Corrosion & Its Control

Corrosion and its control

(Syllabus)

• Mechanism of Dry (Chemical) and wet (electrochemical)

corrosion
• Types of electrochemical corrosion (differential aeration
corrosion, galvanic corrosion, pitting corrosion, waterline
corrosion)
• Factors influencing corrosion,
• Protection from corrosion (Sacrificial protection, Cathodic
protection, Organic coatings.
 Introduction
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.

Except few metals such as gold, platinum (called noble metal) are prone to
corrosion.

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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 Factors influencing corrosion

Corrosion is enhanced by the presence of

• impurities
• air and moisture
• electrolytes
• strains in metals like dent, scratches etc.
 Mechanism or causes of corrosion
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
 Types Of Corrosion
 Dry or Chemical Corrosion

 Wet or Electrochemical
Corrosion
 Types of corrosion
• Chemical (or dry) corrosion: It involves direct chemical attack of
atmospheric gases like CO2, O2, H2S, SO2, halogen, moisture and inorganic
acid vapours on metal..
Example, turnishing 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.
 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
 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)
1/2O2 (g) + 2e- O2

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

Metal Oxide
 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 – Bed Worth Rule

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
 Types of dry corrosion
Corrosion by Other Gases
• 2AgCl + Cl2 AgCl
• (Non-Porous layer)

• Fe + H2S FeS + H2
• (Porous Layer)

• Sn + 2Cl2 SnCl4
• (Volatile Layer)

Liquid Metal Corrosion

• Occurs due to the action of flowing liquid metal at high temp on solid metals or
alloys.
• Observed in nuclear reaction where Na metal used as a coolant leads to
corrosion of Cd.
 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 electochemical 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 enviornment, electrons released at anode are consumed at
the cathodic area by two ways :
 Evolution of H2
 Absorbtion of O2
 Mechanisms Of Corrosion by H2 Evolution

 Anode :
 M (S) M+n + ne- (Oxidation)
 Cathode :

 2H+ + 2e- H2 (g) (Reduction)

 Over All Rxn :

 2M (S) + 2n H+ 2M+n + nH2 (g)


 Mechanisms Of Corrosion by O2
Absorbtion

 Anode :
 M (S) M+n + ne- (Oxidation)

 Cathode :
 O2 + 4e- + 2H2O 4OH- (Reduction)
 Over All Rxn :
 4M (S) + 2nH2O 4M+n + 4OH-
Rusting of Iron
 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 cells

metal surface

Slow Process Rapid Preocess

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

Process of corrosion is uniform Depends on the size of the anodic part of the
metal
 Types of electrochemical corrosion
 Galvanic Corrosion:- When two different metals are present
in contact with each other in conducting medium

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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
Water Line Corrosion
 Pitting Corrosion
• Formed as a result of pit and cavities
• Localized attack and formed by cracking protective coating
 Factors Affecting Corrosion
 Nature of Metal
• Purity of metal
• Physical state of metal
• Position of metal in Galvanic series
• Nature of oxide fim
• 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
Protective Measures Against Corrosion
 Prevention of corrosion
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.
 Prevention of corrosion(contd)…
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
 Prevention of corrosion(contd)…
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 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
 Prevention of corrosion(contd)…
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 bathof 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.
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 :
 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 current.Thus
the metal to be protected act as cathode & get protected.
 Text books references
1. Jain P C and Jain M: Engineering Chemistry (15th Edition) 2006 Dhanpat
Rai Publishing Company, NewDelhi.
2. Dara S.S. & Umare S.S. A Text Book of Engineering Chemistry(12th
Edition ) 2008 S.Chand Publishing Company, New Delhi
3. Chawla Shashi: A text book of Engineering Chemistry (3rd Edition) 2010
Dhanpat Rai Publishing Company, New Delhi.
4. Palanna O G : A text book of Engineering Chemistry(4th Reprint) 2012
McGraw Hill, New Delhi
5. Sharma BK, Industrial Chemistry (16th Edition), 2014, Krishna Prakashan
Media (P) ltd. Meerut.