UNIT – 1

CORROSION
INTRODUCTION

We have all seen that when a piece of iron or an article made of iron is left in the open, it develops a reddish-brown
coating. If this is left unattended for a long time, then the metal becomes weak and brittle and breaks off. A similar
phenomenon is observed in copper that develops a greenish coating; similarly silver loses its luster and so on. Thus,
metals degenerate in the presence of moisture and air. This is called corrosion, which may be defined as the process of
spontaneous deterioration or disintegration of metals (except gold and platinum) caused by direct chemical or indirect
electrochemical attack by reaction with the environment.

EXAMPLES
• Rusting of Iron
• Formation of a green layer of basic carbonate on the surface of copper
Why does corrosion occur?

Metals exist in nature in combined forms like oxides, sulphides, sulphates, carbonates, etc. These combined states (ores) are
thermodynamically stable states of the metal. Energy is supplied to extract such metals from their ores. The extracted metal is at a
higher energy level and hence it is in a thermodynamically unstable state. Metals try to get back to their stable states by combining
with other elements, and in this process, corrosion occurs and oxides, sulphides, chlorides, sulphates, and so forth are formed.
Although corroded metals are thermodynamically more stable than pure metals, corrosion affects the useful properties of the
metals like malleability, ductility and electrical conductivity.
 Effects of Corrosion

The corrosion process, although slow, affects the metal drastically. The gravity of the problem can be realized by the
fact that the approximate loss due to corrosion of metals is 2 to 2.5 billion dollars per annum all over the world. The
common consequences of corrosion are as follows:

 Corrosion causes severe economic loses and hampers the safety of equipment. It leads to direct economic loses
that occur due to money being spent on maintenance and replacement of the corroded parts. Painting, maintaining
cathodic protection devices, cost involved in protection techniques, such as galvanization, modifying external
environment by deaeration and dehumidification, all incur heavy financial loses.
 Metal loses its useful properties because of corrosion. It can become brittle, leading to the failure of machine
parts.
 Frequent replacement and maintenance of the corroded parts leads to indirect financial loses, which include
production loss during replacement and maintenance.
 Corroded pipes may lead to leakage of inflammable and toxic gases resulting in fire hazards; toxic gases lead to
environmental pollution and affect the human and animal population adversely.
 It causes contamination of the products. For examples traces of metals may alter the color of dyes. Food articles in
corroded containers may get spoilt due to contamination.
 It has been estimated that nearly 25% of the annual production of iron is wasted because of corrosion.
 Theories/Mechanism of Corrosion

Several theories of corrosion have been proposed from time to time.

The two basic theories of corrosion are:
• Dry or chemical corrosion.
• Wet or electrochemical corrosion.
 Dry or Chemical Corrosion

Also called direct corrosion, it occurs because of direct chemical action of the environment on the metal surface in the absence of
moisture or a liquid electrolyte. It generally occurs at a temperature higher than 100 °C when it is not possible to develop a surface
water layer. It is generally of three types:
 Oxidation Corrosion

It is brought about by the direct action of oxygen on the metal surface at high or low temperature. At low temperature,
alkali and alkaline earth metals are oxidized and at high temperatures except Ag, Au and Pt, all other metals are
oxidized. It generally takes place in the absence of moisture. For example, copper oxidizes in air at a low temperature
of about 260 °C forming a film of Cu2O. At temperatures between 260°C and 1025°C the Cu2 O layer is overlaid by a
layer of CuO film. Similarly, iron oxidizes at a low temperature of approximately 250°C, forming an oxide consisting
mainly of Fe3O4 .

Mechanism:
The metal surface reacts directly with oxygen forming an oxide layer. This oxide layer acts as a barrier and prevents
further oxidation of the metal. For further oxidation to take place, either the metal must diffuse outward through the
oxide layer or oxygen must diffuse inward. Both the transfers occur, but the outward diffusion of the metal ion is
faster as the size of the metal ion is smaller than that of the oxygen atom or the O2– ion.

Chemical reactions involved

• 2M → 2 Mn+ + 2n e– (loss of electrons – oxidation)
• (n/2) O2 + 2 ne– → nO2– (Gain of electrons – reduction)
• 2M + (n/2) O2 → 2 Mn+ + n O2–
 Corrosion by other gases

In this, dry gases like H2 , Cl2 , F2 , SO2 and CO2 directly attack the metal surface. Rate of corrosion depends upon
the chemical affinity between the metal and gas and also on the nature of the film formed.
For example,
• 2Ag + Cl2 → 2AgCl. The AgCl film is nonporous and protective (volume of the film > volume of the metal) and
thus it protects the metal from further attack.
• Sn + 2Cl2 → SnCl4 . SnCl4 being volatile, Sn undergoes excessive corrosion. The rest of the mechanism is the
same as that of oxidation corrosion.
• H2 S attacks steel forming FeS layer, which is porous in nature.
 Liquid Metal Corrosion

It occurs when an anhydrous liquid attacks the metal surface. When a liquid metal flows over a solid metal at high
temperature it weakens the solid metal because of
• Its dissolution in liquid metal.
• Penetration of liquid metal into solid metal. For example, sodium metal (coolant) leads to the corrosion of
cadmium in a nuclear reactor.
 Wet or Electrochemical Corrosion

This type of corrosion occurs under wet or moist conditions, and is more common than dry corrosion. It occurs when
• A metal is in contact with a conducting liquid
• When metals of different reactivities are in contact with a solution.

Rusting of iron is the most common example of electrochemical corrosion. The following conditions must be fulfilled for the
formation of electrochemical cell.
• There must be separate anodic and cathodic areas.
• There must be electrode potential between the anode and cathode.
• There must be a metal path connecting the anode and cathode.
• Conducting liquid should be present between the two electrodes.
Difference between Chemical Corrosion and Electrochemical Corrosion
Types of Corrosion
 Galvanic Corrosion

It is also called bimetallic corrosion or differential metallic corrosion. It occurs when two dissimilar metals (for example, Zn and
Cu) are electrically connected and exposed to an electrolyte and then the metal higher in the electrochemical series undergoes
corrosion.
For example, if Zn and Cu are connected, Zn acts as anode and undergoes corrosion, whereas Cu acts as cathode.
Mechanism: In a Zn – Cu couple
(At anode) Zn → Zn2+ + 2e–

The reaction at the cathode depends upon the environment.

Acidic environment: 2H+ + 2e– → H2 → (evolution of hydrogen)
Alkaline or neutral environment: (½) O2 + H2 O + 2e– → 2OH– (absorption of oxygen)
Zn2+ and 2OH– ions interact to form Zn (OH) 2.

Hence, Zn dissolves and Cu is protected.

 Concentration Cell Corrosion
Concentration cell corrosion takes place when different areas of a metal surface are in contact with an electrolyte of different
concentration (caustic embrittlement) or varying aeration (pitting corrosion, waterline corrosion, corrosion under a block of wood
or a drop of water, etc.). The difference in electrolyte/air concentration may be because of local temperature differences or
inadequate stirring or slow diffusion of metal ions.

Differential Aeration Corrosion (DAC)

This is the most common type of concentration cell corrosion. It occurs when one part of the metal is exposed to a different air
concentration than the other. There will be a difference of potential between differently aerated areas.
Experimental observations have shown that
• Poorly oxygenated areas become anodic
• Highly oxygenated areas become cathodic.

Corrosion occurs at the anode.

 Waterline Corrosion
If a Zn metal is partially immersed in a neutral solution (say NaCl) and the solution is not stirred, the parts above and close to the
waterline are well aerated and act as cathode. Areas deep inside the solution are anodic, as the concentration of oxygen is less.
Thus, a potential develops that causes a flow of current between two areas of the same metal. Zn dissolves at the anodic area

Similarly, you must have observed rusting along a line just beneath the level of water stored in an iron tank. This is also waterline
corrosion and is because of differential aeration. The area just above the waterline is well aerated and acts as cathode, whereas the
areas below the waterline are poorly aerated/oxygenated and hence become anodic and get corroded. The reactions at anodic and
cathodic areas are
(Anodic reaction) Fe → Fe2+ + 2e–
(Cathodic reaction) (½) O2 + H2 O + 2e– → 2OH–
The Fe2+ ions (at anode) and OH- ions (at cathode) diffuse and when they meet ferrous hydroxide is precipitated
Fe2+ + 2OH– → Fe(OH)2
 Pitting Corrosion

It is also an example of differential aeration corrosion. It is a localized type of corrosion and occurs in areas of pits, cavities and
pinholes that penetrate deeply within the metals. The pit is oxygen deficient and acts as anode, whereas the plane surface is
oxygen-rich and acts as cathode. As the area of anode is small the rate of corrosion will be high. Anodic metal dissolves and the pit
gradually deepens resulting in the weakening of the metal in these areas. If the pits are small they may be covered by corrosion
products. Therefore, it is difficult to detect pitting corrosion till sudden failure of the metal occurs.
Pitting of metal generally occurs because of breakdown or cracking in the protective film on the metal surface at specific points. It
may be due to scratches, surface roughness, chemical attack, stresses and strains, etc.
 Drop Corrosion
If a drop of electrolyte solution, block of wood, leaf, metal or stone is in contact with a metal surface, rusting occurs in the central
region beneath the drop, block of wood, leaf, metal or stone. The area around these objects is oxygen-rich and hence becomes
cathodic, whereas the central region beneath these objects is poorly oxygenated/aerated and hence becomes anodic.
At this region, Fe2+ is oxidized to Fe3+ and gets corroded.
 Stress Corrosion (Season Cracking)
It occurs because of the combined effect of
 Static tensile stress
 Corrosive environment near the metal.

The metals develop internal stress during manufacture process like fabrication, heat treatment, rolling, insufficient annealing, etc.
Thermodynamically, areas under stress are at higher energy level. Therefore, they have high electrode potential and act as anode.
The stress-free areas are at lower electrode potential and act as cathode. The difference in potential of these two is quite low and
corrosion is concentrated in small path that is anodic. The anodic area becomes highly reactive and is attacked even by a mild
corrosive environment, resulting in the formation of a crack. Examples of stress corrosion are

 Caustic alkalis and strong nitrate solution for mild steel. When mild steel under stress is exposed to hot concentrated alkaline
or hot concentrated nitrate solutions (like boiling 60% Cr(NO3 ) 2 + 3% NH4 NO3 ) it cracks along the intergranular path by
stress corrosion cracking.
 Underground steel pipelines used for transmitting oil and gas are under high internal pressure and hence fail by stress
corrosion cracking. Intergranular cracking of stressed steel also occurs when steel is in contact with SbCl2 + HCl + AlCl3 in a
hydrocarbon solvent.
Examples of stress corrosion are as follows

(i) Season cracking in brass It is a term that applies specifically to stress corrosion in brass (copper alloy). Pure copper is immune
to stress corrosion but the presence of alloying agents like Zn, Al, P and Sb makes it prone to stress corrosion. Brass undergoes
intergranular cracking in an atmosphere having traces of NH3 . The orientation of atoms in adjacent grains of brass is different
and hence it becomes highly reactive. They react with NH3 forming [Cu(NH3 ) 4 ] 2+ and [Zn(NH3 ) 4 ] 2+, respectively. Brass
dissolves, initiating assure that later forms a crack in the presence of high tensile stress. is can be avoided by avoiding
contamination of air with NH3 .
(ii) Caustic embrittlement It is corrosion in boilers due to excess NaOH. Inside the boiler the riveted areas, and areas of bends and
joints are under great stress and hence undergo corrosion.

Stress corrosion can be prevented by severe cold working, heat treatment (annealing and quenching), use of special alloys (steel
containing small amount of aluminum, titanium or niobium plus tantalum show resistance to stress corrosion).
 Crevice Corrosion
It is produced at gaps in the region of contact between metals with metals or nonmetals. The gaps are very narrow so that the liquid
penetrates in them and stagnates. It occurs at crevice between different metallic objects such as bolts, rivets, washers, nuts, etc.
Supply of oxygen is restricted in the areas of the crevices; hence, differential aeration corrosion takes place. The areas of the
crevice become anodic and undergo corrosion. Corrosion is further accelerated by the deposition of dirt, scales, debris, etc. Crevice
corrosion is affected by several metallurgical, physical and environmental factors, the most important being the crevice gap.
 Intergranular Corrosion

This type of corrosion occurs along the grain boundaries. When a metal is solidified, the solidification starts at a number of
randomly distributed nuclei within the molten mass. Each of them grows in a regular pattern or atomic array to form grains.
Because of random distributions of the nuclei, the planes of atoms in adjacent grains do not match and these mismatched areas
between adjacent grains are known as grain boundaries.

Certain compounds precipitate along the grain boundaries. The precipitated compounds as well as the grain centers behave as
cathode, whereas the grain boundaries behave as anode. Owing to the precipitation of certain compounds at the grain boundaries
the solid metal solution adjacent to the boundary becomes depleted in those constituents. Thus, a potential difference is created
leading to the corrosion at the anodic grain boundaries
 Protection against Corrosion (Corrosion Control)

The various methods by which corrosion can be controlled and prevented are as follows

 Protection by proper designing

 Material selection
 Modifying the environment
 Modification of properties of the metal
 Use of inhibitors
 Cathodic protection or electrochemical protection
 Use of protective coating
 Protection by Proper Designing

Corrosion can be prevented by using proper design.

Important design principles are as follows:

 Avoid direct contact of two dissimilar metals in a corroding medium. If it cannot be avoided then use an insulating fitting
between them to avoid direct metal–metal electrical contact. For example, metal washers should be covered with plastic
washers to avoid direct contact between the two metals.

 When two dissimilar metals in direct contact are to be used then:

 They should be as close as possible in the galvanic series.
 The anodic material should have a large area and the area of cathodic material should be as small as possible.
 The screws, bolts, nuts and welds should be of less reactive metals so that they can act as cathode with small area.

 Joints should be welded with same metal/alloy. Riveting or bolting with other metal results in crevice corrosion.
 As moisture has an important role in corrosion, the design should be such that moisture retention is as low as possible. Sharp
corners should be avoided and storage containers should be designed in such a way that they can be completely drained and
cleaned
 Wherever possible, equipment should be supported on legs to allow free circulation of air otherwise corrosion will occur due to
differential aeration
 Material Selection

 Using Pure Metals: Impurities in metals cause heterogeneity that leads to corrosion. Pure metal is less prone to
corrosion. However, pure metals are expensive and are usually weak and do not possess the required strength.

 Using Metal Alloys: The metals can be made corrosion-resistant by alloying them with suitable alloying
elements. For example, chromium is used as alloying metal for iron and steel as it produces an exceptionally
coherent oxide film, which protects the steel from further corrosion.
 Modifying the Environment

The corrosive nature of the environment can be reduced by

• De-aeration Removal of gases like oxygen and carbon dioxide from the environment reduces corrosion.

• Deactivation It involves addition of chemicals that remove oxygen. For example, addition of Na2 S, Na2 SO3 or

hydrazine removes O2 .

2 Na2 SO3 + O2 → 2Na2 SO4

N2 H4 + O2 → N2 + 2H2 O

• Dehumidification Alumina or silica gel may be added to remove moisture from the environment.

• Alkaline neutralization The acidic substances in the environment (like H2 S, CO2 , SO2 , etc.) can be neutralized

by adding bases like NH3 , NaOH, lime, etc.

 Modification of the Properties of the Metal

The properties of the metals can be modified to decrease the effects of corrosion. The properties can be modified by

1. Alloying: Alloys are more resistant to corrosion than pure metals.

2. Refining: As pure metals are more corrosion-resistant, refining can increase the corrosion resistance of the metal.

The amount of S and P in steels and C in stainless steels is reduced by refining.

3. Annealing: It is a heat treatment given to the metals to reduce residual stress.

 Use of Inhibitors
A substance that when added to the corrosive medium effectively decreases the corrosion of the metal is known as a
corrosion inhibitor. Inhibitors are of two types

(i) Anodic Inhibitors: They get adsorbed on the anodic surface forming a passive film on it (example chromates,
phosphates, tungstate's, etc.), thereby decreasing the corrosion rate.
(ii) Cathodic Inhibitors: They slow down the reactions taking place at the cathode (i.e. , H2 evolution in acidic
medium). For example, organic inhibitors like amines, mercaptans, substituted ureas and thioureas, heavy metal
soaps, etc., decrease the H2 evolution process by decreasing the diffusion of H+ ions considerably.

Inhibitors like Mg, Zn or Ni salts react with the hydroxyl ions at the cathode forming corresponding hydroxides that
deposit at the cathode and decrease the O2 absorption process.
 Cathodic Protection or Electrochemical Protection
The principle involved is that the metal to be protected is made to behave like a cathode. This can be done in two ways

1. Sacrificial Anode Cathodic Protection Method (SACP): In this method, the metal structure to be protected is connected to a
more reactive metal. For example, if an iron structure is to be protected it is connected to a more reactive metal like Zn or Mg. The
more reactive metal behaves as an anode and the iron structure becomes cathodic. Thus, the iron structure is protected and the
anode undergoes corrosion. After sometime, the anode is corroded completely and is replaced with a fresh anode. This anode (Zn
or Mg), which is sacrificed to protect the base metal is called the sacrificial anode and the method is called sacrificial anode
cathodic protection method. This type of protection method is used in industry to protect buried pipelines, underground cables,
ship hulls and even in railway tracks.
2. Impressed current cathodic protection (ICCP): In this method direct current from an external source is impressed (applied in
opposite direction) to nullify the corrosion current and convert the corroding metal from anode to cathode. e positive terminal of
the direct current source is connected to the anode and the negative terminal to the structure to be protected. Anode is made of inert
material like graphite, carbon, stainless steel and is buried in a backfill like gypsum to increase electrical contact between itself and
the surrounding soil

Applications
 Ships and submarines are protected against corrosion by connecting the surface to negative terminal of DC generator.
 Water tanks, buried oil or water pipelines, transmission line towers are protected by this method.
 Canal gates, off shore oil drilling structures, bridge decks, parking garages are also protected by this method