of an alloy material followed by rapid cooling to avoid
the precipitation of a compound of alloying elements (like CrC) which normally takes
place with slow cooling.
• It can also be avoided by using steels with less carbon content or by inclusion of
titanium.
• Hence by taking precaution during manufacture of alloy intergranular corrosion can be
avoided.

Stress Corrosion

• Stress corrosion or stress cracking is due to the presence of stress caused by heavy
working like rolling, drawing or insufficient annealing.
• This type of corrosion is the combined effect of static tensile stress and the corrosive
environment like,

11
 Strong caustic alkalis or nitrates (which affected mild steel)
Traces of ammonia (Affecting brass)
Marine water or H2S gas or solution of acid halides (chlorides particularly) affecting
stainless steel etc.
• Stress corrosion is probably due to localized electrochemical reaction, forming local
anodic & cathodic areas on the metal surface.

• Some typical examples of stress corrosion are,

Season cracking: It occurs in brass alloys (Cu + Zn) when exposed to ammonia (such as
cartridge cases). Because Cu and Zn react with ammonia to form complex ions of
Cu(NH3)4 +2 and Zn(NH3)4 +2. This causes dissolution of brass which initiates the
formation of fissures that ultimately propagates which leads to formation of cracks in the
presence of high tensile stress.
Caustic embrittlement: This is the most dangerous form of stress corrosion which
occurs in mild steel when it is exposed to alkaline solution at high temperature as well as
stress. Following reaction takes place,
Na2CO3 + H2O → NaOH + CO2
• The NaOH(caustic soda) flows into small cracks in the steel by capillary action.
• As the water evaporates the concentration of NaOH increases which reacts with Fe
present in steel and corrodes it.

Q. What is polarization of electrodes?

• The driving force of an electrochemical corrosion is the potential difference between

anode and cathode. And the corrosion rate is controlled by the current flowing in the
circuit.
• Any factor that decreases the potential difference between the electrodes decreases
the current flow and thereby decreases the rate of corrosion.
• The corrosion current is reduced due to back e.m.f, which is due to formation of small
concentration cell. This phenomenon is called polarization.
• Polarization of the electrodes is due to concentration changes in the electrode region,
overvoltage and presence of surface film.

12
 • Therefore, polarization decreases the rate of corrosion.

FACTORS INFLUENCING CORROSION:

A) Nature of metal:

1)Position of metal in galvanic series(oxidation potential):-

• The extent of corrosion depends upon the position of metal in the galvanic series.
• If the position of the metal in the galvanic series is higher, it acts as an anode and
corrodes faster.
• Further, for two metals if the difference in their position in galvanic series is large faster
will be the corrosion of anodic metal.
• Metals close to each other in the galvanic series show fewer tendencies to corrode when
in contact with each other.

2) Potential difference:
Greater the difference in the electrode potential between the two metals in contact, higher is the
rate of corrosion.

3) Purity of metal (impurities):-

• Pure metals do not undergo corrosion.
• If the metal itself contain impurity, tiny galvanic cell can be set up easily. This increases
rate of corrosion.
• The effect of impurities on the rate of corrosion of Zinc can be seen from the following
table.

Metal % purity Corrosion rate(comparative)

Zn 99.999 1
Zn 99.99 2650
Zn 99.95 5000

4) Relative areas of cathodic & anodic parts:

Rate of corrosion α Area of cathode

Area of anode
• When two dissimilar metals are in contact, “the rate of corrosion is directly
proportional to the ratio of areas of cathodic part & anodic part.

13
 • This is because when the cathodic area is larger, demand for electrons is more. To
meet this demand anodic area undergoes faster corrosion. Thus smaller the area of the
anode faster is the rate of corrosion.
• E.g: steel screw (small anode) in copper plate (large cathode) gets completely
corroded in corrosive environment.

5) Nature of corrosion product (oxide film):

• Metals form oxide film on their surface by corrosion due to oxygen.
• This film can be stable, unstable and volatile.
• The stable film can be porous or non-porous in nature.
• If the film is non-porous, the underlying metal is prevented from further corrosion since
the film act as a protective covering. E.g:- Metals like Al, Cr etc. form this oxide such as
Al2O3, Cr2O3 etc.
• On the other hand if the film is porous further attack of oxygen is possible. E.g:- Na, K
Ca, Mg react with oxygen, forming porous oxide film such as Na2O, K2O, CaO, MgO
etc.
• Where the oxide film formed is unstable & it decomposes back into metal & oxygen.e.g.
Oxides of metals like Gold, Silver, and Platinum etc.
• If the corrosion product is volatile, it evaporates as soon as it is formed, there by leaving
the underlying metal surface exposed for further attack. E.g MoO 3, the oxidation
corrosion product of Mo is volatile.
Solubility of corrosion products:
• If the corrosion product is soluble in the corroding medium, then corrosion proceeds at a
faster rate.
6) Physical state of metal:-
• The rate of corrosion is influenced by physical state of the metal (such as grain size
orientation of crystals, stress etc.) For instance the smaller the grain size of the metal or
alloy the grater will be the solubility & greater (as compared to the macroscopic crystals)
will be its corrosion.

• The corrosion rate may also be influenced by the orientation of crystal at the metal
surface e.g. the corrosion rate of copper ions was found to be different on different faces
of a pure copper crystal. Moreover areas under stress, even in a pure metal tend to anodic
& corrosion takes place at these areas. This is due to the fact that “atoms of a metal at the
boundaries having electrode potential different than that of the atoms in the proper grain
size. Consequently anode & cathode is developed.
•
The grain boundaries zone may be considered to be stressed since atoms are not at their position
at lowest energy state. Similarly the electrode potential of stressed metal is lower than that of
annealed metal.

6) Over voltage:-
Overvoltage is the difference between the actual and theoretical value of decomposition potential
of the electrode.

14
For the evolution of hydrogen gas, this potential difference is called hydrogen overvoltage.
Higher the overvoltage lesser is the rate of corrosion.
E.g. If pure Zn is placed in 1N H2SO4 it undergoes corrosion at very slow rate because of the
high overvoltage (about 0.7V). However if few drops of copper sulphate (CuSO 4) are added, the
corrosion rate of Zn accelerates because some copper gets deposited on the Zn metal forming
minute cathodes and over voltage drops to 0.33V. Thus the reduction in the over voltage plays
on important part in accelerating corrosion

B) Nature of the environment:-

1) Temperature:
• The rate of corrosion increases with temperature, because ionization, mobility and
diffusion rate of reacting ions & molecules increases.
• However solubility of gases such as O2 which affect corrosion decreases with
temperature so in some environment rate of corrosion is less at high temperature.

2) Presence of moisture: (Humidity of air)

• Atmospheric corrosion of iron is slow in dry air but increases rapidly in the presence of
moisture.
• This is because moisture acts as the solvent for setting up an electrochemical corrosion
cell.
• Nature of moisture source also plays an important role.

3) Effect of pH:
• Acidic media are generally more corrosive than alkaline & neutral media.
• In acidic media corrosion takes place by evolution of H2 gas at the cathode, while in
alkaline media the corrosion takes place by absorption of O 2, thereby forming oxide film,
which gets adhered to the metal surface and further the rate of corrosion is governed by
the nature of oxide film.
• E.g: Zinc is rapidly corroded even in weakly acidic solution such as carbonic acid and
suffers minimum corrosion at PH 11.

4) Concentration of electrolytes/Formation of oxygen concentration cells:

• The rate of corrosion increases with increasing supply of oxygen or air on the most metal
surface.
• Poorly oxygenated part becomes anodic where the corrosion occurs. The highly oxygenated
part becomes cathodic and no corrosion occurs.
• Both anodic and cathodic areas lead to the formation of oxygen concentration cell. The
reactions involved are as follows,

Fe → Fe++ + 2e- (Oxidation)

½ O2 + H2O + 2e- → 2OH- (reduction)

Thus formation of oxygen concentration cell promotes corrosion at anode.

15
5) Presence of impurities in atmosphere:-
Atmosphere in the vicinity of industrial areas contains corrosive gases like CO2, H2S, SO2&
fumes of HCl, H2SO4 etc. In presence of these gases the acidity of the liquid adjacent to the
metal surface increases & its electrical conductivity also increases. This consequently results in
an increase of corrosion current flowing in the local electrochemical cells on the exposed metal
surfaces. Similarly in the marine atmosphere presence of sodium & other chlorides leads to
increased conductivity thereby corrosion is speed up.

6) Nature of ions :- (anions & cations)

Chlorides ions present in the medium destroy the passive film & corrode many metal & alloys.
On the contrary, some anions like silicates may form an insoluble reaction product (eg silica gel)
which inhibits corrosion. Traces of cell or more noble metals accelerate the corrosion of the irons
pipes carrying mine water. Many metals including iron corrode more rapidly in ammonium salts
than in sodium salts of identical concentration.

7)Conductance of the medium:-

The conductance of the medium is of profound importance in the corrosion of underground or
submerged stricture because of the corrosion current depends on this factor. Conductance of clay
& mineralized soils is higher than that of dry & sandy soils. Hence stray current from power
leakage will damages the metal structure buried under soils of higher conductance to a greater
extent than these under dry sandy soils having higher resistance.

Prevention & control of corrosion

The following are the methods which can be used either singly or in combination in order to
protect the metals from corrosion.

Proper selection of materials and

Improvement of design (proper design)
Use of inhibitors.
Use of alloys/ Pure metal.
Cathodic & Anodic protection
Application of protective coating. e.g. i) Metallic coatings & ii) Organic coatings.

Proper selection of materials

Proper selection of material:

16
Proper selection of material is the main factor for corrosion control. This can be done by taking
following precaution.

1. Avoid contact of dissimilar metals especially if the working environment is

corrosive. Example:- Joining different part to make a ship, if iron metal strips are used to
join the wooden parts together & of screws used are of brass ( Cu & Zn alloys) when ship
floats on marine water , localized corrosion enhanced tremendously & highly active
metal starts (Zinc) acting as anode.
2. Suppose if it is unavoidable to choose two dissimilar metals, then area of anodic metal
should be larger than that of cathodic metal.
3. If two dissimilar metals are to be selected, then metals should be chosen in such a way
that they are as close as possible in the galvanic series.
4. When two dissimilar metals are required to be joined their direct contact should be
avoided by inserting a piece of hard plastic or rubber into the joint. The piece acts as
an insulator & current flow should be reduced & minimizes galvanic corrosion.
5. When two dissimilar metals are used in contact the anodic metal should not be
painted or coated. Any crack lead to rapid localized corrosion.

2. Proper designing:
• Corrosion resistance of metal parts or machines can be improved by improving the
design.
• The design of the metal should be such that “corrosion even if it occurs is uniform &
does not result in intense & localized corrosion.
• A better design should always avoid sharp bends, corners, projected parts etc.
• As far as possible use of screws, nuts, and bolts should be avoided, rather welding can be
used since welded joints do not allow the entry of gases & liquids inside, which cause
corrosion.
• As far as possible metal washer should be replaced by rubber or plastic washer as they do
not absorb water & do not generate galvanic couples.
• The surfaces of two joining parts should be as smooth as possible, which avoids
accumulation of the corrosive liquids, suspended particle, dust, dirt. The equipment
should be kept free from dust & dirt to reduce rusting due to pitting & differential
aeration effect.
• Wherever possible the equipment should be supported on legs instead on large block to
allow free circulation of air & prevent the formation of damp areas. Design of joints
should be such that the chance of water entering inside is limited.

17
5. Cathodic & Anodic protection:

1) Cathodic protection:
• The principle involved in this method is to force the metal to be protected to behave like
a cathode, thereby corrosion does not occur.
• There are two types of cathodic protections:
i) Sacrificial anode method
ii) Impressed current method

a) Sacrificial anode method:

• In this protection method, the metallic structure to be protected is connected by a wire to a

more anodic metal, so that all the corrosion is concentrated at this more active metal.
• The more active metal itself gets corroded slowly, while the parent structure is protected.
• Since the more active metal sacrifices itself, by undergoing corrosion and saving the base
metal, the method is named as Sacrificial anode method or auxillary anode method.
• When the piece of more active metal gets corroded completely, it is simply replaced by new
piece.
• Most of the common sacrificial anodes are based on the alloys of magnesium, zinc and
aluminium which are placed above iron in electrochemical or galvanic series.
• Applications of this method are seen to protect cables or iron pipelines, by connecting them
to Mg- block and in case of marine structures ships are protected by using Zn-plates as
sacrificial anode. Even water tanks, boilers are protected by using Zn metal.

18
b) Impressed current method:

• During corrosion, electrons flow from anode to cathode and corrosion current flows from
cathode to anode.
• In this method, an impressed current is applied in opposite direction to that of corrosion
current; thereby nullify the effect of corrosion current, and converting the corroding
metal from anode to cathode.
• In this method, the insoluble material (Like stainless steel, platinum, scrap iron, graphite
or high silica iron) is usually kept in backfill made up of gypsum or any such material,
which can help in increasing electric contact with soil.
• This insoluble material is buried underground. Usually D.C. current by using battery or
dry cell is applied to it and it is then connected to the structure to be protected.

• As a result of impressed current, the burried material starts acting as anode and
deteriorates and the structure to be protected acts as cathode.

19
 • The burried anode has to be replaced periodically.
• This anode may be single (as in simple applications) or many anodes (as in pipe lines).
Applications:
• This type of cathodic protection by impressed current is applied to open water box
coolers, water tanks, buried water or pipelines, condensers, transmission line towers,
marine piers, laid-up ships etc.

2) Anodic protection:

• This is another important form of corrosion control in which the anodic metal is made
more anodic ( passivated) by applying current.
• In this the basic principle involved is to grow a protective oxide film on the surface of
anodic metal. This phenomena is called passivity.
• This method can be used for only those metals which exhibit passivity like Fe, Cr, Al and
Ti.
• Thus the principle involved is to increase the passivity of the base metal by applying
current in the direction in which the metal would become more anodic.

The schematic arrangement for anodic protection is as shown in the fig.

To protect structure anodically, a device called ‘potentiostat’ is used. Potentiostat is a device to
maintain the metal at constant potential with respect to the reference electrode. A potentiostat has
three terminals, one is connected to the structure that is to be protected, and the other connected
to platinum electrode and the third to a reference calomel electrode. The metal specimen to be
protected is kept in a suitable oxidizing atmosphere and acts as a working electrode (anode). The
potentiostat maintains a constant potential between the specimen to be protected and the
reference electrode. Due to the constant potential, meta to be protected is passivated(covered
with a thin protective film).
Advantages of anodic protection:

20
 1) Low operating cost
2) Applicability to wide range of corroding environment.
3) Ability to protect complex structures.
4) Needs few auxiliary or sacrificial electrodes.

Disadvantages of anodic protection:

1) Suitable for only those metals and alloys, which show passivity.
2) High installation cost requiring a potentiostat, reference electrode and auxiliary electrode. 3)
If the system goes out of control, high corrosion rate may occur..

Distinguish between cathodic and anodic protection.

Cathodic Protection Anodic Protection

1 1 This method is applicable to only those
This method is applicable to all metals. metals which show passivity.

2 Useful for weak or moderate 2 More aggressive corrosive environments

environments can be handled.
3 Lower installation costs but higher 3 Higher installation costs but lower
operating cost. operating costs.
4 Applied current cannot give any indication 4 Applied current gives an indication of
of corrosion. corrosion rate.

6. Application of protective coating.

In order to protect the metal from corrosion effects, it is possible to cover their surface in various
ways.
The main types of protective coatings may be classified as
1) Metallic coatings and, metallic cladding
2) Non-metallic coatings
3) Organic coatings

1) Metallic coatings:

Metallic coatings can be divided into anodic and Cathodic coatings. The metal to be protected
is
called the base metal; whereas the metal used for protection is called the ‘coating metal’.

a. Anodic coating (coating with more active metal)

• For example coating of zinc on steel.
• If any cracks, pores or breaks occur in such anodic coatings, a galvanic cell is formed
between the coating metal and the exposed part of base metal.
• Zinc, being anodic to iron forms anode and will dissolve.

21
 • The iron being Cathodic is protected.
• Thus, no attack on iron occurs until practically all the zinc first corroded in the vicinity of
exposed iron parts. Hence, zinc coating protects iron “sacrificially”.

Cathodic coatings:

• For example coating of tin on steel.

• If any cracks, pores or breaks occur in such Cathodic coatings, a galvanic cell is formed
between the coating metal and the exposed part of base metal.
• Iron , being anodic to tin forms anode and undergoes corrosion.
• The tin being Cathodic is protected.
• Thus, if such coatings are broken or punctured much more damage can be done to a base
metal .

Methods of applications of metal coatings:

The protective metallic coating can be made by the following methods:

1) Hot dipping - a) Galvanizing b) Tinning
2) Metal spraying
3) Sherardising 4) Electroplating 5) Metal cladding.

)Hot dipping A)
Galvanizing:
It is a process of coating the base metal, like iron or steel, with appropriate thickness of zinc
coating, to prevent the base metal from corrosion. Zinc being more electropositive than iron, in
electrochemical series, becomes anode, Fe forms cathode and remains unaffected, thus it is
prevented from undergoing corrosion. The method is used for coating iron or steel sheets, wires,
tubes etc. for the purpose.

Process:
• The process of galvanizing involves initial cleaning of base metal articles by pickling it in
the solution of dilute sulphuric acid at 60 to 90oC for 10 to 20 minutes to remove any
adherent scale, rust and any other impurities. It is then thoroughly washed with water and
dried.
• It is then dipped in the bath of molten zinc maintained at 425-430 oC.
• The surface of the bath is kept covered with a flux of ammonium chloride to prevent any
oxidation. On taking out the sheet, it is found to be covered with zinc.
• To make the coating more uniform it is next passed through a pair of hot rollers, which
removes any excess deposit.

22
 • Finally the sheet is annealed at a temperature of 6500C and then cooled slowly to room
temperature to improve its machinability (see fig. below)

Applications:
The process of galvanizing is commonly used for coating the iron or steel sheets, tubes, pipes,
screws, nuts, bolts and wires for protection against corrosion.

Advantages:
Zinc offers better protection against corrosion because even if any cracks are developed over the
film of deposit, at a later stage, zinc being more reactive than iron or steel, undergoes corrosion
keeping the base metal article unaffected.

Disadvantages:
Galvanized zinc coated utensils or containers can not be used for preparing or storing food stuffs,
particularly those which are acidic in nature. This is because zinc dissolves to form poisonous
zinc compounds which are injurious to human health.

B) Tinning:
It is similar to that of galvanizing i.e. it is also a process of hot dipping. Tinning is a process of
converting iron or steel articles with a thin coating of tin, to preventing it rusting.

Process:
• The article to be coated is first cleaned by pickling in dilute sulphuric acid for the
removal of rust and any other impurities (if any) followed by through washing with
water.
• Then the article is dipped in the bath of molten zinc chloride flux which helps molten
metal to get adhered to the base metal.
• The article is next dipped in molten tin. And finally after passing through a layer of palm
oil (which prevents oxidation) the steel sheet comes out which is found to be coated with
a layer of tin
• It is then passed through a pair of hot rollers to make the deposit more uniform and to
remove any excess deposit. (see fig. below)

23
Applications:
1. Tin coated sheets are used for making trunks, boxes, for containers of petroleum products
etc.
2. Copper wires are tinned to facilitate soldering.
3. Copper wire is usually tinned first to protect it from the attack of rubber insulation.
4. The tinned copper sheets are used for cooking utensils, refrigeration equipment and
copper tubes used in refrigerators.

Advantages:
Tin coated containers can be used for preparing and storing food stuffs, chemicals etc., as tin
do not form any poisonous products with such acidic materials.
Tin forms a better protective coating than that of zinc.

Disadvantages:
1. Tin only provides a mechanical protection against corrosion. It acts as a cathode to more
active metal like iron and so. If any cracks are developed in the protective layer, then more
rapid corrosion takes places the underlying exposed metal becomes anode.

Distinguish between galvanizing and tinning:

Galvanizing Tinning

1 It is the process of coating iron or steel 1 It is a process of coating steel sheets with a
sheets with a thin coat of zinc by hot thon layer of tin to prevent them from
dipping to prevent them from rusting corrosion.

24
2 Zinc metal protects iron as it is more 2 Tin protects the base metal as it is less
anodic to iron. electropositive than iron. It is more resistant
to chemical attack.

3 Zinc continues to protect the metal by 3 In tinning, tin protects the metal till the
galvanic action, even if the coating is coating is perfect. A break in coating causes
broken. rapid corrosion.

4 Galvanized container cannot be used 4 Tin containers can be used for storing acidic
for storing acidic food stuffs, as acids food stuffs as tin does not form any
react with zinc to form poisonous poisonous products.
compounds.

25
26