Unit II Corrosion & corrosion control

Corrosion :
Types –dry and wet corrosion, causes of corrosion –Forms of
corrosion [Differential aeration, pitting, Galvanic(Galvanic series)],Factors
influencing corrosion, corrosion control.
Corrosion control:
Protective coatings –Electroplating,Galvanising, Tinning, Metal
cladding–Definition, Process and applications, Physical& Chemical vapour
deposition.
 Natural Abundance of Metals

In the form of oxides, carbonates,

chlorides, silicates etc.
Corrosion
Any  process  of  deterioration  and 
consequent  loss  of  solid  metallic  material, 
through an unwanted chemical or electrochemical 
attack by its environment
Corrosion
(Oxidation)
Metal metallic compounds + Energy
Extraction of
Metals
Types
• Acid Corrosion
• Dry or Chemical Corrosion
• Wet or Electrochemical Corrosion
Dry or Chemical Corrosion

1.Oxidation Corrosion

2.Corrosion by other gases

3.Liquid Metal Corrosion

Oxidation Corrosion
Oxygen present in the atmosphere attacks the
metal surface
– formation of oxide layers
2M n+ +2n e-
2M
n - n O2-
O
2 2 + 2n e
n
+
2M 2 O2 2 Mn+ + n O2- (or) MO
Mechanism
Nature of the Oxide
– When oxidation starts, a thin layer of oxide film will be
formed on the surface and the nature of the film decides the
further action!
i.e. Porous film or non-porous film
Pilling – Bedworth rule

If the volume of the metallic oxide is equal or greater in

volume to the metal surface
- The metal surface is compact, non-porous
productive

Eg. Cu, In, Al, Ni, Cr forms oxides whose volume is

greater than the volume of the metal

If the volume of the metallic oxide is less than the

volume of the metal surface
- the oxide layer is porous, non-protective

Eg. Alkali and alkaline earth metals – Li, Na, K, Mg

The oxide films are classified as
1. Stable oxide layer

A fine-grain of oxide which forms a compact surface

adhered tightly to the parent metal surface
Eg. Oxides of Al, Sn, Cu, etc.

Impervious in nature (which cuts of the penetration of O2)

Such a films behaves like a protective Coating

2. Unstable oxide layer

Metallic Oxide Metal + Oxygen

Oxides of noble metals such as platinum, silver etc.

3. Volatile layer

Oxide layers volatilize as soon as they are formed

Excessive corrosion
Molybdenum oxide (MoO3)

4. Porous Oxide layer

Oxide layers with minute pores

Volume of the oxide layer is ……….. than metal

Corrosion ……………..
Corrosion by other gases
SO2, CO2, Cl2, H2S, F2 etc.
The extent of corrosive effect depends mainly on the chemical
affinity between the metal and gas

It can form

Protective layer (AgCl)

Non-protective (SnCl4)
Liquid Metal Corrosion

Chemical action of flowing liquid metal at high

temperatures on solid metal or alloy

a. dissolution of solid metal by liquid metal

b. internal penetration of the liquid metal in to the solid
metal
 Wet or Electrochemical Corrosion
¾When a conducting liquid is in contact with the metal

¾When two dissimilar metals or alloys either immersed or

partially dipped in a solution
Existence of separate “anodic” and “cathodic” areas/parts,
between which current flows through the conducting solution
At Anode
n+ n e -
M M + Corrosion Always 
Dissolves in solution occurs at anode
Forms compounds like oxides
At Cathode

Reduction reaction- Gain of electrons

Cathodic reactions do not affect the cathode – Most of the metals

can’t be reduced
The principle of electrochemical corrosion is
involved in the following types of corrosion

1.Hydrogen Evolution Corrosion

2.Oxygen absorption corrosion

3.Galvanic Corrosion

4.Concentration Cell Corrosion
Galvanic Series
 Factors Influencing Corrosion
Nature of the

Metal Environment
Position in galvanic series Temperature
Humidity
Overvoltage
Presence of impurities in atmosphere
Relative areas of anode and cathode Suspended particles
Purity of the metal
pH
Physical state of the metal
Silicates
Nature of the surface film
Conductance
Passive character of the metal
Formation of O2 conc. cell
Solubility of corrosion products
Flow velocity
 Corrosion Inhibitor

Corrosion can be reduced by using corrosion

inhibitor, which is a substance when added in small
quantities to the aqueous corrosive environment,
effectively decreases the corrosion of a metal.

Inhibitors are mainly anodic inhibitors and cathodic

inhibitors.
 Anodic Inhibitors
Anodic inhibitors are the substances which reduce the
corrosion occurring at anode by forming sparingly soluble
salts with the metal ions produced. Eg. tungstates, chromates,
phosphates etc.

Metal surface adsorbs metal ions to form a protective layer to

reduce the corrosion rate. Even though the corrosion control
is highly effective, local corrosion may occur in case of
exposure of even small area.
 Cathodic inhibitors
Cathodic inhibitors are mainly added to reduce the diffusion
of hydrated H+ ions to the cathode. The H+ ions formed are
combining to form hydrogen gas, which is evolved.
2H+(aq) + 2e- → H2(g)
The formation of H2 gas can be controlled by increasing the
overvoltage of hydrogen evolution.

Organic inhibitors like amines, mercaptans, heterocyclic

nitrogen compounds, substituted ureas, thio ureas, heavy
metal soaps reduce the diffusion of H+ ion considerably.

These inhibitors are being adsorbed at the metal surfaces and

form an adherent film of metals at the cathodic area thereby
increase the hydrogen overvoltage considerably.
 Cathodic Inhibitors
However, in neutral solution, the cathodic reaction is
H2O + ½ O2 + 2e- → 2OH-
Hence, the corrosion can be controlled either by removing
oxygen from the corroding environment or by reducing its
diffusion to the cathodic areas.

The oxygen can be eliminated by adding reducing agents like

Na2SO3 or by deaeration. The diffusion of oxide ion is reduced
by using inhibitors like Mg, Zn or Ni salts.

These react with hydroxyl ions forming corresponding

insoluble hydroxides, which are deposited on the cathode
forming impermeable self barrier.
 Electroplating
It is a process by which a coating metal is deposited on the
base metal by passing direct current through an electrolytic
solution, containing the soluble salt of the coating metal.

Electroplating is done both for protecting the metal from

corrosion and for decorative purposes.

A well cleaned and properly pre treated surface of any

material to be electroplated is necessary for obtaining the
coating of long life.

To get an adherent coating, base metal should be free from

any dirt and extraneous matter like grease.

To get good film complexing agents, organic additives,

levelers, structure modifiers and wetting agents are added.
 Electroplating
Current density is adjusted to get an adherent film. The
electrolyte is selected in such a way that it is a good
conductor and highly soluble.

It should not undergo hydrolysis, oxidation, reduction and

other chemical changes. It should possess sufficient
covering power.

Hence mixture of two or more electrolytes is used for

preparing electrolytic bath.
 Electroplating

For a good electrodeposit, the pH of the bath must be

properly maintained. For most plating baths, pH ranges
from 4 to 8.

Electroplating method depends upon the type of metal to be

electroplated, the size and type of article to be electroplated,
its main objectives and economics involved.

Normally plating is carried out in rectangular tank made of

wood or steel with a ceramic or polymer layer inside so as
to provide thermal insulation. The volume varies between
25 to 2000 L.
Electroplating
 Plating bath solution

It is a highly conducting salt solution of the metal which is

to be plated. However, non-participating electrolytes are
added to the bath solution to increase the conductivity and
the throwing power.

The level of the plating bath should cover completely the

cathode and sufficient area of anode. Heating if required is
provided by heating coils or hot gases. Air sparger or
nitrogen sparger is employed to introduce convection current
in the plating bath solution.

DC source is used for electroplating with a voltage of 8-12V

and a current density of 1-200 mACm-2.
In large plating operations, pumps and filters are
employed to filter out regularly the metallic particle. The
anode sludge can be retained by anode in cotton bags.

Copper, brass or Al bus bars are usually employed for

supplying the power to electrodes. The anodes and
cathodes are suspended alternatively from the bus bars
through the entire width of the tank. Usually, anodes are
made of the plating metal, but in some cases insoluble
anodes are used.

Anodes can be rod type, plate type or even as pellets kept

in mesh basket. Cathodes are either articles to be
electroplated or jigs connected to the bus bars.
 Physical Vapour Deposition
This is a process of depositing some material by atom by atom or
molecule by molecule or ion by ion.
Applications
1. This process is widely used to produce decorative coatings on
plastic parts those are resembling shiny metal.

2. Many automobile parts are plastic with a PVD coating of

aluminium.

3. A lacquer coating is applied over the decorative coating to

provide corrosion protection.

4. This process is also used to apply relatively thick (1mm) coatings

of heat resistant materials on jet engine parts, A special alloy of
chromium, aluminium and yttrium is used for this type of coating.
PVD – Thermal Evaporation
 PVD - Sputtering
Sputtering :
A popular method for adhering thin films onto a substrate.
Sputtering is done by bombarding a target material with a charged
gas (typically argon) which releases atoms in the target that coats the
nearby substrate. It all takes place inside a magnetron vacuum
chamber under low pressure.

1. High technology coatings such as ceramics, metal alloys and organic and
inorganic compounds are applied by sputtering.

2. The substance to be coated is connected to a high voltage DC power supply.

3. When the vacuum chamber has been pumped down, a controlled amount of argon
or another gas is introduced to establish a pressure of about 10-2 to 10-3 torr.

4. On energizing current supply, plasma is established between the work and the
material to be coated.
The gas atoms are ionized and they
bombard the material to be coated.

The energy of imposing ions cause atoms

of the target material to be sputtered off
and they are transported through the
plasma to form a coating.

Direct current sputtering is used when

the target is electrically conductive.

Radio-frequency sputtering, which uses a

RF power supply is used when the target
is a non conductor such as polymer.
 PVD – Ion Plantation
1. A third variation of the PVD process is ion plating.

2. Metal is evaporated thermally and plasma is established to ionize the

evaporating species

3. Evaporant ions bombard the substrate with energy

4. They physically implant into the substrate to produce an extremely

strong coating bond.

5. Sputter and ion plated coatings are used in design for very thin films for
electrical, optical and wear-resistant applications.

6. The wear properties of tools are widely enhanced by hard thin film
coatings.
PVD applications
 Applications
1. This process is widely used to produce decorative coatings on
plastic parts those are resembling shiny metal.

2. Many automobile parts are plastic with a PVD coating of aluminium.

3. used largely in the production of semiconductors

4. A polish coating is applied over the decorative coating to provide

corrosion protection.

5. This process is also used to apply relatively thick (1mm) coatings of

heat resistant materials on jet engine parts, A special alloy of
chromium, aluminium and yttrium is used for this type of coating.
 Chemical vapour deposition
Chemical vapour deposition or CVD is a generic name for a group of
processes that involve depositing a solid material from a gaseous phase
and is similar in some respects to physical vapour deposition (PVD).

PVD differs in that the precursors are solid, with the material to be
deposited being vaporised from a solid target and deposited onto the
substrate

Precursor gases (often diluted in carrier gases) are delivered into the
reaction chamber at approximately ambient temperatures. As they pass
over or come into contact with a heated substrate, they react or
decompose forming a solid phase which and are deposited onto the
substrate. The substrate temperature is critical and can influence what
reactions will take place.

Eg. Ni(CO)4 for the deposition of Ni

Chemical Vapour Deposition
CVD Apparatus
A CVD apparatus will consist of several basic components:
Gas delivery system – For the supply of precursors to the reactor chamber

Reactor chamber – Chamber within which deposition takes place

Substrate loading mechanism – A system for introducing and removing
substrates, mandrels etc

Energy source – Provide the energy/heat that is required to get the

precursors to react/decompose.

Vacuum system – A system for removal of all other gaseous species other
than those required for the reaction/deposition.

Exhaust system – System for removal of volatile by-products from the

reaction chamber.

Exhaust treatment systems – In some instances, exhaust gases may not be

suitable for release into the atmosphere and may require treatment or
conversion to safe/harmless compounds.

Process control equipment – Gauges, controls etc to monitor process

parameters such as pressure, temperature and time. Alarms and safety
devices would also be included in this category
 Chemical Vapour Deposition
Advantages and Disadvantages

• This coating finds application on glass containers to make explosion

or shatter resistant glasses.

• All surfaces in the reaction chamber get coated.

• Separate process and reaction must be developed for each coating.

Some of the gases are toxic and dangerous.

• But greatest disadvantage is temperature should be very high at 700°C.

At this temperature, many metals soften.
 CVD Applications
1. A newer process known as plasma assisted chemical vapour deposition. This process is
used to apply diamond and diamond like carbon coatings.
2. used largely in the production of semiconductors

3. Silicon carbide barrier coatings are applied on plastic films and semiconductors.

4. Chemical Vapour Deposition is used to produce bulk shapes of high purity silicon
carbide. Reactants are deposited on a chamber wall to a thickness in terms of
millimeters.

5. Thin-film coatings are key to the manufacture of many electronic devices. They
involve the application of dopant, sealant and other microelectronic paste.

6. Thermal evaporation is a low cost process, but all these processes are normally batch
processes because of vacuum chamber requirements.