- Prof.

Priyanka Patil
Corrosion
• Introduction
• Causes
• Classification
• Atmospheric corrosion ( Oxidation corrosion )
• Electrochemical Corrosion ( Hydrogen evolution and Oxygen absorption
mechanism)
• Factors affecting rate of corrosion
• Prevention of corrosion by proper design and material selection
• Protection from corrosion ; Cathodic protection
Anodic protection
Corrosion –
corrosion can be defined as the loss of materials as a result of
chemical or electrochemical reaction with the environment.
• The annual cost of corrosion in India is around Rs. 600 crores.
The loss due to corrosion include the cost of repair or replacement of the
corroded component or equipments.
• By making proper use of existing corroded materials and techniques for
corrosion prevention, about 25% of the estimated amount (Rs. 150 crores
in India) can be saved.
• Now a days it is necessary to pay more attention to corrosion because of
increasing use of metals in all fields of technology and increase in air and
water pollution there by resulting in a more corrosive environment.
Definition :
Metals combines with oxygen gives metal oxide is called
corrosion. E.g Iron rust
Destruction of metals (or) deterioration of metals by the attack of
environment is called corrosion. Corrosion (irreversible process) is a natural
process
Causes of corrosion;
Metals occur in nature are in the following two forms :
1. Native state
The metals occur in native (or) free (or) uncombined state are non-reactive
with the environment. They are noble metals exist as such in the earth crust
they have very good corrosion resistance.
Example : Au, Pt, Ag, etc.
2. Combined State
Except noble metals, all other metals are reactive and react with environment
and form stable compounds, as their oxides, sulphides, chlorides, and
carbonates. They exist in their form of stable compounds called ores and
minerals.
Example : Fe2O3, ZnO, PbS, CaCO3, etc.
The metal ores are converted into pure metal by the use of metallurgical
process. The pure metal at higher energy will always have a tendency to go
into the lower energy state by the attack of environment is called corrosion.
Metallurgical Process
(Reduction)
Metal ore Pure metal
(Impure form) (Higher energy state)

(more Stable) Corrosion (less stable)

(Oxidation)
Some of the main and popular causes of corrosion are as follows:-
• Too much humidity or condensation of water vapour on metal surfaces are
the primary causes of corrosion.
• Corrosive gases such as chlorine, hydrogen oxides, ammonia, sulfur
oxides, amongst others can result in corrosion of parts of electronic
equipment, etc.
• Corrosion can also occur due to hydrogen and oxygen exposure.
• Corrosion in steel can occur when it is placed under too much stress and
the material develops a crack in it.
• Metals exposed to electrical currents for a long time can experience
electronic corrosion.
• Exposure to dirt and bacteria can cause corrosion in metals.

CLASSIFICATION OF CORROSION-
The corrosion process is classified on the basis of
mechanisms.
(i) Dry corrosion (or) Chemical corrosion/ atmospheric corrosion-
(ii) Wet corrosion (or) Electro chemical corrosion-
• Dry Corrosion (or) Chemical Corrosion-
This type of corrosion occurs through direct chemical
action of environment /atmospheric gases (or) corrodents such as oxygen,
halogen, H2S, SO2, etc.,
There are three main types –
1. Oxidation corrosion.
2. Corrosion by other gases .
3. Liquid metal corrosion.

1. Oxidation corrosion./Corrosion by oxygen-

Oxygen present in the atmosphere attacks metal
surface resulting in the formation of metal oxide which is known
as corrosion product and this process is known as oxidation
corrosion.
At ordinary temperature, metals in general are very slightly attacked.
However alkali metals ( Li,Na,K,Rb) and alkaline earth metals
(Be,Ca,Sr etc) are even rapidly oxidised at low temperature. At high
temperature almost all metals ( expcet Ag,Au,Pt) are oxidised.
Mechanism-
Oxidation first occurs at the surface of the metal resulting
in the formation of metal oxide scale forms a barrier that tends to
restrict further corrosion.
For oxidation to continue , either the ,metal must diffuse outward through
the scale to the surface or oxygen must diffuse inward through the scale to
the underlying metal. But the outward diffusion of metal is generally much
more fast than inward diffusion of oxygen.
Nature of oxide formed plays an important role in oxidation corrosion
process.
Metal + Oxygen Metal Oxide ( corrosion product)
Nature of the metal oxide films formed -
There are generally four types of metal oxide films are formed.
i) Stable film -
If the oxide film is stable, there is no further penetration of oxygen
ions to the metal part. There is no further corrosion takes place. Thus the
stable film act as protective coating.
Examples : Al, Sn, Pb, Cu, etc.
(ii) Unstable film -
In the case of noble metals the metal oxides formed decomposes
reversibly to the metal and oxygen.
Metal + Oxygen Metal oxide
In this case, oxidation corrosion is not possible.
Examples : Pt, Ag, Au, etc.,
(iii) Porous film -
The oxide layer formed in some cases are porous. In this case
atmospheric oxygen can easily move to the metal surface.So corrosion is a
continuous process.
Examples : Li, Na, K, etc.,

(iv) Volatile film -

The oxide layer formed in some cases are volatile. So the oxide film
volatises as soon as they are formed. The fresh metal surface is kept exposed
all the time for further attack. Thus it act as a non-protective coating.
Example : Molybdenum oxide film.
Pilling - Bed Worth rule -
• An oxide layer is protective (or) non-porous, the volume of the metal
oxide formed is greater than the volume of the metal.
• An oxide layer is non-protective (or) porous, the volume of the metal
oxide formed is less than the volume of the metal.
-Protective layer metals e.g., Al, Sn, Pb, Cu, etc,.
-Non protective metals e.g., Li, Na, K, Mg, Ca, Sr, etc,.
2.Corrosion by other gases -
Other gases present in the atmosphere like SO2, CO2, Cl2, H2S etc,. can
also attack the metals.
For example,
1. Chlorine attacks on silver forms protective layer of silver chloride, it
prevents further corrosion.
Cl2 + 2 Ag 2AgCl
2.But Sn reacts with chlorine present in the atmosphere forms SnCl2.It is
volatile. So the corrosion is a continuous process.
Cl2 + Sn SnCl2
3.Metals combines with H2S gas to liberate atomic hydrogen
H2S + Fe FeS + 2H
The atomic hydrogen is very reactive and penetrate the metal and occupies
the voids of the metal.The atomic hydrogen recombines inside the metal and
develop pressure which leads to cracking of the metal. This is known as
“ Hydrogen Embrittlement”
3 . Liquid metal corrosion -
This type of corrosion is due to the chemical action of flowing liquid
metals at high temperature on solid metal. Such type of corrosion are found
in nuclear power plants.

• Wet Corrosion (or) /Electrochemical Corrosion -

This type of corrosion occurs when,
(i) The conducting electrolytic liquid is in contact with metal.
(ii) Two dissimilar metals are partially dipped in the electrolyte.
In the above condition one part of the metal becomes anode and the
remaining part becomes cathode
B) ABSORPTION OF OXYGEN
Rusting of iron in neutral aqueous solution of electrolytes in presence of
atmospheric oxygen.Usually the surface of iron is coated with a thin film of
iron oxide.If the film develops cracks, anodic areas are created on the
surface.While the metal parts act as cathodes.Anodes are small areas, while
the rest metallic part forms large cathodes.
At anode: The metal ion dissolves as ferrous ion with liberation of electron
Fe Fe2+ + 2e- (Oxidation)
At cathode: The released electrons flow from anode to cathode through iron
metal
.½ O2 + H2O + 2e 2 OH- (Reduction)
Fe 2+ ions and OH – ions diffuse and when they meet ferrous hydroxide is
precipitated.
Fe 2+ + 2OH- Fe(OH)2
If enough oxyen is present ferrous hydroxide is easily oxidised to ferric
hydroxide.
Fe(OH)2 + O2 + 2H2O Fe (OH)3
The product called yellow rust corresponds to Fe2O3. H2O
If supply of oxygen is limited the corrosion product may be even black
anhydrous magnetite Fe3O4.
 Non

carbon steels, alloy steels, stainless

steels, tool steels, cast iron, cast steel, aluminium, copper, lead, nickel, tin,
maraging steel, and specialty or titanium and zinc, as well as copper
proprietary iron-based alloys. alloys like brass and bronze.
FACTORS INFLUENCING CORROSION :
The rate and extent of corrosion, depends on the following factors :
1. Nature of the metal:

(i) Position in the galvanic series: - The greater the oxidation potential,
when the metal is higher up in the galvanic series, greater is its tendency
to become anodic and hence greater is the rate of corrosion.
(ii) Purity of metal: - Lesser is the percentage purity of a metal, faster is the
rate of corrosion. The impurities present in a metal cause heterogeneity
and thus tiny electrochemical cells are set up at the exposed part of the
impurity and corrosion of metal around the impurity takes place due to
local action.
(iii) Physical state of the metal: - The rate of corrosion is influenced by
physical state of metal. The smaller the grain size of the metal or alloy,
the greater will be its corrosion. Moreover, areas under stress, even in a
pure metal, tend to be anodic and corrosion takes place at these areas.
(iv) Nature of the oxide film: - The ratio of the volumes of the metal oxide
to the metal, is known as "specific volume ratio". Greater the specific volume
ratio, lesser is the oxidation corrosion rate.
(v) Relative areas of the anode and cathode: - When two dissimilar metals or
alloys are in contact, the corrosion of the anodic part is directly proportional
to the ratio of the cathodic part and the anodic part. When cathodic area is
smaller, the demand for electrons will be less and this result in the decreased
rate of disolution of metal at anodic regions.
(vi) Solubility of corrosion products: - In the electochemical corrosion, if the
corrosion product is soluble in corroding medium, then corrosion proceeds at
a faster rate. For example, Pb in H2SO4 medium forms PbSO4 which is
insoluble in the corroding medium, hence corrosion proceeds at a smaller
rate.
vii) Volatility of corrosion products: - Rapid and continuous corrosion of
metal take place if corrosion product is volatile. This is due to the fact that as
soon as corrosion product is formed, it volatilize, thereby leaving the
underlying metal surface for further attack.

2. Nature of the corroding environment:

Temperature: -With increase of temperature of environment, the reaction as
well as diffusion rate increase, thereby corrosion rate is generally enhanced
(ii) Humidity of air :- The greater is humidity, the greater is the rate and
extent of corrosion. This is due to the fact that moisture acts as a solvent for
O2, H2S, SO2 and NaCI etc. to furnish the electrolyte essential for setting up
a corrosion cell.
iii) Effect of pH:- Corrosions of those metal which are readily attacked by
acids can be reduced by increasing the pH of the attacking environment.
(iv) Presence of impurities in atmosphere:- Corrosion of metals is more in
areas near to the industry and sea. This is due to the fact that corrosive gases
like H2S, SO2, CO2 and fumes of H2SO4 and HCI in the industrial areas and
NaCI of sea water leads to increased conductivity of the liquid layer in contact
with the metal surface, thereby increase the corrosion rate.
(v) Presence of suspended particles in atmosphere: -In case of atmospheric
corrosion; (a) if the suspended particles are chemically active in nature [like
NaCl, (NH4)2SO4], they absorb moisture and act as strong electrolytes,
thereby causing enhanced corrosion;
Organic coatings – durable protective coating applied to a substrate for
decorative or specific technical properties. The main component responsible
for the creation of well-adhering film (membrane) are organic compounds:
polymers, oligomers, monomers, or mixtures thereof.
3 The types of organic coatings:
Primers - adhesion to the substrate, corrosion protection, paint adhesion,
Adhesive cements - materials with a suitable consistency coatings used for
surfacing,Topcoats with high resistance to external factors:
Varnish - solution of film-forming substance in an organic solvent, for
example: colorless varnish,
Enamel - solution of film-forming substance, pigments (colorants),
modifiers, additives in an organic solvent. Enamel Paint They are usually
available as ready made paints and consist mainly of white lead or Zinc
White, petroleum resinous matter, and a oil. • An enamel paint forms a hard,
impervious enamel like surface on drying.
.
Electroplating -
Electroplating is the method of coating one metal with another. It is
most commonly used for decorative purposes, appearance and protection.
Electroplated items include chrome bumpers, jewelry, electronics, circuit
boards and airplane parts.
Electroplating procedure
1. Preparation of the workpiece. Solutions such as alkaline cleaners, solvent
degreasers or acidic pickling mixtures are used to remove dirt, greases,
oxidation and contaminants from the piece.
2. The piece to be plated is connected to the negative pole (cathode) of the d.
c. power supply while the plating (coating) metal anode is connected to the
positive pole (anode). Multi-range ammeter (in series) and voltmeter (in
parallel) are connected to the cell to measure the cell current and voltage.
3. The piece is then immersed in the plating solution until coated and rinsed
and then buffed or polished, if necessary.

. Enamels -Enamels are glassy layer applied to the metal by dipping it in a

suspension of powdered glass, and then the metal is heated in a stove
(furnace) at high temperature where the glass powder melts and coat the
metal.
iv. Cement coating It is used to coat the inner side of steel pipelines carrying
water or wastewater. i. Paints: Paint consists of; 1. a film forming substance
such as linseed oil or a polymer (resin), 2. an organic solvent and 3. a pigment
(usually an inorganic oxide or metal powder). Before applying paint to a steel
surface, the metal surface should be cleaned of oxides by sand blasting or
acid pickling. After cleaning, the metal surface is coated with a thin layer of
primer.
Surface conversion coating (non metallic)-
i. Oxidation (passivation) –
Steel can be coated with an oxide film by a). Heating at high
temperature, b). Chemical oxidation by treating steel with hot alkaline
nitrate, or persulphate or perchlorate c). Anodic oxidation by making the
steel structure an anode in electrolytic cell.
ii. Phosphating -
Steel is coated with a layer of iron phosphate by dipping in a
solution containing phosphoric acid and zinc phosphate. The iron
phosphate film is not highly protective because it is porous so it usually
covered with paint. The phosphate film improves the bond between the
metal and the paint. i.e. Phosphating is a pre-painting step.
Hot Dipping –

“Hot dipping is a process of coating the base metal ( having high

melting point ) by dipping it into bath containing molten coating metal
(having low melting point ). “

Types of Hot dipping _

1. Galvanizing ( Anodic coating)-

e.g. Zn coating on Cu, Fe, steel.

2. Tinning ( Cathodic Coating ) –

e.g. Sn coating on Cu, Fe, steel.
1. Galvanizing Process –
Galvanizing is a process of coating the base metal ( metal having
high m.p ) which is less active by dipping into bath containing molten
coating metal ( low m.p) which is more active.
There are different steps –

• Degreasing/ Caustic treatment –

remove dirt, oil , grease.

• Pickling –
Dilute HCl or H2SO4 – removes oxides and scales.

• Fluxing –
ZnCl2/NH4Cl – protective layer to prevent oxidation of base
metal.

• Drying –
Hot air – Reduces splash and increases dip speed.

• Molten metal – 98% Zn

• Temperature – 438 -460 °C ( 820-860 °F)
• Dipping Time – 10 minutes
Post treatment –
1. Quenching – Water and chemicals to form passivation layer to protect
galvanized component.
2. Removal of Zn drips or spikes – by grinding .
Uses-
• Galvanized steel wires, pipes ,nails, screws, nuts , bolts.
• Galvanized steel frames and roof top for construction .
• Door frames , window frames and bars.
• Domestic applications such as washing machines, hair dryers, trimmers ,
computer parts , Ac housings ,etc.
• Protective gears, high way signs, high tension electric towers .

*Galvanized containers cannot used to store food stuffs, as zinc dissolves

especially when acidic food is stored and poisons the food.
2. Tinning Process -
Tinning – (cathodic coating)
Coating of more active metal ( less m.p) over more active metal(
high m.p).
Tinning is a process of coating the base metal ( metal having high
m.p) by dipping into a bath containing molten tin (metal having low m.p).

Steps –
• Pickling – dilute HCl/ H2SO4 ( 5 min.)
removes oxides /scales forming greenish black slime

• Annealing – Heated for 10h and cooled slowly

removes greenish black slime.

• Cold rolling - Passed through a series of rollers

to bring the plates / sheets to proper dimension

• Annealing – Heated and cooled slowly

removes strain hardening
• Pickling - dilute HCl/H2SO4
Removes oxides and scales.

• Fluxing – ZnCl2
dries the surfaces and prepares for good adhering of tin.

• Tinning _ molten tin ( 250 -290 ° c)

Coating of tin

• Oil/ grease – prevents oxidation of the hot tin coating surface.

Advantages –
• Improve corrosion resistance /prevent rusting of steel and iron.
• Wear resistance than base metal.
• Solderable for electronic components .
• Prevents oxidizing of copper and its alloys.
• Prevents whisker growth
• Less porous ,more ductile , more economical than electroplating .

Drawback- Thickness not controlled well.

Uses –
• Aerospace
• Automotive
• Food service
• Electrical and electronics
• Telecommunication
• Medical
• Energy
• Jewellery

* Tinned containers are used to coat cooking utensils and storage

containers made of copper , brass, steel ,etc.
Cathodic Protection –
Principal – The metal to be protected is forced to behave as cathode.

1. Using Sacrificial Anode-

2. Using Impressed Current –
2. Using Impressed Current –
Anodic Protection -