Dr.

Jeshma

CORROSION

Introduction: - Many metals exist in nature in combined form as their oxides, carbonates,
sulphides, chlorides and silicates (except noble metals) such as Au (gold), Pt (Platinum) etc.
During extraction process these are reduced to their metallic state from their ores and during
extraction of ores considerable amount of energy is required. Compounds are in lower
energy state than the metals. Hence when metals are put into use in various forms, they get
exposed to environment such as dry gases, moisture, liquids etc. and slowly the exposed
metal surface begin to decay by conversion into a compound.

Definition: - Any process of deterioration or destruction and consequent loss of a solid

metallic material through an unwanted chemical or electrochemical attack by its
environment at its surface is called corrosion. Thus corrosion is a reverse process of
extraction of metals.
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.
Examples:-
I. Rusting of iron – when iron is exposed to the atmospheric conditions, a layer of
reddish scale and powder of Fe3O4 is formed.
II. Formation of green film of basic carbonate- [CuCO3 + Cu(OH)2] on the surface of
copper when exposed to moist air containing CO2.

Disadvantages of corrosion: The process of corrosion is slow and occurs only at surface of
metals but the losses incurred are enormous. Destruction of machines, equipment, building
materials and different types of metallic products, structures etc. Thus the losses incurred are
very huge and it is estimated that the losses due to corrosion are approximately 2 to 2.5
billion dollars per annum all over the world.
Theories of corrosion: - Corrosion can be explained by the following two theories.
1. Dry or chemical corrosion.
2. Wet or electrochemical corrosion.

1. Dry or Chemical theory of corrosion: - This type of corrosion occurs mainly by the direct
chemical action of the environment i.e., by the direct attack of atmospheric gases such as O 2,
halogens, H2S, SO2, N2 or anhydrous inorganic liquids on the metal surface with which they
are in contact.
There are 3 main types of chemical corrosion.
a) Corrosion by oxygen (or) oxidation corrosion.
b) Corrosion by other gases like SO2, CO2, H2S and F2 etc.
c) Liquid metal corrosion
a) Oxidation corrosion: (Corrosion by oxygen)
 It is brought about by direct action of oxygen at low (or) high temperatures, usually in
the absence of moisture.
 At high temperatures all metals are attacked by oxygen and are oxidized – except noble
metals like Ag, Au, and Pt.
 At ordinary temp generally all the metals are slightly attacked. However alkali metals –
Li, Na, K, Rb etc. and alkaline earth metals – Be, Ca, Sr etc. are attacked very rapidly and
get oxidized readily.

Mechanism:

 Oxidation occurs first at the surface of the metal and a scale of metal oxide is formed
on the surface of the metal and it tends to act as a barrier for further oxidation.
 Therefore, for oxidation to continue either the metal must diffuse outwards through
 the scale to the surface or the oxygen must diffuse inwards through the scale to the
underlying metal. Both transfers occur, but the outward diffusion of the metal is
generally much more rapid than the inward diffusion of oxygen.
 Since the metal ion is appreciably smaller than the oxide ion, therefore the metal ion
has much higher mobility.
M+2 + 2e- M (Oxidation)

1/2O2 + 2e- O2- (Reduction)

M + 1/2O2 M2+ + O2- (Metal oxide)

Nature of the oxide formed: It plays an important role in further oxidation corrosion process.

Metal + oxygen metal oxide (corrosion product)

When the oxide film formed is

i) Stable layer: A stable layer is fine grained in structure and can get adhered tightly to the
parent metal surface. Such a layer will be impervious in nature and hence behaves as
protective coating, thereby shielding the metal surface. Consequently further oxidation
corrosion is prevented.
E.g.: Al, Sn. Pb, Cu, etc. form stable oxide layers on surface thus preventing further oxidation.

Oxygen Stable oxide layer

Metal No corrosion

ii) Unstable Layer: The oxide layer formed decomposes back into metal and oxygen
Metal + oxygen Metal oxide
Consequently oxidation corrosion is not possible in such cases.
Eg: Ag, Au and Pt do not undergo oxidation corrosion.

Oxygen Un Stable oxide layer

Metal + O2 Metal

iii) Volatile Layer: The oxide layer formed is volatile in nature and evaporates as soon as it is
formed. There by leaving the under lying metal surface exposed for further attack. This
causes rapid continuous corrosion, leading to excessive corrosion
 eg: Mo- molybdenum forms volatile MoO3 layer.

Oxygen Volatile layer

Metal for further attack

iv) Porus Layer: Contains pores and cracks. In such a case the atmospheric oxygen has access
to the underlying surface of the metal through the pores or cracks of the layer, there by
corrosion continues until the entire metal is converted to its oxide.
Eg: Iron when attacked by H2S at high temperature forms porous FeS layer.

Porus Metal oxide layer further attack

Metal through pores
continues

b) Corrosion by other gases:

 This type of corrosion mainly depends on chemical affinity between metal & the gas
involved.
 The intensity of attack depends on formation of protective or non-protective films on
metal surface.
 If the film is protective or non porous, the volume of metal oxide layer is greater than
that of metal. So further corrosion of metal doesn’t take place.

Example: i) Formation of AgCl film by the attack of chlorine on Ag: The intensity of corrosion
decreases due to formation AgCl non porous film on its surface which is tightly adherent on Ag.
If the film is non- protective or porous, the volume of metal oxide layer is lesser than that of
metal so further corrosion takes place.
ii) SnCl4 formed by attack of Cl2 on Sn (tin) which volatiles immediately there by leaving fresh
metal surface for further corrosion.

c) Liquid metal corrosion:

 This is due to chemical action of flowing liquid metal at high temperature on solid metal
or alloy.
 This type of corrosion is seen in devices used for nuclear plant.
 The corrosion reaction is carried out either by dissolution of solid metal or by liquid
metal or internal penetration of liquid metal into solid metal.
 Both reactions lead to weakening of solid metal.
Example: Na metal causes corrosion of Cd in nuclear reactor.
2. Wet or electrochemical theory of corrosion:
 A conducting liquid is in contact with a metal (or) when two dissimilar metals (or) alloys
are either immersed (or) dipped partially in a solution.
 The corrosion occurs due to the existence of separate anodic and cathodic areas or
parts between which current flows through the conduction solution.
 In the anodic area oxidation reaction takes place so anodic metal is destroyed by
dissolving (or) forming a compound such as an oxide.
 Hence corrosion always occurs at anodic areas
Mechanism :

i) Evolution of hydrogen:

In acidic environments:

For example in the corrosion of iron metal the anodic reaction is dissolution of Fe as ferrous
ions with liberation of electrons.

At Anode:
Fe Fe+2 + 2e- (oxidation)

These electrons flow through the metal from anode to cathode (acidic region) where H+ ions
are eliminated as H2 gas.

At Cathode:
2H+ + 2e- H2 (reduction)

The overall reaction is

Fe + 2H+ Fe2+ + H2

This type of corrosion causes “displacement of hydrogen ions from the acidic solution by
metal ions.
In hydrogen evolution type corrosion, the anodes are very large areas, where as cathodes are
small areas.
All metals above hydrogen in the electrochemical series have a tendency to get dissolved in
acidic solution with simultaneous evolution of hydrogen.

In Neutral Medium:
At Anode:
The Formation of OH- takes place along with the liberation of hydrogen

Fe Fe+2 + 2e- (Oxidation)

At Cathode:
2H2O + 2e- 2OH- + H2 (Reduction)

The Fe+2 and OH- ions diffusion towards each other through conducting medium and forming
the corrosion product in between cathodic and anodic areas.

Fe+2 + 2OH- Fe(OH)2 + H2

If enough O2 is present Fe(OH)2 is easily oxidized to Fe(OH)3 (ferric hydroxide)

4 Fe(OH)2 + O2 + 2H2O 4Fe(OH)3 or 2[Fe2O3.3H2O]

Rust Chemical composition

ii) Absorption of oxygen:

Rusting of Fe in neutral aqueous solution of electrolytes like NaCl in the presence of
atmospheric oxygen is a common example of this type of corrosion.

 The surface of iron will be usually

coated with a thin film of iron oxide. However if this oxide film develops some cracks,
anodic areas are created on the surface.
  While pure metal parts act as cathode
 Thus anodic areas are very small surface parts.
 The rest of the surface of the metal forms cathodes.
 Thus at the anodic part iron metal dissolves as Fe+2 ions with the liberation of
electrons
At Anode:
Fe Fe+2 + 2e- (Oxidation)
 The liberated electrons flow from anodic to cathodic areas through iron metal during
which they interact with dissolved oxygen and moisture.
At Cathode:
½ O2 + H2O + 2e- 2OH-

The Fe+2 ions and OH- ions diffuse and form ferrous hydroxide precipitate when they meet
with each other
Fe+2 + 2OH- Fe(OH)2

If enough O2 is present Fe (OH) 2 is easily oxidized to Fe (OH) 3 (ferric hydroxide)

4 Fe (OH) 2 + O2 + 2H2O 4Fe (OH) 3 or 2[Fe2O3.3H2O]

Rust Chemical composition

Difference between chemical Corrosion and electrochemical corrosion:

chemical Corrosion electrochemical corrosion

1. It takes place in dry condition
2. It involves the direct chemical attack of
environment of the metal.
3. It takes place on homogeneous and
heterogeneous surfaces.
4. Corrosion product accumulates at the same
place where corrosion is taking place.
5. Uniform corrosion takes place.
1. It takes place in wet condition such as in the
presence of electrolytes
2. It involves the formation of large number of
galvanic cells
3. It takes place on heterogeneous surfaces
only.
4. Corrosion product accumulates at cathode,
but corrosion takes place at anode
5. Non – Uniform corrosion takes place

Pilling – Bedworth Rule:

 The rule states that ‘an oxide is protective or non-porous if the volume of the oxide is at
least as great as the volume of the metal from which it is formed’.
  The smaller the specific ratio, greater the oxide corrosion since the formed oxide film
will be porous. So oxygen can diffuse and further corrosion takes place.

This is expressed in terms of specific ratio.

𝑃 − 𝐵 𝑟𝑎𝑡𝑖𝑜 = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑜𝑥𝑖𝑑𝑒

𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑐𝑜𝑛𝑠𝑢𝑚𝑒

Applications of P -B ratio:
 If P -B ratio < 1, then metal oxide is non protective. Ex: Mg. since oxide film is too thin
so, which can be easily broken, and it does not provide any protective effect to the
metal surface.
 If P-B ratio 2 >P -B ratio >1, then oxide is protective Ex: Al, Ti, Cr. Here oxide layer is
passivating in nature and it provides the protection against future surface oxidation.
 If P-B ratio >2, then oxide is non protective Ex: Mo (Molybdenum), W (Tungsten), Nb
(Niobium). In nature and here the oxide layer is too thick, and the oxide layer may easily
breakdown and will not provide protective effect.

Factors influencing corrosion:

i. Nature of metals
ii. Nature of the corroding environment.

i) Nature of metals:

a) Position in galvanic series: The metal higher in series is more active and suffers corrosion.
The rate and extent of corrosion is directly proportional to electrode potential difference
between them.

b) Purity of metal: Impurity of a metal generally causes heterogeneity and form minute
electrochemical cells and the anodic part gets corroded. For eg: Zn metal containing impurity
such as Pb (or) Fe undergoes corrosion. The rate and extent of corrosion increases with extent
of impurities.

c) Relative areas of anode & cathode: Small anodic & large cathodic area causes severe
corrosion when two dissimilar metals or alloys are in contact the corrosion of anode part is
directly proportional to ratio of areas of cathodic & anodic part. Eg: A small steel pipe fitted in a
large copper tank.

d) Nature of the corrosion product: Solubility of corrosion products : If the corrosion product is
soluble in the corroding medium, then corrosion proceeds at a faster rate otherwise if it is
insoluble, corrosion will be suppressed e.g: PbSO4 formation in case of Pb in H2SO4.
Volatility of corrosion products: - If the corrosion product is volatile , it evaporates as soon as it
is formed, there by leaving the underlying metal surface exposed for further attack. This causes
rapid and continuous corrosion. For eg: Mo forms MoO3 volatile oxide.

e) Nature of the surface film: when metals are exposed to atmosphere, practically all metals
get covered with a thin surface film of metal oxide. The ratio of the volume of metal oxide to
the metal is known as specific volume ratio. Greater the specific volume ratio, lesser is the
oxidation corrosion rate. For eg: the specific volume ratio of Ni, Cr, W are 1.6, 2.0 and 3.6
respectively. Consequently the rate of oxidation corrosion is least for (w) tungsten.

f) Anodic index:- Greater the anodic index more will be the rate of corrosion

Eg: Steel anodic index is 0.6 and Aluminium anodic index is 0.75 therefore steel acts as cathode
and Aluminium act as an anode (undergoes corrosion)

II) Nature of the corroding environment.

a) Temperature: With increase of temperature, the corrosion rate also increases because the
reaction as well as diffusion rate of ions in the corrosion medium increases.

b) Humidity: The higher the humidity of the atmosphere the greater is rate and extent of
corrosion because the moisture acts as medium for O2 in air and behaves as an electrolyte

c) Effect of pH: Generally acidic media are more corrosive than alkaline and neutral media.
Hence metals may be virtually classified according to pH range in which they will be affected
(or) resistant. However atmospheric metals like Al, Pb etc. are corroded in alkaline medium and
the corrosion rate of iron in O2 free water is slow, until the pH is below Zn is rapidly corroded in
weakly acidic solutions.
Corrosion control (Protection against corrosion):
1. Cathodic protection
The method of protecting the base metal by making it to behave like a cathode is called
as cathodic protection.
This is two types
a. Sacrificial anode method
b. Impressed current method
a. Sacrificial anode method
 The metallic structure to be protected (base metal) is connected by a wire to a more
anodic metal so that all the corrosion is concentrated at this more anodic metal
 The more anodic metal itself gets corroded slowly, while the base metal (cathodic) is
protected
 The more active metal is called sacrificial anode
 When the corroded sacrificial anode consumed completely it is replaced by a fresh one
 Ex: Sacrificial anode are Mg, Zn, Al and their alloys which possess low reduction
potential and occupies higher end in electrochemical series
 Ex: A ship-hull which is made up of steel is connected to sacrificial anode (Zn-blocks)
which undergoes corrosion leaving the base metal protected.

Advantages:

 Provides protection without power requirement.

 Low cost
 Disadvantages:
 Periodic replacements of the anode.
 Increased noise level from the anodes.
 Current output cannot be regulated

Applications: Sacrificial anodes are used for the protection of buried pipe lines underground
cables, marine structures, ship hulls, water tanks etc.

b) Impressed current method:

 An impressed current is applied in opposite direction to nullify the corrosion current,

and convert the corroding metal from anode to cathode.
 Usually a sufficient D.C. is applied to an insoluble anode, buried in the soil and
connected to the metallic structure to be protected.
 The anode is usually in a backfill (composed of cock breeze or gypsum), so as increase
the electrical contact with the surrounding soil.
 This kind of protection technique is useful for large structures for long term
operations.

Advantages: They can be automatically controlled which reduces

maintenance and operational costs.
Applications: This type of protections is used in buried structures such as
tanks and pipelines, transmission line towers, marine piers, laid up ships
etc.
2. Electroplating:
“Electroplating is the deposition of a metal, over the surface of another metal or alloy
or any conductor by the process of electrolysis.”

In this process, a metal is deposited on another metal or alloy by passing a direct current
through an electrolyte solution containing metal ions to be deposited.

Theory of Electroplating:
The article to be plated is made as cathode (substrate) and the metal to be plated on
cathode is made as anode. Electroplating is carried out in an electrolytic cell. It consists of
two electrodes the metal to be coated is taken as cathode and connected to negative
terminal of a DC power source. Anode is connected to positive terminal of the power source
the electrodes are dipped in an ionic solution of the metal to be plated on applying direct,
cations move towards cathode and get reduced to metal atoms and deposited over cathode.
Cathode reaction Mn+ + ne- M
A ions move towards anode and get oxidized at the anode surface if the anode is inert. if the
anode is dissolvable the electrode itself get oxidized
Anode reaction M Mn+ + ne-

Hence, plating is an redox reaction, where oxidation occurs at anode and reduction at
cathode.
Commonly used coating metals are Zn, Cu, Cr, Ni, Ag, Pt, Au etc...
The plating process is carried out by pretreating the object followed by electrolysis.

Pretreatment (Surface Preparation):

It is necessary to clean surface of metal electroplating in order to get a good deposit. The
impurities found on the surface may be grease, oxide film, oil, dust etc…
Various methods are available to clean the surface of metal:
1) Solvent cleaning: Organic solvents (like CCl4, toluene, trichloroethylene, etc) are used
to remove impurities like oil, grease, etc.. from the surface of metal.
The process involved is: solvent is vaporized by heating process, these vapours are then
made to condense on the metal surface to be cleaned. The condensed liquid dissolves and
washes away the impurities present
 2) Acid cleaning(pickling): It is used to remove oxides. After the removal of organic
impurities, the substrate is immersed in dilute HCl or H2SO4, this removes oxides.
3) Alkali cleaning: This method is employed to remove old paint from the metal surface
using alkali solutions (i.e., solution of NaOH, sodium silicate, sodium carbonate etc..)
Alkali reacts with oil, grease and removes it.
Process /Method:

1. The cleared article is then made as cathode of an electrolytic cell. The anode is either
the coating metal itself or an inert material of good electrical conductivity like graphite.
2. The electrolyte is a solution of a soluble salt of the coating metal. When direct current is
passed coating metal ions migrate to the cathode and get deposited there.
3. Thus a thin layer of coating metal is obtained on the article made as cathode. For
brighter and smooth deposits, favorable conditions such as low temp, medium current
density and low metal ion concentrations are used.

CuSO4 –---------> Cu+2 + SO4 -2

On passing current Cu+2 ions go to the cathode (the article to be plated) and get
depositedthere.

Cu+2 + 2e- –-----> Cu (at cathode)

The free sulphate ions migrate to the Cu anode and dissolve an equivalent amount of the
Cu toform CuSO4.

Cu + SO4 -2 –--------> CuSO4 + 2e- (at anode)

The CuSO4 thus formed dissolves in the electrolyte thus there is continuous replenishment
ofelectrolytic salt during electrolysis.
 Cu plating Conditions
1) Bath composition Copper Sulphate solution
2) Anode Copper (Superior Metal)
3) Cathode Article to be electroplated (Base Metal)
4) PH 4
5) Temperature 40-70 0C
6)Current density(mACm-2) 20-30 mA/cm2

Advantages:
1. Corrosion resistance: a corrosion-prone substance such as iron can be coated with a
layer of non-corrosive material, thereby protecting the original material.
2. Decorative items: shine and luster can be imparted to otherwise dull surfaces. This
makes for great decorative items.
3. Cheaper ornaments: instead of making ornaments out of gold or silver, one can make
them using cheaper metals and electroplate the ornaments with gold. This reduces the
cost of ornaments greatly.
4. improving mechanical characteristics: electroplating can also improve the mechanical
characteristics of metals.
Disadvantages :
1. Pollution potential: the electroplating solution, after use, needs to be disposed off safely
and is a cause of environmental concern.
2. Non-uniform plating: electroplating may or may not be uniform and this may result in a
substandard appearance of the plated material.
3. Cost: the process is costly and time consuming.

3. Electroless Plating:
“It is a technique of depositing a metal from its salt solution on a catalytically active
surface of the substrate by controlled reduction of metal ions using a suitable reducing agent
without the use of electicity.”

The reducing agent converts the metal ions to metal which gets plated over the catalytic
surface.
Mn+ + reducing agent → M + oxidized product
The driving force in this process is the autocatalytic redox reaction on the preheated catalytic
surface.The main advantage of this method is irregular shapes can be plated uniformly.
 Electroless plating of Nickel:
Before electroless plating process, the surface is thoroughly cleaned. Then,
electroless plating is done under following conditions.

Pretreatment : The article to be plated is degreased and etched by treatment with organic
solvent followed by dil.H2SO4 .
Electroless nickel is deposited directly on metals without any treatment (activation) in
presence of reducing agents. However, non metallic materials like plastics, glass etc., are
catalytically activated by dipping in Sncl2 containing Hcl at250c followed by Pdcl2 .
Sncl2 reduces palladium ions on the surface of the object to palladium which then catalyze
the deposition reaction.
Plating bath composition, conditions and reactions involved in electroless plating of
nickel are given as follows:

Required Conditions:

Metal ion solution Nickel chloride (NiCl2 ) 20g/ l

Reducing agent Sodium hypophosphite ( NaH2PO2 ) 20g/l
Complexing agent Sodium succinate 15g/l
Buffer ( PH = 4.5) Sodium acetate 10g/l
Temperature 930 C
PH 4.5
Plating reactions:

Anode reaction: H2PO2- + H2O H2PO3- + 2H+ + 2e-

Cathode reaction: Ni 2+ + 2e- Ni
Overall reaction: H2PO2- + H2O + Ni 2+ H2PO3 - + 2H+ + Ni
 Since, H+ ions are produces during the reaction the PH decreases. To maintain the pH
at 4.5, buffer salt sodium acetate is added during the reaction.
Advantages:
1) No electrical power required.
2) Plating may also be obtained on insulator and semiconductor.
3) Better throwing power compared to electroplating.
4) Coatings have unique mechanical, chemical and magnetic feature.
5) No hydrogen gas liberates at cathode, this results in good deposit.
6) Levellers are not required.
Disadvantages:
1) Generates more waste than other plating techniques.
2) Deposit is contaminated with oxidized product.
3) Rate of deposition is slow.
Applications:
1. It is used to obtain a wear resistance, corrosion resistance surface.
2. Ni coating on aluminium improves the solderability.
3. In the automotive industry bright nickel can be found on bumpers, rims,
exhaust
pipes and trim etc
4. It is also used in connectors for electronics commonly found in automobiles and
electronic gadgets.
Difference between Electroplating and Electroless plating:
Property Electroplating Electroless plating
1)Source(driving Electrical energy(current) Autocatalytic redox reaction
force)
2) Anode Separate anode is used Catalytic surface of substrate.
3) Cathode Object to be plated(treated to remove Object to be plated(treated to
surfaceimpurities) make surface catalytically
active)
n+ -
4) Reactions At anode: M → M + ne Mn+ + Reducing agent → M +
n+ -
At catode: M + ne → M Oxidized product
5) Reducing Reduction is brought about Reduction is brought about by
agent by electrons. reducing agent.
6) Applicability Applicable only to Applicable to conductors,
conductors semiconductors and insulators
7) Throwing Not satisfactory in case of Satisfactory irrespective of
power objects with irregular shape. shape.