Unit 3: Corrosion and its passivation

 Corrosion: Corrosion is defined as destruction of solid metallic materials, due to chemical or

electrochemical attack, by their environment.
E.g. Rusting of Fe, Formation of green film of basic carbonate on Cu.

 Cause of corrosion: The isolated pure metals have much higher energy than its
corresponding areas i.e. they are highly unstable and hence they exhibit a natural tendency to
return back to their lower energy state (combined state/ore). Thus corrosion is a natural tendency
of metals to revert back to their more stable chemical forms such as oxides, sulfides etc.
 Effects of Corrosion:
1. Life of plant or equipment is very much reduced.
2. Metal loss its efficiency.
3. Maintenance cost and cost of material increases while production rate decreases.
4. The purity of the product gets affected.
5. Many useful properties of metal get altered.

 Types of corrosion

 Dry Corrosion / Atmospheric Corrosion:

“The corrosion in which direct chemical attack of atmospheric gases takes place on metal
is known as dry corrosion”. It is divided into following types;

i) Corrosion due to Oxygen (Oxidation Corrosion):Atmospheric Oxygen attack on the metal

surface and forms metal oxide.

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The oxidation occurs first at the surface of the metal and the resulting metal oxide layer forms a
barrier that tends to restrict further oxidation. In the case of oxygen, oxide film is formed, in the
case of H2S, sulphide is formed. For oxidation to continue either the metal must diffuse outwards
through the film to the surface or the oxygen must diffuse inwards through the film to the
underlying metal.

Oxidation Corrosion

The metal cations are appreciably smaller than the oxygen ions (anions) and therefore, cations
have much higher mobility. Thus the outward diffusion of metal is generally much more rapid
than the inward diffusion of oxygen. When oxidation starts, a thin layer of oxide is formed on the
metal surface, and the nature of this layer of film decides the further action. (A layer is called
film, when its thickness is less than 300 A° and it is called scale, if its thickness exceeds 300 A°).

The oxide films formed are classified into three categories.

a) Stable oxide film: - It is adherent and hence provide protective layer on surface, thereby
reducing rate of further corrosion. But extent of corrosion depends upon type of stable film
formed i.e. porous and non-porous.

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b) Unstable Film:-When the oxide film is unstable, it decomposes back into the metal and
oxygen, as soon as it is formed.
2 M + O2 2MO

Therefore, corrosion is not possible in this case. E.g. Silver, gold, platinum etc.

c) Volatile film: When oxide film is volatile, it vaporizes as soon as it is formed. Hence
continuously the fresh metal surface is exposed to atmosphere and corrosion continues. e.g.
MoO3 and SnCl4.

 Wet Corrosion / Electrochemical Corrosion:-When metal comes in contact with aqueous

acidic/alkaline/neutral solution, there is formation of galvanic cell which give rise to corrosion is
known as Wet Corrosion.”
 Mechanism of electrochemical (Wet) corrosion:
a) By evolution of Hydrogen gas: This type of corrosion occurs, usually in acidic
environments, like industrial waste, solutions of non-oxidizing acids like HCl. For example, steel
tank containing acidic industrial waste and small piece of copper scrap in contact with the steel.

The electrons flow through the metal from anode to the cathode. Here, simply the displacement
of H+ form the solution by metal ion takes place. Therefore, all metals which are above hydrogen
in electrochemical series have tendency to corrode in acid solution by this mechanism. The
portion of steel tank in contact with Cu is corroded most with evolution of H2 gas. The reactions
are:

b) By absorption of Oxygen:

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This type of corrosion occurs, usually in neutral/alkaline environment and when the dissolved
oxygen is present in electrolyte. The surface of iron is usually coated with a thin film of iron
oxide. However, if this iron oxide film develops some cracks, anodic areas are created on the
surface, while the coated metal parts acts as cathode.Thus water acts as electrolyte, the cracks in
the oxide film as anode and the oxide coated steel as cathode. The reactions are:-

Both anodic and cathodic products are water soluble and they diffuse towards each other. When
they meet – Fe (OH) 2 is formed.

In presence of enough oxygen it is converted to Fe(OH)3 (Hard rust) which deposits as rust.

 Factors affecting the rate of corrosion

A) Factors related to metallic material :
1) Position of metal in electrochemical series: In the electrochemical series metals at the top
i.e. more active metals (Li, Na) are easily corroded. However metals at the bottom i.e. less active
metals (Au, Pt) are not easily corroded.
2) Hydrogen over Voltage: The presence of impurities (Pb, Sn) with high over voltage
decreases the rate of corrosion while presence of impurities (Cu, Pt) with low hydrogen over
voltage increases the rate of corrosion of a metal.
3) Area of anode and cathode: Corrosion is much more rapid, if the anodic area is smaller
because in this case the current density is much greater. E.g. Corrosion at cracks on protective
coating of Sn, Ni or Cr on Fe is more intense.
4) Purity of metal: - If the metal carries impurities, the corrosion is faster e.g. Zn metal with Pb
or Fe as an impurity.
5) Physical State of Metal: - Smaller the grain size of a metal, greater will be its solubility and
corrosion. This is called grain boundary corrosion. Presence of uneven surface increases the
corrosion because the crests act as anode and troughs act as cathode. It is called as crevice
corrosion.
6) Nature of surface film: - The metals which form porous oxide film (e. g. Li, Na, Fe etc.), the
corrosion increases. The metals which form non-porous oxide film (e. g. Al, Ni, W, Cr etc.), the
corrosion stops because such oxide films protect metal from further corrosion.
7) Nature of corrosion product: - If the corrosion product is soluble in the corroding medium,
corrosion increases. Whereas if the corrosion product is insoluble in the corroding medium,
corrosion decreases.

B) Factors related to the corroding medium:

1) pH of the Solution:-If the solution or electrolyte is acidic (i.e. pH<7), the rate of corrosion
increases.

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2) Temperature of electrolyte: Corrosion increases with temperature because it increases
ionization and fluidity of solution.
3) Humidity: - The corrosion increases in humid condition because gases like CO2, O2, H2O (v)
etc. get dissolved in water and produce an electrolyte which set up electrochemical cell.
4) Presence of impurities: - The presence of impurities like CO2, H2S, HCl, Cl2, H2SO4 fumes
etc. increases the acidity of liquid and hence increases rate of corrosion.
5) Presence of suspended particles in atmosphere: -suspended particles in air like Na2SO4,
(NH4)2SO4 etc. absorb moisture and act as strong electrolyte. Thus it increases rate of corrosion.

 Methods for prevention of corrosion:

1) Cathodic Protection :
a) Sacrificial anode method: i.e. galvanic protection.

In this method, the metal to be protected from corrosion is connected by a wire to another piece
of metal which is more anodic (More reactive) than the base metal itself. Such more active
metals like Mg, Zn, Al and their alloy are known as sacrificial anode which gets corroded. When
it completely corroded is replaced by new piece. This method is used to protect buried pipelines,
water tanks, underground cables, ship bulls etc.

b) Impressed current method :

In this method, an impressed current is applied in the opposite direction to nullify the corrosion
current. The metal is converted from anode to cathode and thus protected. The impressed current
is taken from a battery or rectifier using an insoluble anode such as platinum, graphite, stainless

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steel etc. This method is useful in protecting box water coolers, water tanks, underground oil or
water pipeline, transmission line towers etc.

2. Electroplating:

Electroplating is carried out in an electrolytic cell. The article is first cleaned with organic
solvents to remove oils, greases etc and then treated with dilHCl, H2SO4 to remove oxide scales.
The cleaned article is connected to cathode and coating metal is connected to anode in presence
of electrolyte which is soluble salt solution of coating metal. Under the influence of electric
current, coating metal ions migrate to cathode and get deposited there. Thus a thin coating of
metal is produced on the article. e.g. In electroplating of cu, electrolyte used is CuSO 4, Anode is
Cu metal and cathode is article.

Advantages: - It improves appearance and hardness.

- It increase resistance to corrosion, wear and chemical attack.
- Can make surface conductive.
Disadvantage: -Current density should not fluctuate.
-Composition of electrolyte should be consistent.
-Temperature should not fluctuate.
-Rate of anodic and cathodic reactions should be same.