Unit 4 CORROSION AND ITS CONTROL_LC (7)

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UNIT 4

CORROSION AND IT’S CONTROL

IT – A

Prepared By,
Dr Likha Chandran
CORROSION AND ITS CONTROL
The surface of almost all the metals begin to decay rapidly when exposed to atmospheric gases,
water or other reactive liquid medium.
The deterioration of a metal by chemical or electrochemical reaction by its environmental attack is known as
corrosion.
Metals undergo corrosion and convert to their oxides, hydroxides, carbonates, sulphides, etc. E.g. Iron
undergoes corrosion to form reddish brown color rust [Fe2O3. 3H2O].
Copper undergoes corrosion to form a green film of basic carbonate [CuCO3 + Cu(OH)2]
Causes of corrosion
1. The metals exist in nature in the form of their minerals or ores, in the stable combined forms as
oxides, chlorides, silicates, carbonates, sulphides etc.
E.g. Iron undergoes corrosion to form reddish brown colour rust [Fe2O3. 3H2O].
Copper undergoes corrosion to form a green film of basic carbonate [CuCO3 + Cu (OH)2]
2. During the extraction of metals, these ores are reduced to metallic state by supplying considerable
amounts of energy.
3. Hence the isolated pure metals are regarded as excited states than their corresponding

ores. So metals have natural tendency to go back to their combined state (minerals/ores).
When metal is exposed to atmospheric gases, moisture, liquids etc., and the metal surface reacts and forms
more thermodynamically stabled compounds.
Effects of corrosion
1. Wastage of metal in the form of its compounds.

2. The valuable metallic properties like conductivity, malleability, ductility etc. are lost due to corrosion.
3. Life span and efficiency of metallic parts of machinery and fabrications is reduced.
4. Life of equipment and machinery gets reduced.
5. Necessity for replacement of corroded product.
6. Probability of plant shut down due to machine failure.
7. Buildings and other historic monuments are damaged.
8. Loss of valuable metallic properties such as conductivity.
9. Ductility, malleability and luster etc.
10. Contamination of drinking water.
11. Leakage of inflammable gases can cause fire hazards.
Theories of corrosion
Chemical corrosion (Dry corrosion)
This type of Corrosion occurs mainly through the direct chemical action of atmospheric gasses like O2,
halogens, H2S, SO2, N2 or anhydrous inorganic liquid with the metal surface.
There are three types of chemical Corrosion:
(1). Oxidation corrosion
(2). Corrosion due to other gases
(3). Liquid metal corrosion
(1) Oxidation Corrosion: This is carried out by the direct action of oxygen low or high temperatures on
metals in absence of moisture. Alkali metals and Alkaline earth metals are rapidly oxidized at low
temperatures. At high temperature all metals are oxidized (except Ag, Au, and Pt).
2+
M M + 2e- (Oxidation); O2 + 2e- 2O2– (Reduction)

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

Figure 1: Oxidation corrosion


Mechanism: Initially the surface of metal undergoes oxidation and the resulting metal oxide scale
forms a barrier which restricts further oxidation. The extent of corrosion depends upon the nature of metal
oxide.
(a) If the metal oxide is stable, it behaves has a protective layer which prevents further Corrosion.
E.g., the oxide films of Al, Sn, Pb, Cu, Cr, W etc. are stable and therefore further corrosion is prohibited.
(b) If the metal oxide unstable, the oxide layer formed decomposes back into metal and oxygen. Oxidation
corrosion is not possible.
E.g., Ag, Au and Pt do not undergo oxidation corrosion.
(c) If the metal oxide layer is volatile, then the oxide layer volatilizes after formation and leaves the
underlying metal surface exposed for further attack. This causes continuous corrosion which is excessive
in molybdenum oxide (MoO3).
(d) If the metal oxide layer is porous, the oxide layer formed has pores or cracks. In this case the
atmospheric oxygen penetrates through the pores or cracks and corrodes the underlying metal surface. This
cause continuous corrosion till conversion of metal into its oxide is
completed. Ex: Alkali and alkaline earth metals (Li, Na, K, Mg etc.)
(2) Corrosion due to other gases: This type of corrosion is due to gases like SO2, CO2, Cl2, H2S, F2 etc.
In this corrosion, the extent of corrosive effect depends mainly on the chemical affinity between the metal
and the gas involved. The degree of attack depends on the formation of protective or non protective films
on the metal surface which is explained on the basis of Pilling Bedworth rule.
(i) If the volume of the corrosion film formed is more than the underlying metal, it is strongly adherent;
non- porous does not allow the penetration of corrosive gases.
2Ag + Cl2 2AgCl (protective film)
(ii) If the volume of the corrosion film formed is less than the underlying metal, it forms Pores/cracks and
allows the penetration of corrosive gases leading to corrosion of the underlying metal.
Ex: In petroleum industry, H2S gas at high temperature reacts with steel forming a FeS scale. Fe (steel)
+ H2S FeS (porous)
(3) Liquid metal corrosion: This corrosion is due to chemical action of flowing liquid metal at high
temperatures on solid metal or alloy. The corrosion reaction involves either dissolution of a solid metal by
a liquid metal or internal penetration of the liquid metal into the solid metal.
Eg. Coolant (sodium metal) leads to corrosion of cadmium in nuclear reactors.
Electrochemical Corrosion (Wet corrosion)
This type of Corrosion occurs where a conducting liquid is in contact with the metal. This corrosion occurs
due to the existence of separate anodic and cathodic parts, between which current flows through the
conducting solution. At anodic area, oxidation reaction occurs there by destroying the anodic metal either
by dissolution or formation of compounds. Hence corrosion always occurs at anodic parts.
Mechanism: Electrochemical corrosion involves flow of electrons between anode and cathode. The anodic
reaction involves dissolution of metal liberating free electrons.

M Mn+ + ne-
The cathodic reaction consumes electrons with either evolution of hydrogen or absorption of oxygen
which depends on the nature of corrosive environment.
Evolution of hydrogen: This type of corrosion occurs in acidic medium.
E.g., Considering the metal Fe, anodic reaction is dissolution of iron as ferrous ions with Liberation of
electrons.

Fig 2: Hydrogen evolution corrosion

Anode: Fe Fe2+ + 2e- (Oxidation)


The electrons released flow through the metal from anode to cathode, whereas H+ ions of acidic solution
are eliminated as hydrogen gas.

Cathode: 2H+ + 2e- H2 (Reduction)

Overall reaction: Fe + 2H+ Fe2+ + H2


This type of corrosion causes displacement of hydrogen ions from the solution by metal ions. All metals
above hydrogen in electrochemical series tend to get dissolved in acidic solution with simultaneous
evolution of H2 gas. The anodes are large areas, whereas cathodes are small areas.
Absorption of oxygen: For example, rusting of iron in neutral aqueous solution of electrolytes in presence
of atmospheric oxygen. Usually the surface of iron is coated with a thin film of iron oxide. If the film
develops cracks, anodic areas are created on the surface. While the metal parts act as cathodes. It shows
that anodes are small areas, while the rest metallic part forms large Cathodes. The released electrons
flow from anode to cathode through iron metal.

At anode: Fe Fe2+ + 2e- (Oxidation)

At cathode: ½ O2 + H2O + 2e– 2OH- (Reduction)


2+
Overall reaction: Fe + 2OH- Fe(OH)2
If oxygen is in excess, ferrous hydroxide is easily oxidized to ferric hydroxide.
4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3
The product called yellow rust corresponds to Fe2O3. 3H2O.

Fig 3: Oxygen absorption corrosion

Sl. Dry Corrosion Wet Corrosion


No.
1. Occurs in dry Occurs in wet condition in the presence of moisture
condition. & electrolyte.
2. It involves chemical attack of It involves electrochemical attack of
oxygen or other gases. corrosive environment on the metal
surface.
3. Corrosion is uniform. Corrosion is not uniform, depends on the size of
anodic site.
4. Corrosion products accumulate at Corrosion occurs at anode but product accumulates
the site of attack. on cathode.
5. It is a slow process. It is a fast process.
6. e.g. – Corrosion of Fe in the e.g.- Rusting of Fe in the presence of moisture and
presence of HCl gas. oxygen.
Factors effecting corrosion
The rate and extent of corrosion depends upon various factors due to nature of metal and nature of corroding
environment.
Factors due to nature of metal
• Purity of the metal: Heterogeneity of the metal is due to the presence of impurities which form tiny
electrochemical cells at the exposed parts. The anodic parts get corroded.
• Electrode potentials: metals with higher reduction potentials do not corrode easily. They are noble metals
like gold, platinum and silver. Whereas, the metals with lower reduction potentials readily undergo
corrosion (e.g. Zn, Mg, Al etc.).
1. Position of metal in galvanic series: Metals which possess low reduction potentials and occupy higher
end of galvanic series undergo corrosion easily.
2. Metals which possess high reduction potentials and occupy lower end of galvanic series do not undergo
corrosion and they get protected.
When two metals are in electrical contact in presence of an electrolyte, then the metal which is more active
undergoes corrosion. The rate of corrosion depends on the difference in their position in Galvanic series.
Greater the difference more will be the extent of corrosion at anode.
Example: The potential difference between Fe and Cu is 0.78V which is more than that between Fe and Sn
(0.30V). Therefore, Fe corrodes faster when in contact with Cu than that with Sn. on this account, the use
of dissimilar metals should be avoided wherever possible (E.g. Bolt & nuts, screw & washer).
4. Relative areas of anodic and cathodic cells: The relative areas of corrosion is influenced by cathodic
to anodic cells. If the metal has small anodic and large cathodic area, the rate of corrosion is very high. This
is because the electrons are liberated at anode which is consumed at cathode. If the cathodic area is larger,
the liberated electrons are rapidly consumed at cathode. This further enhances the anodic reaction leading
to increase the rate of corrosion.
5. Passivity: If the corrosion product formed is more stable, insoluble and nonporous, it acts as protective
layer and prevents further corrosion (Eg. Ti, Al and Cr). If the corrosion product is porous, volatile and
soluble, it further enhances the corrosion (Fe, Zn and Mg).
Factors due to nature corrosive environment
1. Temperature: The rate of corrosion reactions increases with increase in temperature.
2. Humidity in air: The moisture or humidity present in atmosphere furnishes water to the electrolyte which
is essential for setting up of an electrochemical cell. The oxide film formed has the tendency to absorb
moisture which creates another electrochemical cell.
3. pH value: pH value of the medium has the greater effect on corrosion. Acidic pH increases the rate of
corrosion.
Types of Corrosion

What is galvanic corrosion? How is it prevented? Give examples?


Galvanic corrosion: This type of electrochemical corrosion is also called bimetallic corrosion. When two
dissimilar metals are connected and exposed to an electrolyte, they will form a galvanic cell. The anodic
metal will be oxidised and it will undergo corrosion. Zinc and copper metals connected with each other
in an electrolyte medium form a galvanic cell. Zinc acts as anode and undergoes corrosion while cathode
will be unaffected.

Eg: When Zn an Cu are connected and exposed to corroding environment, Zinc (higher in
electrochemical series) forms the anode; undergoes oxidation and gets corroded. Cu (lower in
electrochemical series) acts as cathode; undergoes reduction and protected as the electrons released by
Zn flow towards Cu.
Prevention:
1) Galvanic corrosion can be avoided by coupling metals close to the elec- trochemical series.
2) Fixing insulating material between two metals.
3) By using larger anodic metal and smaller cathodic metal.
Example of galvanic corrosion:
1) Steel screws in brass marine hardware,
2) steel pipe connected to copper plumbing,
3) steel propeller shaft in bronze bearing,
4) zinc coating on mild steel,
5) lead–tin solder around copper wires.

Anode: Zn Zn2+ + 2e-


Cathode: ½ O2 + H2O +2e- 2OH-
Net cell reaction : Zn + ½ O2 + H2O Zn2+ + 2OH-
Differential aeration corrosion: or Concentration cell corrosion:

If a metal rod is dipped in an electrolyte, the portion dipped in water is poor in oxygen concentration
and works as anode which gets corroded and the portion above water acts as cath-ode which is
protected. The system will act as a concentration cell and the chemical reactions for zinc dipped in water
are given as: Zn(OH)2 appears as corrosion products .Examples: Water line corrosion, Drop corrosion.

WATERLINE CORROSION

When water is stored in the steel tank, then corrosion starts, along the line beneath the level of water meniscus.
As we know that beneath the water level concentration of oxygen is very low therefore metal part below the
water level acts as anode and metal part above the water level have higher concentration of oxygen therefore
this region act as cathode. The reaction involve are as follows:

PITTING CORROSION

In pitting corrosion, a pit is formed when the protective coating on the metal surface break, a micro pit (anode)
formed on the metal surface. Once the pit is form the process of corrosion become very fast due to different
amount of oxygen in contact with metal surface. The portion (pit) with lower concentration of oxygen become
anode and portion with higher concentration of oxygen becomes cathode.
Corrosion Control Methods

➢ The amount of the material lost due to corrosion is substantial hence it is important to protect
the metals from corrosion.
➢ These methods rely on metal and
environment. Different corrosion control methods
are:
1. Cathodic protection
I. Sacrificial anodic protection method
II. Impressed current cathodic protection method
2. Protective coatings
A. Metallic coatings
B. Organic coatings - Paints (constituents and functions)
I. Cathodic protection
The method of protecting the base metal by making it to behave like a cathode is called as cathodic
protection.
There are two types of cathodic protection:
(a) Sacrificial anodic protection method
(b) Impressed current cathodic protection method.

SACRIFICIAL ANODIC PROTECTION METHOD


In this protection 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 parent structure (cathodic) is protected. The
more active metal so employed is called sacrificial anode. The corroded sacrificial anode is replaced by
a fresh one, when consumed completely.
Metals commonly employed as sacrificial anode are Mg, Zn, Al and their alloys which possess low
reduction potential and occupies higher end in electrochemical series.

Eg: A ship-hull which is made up of steel is connected to sacrificial anode (Zn-blocks) which undergoes
corrosion leaving the base metal protected.
Eg: The underground water pipelines and water tanks are also protected by sacrificial anode method. By
referring to the electrochemical series, the metal with low reduction potential is connected to the base metal
which acts as anode.

Fig 4: Sacrificial anode method: ship hull and underground water


pipeline
Advantages:
(a) No external current is required.
(b) Easy to install and inexpensive if installed at time of construction.
(c) Anode can be easily replaced.
(d) Minimum maintenance is required.
Limitations:
(a) Limited driving potential.
(b) Ineffective in high resistivity environment.
(c) Installation can be expensive if installed after construction.
Applications:
• Protection of buried pipelines, underground cables, water tanks etc.
IMPRESSED CURRENT CATHODIC PROTECTION
In this method, an impressed current is applied in opposite direction to nullify the corrosion current,
and convert the corroding metal from anode to cathode. The impressed current is slightly higher than

the corrosion current. Thus the anodic corroding metal becomes cathodic and protected from
corrosion. The impressed current is taken from a battery or rectified on A.C. line. The impressed
current protection method is used for water tanks, water & oil pipe lines, transmission line towers
Advantages:
❖ Large structure can be protected for long term operations.
❖ It can be applied in high resistivity environment.
❖ Effective in protecting uncoated and poorly coated structures
Limitations:
1. Requires periodic maintenance.
2. Requires external power, resulting in monthly power cost.
3. Over protection can cause coating damage.
4. It is subject to power failure.
Applications:
❖ This method is applied in protecting water tanks.
❖ Open water-box cooler.
❖ Buried oil and water pipes
❖ Transmission line towers.
❖ Marine Pipes.

METALLIC COATING

GALVANIZATION

Galvanizing is the process of coating iron or steel sheets with a thin coat of zinc to prevent
them from rusting. For carrying out galvanizing firstly the iron or steel article such as sheet,
pipe or wire is cleaned by pickling with dil H2SO4 solution for 15-20 mts at 60-900C. In pickling
any scale, dirt, oil, grease or rust and any other impurities are removed from the metal surface.
The article is washed well and then dried. It is then dipped in bath of molten zinc maintained at
425- 430oC. The surface of bath is kept covered with ammonium chloride – flux to prevent oxide
formation. The article is covered with a thin layer of zinc when it is taken out of bath. It is then
passed through a pair of hot rollers, which removes any excess of zinc and produces a thin film
of uniform thickness then it is annealed and finally collected slowly.
Uses: - Roofing sheets, wires, pipes, nails, bolts, screws, buckets, tubes etc. which are made of
iron are protected from atmospheric corrosion by galvanizing them. But galvanized utensils cannot
be used for preparing and storing food stuffs, especially acidic ores since zinc gets dissolved in all
acids forming highly toxic compound

TINNING

Tinning is a coating tin over the iron or steel articles. The process consists in first treating steel sheet in dilute
sulphuric acid (pickling) to remove any oxide film. After this, it is passed through a bath of zinc chloride flux.
The flux helps the molten metal to adhere to the metal sheet. Next, the sheet passes through a tank of molten tin
and finally through a tank of molten tin and finally through a series of rollers from underneath the surface of a
layer of palm oil. The palm oil protects the hot tin -coated surface against oxidation. The rollers remove any
excess of tin and produce a thin film of uniform thickness on the steel sheet.

Uses: tin possess considerable resistance against atmospheric corrosion. Moreover, because of non-toxic
nature of tin, tinning is widely used for coating steel, copper and brass sheets, used for manufacturing
containers for storing foodstuffs, ghee, oils, kerosene and packing food materials. Tinned- copper sheets
are employed for making cooking utensils and refrigeration equipments

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