CORROSION – Lesson 1

Dr.S.Kanungo
Dry Cell Batteries
Consequence…………..
Inference

Anode : Zinc Container

++ -
Zn 🡪 Zn + 2e

Cathode: carbon is conducting but not reacting. So the electrons released by anode
enter into reaction at the interface with the available +ve ions.
Takeaway: The electrochemical processes that
occur during galvanic corrosion make it ideal for
electricity generation and the protection of
specific steel elements.
• Galvanic corrosion is a degenerative electrochemical process that
occurs when two dissimilar metals are in contact with each other
while exposed to an electrolyte. During this type of corrosion, one
metal undergoes accelerated deterioration while the other metal
remains unaffected. In other words, one metal sacrifices itself by
corroding preferentially, thereby protecting the other metal.

• Although galvanic corrosion causes millions of dollars in damage

annually worldwide, there are instances where this electrochemical
process can be used to benefit specific applications.
 Electrochemistry
Electrochemistry is the study of chemical reactions using electricity.
• It can involve:
1. Electrolysis
2. Electroplating
3. Anodizing,
4. Electrorefining.
 Electrolysis
Electrolysis is the breaking down of a substance by an electric current.
It was used to discover new elements and split water, and eventually
led to a new field of science: electrochemistry. Many industrial
processes use electrolysis to separate useful elements from solutions.
Electroplating
Electroplating is the
use of electricity to
coat a thin layer or
metal on to an
object. This process
can produce
cheaper, stronger,
and less corrosive
products.
 Other Electrochemical Applications
Anodizing is a process to coat aluminum parts with a layer of aluminum
oxide. This makes the aluminum much stronger (e.g., iPods).
Electrorefining is used to remove impurities from metals (e.g., AuNO 3 ).

https://www.youtube.com/watch?v=1yaBrMNZHBw
 How Does Electrorefining Work?
1. Need a strong acid electrolyte.
2. Negative electrode is the impure
bar with gold.
3. Positive electrode is a pure thin
strip of gold.
4. Flow of electrons causes the gold
from the impure bar to dissolve
and then attach to the strip of
pure gold.
5. It can produce very pure gold.
 WILL MEET AGAIN

Stay Safe and Healthy

 Concept of Concept of
Galvanic Cell Electrolytic Cell
 Galvanic Cell
-
Electrical
e Continuity

cathodic reactions

ANODE 1. Electrolyte is distilled water

Cathode
NO REACTION
Anodic Reaction
+n - e- 2. Electrolyte is acidic water
A 🡪 A + ne e-
H2 e- H+ + 2e 🡪 H2
e-
A+ e- 3. Electrolyte is acidic water with
dissolved Oxygen
A+
4H+ + 4e + O2 🡪 2H2O
4. Electrolyte is water with
Electrolyte dissolved Oxygen
2H2O + 4e + O2 🡪 4OH-
21-09-2020
 Define Anodic And Cathodic Sites
Differential
Till now you know that Differential is based on Difference Between EMF due to material property.

THIS MEANS DISSIMILAR METALS

Examples ---- Cu/Zn, Fe/Al etc

CAN A GALVANIC CELL BE FORMED ON THE SAME METAL ????

LET US SEE
Differential

SW SW

Fig -1 Fig-2

Please form a Galvanic Cell

Stress Corrosion Cracking
 Crevice Corrosion
4. Electrolyte is water with
dissolved Oxygen
Remember this Cathodic Reaction ? 2H2O + 4e + O2 🡪 4OH- Does this give you any hint???

If a cathode exists , there has to be an anode…. And Vice a

versa
So where is the differential
…..
Mechanism -------
Differential Oxygen Concentration too.
M 🡪 M+ + e-

M+ + Cl- 🡪 MCl

MCl + H2O 🡪 MOH + HCl

2HCl + 2 M 🡪 2MCl + H2
Pitting Corrosion
Selective Leaching

De zincification
Graphitization
Cast iron differs from steel in that it has a higher carbon (>2%) and silicon (> 1%) content which makes it cheaper to produce than steel. Cast
iron corrosion resistance is comparable to that of carbon steel or even better depending on the alloy content. In view of the high carbon
content, graphite, which is cathodic compared with iron, forms in the alloy microstructure where it can be found as chips (grey iron) or nodules
(ductile iron) depending on its composition and heat treatment.

This potential differential creates a mechanism known as graphitic corrosion or graphitization; this phenomenon occurs in non-alloy cast iron
exposed to medium acid or soft water. Water that has a low hydrogen sulphide content (1 ppm) also encourages graphitisation. Graphitisation
tends to penetrate into the metal but at slow rates of progress. When this type of corrosion occurs, a layer of iron oxide containing graphite
forms on the surface. This layer preserves the shape of the part while corrosion is taking place and, therefore, this type of corrosion cannot be
detected by means of a visual inspection.

The service life of most cast iron components in aerated and alkaline domestic water systems at ambient temperatures has proved quite
satisfactory, mainly due to the thickness of moulded parts and to a uniform, moderate level of corrosion.

In the distribution system, cast iron network longevity can exceed one hundred years but, in the main, these systems will require protection in
the long term. In days gone by, the inside of cast iron pipes used to be protected using simple linings of the bituminous varnish type.
Nowadays, we use cement mortar based linings that will also withstand wastewater that contains sulphides. We are witnessing an increasing
use of linings based on an approved plastic material.

External protection against corrosion often consists of a several hundred micron thick bituminous coating. Added protection can be provided at
coating joins in the form of sacrificial anodes, zinc spray or a cathodic protection based on the potential imposed by the corrosive nature of the
ground.

The use of tubes constructed of ductile iron has increased strongly due to their high mechanical strength. These tubes have a slightly shorter
life expectancy compared with those constructed of grey iron because they are thinner and because of a faster rate of initial corrosion.
 What is Selective Leaching
Selective corrosion is observed in alloys in which one part or impurity is
clearly less noble than the other parts of the material. The corrosion
mechanism implies that the less noble element is removed from the
material. A porous material with very low strength and ductility is the
result.
Selective leaching is the removal of an element from an alloy by corrosion. The most common example
is dezincification, the selective removal of zinc in brasses. Many alloys are susceptible to selective
leaching under certain conditions. The elements that are more resistant to the environment remain
behind, provided they have a sufficiently continuous structure to prevent them from breaking away in
small particles.

Two mechanisms have been described for selective leaching: (1) two metals in an alloy are dissolved,
and one redeposits on the surface; and (2) one meta) is selectively dissolved, leaving the other metals
behind. Dezincification of brasses occurs by the first mechanism; the loss of molybdenum from nickel
alloys in the molten sodium hydroxide occurs by the second. In some alloys, selective leaching takes
place by either mechanism, depending on temperature and on the type, concentration, and flow rate of
the corrodent.
Intergranular Corrosion
Erosion Corrosion
Filliform Corrosion or Under Film
Corrosion
Filiform corrosion occurs under the protective paint film and
can be seen as thin filaments randomly distributed on the
surface. Filiform corrosion is mainly an aesthetic effect and
does not usually weaken the material or significantly reduce
its functionality.
The filaments start from an edge or a defect in the surface
coating. They have an active head and a corrosion product
tail; the corrosion occurs only in the active head of the
filaments, never in the inactive tails. The filaments tend to
move in straight lines and do not cross each other.
The relative humidity of the atmosphere is the single most
important factor for initiating filiform corrosion. The most
favourable humidity for filiform corrosion is 65-90%. The
type of the coating on the surface is less important and thus
filiform corrosion can be seen even under metallic coatings.
Coatings with very low moisture permeability inhibit filiform
corrosion.
Filiform corrosion is most often seen on aluminium
substrates, zinc-coated steel is less prone to this type of
corrosion defect.
Fretting Corrosion
Hydrogen Blisters
Corrosion Prevention
Selection of proper material
Corrosion should not be permitted in fine wire screen, orifice and other items in which the dimensions are critical and
change is not permitted.
In some cases, non metallic materials will be more economic and have good performance. It should be considered if their
strength, temp and design is satisfactory.
The corrosion characteristics of chemicals and limitation of construction material can be considered.
The processing conditions should also be considered.

Proper design of equipment

In the design of equipment, the number of fittings like, baffles, valves and pumps should be considered.
Corrosion can be minimized if the equipment design facilitates
Elimination of crevices
Complete drainage of liquids
Ease of cleaning
Ease of inspection and maintenance
A direct contact between two metal is avoided, if they are seperated widely in elecrochemical series. Or they should be
insulated.
Coatings and Linings
Nonmetallic coatings and linings can be applied on steel and other materials of construction in order to combat
corrosion.
Coating methods: electroplating, cladding, organic coating.
The thickness of lining is important.
Effective linings can be obtained by bonding directly to substrate metal or building multiple layers.
Organic coatings can be used in tanks, piping and pumping lines.

Altering Environment
Corrosion can be reduced by employing following conditions:
1. Removing air from boiler feed water prevents the influence of water on steel
2. Reducing the temp
3. Eliminating moisture
4. Reducing the velocity of turbulence
5. Shortening the time of exposure
6. Pumping the inert gas into solutions
7. Reducing aeration.
Inhibitors
The corrosion inhibitors are added to the environment to decrease corrosion of metals. This form protective films.
Adsorption type, e.g. adsorbed on metal
Scavenger phase type, e.g. remove corrosion agent
Vapor phase type, e.g. sublime and condense on metal surface.
Inhibitors are generally used in quantities less than 0.1 % by weight.

Inhibitors e.g. of inhibitors

Chromate, Phosphates & Silicates protect iron and Steel in aq solution.
Organic sulphide and Amines protect iron and Steel in acidic solution.
Copper sulphate protects S.S in hot diluted solution of H2SO4.
Cathodic protection
It is based on the galvanic action between the metals of the anode and cathode suspended in the solution.
The metals to be protected is made a cathode.
Electrons are supplied , there by dissolution of metal is suppressed.
It can be achieved by:
1. Sacrificial anode method
2. Impressed emf method

Sacrificial anode method

In this method, anodes are kept in electrical contact with the metal to be protected.
The anodes are sacrificed, since it goes into solution.
E.g. for the protection of iron and steel tanks, the metals such as Zinc, Al, Mg and their alloy are used as sacrificial
anodes.
This are used in limited pH range.
Anode metal is selected from electrochemical series.
The anodes should not be poisonous and not detrimental to the pdts
 Impressed emf method
It is also known as applied current system, i.e., external voltage is impressed between tank and electrodes.
The negative terminal of power is connected to the material to be protected.
So the natural galvanic effect is avoided and the anode is maintained positive.
Since anode is not consumed, metal or non corrodable material can be used