Corrosion and its Control

Metals exist in nature in combined forms as their oxides,

carbonates, hydroxy carbonates, sulphides, chlorides & silicates
(lower energy state).
During extraction process energy has been supplied to isolate the
pure metals (Excited state).
Corrosion
(Oxidation)
Metal Metallic Compound + Energy
(State of Extraction (State of low energy)
High energy) (Reduction)

Metals are exposed to environment, the exposed metal surfaces

begin to decay (destruction or deterioration) more or less rapidly
either by direct chemical attack or electrochemical attack.
Any process of deterioration (or destruction)
and consequent loss of a solid material, through
an unwanted (or unintentional) chemical or
electrochemical attack by its environment,
starting at its surface is called corrosion (Reverse
of Extraction Process).
Examples:
Reddish powder of iron oxide (Fe3O4)
Green film of basic carbonates on the surface of
copper (CuCO3 + Cu(OH)2)
Dry or Chemical Corrosion
Wet or Electrochemical Corrosion
Galvanic Corrosion
Concentration Cell Corrosion
Passivity
Pitting Corrosion
Inter-granular Corrosion
Waterline Corrosion
Stress Corrosion
 Dry or Chemical Corrosion: Direct chemical action of environment /
atmospheric gases such as O2, X2, H2S, SO2, nitrogen or anhydrous
inorganic liquid with metal surfaces in immediate proximity. There
are three main types of chemical corrosion. At ordinary temp.
metals in general are very slightly attacked. However alkali and
alkali earth metals are rapidly attacked even at low temp. At high
temp almost all metals are attacked.

The metal is oxidized by the loss of electron during corrosion.

2M 2Mn+ + 2ne-
These lost electrons are gained by oxygen for conversion into oxide ion.
n/2O2+2ne- nO2- (Oxide ion)
Hence the overall reaction can be
2M + n/2 O2 2Mn+ (Metallic ion) + nO2- (Oxide ion)
These two are forming metal oxide.
Further oxidation is restricted if the oxidation of the metal forms a
barrier since the oxidation occurs at the surface of the metal.
For further oxidation, there are two possibilities.

metal ions must diffuse through the scale to the surface from the
bulk. [Rapid - Due to the grater mobility since smaller size of the
metal ion (than the oxygen ion)]

The other one is the oxygen must diffuse inwards through the scale
to the underlying metal.
However, the nature of the oxide layer formed (product of corrosion)
plays an important role on the oxidation corrosion process.

After the formation of a layer of thin oxide film, further corrosion is

decided by the nature of the film.

Depending upon the nature of the film formed, the oxide layer can
be divided into four types.
stable,
unstable,
volatile
and
porous
Stable layer forms a tightly adherent film on the
metal surface.
Since it forms an adherent layer, it is impervious
to the attack of oxygen.
Such a film behaves as protective coating in
nature and hence further oxidation corrosion is
prevented. Hence it acts as a shield to the metal
surface.
Oxide films of Al, Sn, Pb, Cu are examples.
Unstable layer forms an oxide which decomposes
again into metal and oxygen.
As a result corrosion by oxygen is not possible in
such cases. Eg., Ag, Au, Pt etc.
These metals do not undergo corrosion as these
oxides decompose back to metal and oxygen.

Fig -1 Formation of unstable metal oxide

• Volatile layer volatilizes on formation, exposing fresh
surface of underlying metal.

• This speeds up the rapid and continuous corrosion

leading to excessive corrosion. Eg. MoO3.

• This is a volatile oxide and this exposes the Mo leading

to complete corrosion of Mo.

Fig - 2 Formation of volatile metal oxide

Porous oxide is having pores or cracks on the surface.
As a result atmospheric oxygen can reach the underlying
metal through the pores or cracks.
As a result the corrosion continues unabated, until complete
conversion of metal to its oxide.

Fig - 3 Formation of porous metal oxide

• Pilling – Bedworth rule.
• Formed oxide layer is non – protective if the volume of
formed oxide layer is less than the volume of the metal.
In this case the oxide layer allows oxygen inside the
metal.
• The layer formed by oxidation is protective if the volume
of the formed oxide layer is at least equal to the volume
of the metal from which it is formed.

• Alkali and alkaline earth metals (Li, Na, Mg etc.)are

forming non-protective oxides. As a result on slight
application of stress and strain, the corrosion takes place
and continues till the complete metal is exhausted.
Similarly, aluminium forms extensively tight – adhering
non-porous oxide layer.
 Corrosion by other gases

Corrosion is also caused by other gases like SO2,

CO2.Cl2, H2S, F2 etc. However, the corrosion effect
solely depends on the chemical affinity between
the metal and the corroding gas. The formation
of protective or non-protective film determines
the severity of the attack.
 Liquid metal corrosion
This corrosion is occurs mainly where the
flowing liquid is having chemical action on
metal or alloy at high temperature. This
corrosion is very much common in devices
used in nuclear power station. The corrosion is
due to dissolution of a solid metal by a liquid
metal or by internal penetration of the liquid
metal into the solid metal.
 Wet or Electrochemical corrosion
For wet corrosion to occur two conditions should be satisfied.
i) The presence of conducting liquid in contact with metal, the
presence of two dissimilar metals or alloys in contact in the
solution.
ii) The existence of separate cathodic and anodic areas is essential
for this type of corrosion to occur.

Between these two areas the current flows through the

conducting solution. At anodic area, oxidation (release of
electrons) occurs. This oxidation leads to the destruction of anodic
metal by dissolution. As a result corrosion takes place at the
anodic area. At anode the following reaction takes place.
M gives Mn+ + ne- (loss of electron-oxidation)

M Dissolves in solution - Forms compound

 In the cathodic area reduction reaction takes place (addition
of electrons) and this reaction does not affect the cathode, as the
metallic form is the most reduced form.
The dissolved constituents in the conducting medium
accept the electrons to form some ion like OH- and O2-.
The metallic ions (formed by the oxidation of cathodic
part) and the ions formed by the dissolved constituents by
reduction will be formed somewhere between the anode and
cathode.
Hence the electrons released by the anode will travel
through the conducting medium to the cathode where it will be
consumed.
Hence in a nutshell the anode, the cathode and conducting
medium are necessary for electrochemical corrosion.
The anodic part undergoes corrosion and the product is
formed somewhere between the anodic and cathodic areas.
 Mechanism of electrochemical corrosion
Electrochemical corrosion is caused by the flow of electrons from the anodic
area to cathodic area through the electrolyte. The anodic reaction is the
oxidation of metal to the metallic ion through oxidation with the liberation of
free electrons. The cathodic reaction is the reduction of hydrogen ion or
absorption of oxygen depending on the nature of the corrosion.

Evolution of hydrogen occurs usually in acidic environment. Eg metals like Fe

is oxidized into metallic ions with the liberation of electrons.

Fe Fe2+ + 2e- (Oxidation)

The electrons flow from anode to cathode through the electrolyte and evolve
hydrogen gas which is formed by the reduction of H+ ions

2H+ + 2e H2 (Reduction)

The overall reaction is Fe + 2H+ Fe2+ + H2

 Mechanism of wet corrosion by hydrogen evolution

Hence the type of corrosion causes displacement of hydrogen ions from the
anodic solution by metal ions. All the metals in the electrochemical series above
hydrogen have a tendency to get dissolved in acidic solution with the evolution
of hydrogen.
 Oxygen Absorption type
Absorption of oxygen mainly occurs in neutral solution. Eg. Rusting of iron in neutral solutions like NaCl
in the presence of atmospheric oxygen. An iron oxide films usually formed over the surface of iron.
However, a small exposure of the metal by a thin crack of this film forms the anodic area and the
rest of the surface of the metal acts as larger cathodes.

At anodic area the iron undergoes oxidation to form ferrous ions with the liberation of electrons

Fe Fe2+ + 2e- (Oxidation)

The liberated electrons leave the anode and travel to reach the cathode. But immediately after leaving
cathode they are intercepted by the dissolved oxygen and they form the hydroxide ions.

O2 + H2O + 2e- 2OH-

The Fe2+ ions from anode and OH- ions from the near cathode diffuse and they form ferrous hydroxide
as follows.

Fe2+ + 2OH- Fe(OH)2

Ferrous hydroxide is oxidized to ferric hydroxide on availability of enough oxygen.

4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3

This is actually the yellow rust and having the formula of Fe2O3.H2O. However, on limited supply of
oxygen anhydrous magnetite, Fe3O4, which is black in color, is formed.
 Factors influencing corrosion

The extent and rate at which corrosion occurs depend on the

following factors.

1. Nature of metal: When two metals or alloys are on electrical

contact with each other through an electrolyte, the metal

occupying the higher position in ECS (more active metal)

undergoes corrosion. The extent and rate depend upon the

difference in their positions. If they are far apart the corrosion of

the active metal will be more. However, in addition to the active

nature of metal the corrosion is also affected by the following.

(ii) Relative areas of the anodic and cathodic parts

On electrical contact through the electrolyte of the two

materials, the active material undergoes corrosion and the
corrosion is directly proportional to the ratio of areas of the
anodic part and cathodic part.

If the anodic part is very small the corrosion is severe and

very fast. Eg. small steel pipe in a large copper tank. Since
the current density is smaller, the demand for electrons by
large cathodic areas is great. This can be met by smaller
anodic areas only by brisk corrosion.
(iii) Purity of metal

Heterogeneity of metal results from the presence of impurities

in a metal. Presence of impurities in minute quantities form

electrochemical cells, as a result anodic part gets corroded. Eg.

zinc metal with impurities like Pb and Fe undergoes corrosion

rapidly because of the formation of local electrochemical cells.

The rate and extent of corrosion increase with the extent and

increase in exposure to the impurities. Hence the corrosion

resistance of a metal can be increased by increasing its purity.

(iv) Physical state of metal

The physical state of a metal influences the rate of

corrosion. Eg. grain size, stress and orientation of
crystals. The corrosion will be more if the grain size
of the metal or alloy is smaller. Because of its
smaller size the solubility will be more and hence
the corrosion will be more. Similarly under stress
even pure metal can act as anode and can undergo
corrosion.
(v) Nature of surface film

In an aerated atmosphere, all metals undergo corrosion initially

to form metal oxides. However, further corrosion depends on
the nature of oxide film formed.

The ratio of the volumes of the metal oxide to the metal is

known as specific volume ratio. If the specific volume is less,
the corrosion will be more.

The values of specific volume of Ni, Cr and W are 1.6, 2.0 and
3.6 respectively. As a result of this corrosion of tungsten is very
less even at high temperature.
(vi) Passive character of metal

The metals which are passive are having much higher corrosion
resistance than expected from the positions in galvanic series.
This is due to the formation of highly protective thin films of
oxides on the metal surface. Eg. Tl. Al, Cr, Mg, Ni and Co. The
greatest advantage of such films is self – healing. If broken
unexpectedly again it undergoes oxidation to form protective
oxide film on exposure to oxidizing conditions. Hence in stainless
steel the corrosion resistance is due to the passivation of
chromium present in it.
(vii) Solubility of corrosion products

The corrosion is proceeding at a faster rate if the corrosion

product is soluble in the corroding medium.

If the corrosion product is insoluble in the medium or as a

result of interaction with the medium it forms an insoluble
product, the corrosion product acts a protective one and
suppresses further corrosion.
(viii) Volatility of corrosion products
If the corrosion product is a volatile one, it
volatilizes as soon as it is formed leaving the
underlying metal surface exposed for further
attack.
This causes continuous and fast corrosion leading
to excessive corrosion. Eg. MoO3 the oxidation
product of molybdenum is volatile.
 Nature of the corroding environment

(i) Temperature
The rate of the corrosion is increased if the
temperature is increased since the corrosion
reaction and the diffusion of products are
enhanced.
(ii) Humidity
Humidity of atmospheric air is a deciding factor for corrosion. The
relative humidity above which the corrosion rate of the metal
increases sharply is known as critical humidity.
However, the value of critical humidity depends on the physical
characteristics of the metal and the nature of the corrosion
products. The gases and vapors present in the atmosphere
furnish water the electrolyte to the metal for setting up of an
electrochemical corrosion. This is the reason for the corrosion of
metal becomes faster in humid atmospheres. Even though the
oxide film formed by the initial corrosion is solid, it can absorb
moisture necessary for the occurrence of electrochemical
corrosion. As a result the rate of corrosion is increased. Similarly
the nature of moisture source also plays a very important role. Eg.
Rain water in addition to supplying necessary moisture can wash
the oxide film formed on the metal surface. This results in an
enhanced atmospheric attack, if the film formed is not
exceptionally adherent. Adherent films can be formed by Cr and
Al.
(iii) Presence of impurities in atmosphere
In industrial areas, the atmosphere contains corrosive
gases like CO2, H2S, SO2 and fumes of HCl, H2SO4.
In presence of these gases, the acidity of the liquid,
adjacent to the metal surface is more and the
conductivity is also more.
This results in an increase of corrosion current which
passes through the electrochemical cell that is set up
locally.
Similarly, in the marine atmosphere the presence of
the chlorides of metal like sodium chloride increase
the conductivity of the liquid layer in contact with the
metal surface. The speed of the corrosion increases in
this case.
(v) Nature of ion present
The presence of insoluble product forming ions like
silicates, which may come from silica gel, prevents
further corrosion.
If chloride ion is present, it will destroy the
protective, passive and non-reactive surface film.
This exposes fresh metal surface for corrosion.
Similarly presence of ammonium salts in the
corroding medium enhances the corrosion rapidly.
Eg. Iron.
Presence of even traces of noble metals like Cu
increases the corrosion of iron pipes as these noble
metals can act as cathodes with respect to anions
present.
(viii) Formation of oxygen concentration cells
The corrosion is prevented with increase in supply of
air/oxygen to the moist-metal surfaces.
Less oxygenated area becomes anodic whereas more
oxygenated parts become cathodic.
This formed a oxygen concentration cell in which the
anodic part suffers corrosion.
Anodic reaction (for example if iron is the metal)
Fe → Fe2+ + 2e-
Cathodic reaction
2H2O + O2 + 4e- → 4OH-
Corrosion due to concentration cell occurs when
oxygen concentration is less. Eg. Water line corrosion
of buried pipeline and cable and crevic corrosion.
(ix) Flow velocity of process stream
In corrosion, flow velocity plays an important role
which is diffusion controlled.
The corrosion of the metal is enhanced if the flow
velocity of the medium increases.
However, this is possible only when the metal
does not become passive under diffusion control.
In other words, minimization of flow velocity
decreases the corrosion rate in non-passive type
of metals.
(x) Polarization of electrodes
For electrochemical corrosion, the driving
force is the difference in potential between
the anode and cathode.
However, the corrosion depends on the
current flowing in the circuit.
The concentration of corrosive electrolyte
species gets accumulated at the anode and
depleted at the cathode.
This creates a concentration difference
between the area near the electrodes and the
body of the electrolytes.
• The addition of certain inorganic and organic
substances reduces the extent of corrosion.
• These substances are called corrosion inhibitors.
• Certain irreversible changes around the electrode
are caused by these inhibitors.
• These changes oppose the direction of the
corrosion current flow.
• This polarization reduces the potential of the
cathode to less cathodic and anodic to less
anodic. As a result, it reduces the corrosion rates.
(vi) Conductance of the corroding medium
Conductance of the corroding medium is very
important in underground corrosion and
corrosion of submerged structure.
The clay and mineralized soils have more
conductance than dry sandy soils.
As a result the stray currents from power
leakage can cause more damage to the
metallic structure when buried under clay
and mineralized salts than to those under dry
sandy – soils.
(vii) Influence of pH
In general alkaline and neutral media are less
corrosive than acidic media.
However, amphoteric metals like Al, Zn, Pb etc.
can dissolve in alkaline solutions as complex ions.
The corrosion rate of iron in oxygen free water is
slow if the pH is below 5. However, the corrosion
of iron in presence of oxygen is much higher. As a
result corrosion of metals, which are readily
attacked, can be reduced by increasing the pH of
the corroding medium. Eg. Zn suffers only mild
corrosion at a pH of 11 even though it is
amphoteric.
 Corrosion Control
1.Proper designing
The design of a material should reduce the localized corrosion
and it should occur uniformly. This can be achieved by
(i) avoid the contact between dissimilar metals in the presence
of a corroding medium. On contact of dissimilar metals the
corrosion will be highly localized on the more active metal.
(ii) if the two dissimilar metals are to be in contact with each
other the anodic material should have large area with respect
to cathodic material
(iii) if the two dissimilar metals are to be in contact with each
other choose in such a way that they are very close to each
other in electrochemical series.
(iv) apply an insulating fitting between two direct joining of
dissimilar metals which are to be in contact.
• (v) have no coating on the anodic part if the two
metals are in contact with each other. Because on
breaking down of the coating the localized
corrosion will occur.
• (vi) preventing the inhomogeneity in the metal
and in the corroding medium.
• Cervices should be avoided even if the metal is
same.
• Bolts and rivets are, therefore, undesirable and
these should be preferentially replaced by butt-
weld.
• If the cervices are unavoidable the corroding
medium is denied access to the cervices with an
impervious material or by painting.
 Fig- represents Different types of joints

avoiding sharp corners and recesses, since these are forming the stagnant area
and accumulation of solids.

Fig- represents Prevention of corrosion by having smooth corners

• (viii) supporting the equipment on legs to
allow free circulation of air and preventing the
formation of stagnant pools or damp areas.

• (ix) having an uniform flow of corrosion liquid.

Highly turbulent flows as well as stagnant
curves cause corrosion. Hence as much as
possible uniform flow rates should be
maintained.
(x) having proper design to give uniform stress to the entire structure.
A stressed area can develop galvanic cell by acting as anode

Prevention of corrosion by design

2. Using pure metal:
The corrosion can be avoided- by using pure
metal-which decreases the heterogeneity. By
increasing the purity corrosion resistance can
be improved.
• A coherent and impervious oxide film is
formed on the surface of pure Al, Mg etc.,
when exposed to environment.
• However, the corrosion resistance mainly
depends on the nature of corrosive
environment.
• For example the corrosion resistance of Al
depends on the oxide film which is highly
protective rather than pure metal.
• However, if the environment is alkaline both
pure Al and Al2O3 will undergo corrosion.
• The cost consideration and inadequate
mechanical properties like softness and low
strength prevents the production of metal of
high chemical purity.
• However, the purity of metal plays a major
role in corrosion if the corrosion is purely on
electrochemical mechanism and not by direct
chemical attack.
3. Using metal alloys
The corrosion resistance of a metal can
considerably be increased by alloying them
with suitable elements. However, for getting
maximum corrosion resistance alloy must be
completely homogeneous. Eg. Chromium is the
best alloying metal for iron and steel. It is self –
healing. Steel with chromium upto 13% is used
in cutlery, surgical instruments, springs etc. Iron
alloys containing 13 to 25% (ferrite stainless
steel) are used in turbine brackets, heat
resisting parts etc.
4.Cathodic protection

The metal to be protected will be made as cathode in

this method. Hence corrosion is reduced.
(i) Sacrificial anodic protection method
In this method the metallic structure which is to be
protected from corrosion is connected by a wire to a
more active metal. As a result of this corrosion is only
concentrated on the active metal. Since the metal
protecting the structure itself is undergoing corrosion,
the metal employed as anode is known as sacrificial
anode. The corroded sacrificial anode is replaced
periodically when it is consumed almost completely.
The metals usually used as anodes are zinc, aluminium,
magnesium and their alloys.

Uses: to protect buried pipelines, underground cables, marine

structures, ship hulls, water tanks etc.
Cathodic protection using sacrificial anode

Impressed current cathodic protection

(ii) Impressed current cathodic protection
In this method, the corrosion current is nullified by
impressing current in the opposite direction. This converts
the corroding metal into cathode from anode.

Generally the impressing current is obtained from a battery

or rectifier with an insoluble anode, buried in the corroding
medium and it is connected to the metallic structure which
is to be protected. The anode is usually made of coke or
gypsum to increase the electrical contact with the
surrounding soil.

Used in: open water-box coolers, water tanks, buried oil and water pipes,
condensers, transmission line towers, marine piers, laid-up ships etc.
Larger structures used in long-term operations are protected by this kind
of protection technique.
5. The effect of corrosion can be reduced by
modifying the environment.
The modification of environment can be achieved
by removing the harmful constituents and by the
addition of specific substances, which neutralize
the effect of corrosive constituents of the
environment.
Oxygen concentration cell corrosion of the metal
can be reduced by excluding oxygen from the
aqueous environment by adjusting the temperature
with mechanical agitation.
This method also reduces the CO2 content of water.
This reduction in CO2 decreases the corrosion rate of
steel pipelines carrying steam condensate from
boilers. This is called deaeration.
The deactivation is the process of involving the
addition of chemicals capable of combining rapidly
with the oxygen in aqueous solution. Eg. sodium
sulphite (Na2SO3).

2Na2SO3 + O2→ 2Na2SO4

Hydrazine hydrate (NH2.NH2.H2O) is advantageous
over the sodium sulphite, because the reaction
products are nitrogen and water.

N2H4 + H2→ N2 + H2O

(ii) Dehumidification is a process of reducing the
moisture content of air. By this process the
moisture content is reduced to - the amount
of water condensed on the metal is too small
to cause corrosion.
Alumina or silica gel is used for adsorbing
moisture preferentially on their surfaces.
However, they are used in closed areas.
• (iii) If the acidic character of corrosive
environment is neutralized by alkaline
neutralization, the corrosion will be reduced to a
greater extent.
• The acidity is due to the presence of H2S, HCl,
CO2, SO2 etc.
• The alkaline neutralizers commonly used are
NH3,NaOH, lime, naphthanic soaps.
• These neutralizers are injected into the corroding
system either in the liquid form or vapor form.
• This method is widely used in refining equipment
to control the corrosion.
 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.
 Application of protective coatings
Protecting the surface of an object by the
application of coating is the oldest common
procedures for corrosion protection. The
coating isolates the metal from the corroding
environment.
The limitation of this method is the service
behavior of the protective coatings. The
coating should be chemically inert. It should
prevent the penetration of the environment to
the material.
 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
 Importance of cleaning of metallic
articles before electro-deposition
• To impart corrosion, abrasion, wear, thermal and
impact resistances
• To provide electrical or thermal conducting
surfaces
• To provide enhanced optical or thermal
reflectivity to the surface
• Aiding the manufacture of good quality
electrical/electronic components like capacitors,
contacts, printed circuit boards etc
• To build up restoration
 Methods of Cleaning Articles
• Solvent Cleaning: Used to remove oils, greases,
buffing compounds and fatty substances by
applying Naphtha, chlorinated hydrocarbons like
CCl4, toluene, Xylene or acetone. It is followed
Cleaning with steam and hot water, containing
wetting agents & alkalis
• This method provides to a metal surface readily
wetted by aq. Sol. Which is particularly required
for electroplating.
 Alkali Cleaning
Adopted to remove old paint.
Trisodium phosphate along with soaps and wetting
agents like caustic soda.
Treatment always followed by a very thorough
rinsing with water and then immersion in a slightly
acidic solution of 0.1% chromic acid (Na2CO3 or
K2CO3) to remove the trace of alkalis.
Method can be made more effective by the
application of an electric current and making the
“metal cathodic” in alkaline medium.
The copious evolution of H2 at the cathode metal
results in strong agitation which helps to dislodge the
oily substances.
 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.
 Pretreatment of surface of substrate
Removal of organic impurities and grease; employing
organic solvents like
trichloroethylene,
methylene chloride
Hot aqueous alkalis; pH increase catalyses the hydrolysis
of fatty impurities.
using a current of 30-80 mA Cm-2 at 60-80˚C, alkali
treatment can also be carried out.
The organic impurities are removed by the hydrogen so
liberated on the electrode.
The excess alkali is then removed by dipping the article in
10% H2SO4 solution.
The surface can be cleaned by polishing and rinsing in
water, followed by drying.
• The electroplating of copper; using sulphate
bath or cyanide bath.
Sulphate bath is prepared by using 200-250g
CuSO4 and 50-75g H2SO4 in one litre of water.
Additives: Gelatin or dextrin and sulphuric
Bath is maintained at 20-50mACm-2.
Anode: rolled Cu.
Current efficiency is 45-98%.
Uses: It is used in printed circuit boards.
 Cyanide bath
The bath is, 40-50g CuCN, 20-30g of KCN and
10g of K2CO3. Sodium thiosulphate is added as
additive.
The Temp: at 40 -70˚C.
The current density: at 10-40mACm-2.
The anode: oxygen-free high conducting copper.
Current efficiency is 60-90%.
Uses: This bath is used undercoat for Cr plating
and printed circuit board.
 Electroplating of Nickel
• sulphate or sulphamate bath.
The sulphate bath: dissolving 250g NiSO4, 45g of NiCl2 and 30g
of boric acid in one liter of water.
pH of the bath is maintained at 4.5.

Additives: Coumarin, saccharin and benzene sulphonamide.

Temp: 40˚C and 70˚C.

The current density; at 20-50mACm-2.

anode :Ni pellets or pieces in titanium mesh basket

Current efficiency is 95%. It is used as undercoat for Cr plating.

 The sulphamate bath:
Bath: by dissolving 600g of nickel sulphamate, 5g
of nickel chloride and 40g of boric acid in 1litre of
water.
The pH: at 4.
Additives: Naphthalene-1,3,6-trisulphonic acid
Temp: 50-60˚C.
The current density: 50-400mACm-2.
Uses: Nickel pellets or pieces in titanium mesh basket are used
as anode. Current efficiency is 98%. It is mainly used for
decorative purposes
 Electroplating of chromium
• Is carried out in a bath consisting of 100 parts of
chromic oxide (CrO3) and one part of sulphuric
acid.
• Current density: 100-200 mACm-2 .
• The temperature: 45˚C to 60˚C.
• The current efficiency is 8-12%.
• Anode: Pb-Sn or Pb-Sb alloy coated with PbO2.
Uses: The plating is used for corrosion resistance and decorative
finish.
Thin-film coatings
• Thin-film deposition is any technique for
depositing a thin film (about 1 mm) of
material onto a substrate or onto previously
deposited layers.
• "Thin" is a relative term, but most deposition
techniques allow layer thickness to be
controlled within a few tens of nanometers,
and some (molecular beam epitaxy) allow one
layer of atoms to be deposited at a time.
 Thin film coatings
The process of depositing some materials over solid surfaces.

Physical Vapour Deposition (PVD)

A process of depositing some material by atom by atom or

molecule by molecule or ion by ion.

Methods of PVD are thermal evaporation, sputtering

and ion plating.

are performed in vacuum systems, oldest-PVD

 PVD (Physical vapor deposition)
• Physical vapor deposition (PVD) is a group of
vacuum coating techniques used to deposit thin films
of various materials onto various surfaces.
• Two technologies are often used:
(1) Evaporator:
- Thermal evaporator: Material is heated to attain
gaseous state.
- Electron beam evaporator
(2) Sputtering:
- Carried out under high-vacuum conditions
(~5x10-7 torr)
- Plasma as the particle source to strike the
target
Physical Vapor Deposition
• Evaporation
• Ion Plating
• Sputter Deposition
Process:
• source material -> gaseous state
• transport source atoms to substrate
• deposit atoms on substrate
 PVD
In this method the metal to be coated is placed in a
refractory metal boat or crucible.
The boat is heated to melt the content or an electron
beam is focused on the contents to melt.
The contents after melting form an electron cloud in
the shape of ice cream cone with the tip of the cone at
the source.
It coats all surfaces in the line of sight of the boat or
crucible.
• This process is widely used to produce decorative
coatings on plastic parts those are resembling
shiny metal. Many automobile parts are plastic
with a PVD coating of Al. A lacquer coating is
applied over the decorative coating to provide
corrosion protection.
PVD – Thermal Evaporation
 PVD - Sputtering
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.

5. The gas atoms are ionized, and they bombard the material to be
coated.
 PVD - Sputtering
6. The energy of impinging ions cause atoms of the target material to
be sputtered off, and they are transported through the plasma to
form a coating.

7. Direct current sputtering is used when the target is electrically

conductive.

8. Radio-frequency sputtering, which uses a RF power supply is used

when the target is a non conductor such as polymer.
Sputtering

• Sputtering is a physical process whereby atoms

in a solid target material are ejected into the gas
phase due to bombardment of the material by
energetic ions.
• The ions for the sputtering process are supplied
by a plasma that is induced in the sputtering
equipment.
• Sputtering relies on a plasma (usually a noble gas,
such as Argon) to knock material from a "target"
a few atoms at a time.
 Types of thin films
Metals (Au, Al, Ag..)–
-Used for electrical connections
-Doping
-Optical reflectors
Dielectrics (SiO2 , Si3 N4 ..)–
-Optical filters,
-antireflection coatings
-Electrical isolation
Semiconductors (Si, Ge, GaAs..)
- Epitaxial films (CVD, MBE)
- Amorphous & polycrystalline films for solar cells,
- Optical films
 PVD – Ion Plantation
1. A third variation of the PVD process is ion plating, which involves the
evaporation.

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

strong coating bond.

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

4. The wear properties of tools are widely enhanced by hard thin film
coatings.

5. Sputtered coating processes produce microscopic modules of diameter of

several micrometers and they are called macros.

6. These macros are undesirable for metal to metal sliding systems.

7. On the other hand they are usually beneficial to cutting tools.

Ion Implantation
 Ion Implantation
1. The common systems in use are ion implantation, laser treatment and
electron beam treatment.

2. In ion implantation ions of specific element with sufficient energy are

impinged on the surface of a material with sufficient energy.

3. The ions so impinged are embedded into the atomic lattice of substrate.
This process is performed in a vacuum chamber.

4. Usually ion gun produce the ions. It is done by passing the gas through
an electron beam or plasma. The gas atoms on collision with the electron
beam or with the species in plasma become ions.

5. The ions are accelerated by an applied magnetic field. These ions

impinge on the work surface. The surface of the metal is hardened by
creating atomic defects or misfits by the impinged ions.

6. The depth of implantation is usually about 0.1μm. However, the sphere

of influence is much deeper, may be a micrometer.
PVD applications
 Physical Vapour Deposition
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 Al.

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.
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, mandels 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

• Nickel deposition by CVD method finds application on glass containers

to make explosion or shatter resistant glasses.

• All surfaces in the reaction chamber get coated.

Advantages:
• high growth rates possible
• can deposit materials which are hard to evaporate
• good reproducibility
• can grow epitaxial films (high quality crystal growth)

Disadvantages:
• high temperatures (may soften tool steel > 700º)
• complex processes
• toxic and corrosive gasses
 Chemical Vapour Deposition
Advantages and Disadvantages

• This coating finds application on glass containers to make explosion or

shatter resistant glasses.

• The main advantage of CVD process over PVD is that it is not line of
sight.

• 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
Steps involved in a CVD process
(schematic)

1. Transport of reactants by forced convection to the

deposition region.

2. Transport of reactants by diffusion from the main gas

stream through the boundary layer to the wafer surface.
• 3. Adsorption of reactants on the wafer surface.
• 4. Surface processes, including chemical
decomposition or reaction, surface migration to
attachment sites (such as atomic-level ledges and
kinks), site incorporation, and other surface
reactions.
• 5. Desorption of byproducts from the surface.
• 6. Transport of byproducts by diffusion through
the boundary layer and back to the main gas
stream.
• 7. Transport of byproducts by forced convection
away from the deposition region.
110
 Types of Chemical Vapor Deposition

• Atmospheric pressure chemical vapor

deposition (APCVD)
• Low pressure chemical vapor deposition
(LPCVD)
• Plasma assisted (enhanced) chemical
vapor deposition (PACVD, PECVD)
Chemical Vapor Deposition
A magnetron sputter gun
 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. Silicon carbide barrier coatings are applied on plastic films and

semiconductors.

3. 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.

4. Thin-film coatings are key to the manufacture of many electronic

devices. They involve the application of dopant, sealant and other
microelectronic paste.

5. Thermal evaporation is a low cost process, but all these processes are
normally batch processes because of vacuum chamber requirements.
• 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)
• For decorative coatings or coatings on optics, thermal evaporation may be the
best suitable for engineering processes.
Sputtering
High technology coatings such as ceramics, metal
alloys and organic and inorganic compounds are
applied by sputtering. The substance to be coated
is connected to a high voltage dc power supply.
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. 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 impinging 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.
 Ion plating (3rd type of PVD)
Evaporated ions physically implant into the substrate to produce an
extremely strong coating bond.
Uses:
Sputter and ion plated coatings are used in design for very thin films
for electrical, optical and wear-resistant applications. The wear
properties of tools are widely enhanced by hard thin film coatings
• The face of a fast wearing tool can be reduced by increasing
abrasion resistance by applying TiN coating. Diamond and diamond
like coating can be performed by physical vapour deposition and
chemical vapour deposition. But we have to determine whether
they adhere to a particular substrate or not.
• The PVD coatings most widely used in machine design are titanium
nitride (TiN), titanium carbonitride (TiCN) and diamond like carbon.
Coating Hardness (HV) Colour

Titanium nitride 2900 gold

Zirconium nitride 2800 gold

Titanium aluminum nitride 2600 brown

Titanium carbonitride 4000 silver

Chromium nitride 2500 silver

Amorphous diamond like carbon 1000 – 5000 black

To give harness to a substrate; 1 to 2 μm to increase the thickness

Different coatings require different temperatures ranging from 300˚C to 800˚C.
At 800˚C. Softening
 Chemical Vapour Deposition
Chemical Vapour Deposition requires availability of volatile metal compound.
The compound decomposes to a metal when it comes in
contact with a substrate at some high temperature.
• Nickel is deposited from nickel carbonyl.
• Coating is having a thickness of 2.5mm at the rate of
0.25mm per hour. This coating finds application on
glass containers to make explosion or shatter resistant
glasses.
• The main advantage of CVD process over PVD is that it
is not line of sight. All surfaces in the reaction chamber
get coated. However, there are disadvantages too.
• 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.
• plasma assisted chemical vapour deposition.
This process is used to apply diamond and
diamond like carbon coatings.
• Some of the coatings may be conducting at
very low temperature. Silicon carbide barrier
coatings are applied on plastic films and
semiconductors.
• 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.
Thin-film coatings involve the application of
dopant, sealant and other microelectronic
paste. Thermal evaporation is a low cost
process.
These processes are normally batch processes
because of vacuum chamber requirements.
 Thermal Spraying

• Thermal spraying is the application of a material to a substrate

by melting the material into droplets and impinging the
softened or molten droplets on a substrate to form a
continuous coating.
Process Description

Flame spraying Powder, rod, wire is melted by oxy flame

Electric arc spraying Wires are motor driven and these wires are

melted by electric arc. The molten drops are propelled by a gas

at the substrate

Plasma arc spraying Powder is melted by an arc-generated

plasma within the gun.

Detonation gun Powder is melted in a gun by spark ignition

of explosive gas.

High velocity oxy fuel Powder is melted in a combustion chamber

containing oxygen, hydrogen and a fuel gas

like methane.
• Flame spraying and plasma spraying are similar. The source
of heat in plasma spraying is the plasma with a temp. over
16,650˚C compared with only about 2760˚C for an oxy
acetylene flame.

• Plasma arc spraying produces denser coatings with less

porosity and better adhesion. It is more suitable for
spraying ceramics. Many types of metals and ceramics can
be applied to almost any metal substrate. There is very little
heating of the substrate and temperature does not exceed
150˚C. Hence thermosetting plastics can even be ceramic
coated.

• Thermal spraying of metals and ceramics is useful for part

buildups and for producing wear resistant surfaces. The
porosity of these coatings makes them suited for
impregnation of substrate.
Ion Implantation