Thickness (mm)

Figure: Approximate thickness of various surface engineering treatments

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 Corrosion has been defined as a destructive chemical and electrochemical
reaction of a metal with its environment (like O2, moisture, CO2 etc.) which
disfigures metallic products leading to reduction in their thickness and also
causes loss of useful properties such as malleability, ductility, electrical
conductivity and optical refractivity.
 Corrosion and wear often combine to cause aggressive damage in a number of
industries, such as mining, mineral processing, chemical processing, pulp
and paper production, and energy production.
 Loss to US Economy due to corrosion ~ $300 B / Year

Typical examples of corrosion

1. Rusting of iron due to formation of hydrated ferric oxide.
2. Tarnishing of silver wares in H2S laden air due to formation of silver
sulphide.

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Corrosion is enhanced by the presence of

• Impurities
• Air and moisture
• Electrolytes
• Strains in metals like dent, scratches etc.

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• Metals are electropositive in nature. Except few metals like gold, platinum (noble
metal) other metals are found in nature as their compounds (such as oxides,
hydroxides, carbonates, chlorides, sulphides, phosphates, silicates etc.) which are
called their ore.
• Metals are thus obtained by extraction from their ores by reduction process.
• In nature, when metals exists as their compounds (or ore) they are stable and they
are in the low energy states.
• However, during extraction of metals from their ores, free metals are become less
stable and are in the higher energy state than in the ionic state.
• So, metals have a tendency to back to the ionic state and hence metal atoms are
prone to get attacked by environment .
• This is the main reason for corrosion of metals.

Mineral Extraction Corrosion Corrosion

or Metal
(M) product
ore (Mn+) by reduction -ne
(Mn+)
+ ne
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 Types Of Corrosion
 Dry or Chemical Corrosion

 Wet or Electrochemical Corrosion

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• Chemical (or dry) corrosion: It involves direct chemical attack of
atmospheric gases like CO2, O2, H2S, SO2, halogen, moisture and inorganic
acid vapors on metal..
Example, tarnishing of silver ware in H2S laden air.

• Electrochemical (or wet)corrosion: It occurs due to setting up of a large

number of tiny galvanic cells in metals in presence of an impurity as well as
in presence of moisture. Generally impurity (more active metal) act as anode
and original metal act as cathode so anode is the area where corrosion
occurs.
Example, rusting of iron in moist atmosphere.

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 Dry or Chemical Corrosion
 Occurs
• Due to direct chemical reaction of atmospheric gases
• Due to molten metal in contact with metal surface

 Types
• Oxidation corrosion
• Corrosion by gases
• Liquid Metal Corrosion

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 Types of dry corrosion
Oxidation corrosion
 Occurs
 due to direct chemical reaction of atm. O2 with metal surface forming metal oxide
 Absence of moisture
 Increases with increase in temp.
 Mechanism
 on exposure to atm., metal gets oxidized to form metal ions
(i) M (S) M+n + ne-
 Electrons lost by metal are taken up by oxygen to forms oxide ions
(ii) 1/2O (g) + 2e- O2
2

2M + n/2O2 2M+n + nO2- M2On

Metal Oxide

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 Nature of metal oxide layer
 Types of Layers
 Stable Layer: - Al, Pb, Cu, Sn
 Unstable Layer :- Ag, Au, Pt
 Volatile Layer:- Mo
 Porous Layer:- Alkali metals &alkaline earth metals

 Pilling – Bedworth Rule/Ratio: The Pilling-Bedworth ratio (PBR) is

the ratio of the volume of metal oxide formed to the volume of metal
consumed. It's used to determine if an oxide film on a metal surface is
protective or not
 A protective and Non-Porous metal oxide layer has volume equal to or
greater than the volume of metal from which it is formed.
 A Non-Protective and Porous metal oxide layer has volume lesser than the
volume of metal from which it is formed.
Specific Volume Ratio = Volume of oxide formed
Volume of metal
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 Wet or Electrochemical or Immersed
Corrosion
Occurs
• When a metal is contact with moist air or any liquid medium
• When two diff. metals are partially immersed in a soln.
• Chemically non- uniform surfaces of metals behave like electrochemical cells in the presence of
water containing dissolved O2 & CO2
• Always occurs at anodic areas

Mechanism
• Involves oxidation- reduction process
• depending on the nature of corroding environment, electrons released at anode are consumed at
the cathodic area by two ways :
 Evolution of H2
 Absorption of O2

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 Rusting of Iron
• Rusting of iron refers to the formation of rust, a mixture of iron oxides, on the
surface of iron objects or structures. ( Rust: FeO and Fe2O3)
• Redox reaction between oxygen and iron in an environment containing water (such
as air containing high levels of moisture)
• It generally proceeds over a considerably large time frame.
• The oxygen atoms bond with iron atoms, resulting in the formation of iron oxides.
This weakens the bonds between the iron atoms in the object/structure.

Rusting causes iron to become flaky and weak, degrading its strength,
appearance and permeability. 12
 Difference

Dry Corrosion Wet Corrosion

Occurs in the absence of moisture Occurs in the presence of conducting

medium

Involves direct attack of chemicals on the Involves formation of electrochemical

metal surface cells

Slow Process Rapid Process

Corrosion products are produced at the Corrosion occurs at anode but rust is
site of corrosion deposited at cathode

Process of corrosion is uniform Depends on the size of the anodic part of

the metal
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 Types of electrochemical corrosion
 Galvanic Corrosion:- Galvanic corrosion is a type of corrosion that occurs
when two or more metals with different electrical potentials come into
contact with each other. It's also known as dissimilar metal corrosion or
electrolysis.

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Conc. Cell or Differential Aeriation Corrosion
• Occurs due to diff. in potential between differently aerated areas
• Part of metal exposed to air is more oxygenated part & acts as Cathode
• Part of metal immersed in electrolyte is poorly oxygenated & acts as
Anode

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 Water Line Corrosion
Waterline corrosion is a type of corrosion that occurs in pipes, tanks, and guttering
when there is a difference in oxygen levels above and below the waterline. It's a form
of localized corrosion that's also known as differential aeration corrosion.

Causes
Differential aeration
The area above the waterline is oxygenated,
while the area below is not. This creates a
difference in oxygen levels, which causes a
corrosive reaction.
Contaminants
Corrosive materials like hydrogen sulfide,
carbon dioxide, and other chemicals can be
present in the water.
Water pH
Water with a pH below 6.5 is corrosive,
especially if it's also low in alkalinity.

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 Pitting Corrosion
• Pitting corrosion is a type of corrosion that causes small holes to form in a
metal surface.
• It's a localized form of corrosion that can be more dangerous than uniform
corrosion because it's harder to detect.

Origin

• De-passivation: A small area of a metal's

protective layer breaks down, exposing the
bare metal
• Anodic and cathodic reactions: The exposed
metal becomes the anode, while a larger area
of the metal or coating becomes the cathode
• Electron demand: The cathode demands
electrons, which are supplied by the anode
• Oxidation: Oxidation occurs in the metal, even
without oxygen

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 Factors affecting Corrosion
 Nature of Metal
• Purity of metal
• Physical state of metal
• Position of metal in Galvanic series
• Nature of oxide film
• Nature of products of corrosion
• Relative areas of Cathode & anode
 Nature of Corroding Environment
• Temp. & Humidity
• Effect of pH
• Presence of impurities in atm.
• Nature of electrolyte
• Solubility of products of corrosion

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Protective Measures Against Corrosion

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 There are many methods of protecting metals against corrosion
• Barrier protection
• Sacrificial protection
• Cathodic protection
• Alloy formation

Barrier protection :
Here, a thin barrier is developed between the surface of iron and
atmosphere by one of the following methods:
a) Painting of the surface
b) Coating the surface with a thin film of some non –corrosive metal like nickel,
chromium copper etc.

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Coating the metal : In order to prevent corrosion, resistant coating is
made between metal and environment. Different types of metallic coatings
are
• Galvanizing (thin coating of Zn on iron)
• Electroplating (coating of Cu, Ni or Cr on iron with aid of direct current.
• Tin plating (coating of tin on iron )
• Sheradizing (it consists of dusting of Zn powder on iron surface followed by heating)
• Cladding

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Alloying the metal
Metal has better resistance to corrosion after forming alloy with other metal
, e.g. stainless steel, in which ordinary steel is alloyed with chromium and nickel.
There are two kinds of alloys:
Homogeneous alloys are solid solutions in which the components are completely
soluble in one another, e.g stainless steel
Heterogeneous alloys are the mixtures of two or more separate phases. The
components of such alloy are not soluble and exist as separate phase.
Solid solution alloys are more corrosion resistant.
•Chromium is used as alloying metals for iron and steel.
• Silicon is also used in making Si-Fe alloy

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Sacrificial protection:
In this case, the surface of iron is covered with a more electropositive metal like zinc or
aluminum. Since this metal loses electrons more readily than iron, rusting is prevented.
As long as metal is present, iron does not get rusted. This type of protection is called
‘sacrificial production’.
Cathodic protection (Electrical protection):
It is protection of the parent metal from corrosion by connecting with a more active
metal like Mg, Al, Zn etc. The more electropositive (active) metal acts like anode
(supplies electrons) and parent metal acts like cathode (receives electrons). Thus,
connected metal undergoes corrosion thereby protecting the parent metal from
corrosion by turning it as a cathode. Hence, the method is called ‘cathodic protection’.

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 Protective Measures Against Corrosion
 Metallic Coating :
• Electroplating : A coating metal is deposited on the base metal by
passing direct current through an electrolytic soln.
• Metal Cladding : The base metal to be protected and coating metal are
sandwiched by presssing through rollers under the action of heat &
pressure.
• Hot Dipping : The base metal to be coated is immersed in a bath of the
molten coating metal.
• Cementation : A uniform surface coating is obtained by heating the
base metal in a power of coating metal.
• Metal spraying : The coating metal in molten state is sprayed on base
metal by means of spraying gun.
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Protective Measures Against Corrosion
 Organic Coating :
• Apply on metallic surface for protection from corrosion & also to
impart decorative value. Such as paints, enamel, Varnishes &
lacquers
 Corrosion Inhibitors :
• Substances which when added in a small amount in an environment
reduces the rate of corrosion of a metal exposed to that
enviornment. These are of two types Cathodic & anodic
 Inorganic Coatings : are produced by chemical or
electrochemical reactions at a metal surface to protect base metal
from corrosion eg. : phophates, oxides etc.
 Using Pure Metal :
 Using Alloys :
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 Protective Measures Against Corrosion
 By Modifying Environment :
• By lowering the temp.
• By reducing the moisture
• By reducing the acidic corrosion environment
 Proper Designing :
• Proper designing of the equipment
• Avoid the direct contact of dissimilar metals
• Electrochemical Protection or Cathodic Protection :
• Sacrifical Anodic Protection : Metal to be protected is connected to more anodic metal
to avoid corrosion
• Impressed Current Cathodic Protection : This process consists of connecting the
material to be protected to –ve terminal of DC source& +ve terminal of DC source is
connected toa insoluble anode . The current supplied is in opposite direction to the
corrosion [Link] the metal to be protected act as cathode & get protected.

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• Methods of corrosion protection employed :
a. Altering the metal by alloying, that is, using a more highly
alloyed and expensive stainless steel rather than a plain
carbon or low-alloy steel
b. Changing the environment by desiccation or the use of
inhibitors
c. Controlling the electrochemical potential by the
application of cathodic or anodic currents, that is,
cathodic and anodic protection
d. Applying organic, metallic, or inorganic (glasses and
ceramics) coatings

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