Corrosion

Patina
 Corrosion
• Corrosion is the deterioration or destruction and consequent loss of a solid
metallic material due to chemical, electrochemical and other reactions of the
exposed material surface with the surrounding environment.

• Corrosion represents a return of metals to their more natural state as minerals

(oxides).

• Deterioration of metals through oxidation- usually but not always- to their

oxides.
Element Element Ore Formula

•Bauxite •Al2O3.2H2O
Aluminium •Cryolite •Na3AlF6
Why are metals not found in their free state? •Corundum •Al2O3

•Zinc blende •ZnS

Zinc •Calamine •ZnCO3
•Zincite •ZnO
•Haematite •FeO3
•Magnetite •Fe3O4
Iron •Iron Pyrites •FeS2
•Spathic Iron Ore •FeCO3

•Malachite •CuCO3•Cu(OH)2
Copper •Chalcopyrite •CuFeS2
•Copper Glance •Cu2S
 Consequences of Corrosion

✓ Due to formation of corrosion product over the machinery, the efficiency of

the machine gets lost.

✓ The products are contaminated due to corrosion.

✓ The corroded equipment must be replaced frequently.

✓ Plant failure due to corrosion.

✓ Corrosion releases toxic products, health hazard, etc.

Basics of Corrosion
Corrosion is essentially the oxidation of metal

Need:
1. An Anode (where oxidation is taking place)
2. A Cathode (where reduction is taking place)
3. Conductive electrolyte
4. Electrical contact between the Anode and Cathode
Different Theories of Corrosion

Corrosion

Chemical Electrochemical
or or
Dry Corrosion Galvanic
or
Wet Corrosion
 Dry or Chemical corrosion
Dry corrosion is due to the attack of metal surfaces by the
atmospheric gases such as oxygen, hydrogen sulphide, sulphur
dioxide, nitrogen, inorganic liquids etc.

There are three (sub-classification) main types of dry corrosion;

1. Oxidation corrosion (or) corrosion by oxygen

2. Corrosion by other gases

3. Liquid – Metal corrosion.

 Oxidation Corrosion

• Oxidation corrosion is brought about by the direct attack of oxygen at

low or high temperatures on metal surface in the absence of moisture.
• Alkali metals like (Li, Na, K, etc) and alkaline-earth metals (Mg, Ca,
Sr, etc) are rapidly oxidized at low temperature.
• At high temperature, almost all metals (expect Ag, Au and Pt) are
oxidized.

M2+
n+ −
2M → 2M + 2 ne O2-

n
O 2 + 2 ne − → nO 2 − Metal M2+ O2- Atmosphere
2
n Mn+
2M + O 2 → 2M n + + nO 2− O2-

MO (Metal oxide)
 Oxidation Corrosion
The nature of oxide film formed on the metal surface plays in important role in
oxidation corrosion.

• Stable oxide layer: a protective coating and no further corrosion can occur.
Example: Al, Sn, Pb etc.

• Unstable oxide layer: mainly produced on the surface of noble metals, which
decomposes back to the metal and oxygen.

Example: Pt, Ag, etc.

• Volatile oxide layer: The oxide layer volatilizes as soon as it is formed,

leaving the metal surface for further corrosion.

Example: Molybdenum oxide.

• Porous oxide layer: Metal oxides having pores and cracks allow penetration
of oxygen to the underlying metal, resulting in the complete conversion of
metal into its oxide.
Example: Rust
 Corrosion by Other Gases
• Corrosion by other gases such as Cl2, SO2, H2S, CO2, F2 or NOx

• The extent of corrosion depends upon the chemical affinity between

metal and the gas.

• In dry atmosphere, these gases react with metal and form corrosion
products which may be protective or non-protective.

• Protective: Intensity or extent of attack decreases after layer formed.

Dry Cl2 reacts with Ag and forms AgCl

• Non-protective: Continuous Attack

SnCl4 is volatile
 Liquid– Metal Corrosion
This is due to the chemical action of flowing liquid metal at high
temperature on the surface of another metal.

The corrosion reaction involves

• Dissolution of a solid metal by a liquid metal

• Liquid metal may penetrate in to the solid metal.

Al

Ga

Gallium is corrosive
Liquid metal
Solid metal base to Aluminium
 Wet or Electrochemical Corrosion
Wet corrosion occurs under the following conditions,

• When two dissimilar metals are in contact with each other in the
presence of an aqueous solution or moisture.

• When conducting liquid is in contact with metal.

Zn undergoes corrosion

Electrolyte Electrolyte
Anodic

Zn, Anode Fe, cathode

EoZn = -0.76V EoFe = -0.44V Cathodic
Fe undergoes corrosion
 Wet or Electrochemical Corrosion
When one part of the metal acts as anode and the other as cathode and
corrosion occurs, and the following electrochemical reactions occur.

At anode: oxidation or dissolution of metal takes place at this electrode

releasing electrons

M → M2++ 2e-

At cathode: Reduction takes place using the electrons released at the anode.

Depends on the nature of the corrosive environment.

• Hydrogen evolution type corrosion (Acidic solutions)

• Hydroxide ion formation corrosion (Neutral/alkaline medium)
 H2 evolution corrosion
If the corrosive environment in acidic in nature, hydrogen gas is evolved

Acidic environment: H+Cl- H+Cl-

Cathodic part
2H+ + 2e- H2

Fe Fe2+ + 2e-

Fe metal: Anodic part

As per the following reaction occurring at the cathode

2H+ + 2e- H2
 Formation of OH- Type Corrosion
• Anode: Fe undergoes dissolution to Fe2+ with the liberation of electrons.

• Cathode: Liberated electrons follow from anode to cathode, where dissolved O2 is

consumed to form OH- ions.

½ O2 + H2O + 2e- → 2 OH-

Fe2+ + 2 OH- → Fe(OH)2

Fe(OH)2 + 2 H2O + O2 → 4 Fe(OH)3 Or Fe2O3

Atmosphere: Neutral electrolyte

H2O O2
H 2O O 2
H2O O2
Fe(OH)3
Fe2+ 2e-

Iron oxide film

Fe metal (cathodic) )part) Crack (anodic part)

Fe Fe2+ +2e-
Corrosion occurs
 Examples for Wet corrosion – Types/Forms

Electrochemical Corrosion

Differential Metallic or
Localized
Bimetallic
• Pitting
Galvanic
• Stress Corrosion
More negative electrode
• Waterline Corrosion
potential act as an anode
• Fretting Corrosion
• Concentration Corrosion
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 GALVANIC CORROSION
• When two different metals are in contact with each other in the presence of an aqueous
solution (or) moisture, galvanic corrosion occurs.

• The more active metal (with more negative electrode potential) acts as anode
and the less active metal (with less negative potential) acts as cathode.

e.g. Steel screw in a brass marine hardware corrodes. Iron (higher position in
electrochemical series) as anode, is attacked and corroded, while Copper (lower in
electrochemical series) acts as cathodic and is not attacked.

Electrolyte

Fe, Anode Cu, Fe undergoes corrosion

EoZn = - cathode
0.44V EoCu =
+0.34V
 Pitting corrosion
• Pitting occur when there is break in protective oxide layer and
imperfections on the underlying metal.
• Caused by localized mechanical damage, chemical damage to a metal’s
oxide film, or poor application of protective coating.
• ”Pits” or “holes” range from deep cavities of small diameter to shallow
depression.
Pitting corrosion
 Concentration Corrosion
• It is due to the presence of oxygen electrolytic cell, i.e. difference in the
amount of oxygen in solution at one point exists when compared to
another.

• Corrosion is accelerated when the O2 is least, for example, under gasket,

stuffing boxes etc.
 Waterline corrosion
• Occurs when a metal is exposed to varying concentration of oxygen or
any electrolyte on the surface of the base metal.
• Metals partially immersed in water (or) conducting solution (called water line
corrosion).
• If a metal is partially immersed in a conducting solution the metal part above the
solution is more aerated and hence become cathodic.
• On the other hand, the metal part inside the solution is less aerated and thus,
become anodic and suffers corrosion.
Zn
Water rod
line More oxygenated part (Cathodic
part)
1/2O2 + H2O + 2e- 2OH-
Brine solution
Zn2
+

Less oxygenated part (anodic part)

Zn2
+ Zn Zn2+ +2e-
ZnCl2 Undergoes corrosion

Zn2+ + 2OH- Zn(OH)2

 Stress Corrosion
• Metal develop internal stress during manufacturing process.
• Area under stress is high energy---- tend to oxidize--- ANODE
• Stress free area---- Cathode
 Fretting Corrosion
• Fretting corrosion occurs when metals slide over each other and cause mechanical
damage to one or both.

• During relative movement of metals, two process may occur,

• frictional heat is generated, which oxidize the metal to form oxide films.

• removal of the protective films resulting in exposure of fresh surface to corrosion

attack.
 Factors Affecting the Rate of Corrosion
Nature of the metal

1. Position of the metal in EMF series

Environment
More the diff. more the corrosion

2. Purity of the metal • Solution pH.

Pure is less prone • Oxidizing agent.
3. Relative area of Anode and Cathode
• Temperature.
Low anodic area and high cathodic
area • Velocity.
4. Physical state (Stress) on the metal • Surface Films.
5. Solubility of corrosion product • Other Factors.
6. Nature of the metal formed
Like volatile?
 Control of corrosion

1. Materials selection
2. Alteration of the Environment
3. Proper Design of articles – Avoid Crevice and sharp bends

4. Cathodic protection methods:

5. Anodic protection method:
6. Corrosion Inhibitors:
7. Protective coating:
 Materials selection
Materials selection
• Using Pure Metals: Impurity in metal causes heterogeneity that leads
to corrosion.

• Using Metal alloys: Corrosion resistant

Example: Cr in Fe or steel produces stable oxide film, which protect the
steel from further corrosion.

• Large anodic area of the metal

• position of the metals in the galvanic series

 Alteration of the Environment
Typical changes in medium are:

• Lowering temperature –

• Removing oxygen or oxidizers – De-aeration or Hydrazine

• Removing Moisture: Dehumidification by silica gel or Alumina

• Alkaline neutralization– Acidity decrease

 Proper Design
• Wall thickness – allowance to
accommodate for corrosion effect.

• Avoid excessive mechanical stresses and

stress concentrations in components
exposed to corrosive mediums.

• Metallic Contact: Avoid galvanic contact

• Avoid crevices – e.g weld rather than

rivet tanks and other containers, proper
trimming of gasket, etc.
 Cathodic Protection methods

• The principle involved in cathodic protection is to force the metal

to be protected to behave like a cathode.

• Since, there will not be any anodic area on the metal, corrosion
will not occur.

There are two types of cathodic protection

• Sacrificial anodic protection method

• Impressed current cathodic protection method

 SACRIFICIAL ANODIC PROTECTION METHOD
• In this method, the metallic structure to be protected is made cathode by
connecting it with more active metal (anodic metal).
• All the corrosion will concentrate only on the active metal
• The artificially made anode thus gradually gets corroded protecting the original
metallic structure
• Hence this process is otherwise known as sacrificial anodic protection.
 Examples of sacrificial anode:
• This method is used for the protection of ships and boats.
• Sheets of zinc and magnesium are hung around the hull of the ship
• Zinc and magnesium being anodic to iron get corroded.

Insulated copper wire

Sacrificial Zn or
Ship hull Mg
 IMPRESSED CURRENT CATHODIC PROTECTION
• In this method, an impressed current is applied in the opposite direction to nullify
the corrosion current and convert the corroding metal from anode to cathode
• This can be done by connecting negative terminal of the battery to the metallic
structure to be protected
• Positive terminal of battery is connected to an inert anode. Inert anode used for
this purpose is graphite (or) platinised titanium.
 Anodic Protection Method
• The principle involved in anodic protection is to force the metal to be protected
to behave like a “more anodic”.

• Used for metals which form protective layer, like Al, Cr, Ni etc.

• In this method, a predetermined potential is applied to the metal specimen and the
corresponding current changes are observed.

• During the initial stage, the current increases indicating the dissolution of the
metal.

• When the current reaches a critical point, passivisation occur, i.e., the oxide layers
set in suitable oxidizing environment.

• At this stage, an increase in potential will not be corrode the metal since the later
is in highly passive state.
 CORROSION INHIBITORS

A corrosion inhibitors is a substance which when added to in small

quantities to the aqueous corrosive environment effectively decreases
the rate of corrosion of the metal.

Inhibitors are classified in to three types,

1. ANODIC INHIBITORS
2. CATHODIC INHIBITORS
3. VAPOUR PHASE INHIBITORS
 ANODIC INHIBITORS
• Chromates, phosphates, tungstates of transition elements, inhibit the anodic
corrosion reaction by forming sparingly soluble compound with a newly
produced metal ion.
• They are absorbed on the metal surface forming a protective film or barrier
thereby reducing corrosion rate.
• This kind of corrosion rate is not fully reliable since certain areas left uncovered
by the film can produce severe corrosion.

Inhibitor
Iron metal rod immersed in
NiCrO4
corrosive medium

corrosive medium
Protective metal
chromate layer Ni2+ CrO42- + Fe3+ → Fe2(CrO4)3
Iron (III) Chromate
 CATHODIC INHIBITORS
• In acidic solution, the main cathodic reaction is evolution of hydrogen.
2H+(aq) +2e- → H2 (g)
• In an acidic solution, the corrosion can be controlled by slowing down the
diffusion of H+ ions through the cathode.
• This can be done by adding organic inhibitors like amines, pyridine, azoles, etc.
They absorb over the cathodic metal surface and act as a protective layer.

Cathode

H2

2e-
Anode
Fe2+

2H+

2H+ 2Cl-
• In a neutral solution, the cathodic reaction is,

H2O + ½ O2 + 2e- → 2OH-(aq)

• The formation of OH- ions is only due to the presence of oxygen.

• By eliminating the oxygen from the medium, the corrosion rate can be
reduced.

• O2 can be removed by adding some reducing agents like, N2H4, Na2SO3 or by

de-aeration.

• Salts of Zn, Mg, Ni are employed as they form insoluble metallic hydroxide
which forms impermeable self barriers.
 VAPOUR PHASE INHIBITORS
Vapour phase inhibitors are organic substances which readily sublime and
form a protective layer on the metal/material surface.

Example : Dicyclohexyl ammonium nitrite

Benzotriazole

Mainly used for metal corrosion

Benzotriazole is an effective corrosion
protection such as automobiles,
inhibitor for copper and its alloys by
internal combustion engines,
preventing undesirable surface
machine tools and tools, spare parts.
reactions. It forms a passive layer, by
It forms a thin protective layer
forming a complex with copper
which can be removed easily
Protective coatings/Metallic coatings

39
 Methods for Metallic Coating

1. Hot dipping
2. Metal cladding
3. Electroplating
4. Cementation
5. Vacuum metalizing
6. Metal spraying
 Hot Dipping
• It is one of the common method of applying metallic coating on the surface
of base metals.
• Hot dipping is a process of coating the base metal by immersing it in the
molten liquid of the metal to be coated.
Examples: Galvanizing and Tinning
 Galvanization process
NH4Cl flux to
avoid ZnO
formation
Hot air Galvanized
Steel sheet Steel Sheet
Pair of Hot
rollers

Annealing
chamber
250oC

Hot air

Washing bath Molten Zn at Excess Zn

Dil. H2SO4 at Collector
60 – 90oC 425 – 430oC

• Coating of Iron pipes, screws, bolts, wires, etc.

• Poisonous for utensils that store food stuffs
 Tinning
Tinned
ZnCl2 flux to Steel Sheet
Steel sheet avoid SnO
formation

Hot rollers

Dil. H2SO4 at
60 – 90oC
Molten Sn Palm oil
Acid Pickling

• Used for the coating of steel, Cu and brass sheets that store food
stuffs.
 Metal Cladding
• It is the process of sandwiching the base metal between two thin layers of
coating metal by hot-rolling the composite to produce a firm bonding.

• The coat metals are usually metals of least reactivity (Cu, Ni, Ag, Pt, Ti)

• Duraluminium (90% Al and Cu, Mg, Mn) sandwiched between Al sheets and hot
rolled to produce Alclad composite which is free from stress corrosion

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 Electroplating
Electroplating is the process in which the metal to be coated is deposited
on the base metal (substrate) by passing a direct current in the presence
of electrolytic solution containing the soluble salt of the metal to be
coated.
 DC battery

Cu (Anode) Steel object

+ ve Cu2+
(cathode) (-ve)
Cu2+

Cu2+ SO42-
Cu deposited
surface

Process
Ionization reaction of electrolyte:
CuSO4 Cu2+ + SO42- ; H2SO4 2H+ + SO42-

On passing current:
Cu2+ + 2e- Cu (at cathode)
Cu + SO42- CuSO4 + 2e- (at anode)
 Organic Coating
• Organic coatings act as a protective barrier against corrosion and
oxidation.

• These are durable coatings applied to a substrate for their decorative

or specific technical properties.

• Organic coatings depend primarily on their chemical inertness and

impermeability.

• Various types of organic coatings are available for industrial purposes

including primers, adhesive cements and topcoats (enamel, varnish
and paints).

• Organic coatings are easy to apply with the help of brushes, sprays,
rollers, dips, or by electrostatic means.

• The coating cures or dries by evaporation or loss of solvent,

polymerization and oxidation.