C O R RO S I O N

AND
I T S C O N T RO L
D R . A S H I M A S R I V A S T A V A

D E P T O F C H E M I S T R Y

J S S A T E , N O I D A
INTRODUCTION

Corrosion refers to the degradation or deterioration and ultimate destruction of the metal due to its
reaction with the surrounding gaseous or liquid environment.

Some common examples of corrosion in metals are:

• Rusting of iron: a layer of reddish brown scale (Fe2O3.x H2O) is formed on the surface of iron.
• Formation of green layer of basic copper carbonate [CuCO3+Cu(OH)2] on the surface of copper
• Tarnishing of silver: Blackening of surface of silver due to the formation of black layer of silver
sulphide on it.
 CAUSE OF CORROSION
• All metals except gold and platinum corrode spontaneously when exposed to atmosphere.
• They exist in nature in combined forms as oxides, carbonates, sulphides, etc.

• The natural combined form of metal called mineral or ore has low energy and thus more stable state of metal.
• High amount of energy is required to extract metal from ore. Thus metal is thermodynamically unstable state.
• It is the natural tendency of metal to revert back to thermodynamically stable state when it comes in contact
with the elements in the environment.
 CAUSE OF CORROSION

Metallurgical process
Ore of metal Pure metal
+ Energy (Thermodynamically
(Thermodynamically
stable state) unstable state)
Corrosion

Corroded metal + Energy

(relatively stable form than pure metal
CONSEQUENCES OF CORROSION
Corrosion has a number of economic and social consequences which include:
i. Enormous waste of machineries and different types of metallic materials.
ii. It leads to unpredictable machinery failure which may lead to dangerous situations such as loss of life.
iii. It leads to decrease in efficiency of machine and frequent replacement of corroded equipment which is an
expensive proposition.
iv. It may cause leakage of inflammable gas from the corroded pipeline resulting into fire hazards and leakage
of toxic product.
v. It caused contamination of potable water.
vi. It has been estimated that 25% of annual world production of iron is wasted due to corrosion.
TYPES OF CORROSION
Corrosion can be broadly classified into two categories based on the nature of corroding environment and
mechanism of corrosion.
These include
(i) Chemical or dry corrosion
(ii) Electrochemical or wet corrosion.
CHEMICAL OR DRY CORROSION:

This corrosion takes place in the presence of dry atmospheric gases such as O2, N2, H2S, CO2, SO2, halogens,
or anhydrous liquids. This corrosion occurs due to direct chemical reactions between the metal and atmospheric
elements.
The chemical corrosion is generally of three types;
(A) oxygen corrosion,
(B) corrosion by other gases and
(C)liquid metal corrosion.
(A) OXYGEN CORROSION (OXIDATION CORROSION)
Oxidative corrosion takes place in the absence of moisture by the direct attack of oxygen on metals.
This corrosion transforms metal into its corresponding metal oxide. All most metals, except Ag, Au, and Pt,
undergo oxidative corrosion at higher temperatures.

DIRECT CHEMICAL ATTACK THEORY

(B) CORROSION BY OTHER GASES

A number of other gases like Cl2, H2S, CO2, SO2, etc. also have corrosive effect on metals. In this case also the
layer of metallic compound is formed on the metal surface and it may be either protective or non-protective in
nature.
e.g.: 2Ag + Cl2→ 2AgCl (protective layer which prevents further attack)

Sn + 2Cl2 → SnCl4 (volatile and hence excessive corrosion)

(C) LIQUID METAL CORROSION

It occurs when liquid metal is allowed to flow over solid metal at high temperature. The solid metal is
weakened either due to its dissolution into liquid metal or penetration of liquid metal into it.

e.g.: The liquid sodium used as a coolant in nuclear reactors cause the corrosion of cadmium rods.
ELECTROCHEMICAL OR WET CORROSION:

This corrosion generally takes place when one or more metals come in contact with moist air or an electrolyte
solution. During this corrosion, the deterioration of metal occurs through electrochemical reactions between the
metal and wet atmospheric elements.
e.g.: Rusting of iron in presence of moist air is a wet corrosion.
• Following conditions must be satisfied for the formation of electrochemical cell for the corrosion
process to start:
• i) Presence of cathodic and anodic area
• ii) Electrical potential between the two
• iii) Metallic path connecting the Both
• iv) Presence of electrically conductive medium
ELECTROCHEMICAL THEORY

• Electrochemical theory explains the mechanism of wet corrosion. According to this theory, when the metal
is in contact with moist environment, a series of electrochemical cells containing anode and cathode will be
formed on the metal surface.
• The atmospheric agents dissolved in moisture provides necessary electrolytic medium.
• At anode the metal atoms undergo oxidation to produce metal ions. The metal ions so produced migrate
towards the cathode in the surrounding electrolytic medium while the electrons migrate towards the cathode
on the metal surface.
• The reduction reactions take place at the cathode. The corrosion product is ultimately formed and gets
deposited near cathode. However, the anode suffers metal loss due to continuous dissolution of metal.
RU S T I N G O F I RO N
Since the rusting of iron is a classic case of electrochemical corrosion, the reactions taking place at anode and
cathode during wet corrosion is explained by taking iron as an example.
• (a) Anodic reactions: Iron oxidizes to ferrous ions at anode.
• Fe → Fe2+ + 2e− (Oxidation)
• (b) Cathodic reactions: The reduction reactions taking place at cathode can be of two types depending upon
the nature of corrosive environment.
(I) EVOLUTION OF HYDROGEN
• In the absence of oxygen and in acidic environment,
evolution of hydrogen takes place. The H+ ions of the
All metals above hydrogen in the electrochemical
acidic solution pick up the electrons and are
series can show this type of corrosion. In evolution
eliminated as hydrogen gas.
of hydrogen type corrosion, anodic area is large as
• 2H++ 2e−→ H2 (Reduction)
compared to its cathodic area.
•

Fig: wet corrosion by hydrogen evolution

(II) ABSORPTION OF OXYGEN
• This type of corrosion takes place in neutral or alkaline The Fe2+ ions produced at anode migrate towards
medium in the presence of oxygen. the cathode through moisture and react with OH−
½ O2 + H2O + 2e−→ 2OH−(Reduction) to form ferrous hydroxide. The ferrous hydroxide
undergoes further oxidation to ferric hydroxide
which ultimately transform into hydrated ferric
oxide (Fe2O3. nH2O).
Fe2+ + 2OH−→Fe(OH)2
4 Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3
or 2 Fe2O3. 3H2O (Rust)

Fig: Mechanism of wet corrosion by absorption of oxygen

DIFFERENCE BETWEEN
CHEMICAL CORROSION AND
ELECTROCHEMICAL CORROSION
Chemical Corrosion Electrochemical Corrosion
1. It takes place in dry It takes place in wet conditions
conditions. such as in the presence of
electrolyte.
2. It involves the direct chemical It involves the formation of large
attack of environment on the number of galvanic cells.
metal.
3. It can take place on It takes place on heterogeneous
homogeneous and surface only.
heterogeneous surfaces.
4. Corrosion product Corrosion product accumulates
accumulates at the same spot at cathode whereas corrosion
where corrosion has occurred. occurs at anode.
5. Uniform corrosion takes place. Non-uniform corrosion takes
place.
6. Less prevalent More prevalent.
PA S S I V I T Y O F M E TA L

• Passivity is the characteristic of a metal exhibited when that metal does not become active in the corrosion
reaction.
• Passivity is caused by the buildup of a stable, tenacious layer of metal oxide on the surface of the metal.
Once the layer, or film, is formed, it acts as a barrier separating the metal surface from the environment.
• For further corrosion to occur, the reactants must diffuse through the oxide film. Such diffusion is very slow
or non-existent, thus corrosion either decreases markedly or stops.
• Metals such as zirconium, chromium, aluminum, Ni form thin, tenacious oxide films when exposed to the
atmosphere or to pure water at room temperature.
• In some cases, the film is extremely thin and may be invisible to the unaided eye, but it is still very effective
in giving these metals a marked passivity.
G A L VA N I C S E R I E S

• A more reliable galvanic series has been given for predicting corrosion behavior in different environments
(sea water). The order of the series is: Mg, Zn, Al, Cd, Duralium, steel, lead-tin (solder), Pb, Sn, Cu and its
alloys, cupro-nickel, bronze, Ni, passive stainless steel, Ag, Ti, graphite, Au, Pt.
• The noble character increases down this series.
TYPES OF CORROSION

GALVANIC CORROSION/
BIMETALLIC CORROSION/
DIFFERENTIAL METAL CORROSION
D I F F E R E N T I A L A E R AT I O N C O R R O S I O N

At anode:
Zn → Zn2+ + 2e− (Oxidation)
At cathode:
½ O2 + H2O + 2e−→ 2OH−(Reduction)

Zn2+ and OH− ions interact to give Zn(OH)2.

Other examples of differential aeration corrosion:

Waterline corrosion:
Drop corrosion
PITTING CORROSION
STRESS CORROSION

Examples :
• copper and its alloys are susceptible to
ammonia compounds,
• mild steels are susceptible to alkalis
• and stainless steels are susceptible to
chlorides.
(i) Season cracking: Season cracking due to stress
corrosion is commonly observed in cold-drawn brass
(Copper+Zinc alloy) articles.
Pure copper is immune to stress corrosion but presence
of alloying agents such as zinc, etc. makes it prone to
stress corrosion.
In the presence of atmosphere containing traces of
ammonia or amines, brass shows intergranular
cracking.
Both copper and zinc present in brass can form stable
complex ions, [Cu(NH3)4]2+ and [Zn(NH3)4]2+ in
ammonia solution and this causes dissolution of brass
leading to the formation of fissures.
Fissures propagates and cause cracking in the presence
of high tensile stress.
• (ii) Caustic embrittlement of mild steel:
Na2CO3 + H2O → 2NaOH + CO2
Concentration cell formation
Anodic area at stressed parts

3Na2FeO2 + 4H2O → 6NaOH + Fe3O4 + H2

Fe3O4 is precipitated and NaOH is regenerated
causing further corrosion.
 Factors affecting corrosion

Nature of Environmental
Metal factors
N AT U R E O F M E TA L
(i) Position of metal in galvanic series
(ii) Purity of metal: The impure metals are more prone to corrosion than the pure ones. Impurities
cause heterogeneity and form tiny electrochemical cells where anodic part gets corroded.
Metal % purity Corrosion rate
Zinc 99.999 1
Zinc 99.99 2650
Zinc 99.95 5000
N AT U R E O F M E TA L
• (iii) Ratio of anodic area to cathodic area (Area Effect)
 N AT U R E O F M E TA L
(iv) Nature of metal oxide film:
(a) Stable, protective and non-porous oxide film
(b) Unstable oxide film
(c) Volatile oxide film
(d) Porous and non-protective oxide film
PILLING-BEDWORTH RULE

Volume of metal oxide formed

Pilling Bedworth Ratio =
Volume of metal comsumed

According to Pilling Bedworth rule,

• If the volume of metal oxide layer is less than the volume of the metal consumed, the ratio is less than unity,
and then the metal oxide layer will be porous and non-protective. For example, oxide layers of alkali and
alkaline earth metals.
• If the volume of metal oxide layer is equal or greater than the volume of the metal consumed, the ratio is
unity or more than unity, and then the metal oxide layer will be non-porous and protective. For example,
oxide layers of Al, Cr, Cu, W.
(v) Physical state of the metal:
Physical state of metal such as orientation of grains, grain size, grain boundaries , localized stresses highly
influence the rate of corrosion.
For example grain boundaries are attacked more rapidly than the grain centres when subjected to corrosive
environment.
E N V I R O N M E N TA L FA C T O R S
(i) Temperature
(ii) Humidity of air
(iii) Presence of impurities in atmosphere: Corrosion increases if the air is polluted by smoke or gases like H2S,
SO2 and electrolytes like NaCl and (NH4)2SO4.
Chloride ions destroys the passive film and expose the metal to corrosion
Silicate ions form insoluble product which inhibits corrosion
(iv) Conductance of the corroding medium:
Dry sandy soils have lower conductance as compared to clay or mineralized soils. Hence the metallic parts
submerged under clay or mineralized soils undergo faster corrosion than in dry sandy soils.
CORROSION CONTROL
Corrosion is an inevitable process but by adopting various methods it can be minimized and prevented.
Common methods for controlling corrosion are
(i) Protection by Proper Designing of materials
(ii) Protection by Proper Material Selection
(iii) Cathodic protection
(iv)Use of corrosion inhibitors
(v) Application of Protective Coatings
PROTECTION BY PROPER
D E S I G N I N G O F M AT E R I A L S
Proper design of material is an determinantal factor in control of corrosion. The corrosion can be minimized in
metal structures by giving below consideration while design of materials:
i) Metals closely placed in electrochemical series should be used in galvanic couplings as it reduces extent of
corrosion.
ii) Direct contact between the different metals which are far apart in galvanic series should be avoided.
E.g. Insulating material should be used to separate them from each other. Plastic washers in place of metal
washers.
iii) Metals occupying lower positions in electrochemical series should be preferred over those in higher
positions as corrosion resistance of metals increase down the series.
iv) Avoid a combination of small anodic and large cathodic areas.
e.g screws, nuts, bolts should be made from more noble materials than the materials which are joined through
them (Cu nuts and bolts to fasten iron sheets)
v) Provide uniform aeration to metal structure.
v) Presence of crevices between adjacent parts of the structures should be avoided. Welding is
better joining technique than mechanical fasteners
• Vi) Use fillers to fill the gaps or crevices
• vii) Avoid designs with sharp corners and bends as accumulation of dust and water may lead to
corrosion by differential corrosion.
• The design should be such that retention of moisture is as low as possible as moisture is the main
factor governing corrosion.
(viii) Water is the main factor governing corrosion, the design of storage tanks should be in such a
way that they can be completely drained and cleaned
P R O T E C T I O N B Y P R O P E R M AT E R I A L
SELECTION

• By using pure metal

• By using alloys
C AT H O D I C P R O T E C T I O N
• In this method, the metal to be protected is forced to act as cathode thus avoiding its corrosion. This can be
achieved by
• (i) Sacrificial anodic protection
• (ii) Impressed Current Cathodic Protection
(I) SACRIFICIAL ANODIC PROTECTION
• In this method, the metal to be protected is
connected by a wire to a more anodic or reactive
metal. Thus during corrosion more anodic metal
gets corroded while the parent metal (cathode) is
protected. The more active metal used is known
as sacrificial anode which is replaced from time
to time by fresh one. Metals commonly used as
sacrificial anodes are magnesium and zinc.
(II) IMPRESSED CURRENT CATHODIC PROTECTION
• In this method, the metallic object to be protected
is made cathode by connecting it with the
negative terminal of the DC source. The positive
terminal is connected to an insoluble anode like
graphite, scrap iron or platinum. The impressed
current nullifies the corrosion current. The
electrons flow to the metallic object as a result it
act as cathode and is protected.
USE OF CORROSION INHIBITORS

Corrosion inhibitors are the chemical substances which reduce the corrosion rate when added in
small amounts to the corrosive environment.
The corrosion inhibitors are of two types, namely anodic and cathodic inhibitors.
(i) Anodic inhibitors: These substances when added in small amounts form a protective film of
insoluble precipitates on the anodic surface.
The protective film suppresses the anodic reactions and thereby providing protection against
corrosion.
e.g: Molybdates, phosphates and chromates of alkali and transition metals.
(ii) Cathodic inhibitors: These substances when added in small amounts get adsorbed on to cathodic
surface and prevent the reduction reactions there by prevent corrosion.
e.g: Organic inhibitors like amines, mercaptans, substituted ureas and thioureas, etc.
They get adsorbed on the metal surface and restrict the diffusion of H+ ions to cathode.
As a result, the cathodic reaction,
2H++ 2e−→ H2, slows down leading to prevention of corrosion.
Another cathodic reaction ½ O2 + H2O + 2e−→ 2OH− can be suppressed by removing oxygen from
the medium through the addition of sodium sulphite.
Sometimes ZnSO4 and MgSO4 are also added which react with OH− ions and the respective
hydroxides are precipitated at cathode surface.
C O M PA R I S O N B E T W E E N T H E T WO
• The cathodic inhibitors are quite safer compared to anodic inhibitors. This is because, even if they are used
in concentrations less than required for complete protection, the partially covered cathodic sites reduce the
surface area of the cathode whereas anodic area remains practically the same. Thus corrosion decreases due
to area effect.
A P P L I C AT I O N O F P R O T E C T I V E
C O AT I N G S

The coating of metal surface with a continuous, non-porous and chemically inert material is another way to
protect metal against corrosion. The coating on the metal surface acts as a physical barrier between the metal
and corrosive environment and prevents invasion of environmental elements leading to protection of the metal.
The protective coating can be of two types: (i) Metallic Coating and (ii) Non metallic coating.
M E TA L L I C C O AT I N G S

In metallic coating, the base metal being protected from corrosion is coated with another metal which is either
anodic or cathodic to the base metal. The metallic coatings often used are of Zn, Sn, Ni, Cu, Cr, Al, Pb.
(i) Anodic coating (sacrificial coating)
Anodic coating is a method of coating a more anodic metal on to the base metal. The anodic coatings provide
absolute protection to the underlying base metal irrespective of whether the protective coating is intact or not.

e.g: The coating of zinc onto iron, known as galvanizing, provides complete protection to Iron. The breakdown
of zinc coating cause severe corrosion in zinc, keeping the base metal (Fe) intact.
(ii) Cathodic coating (noble coating)
Cathodic coating is a method of coating a more cathodic metal on to the base metal. the formation of cracks or
pores on the protective layer can set up severe galvanic corrosion leading to complete destruction of the base
metal.
The cathodic coatings provide complete protection to the underlying base metal as long as the coating is intact.
e.g: The coating of tin on iron, known as tinning, is an example of cathodic coating.
COMPARISON O F G A LVA N I Z I N G AND TINNING

Galvanizing Tinning
1. Coating of iron with zinc to Coating is done with tin.
prevent corrosion
2. It protects the metal sacrificially Protection is due to the noble
character of tin.
3. Protection continues even if Protection is provided only when
coating is broken coating is perfect (continuous).
4. Food materials cannot be stored Tin coating is non-toxic so food
in zinc coated containers as zinc items can be stored.
compounds are toxic.