Electrochemical corrosion

Mechanisms, control and prevention

Corrosion
Corrosion is the process of gradual and irreversible damage or
deterioration of a material due to the unwanted chemical or electro
chemical interaction with its environment on the surface.

 Metals get oxidized

 Cause of corrosion

• Metal exist in nature as its ore

• During extraction, energy is spent to get the pure metal from ore
• So the metal is thermodynamically unstable
• It has the tendency to go back to its original state

Metallurgical
Operation Environment
Ore of Metal Pure Metal Corroded Metal
Energy
Thermodynamically Thermodynamically Comparatively More
Stable Unstable Stable Than Pure
Metal
 Effect of corrosion

1. Loss of useful properties of metal

2. Loss of efficiency
3. Decrease in production rate since efficiency is less
4. Replacement of corroded equipment is time consuming
5. Increase in maintenance and production cost
6. Contamination of product

 Types of corrosion

 Chemical or Dry corrosion: under anhydrous condition

 Electro chemical or wet corrosion
1. Chemical or Dry corrosion
Direct interaction of metal surface with atmospheric gases or anhydrous liquid, leads
to chemical corrosion
It generally takes place in absence of moisture via

2 𝑀 + 𝑛 𝑂2 → 2𝑀𝑛+ + 2𝑛𝑂2− → 𝑀2 𝑂𝑛
Metal Ion Oxide Ion Metal Oxide

Alkali and alkaline earth metals get oxidized at low temperature

Other metals except Ag, Au and Pt gets oxidized at high temperature

Pilling-Bedworth rule:
Smaller the specific volume ratio between the metal oxide and metal, greater is
the corrosion
Volume of metal oxide
Specific Volume Ratio =
Volume of metal
Effect of chemical or dry corrosion
Thin layer of metal oxide formed at the surface of the metal. Different form of
corrosion may be

1. A stable, impervious and tightly bound oxide films on Cu or Al which acts as

protecting coating and prevents further corrosion
2. An unstable metal oxide film which decomposes back to metal and oxide. E.g.
Oxide corrosion on Ag, Au, Pt donot undergo oxidation corrosion
3. A volatile metal oxide which volatilized and exposed surface for further
corrosion. E.g. Mo undergoes volatile corrosion and hence faces excessive
corrosion 𝟐 𝑴𝒐 + 𝟑 𝑶𝟐 → 𝟐 𝑴𝒐𝑶𝟑
Volatile
Liquid metal corrosion

Liquid metal corrosion occurs when liquid metal is allowed to flow over solid
metal at high temperature. It leads to weakening of the solid metal due to
1) Its dissolution in liquid metal
2) Penetration of liquid metal into solid metal
e.g. Na metal leads to corrosion of Cd in nuclear reactor
2. Electro chemical corrosion or wet corrosion :
Mostly takes place under wet or moist condition through the formation of a
short circuit galvanic cells
More common than dry corrosion

 Electro chemical corrosion involves:

1. Separate anodic and cathodic parts between which current flows through the
conducting medium
2. Oxidation (corrosion) takes at the anodic areas which generates metallic ions
3. Non metallic ions like OH- or O2- are formed at the cathodic areas
4. Diffusion of metallic and non metallic ions towards each other through conducting
medium and formation of corrosion product somewhere between anodic and
cathodic areas
Rusting of iron
In neutral aqueous medium in presence of oxygen

In acidic medium with the evolution of Hydrogen gas

Fe2+ irons originates at anode and OH- ions originate at

cathode

Fe2+ ions diffuses more rapidly as the size is small, so corrosion occurs at
anode but rust deposited at cathode
Cathodic reaction

In presence of dissolved oxygen

a) In acidic medium: 4 𝐻 + + 𝑂2 + 4𝑒 − → 2𝐻2 𝑂
b) In neutral or weakly alkaline medium: 2𝐻2 𝑂 + 2𝑒 − → 𝐻2 + 2𝑂𝐻 −

In absence of oxygen

a) In acidic medium: 2𝐻 + + 2𝑒 − → 𝐻2 + 2𝑂𝐻 −

b) In neutral or alkaline medium: 2𝐻2 𝑂 + 2𝑒 − → 𝐻2 + 2𝑂𝐻 −
Comparison of Chemical Corrosion with Electrochemical Corrosion

Sl.
Chemical Corrosion Electrochemical Corrosion
No.
Occurs in wet condition (in the presence of
1. Occurs in dry condition
electrolyte moisture)
Involves direct chemical attack by Involves the setting up of a large number of
2.
environment galvanic cell
Explained by mechanism of electrochemical
3. Explained by absorption mechanism
reactions
Occurs on both homogeneous and
4. Occurs only on heterogeneous metal surface
heterogeneous surface
5. Corrosion is uniform Corrosion is not uniform
6. A slow process A fast Process
Corrosion product accumulates at the same Corrosion occurs at the anode & product
7.
place where corrosion occurs accumulates near cathode
Passivation:-
The phenomenon by which a metal or alloy shows high corrosion resistance
due to the formation of a highly protective, very thin and quite invisible
surface coating

Passivation takes place only in certain environment which tend to maintain the
protective film
e.g.: stainless steel alloy of Fe (Ti, Cr, Al, and Cr)

Exhibit outstanding corrosion resistance in the presence of Oxygen (Formed

Oxide film automatically repairs in oxidizing environment but corrode easily
in reductive environment)

Conc. HNO3 have no effect, presence of Cr maintain a protective oxide and

shows high corrosion resistance in HNO3 solution.
Galvanic series (Electrode potential series):-
The galvanic series plays a vital role in determining and preventing corrosion

Essentially, galvanic corrosion occurs when two different metals immersed in

an electrolyte are joined together.

Passivation makes effective electrode potentials of some metals more positive

so they act as cathodic and exhibit noble behavior
Difference between Electro chemical series and Galvanic series

Electrochemical series Galvanic series

Predicts the relative displacement Predicts the corrosion tendencies of both metals
tendencies of metals and nonmetals and non metals in actual environment
Depends on centration of salt in the It does not
electrolyte (Particularly the same metal)
Reference electrode is SHE Reference electrode is calomel electrode
Position of the alloy is not listed Position of the metal alloy is deferent from
metal
Effect of environment is not predicted Predicted
Types of Electrochemical corrosion

1. Galvanic corrosion
2. Pitting corrosion
3. Crevice corrosion
4. Concentration cell corrosion
5. Waterline corrosion
1. Galvanic corrosion or differential metal corrosion(DMC)

Galvanic Corrosion can occur when dissimilar metals are in contact in

the presence of an electrolyte.

Metal which is higher down in the electrochemical series can act as anode (low
electrode potential) and undergo corrosion

Eg, Zn (corroded) and Cu (protected) It can be minimized

• Zn and Ag Avoiding galvanic couple
• Fe and Cu Providing insulating material

𝑜 𝑜
𝐸𝑍𝑛 2+ /𝑍𝑛 = −0.76 𝑉; 𝐸𝐴𝑔 + /𝐴𝑔 = 0.80
2. Pitting corrosion
Localized corrosion of a metal surface confined to a point or small area, that takes the form
of cavities
This is usually found on passive metals and alloys such aluminum alloys, stainless steels and
stainless alloys
When the ultra-thin oxide film is chemically or mechanically damaged and does not
immediately re-passivate
Pitting corrosion

• Non uniform
• Results in the formation of pits or cavities
• Resulting from a localized accelerated attack
• Once a small pit is formed, the rate of corrosion is high
3. Crevice corrosion
Electrochemical oxidation-reduction (redox) process

Occurs within localized volumes of stagnant solution trapped in pockets, corners or

beneath a shield (seal, deposit of sand, gasket, fastener, etc.).
4. Concentration cell corrosion

When metallic surface is partially immersed in an electrolyte

and partially exposed to air

Poorly oxygenated metallic part becomes anodic and undergoes oxidation

𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 −
Well oxygenated part becomes cathodic

At the cathode, O2 takes up electrons to form OH- ions

1
𝑂2 + 𝐻2 𝑂 + 2𝑒 − → 2𝑂𝐻 −
2
The Zn2+ and OH- ions interact to give Zn(OH)2. Thus corrosion occurs at anode.
5. Water-line corrosion
When water is stored in a metallic tank, it is observed that the metal below
the waterline gets corroded

It is because the metal below the waterline is poorly oxygenated and acts as
an anode
The metal above the waterline is highly oxygenated and acts as a cathode
Hence corrosion of metal below the waterline takes place

Marine plants cause waterline corrosion to ocean going ships

Factors influencing corrosion

Sl.
Nature of The Metal Nature of The Environment
No.
1. Purity of metal Temperature

2. Physical metal of the metal Humidity

3. Nature of the oxide film Effect of PH

4. Position in the Galvanic Series Nature of electrolyte

5. Relative areas of the anode and cathode Conductance of the corroding medium

6. Solubilises of the product of corrosion Formation of Concentration Cell

7. Volatility of corrosion products Presence of impurities in atmosphere

Protective measures against Corrosion
Modification of the environment:
Either by removal of corrosion stimulant or by the use of corrosion inhibitors

Modification of the properties of metal:

e.g. alloying, refining, annealing etc

Use of protective coating (metallic, organic or inorganic) :

Cathodic protection, Electroplating etc
Cathodic protection
In acidic environment,
Metal undergoes oxidation(act as anode)
Accompanied by a reduction reaction

𝑀 → 𝑀𝑛+ + 𝑛𝑒 −
2𝐻 + + 2𝑒 − → 𝐻2

Cathodic protection prevents corrosion by

converting all of the anodic (active) sites on the metal surface to cathodic
(passive) sites
Two types cathodic protection:
1. Sacrificial anodic protection
2. Impressed current cathodic protection
1. Sacrificial anodic protection

• Metal is connected with a wire to a more active metal called sacrificial anode
• The corrosion is concentrated at the more active metal eg, Zn, Al, Mg and their alloys
• Zn is used when there is good electrolyte like sea water
• Mg is used in case of high resistivity electrolytes such as soil

Application (a) Protection of underground cable and pipelines from soil

corrosion

(b) Protection ships and boats hull from marine corrosion, Zn and Mg
sheets are hung around the ship which act as an anode

(c) In domestic water boilers or tanks, Mg is used to prevent the formation of

rusty water
2. Impressed current cathodic protection

Current from an external source is applied in opposite direction to nullify

the corrosion current

This convert the corroding anode to cathode and prevent corrosion

The anode may be an inert material such as graphite, carbon, stainless

steel, scarp iron
Impressed current cathodic protection

cathode

anode

Advantages
• Useful when electrolyte resistivity and current requirement are high.
• Well-suited for large structure and long term applications.
• Maintenance and operating costs are low
• Function well for buried structures such as pipe-lines, tanks marine piers,
transmission line towers, laid-up ships etc.
Electro plating
The process of plating one metal onto a base metal by passing current through
an electrolyte containing soluble salt of the coating metal to prevent corrosion of
the base metal

There are also specific types of electroplating such as copper plating, silver
plating, and chromium plating.

Electroplating enhances the resistance to corrosion, physical appearance,

hardness and surface properties

Clean metal is acting as a cathode and inert material such as carbon or graphite
act as anode

Metal electrolytes are deposited on cathode

 Electro plating

When direct current is passed, coating metal ions migrate to the cathode and get deposited
there in the form of thin-layer