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UNIT – II – CORROSION AND CORROSION CONTROL

Syllabus: 9 hrs.
Chemical corrosion – Pilling – Bedworth rule – electrochemical corrosion – different
types – galvanic corrosion – differential aeration corrosion – factors influencing
corrosion – corrosion control – sacrificial anode and impressed cathodic current methods
– corrosion inhibitors – protective coatings – paints – constituents and functions –
metallic coatings – electroplating (Au) and electroless (Ni) plating.

Session Time Teaching


No Topics to be covered min Ref Aids
10 Chemical corrosion, corrosion due to Oxygen – Pilling – 50 1,2 BB &
Bedworth rule on corrosion products Chalk
11 electrochemical corrosion – Hydrogen evolution and oxygen
absorption cathodic process, different types – galvanic -do- 1,2 -do-
corrosion
12 differential aeration corrosion – factors influencing corrosion
-do- 1,2 -do-
13 corrosion control – sacrificial anode and impressed cathodic
current methods -do- 1,2 -do-
14 corrosion inhibitors
15 protective coatings – paints – constituents and functions -do- 1,2 -do-
16 metallic coatings – Principle and methods of electroplating, -do- 1,2 -do-
electroplating (Au)

17 Principle and methods of electroless plating ,electroless (Ni) -do- 1,2 -do-
plating.
18 Revision -do- 1,2 -do-

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Introduction:

Corrosion is a general term that refers to the deterioration and ultimate destruction
of a metal due to its reaction with the surrounding gaseous or liquid environment.
Corrosion is a decay process in which metals exhibit their natural tendency to revert to
their native combined state of existence as minerals-e.g. as oxides, sulphates, carbonates
etc. All metals and alloys are susceptible to corrosion under different environmental
conditions. Only metals such as gold and platinum exist in nature as metals and are not
susceptible to corrosion under ordinary atmospheric conditions and hence are called
noble metals. Corrosion causes a heavy loss to industries since the modern day domestic
and industrial applications uses mainly metals and alloys.

Types of Corrosion:
Corrosion may be broadly classified into two types based on the mechanism of
corrosion. These include (a) dry corrosion also called as chemical corrosion (b) wet
corrosion also called as electrochemical corrosion``

(a) Dry Corrosion (or) Chemical Corrosion:

One of the most common ways by which metals get corroded is by direct
interaction with atmospheric gases such as oxygen, hydrogen sulphide, halogens, sulphur
dioxide, oxides of nitrogen. Oxygen is primarily responsible for corrosion of most
metallic structure as compared to other gases and chemicals.
Direct attack on metal by oxygen even at ambient temperatures in the absence of
moisture leads to oxidation corrosion, that is, the formation of the corresponding metal
oxide, which is normally thermodynamically spontaneous process.
The oxidative corrosion may be considered to involve the reactions of oxidation of the
divalent metal to form the metal ion with the simultaneous release of electrons and the
combination of the electrons with oxygen to form oxide ions.

M M2+ + 2e-

2
½O2 + 2e- O2-
The overall reaction:
M + O2 M2+ O2- (metal-oxide film)
Diffusion of oxygen are responsible for continued oxidation and growth of the film into
an oxide scale. The growth of an oxide film can occur due to (a) migration of metal ions
outwards to the surface (b) migration of oxide ions from the surface to the bulk, (c)
simultaneous migration of metal ions and oxide ions, and (d) penetration of molecular
oxygen through the metal-oxide interface. In general, outward diffusion of metal ions
and electrons is likely to be more rapid due to the fact that cations are smaller in size
compared to the oxide ions.
M Mn+ + ne- (oxidation)
Mn+
Mn+ O2-

Mn+ Atmospheric Oxygen


- 2-
e O

Metal-M O2-
½O2 + 2e- O2-(reduction)

Mechanism of Oxidation of Metal to Metal oxide

Nature of the oxide formed plays an important role in oxidation corrosion process
i.e. Metal + oxygen metal oxide (corrosion product)

When oxidation starts, a thin layer of oxide is formed on the metal surface and the
nature this film decides the further action. If the film is:
(i) Stable: A stable layer is fine-grained in structure and can get adhered tightly to the
parent metal surface. Such a film behaves as protective coating in nature, thereby
shielding the metal surface. The oxide films on Al, Sn, Pb, Pt, cu etc., are stable.
(ii) Unstable: the oxide layer formed decomposes back into the metal and oxygen

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Metal oxide Metal + Oxygen
Consequently, oxidation corrosion is not possible, thus metals like Ag, Pt, Au do not
undergo oxidation corrosion.
Unstable metal oxide
Exposed area

Metal +O2 Metal metal oxide Metal + O2


decomposes

(iii) Volatile: the oxide layer volatilizes as soon as it is formed, thereby leaving the
underlying metal surface exposed for further attack. E.g. Molybdenum oxide MoO3
Exposed area Volatile metal oxide
Fresh surface
Metal +O2 Metal metal oxide Metal exposed for
Further attack
volatilizes

(iv) Porous: having pores or cracks on the surface of the metal, atmospheric corrosion
have access to the underlying surface of metal, through the pores or cracks of the layer
thereby the corrosion process continues till entire metal is completely converted into its
oxide.
Exposed area porous metal oxide

Metal +O2 Metal Further attack through pores/cracks


continues

Pilling and Bedworth rule:

According to Pilling and Bedworth, the oxidation resistance of a metal is related


to the specific or molar volume ratio of the corrosion product, namely, the metal oxide
and the metal. It is expressed mathematically as

R = (M/D) x (d/m)

Where M and m are the molecular weight and atomic weight of the metal oxide
and the metal respectively, D and d are the densities of the oxide and the metal

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respectively. The ratio r indicates the volume of oxide formed from a unit volume of
metal. If R<1, the oxide layer can cover the metal surface only when it is under tension.
However, such tension will tend to produce cracks thereby exposing the metal surface to
oxygen. On the other hand, if R>1, as in the case of copper-oxygen system the oxide is
able cover the metal surface effectively. The strongly adherent non-porous oxide layer
protects the metal from further oxidation.
Dry corrosion by other gases and chemicals:
Other gases present in the working environment such as chlorine, fluorine,
sulphur dioxide, hydrogen sulphide and oxides of nitrogen are also corrosive.

Hydrogen embrittlement: Hydrogen sulphide attacks metals forming the corresponding


metal sulphide and releases atomic hydrogen. The atomic hydrogen diffuses readily into
the metal and collects at the void spaces where it combines with atomic hydrogen to from
hydrogen gas. The accumulation of the gas develops a high pressure causing cracks and
blisters in the metal. The condition is known as hydrogen embrittlement.

Decarburization: The atomic hydrogen on coming into contact with steel combines with
the carbon of steel to form methane gas which collects in voids. As the pressure
increases due to the accumulation of the gas cracks occur in steel, a condition known as
decarburization.

Wet corrosion or electrochemical corrosion:


The corrosion of metal in aqueous environments is more prevalent than under dry
conditions. Iron undergoes corrosion to form rust. The rust formed on the surface of
iron is loose and does not adhere to the metal surface. According to the electrochemical
theory of corrosion, wet corrosion is a two step process which occur simultaneously,
namely, oxidation and reduction. The surface of a piece of iron in contact with an
aqueous solution of electrolyte becomes a galvanic or a voltaic cell consisting of anodic
and cathodic regions. The galvanic cell formed facilitates the flow of positive current
from the anodic region to the cathodic region through the electrolyte leading to the
dissolution or corrosion of the anodic region.

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M M2+ + 2e-
The electrons are utilized at the cathodic region either to form hydrogen or hydroxide ion
depending on the pH of the medium. In acidic medium hydrogen is evolved.
(a) Evolution of Hydrogen: Considering metal like Fe, the anodic reaction is dissolution
of iron as ferrous ions with the liberation of electrons.
Fe Fe2+ + 2e-
These electrons flow through the metal, from anode to cathode, where H+ ions are
eliminated as hydrogen gas.
Electrolyte
Iron H+Cl-
Fe2+ H+Cl-

2e- H+Cl-
H2 H+Cl-
H+Cl-
Mechanism of Hydrogen evolution

2H+ + 2e- H2
The net reaction is Fe + 2H+ Fe2+ + H2

This type of corrosion causes displacement of hydrogen ions from the acidic solution by
metal ions. Consequently, all metals above hydrogen in the electrochemical series have a
tendency to get dissolved in acidic solution with simultaneous evolution of hydrogen.

In neutral or a weakly alkaline medium, hydroxide ions are formed by the reduction of
absorbed oxygen
(b) Absorption of oxygen: Rusting of iron in neutral aqueous solution of electrolytes in
the presence of atmospheric oxygen is a common example of this type of corrosion. The
surface of iron is, usually, coated with at thin film of iron oxide. However, if this iron
oxide film develops some cracks, anodic areas are created on the surface; while the well-
metal parts act as cathodes. It follows that the anodic areas are small surface parts; while
nearly the rest of the surface of the metal forms large cathodes.
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At anodic areas of the metal dissolves as ferrous ions with liberation of electrons.

Iron Aq. Soln.


H 2O

Fe2+ H2O
2e- OH- O
2

H 2O O2

Mechanism of oxygen absorption


The liberated electrons flow from anodic to cathodic areas, through iron metal,
where electrons are intercepted by the dissolved oxygen as:
½O2 + H2O + 2e- 2OH-
The Fe2+ ions and OH- ions diffuse and when they meet, ferrous hydroxide is precipitated.
Fe2+ + 2OH- Fe (OH)2
If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide.

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


Types of Corrosion:
(i) Galvanic Corrosion: When two different metals are in electrical contact in the
presence of an electrolyte, the metal higher up in the electrochemical series becomes
anodic and suffers corrosion because of its higher oxidation potential. Examples: plain
carbon steel in contact with stainless steel and brass. The Figure represents Fe-Cu
couple, in which iron dissolves to copper here Fe acts as anode i.e. more active metal
when compared to copper which acts as cathode.

Fe Cu

More active Less active


Galvanic corrosion

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The galvanic corrosion may be avoided by a proper selection of metals and alloys
based on their position in galvanic series.
(ii) Differential aeration corrosion:
This type of corrosion occurs, when one part of metal is exposed to a different air
concentration from the other part. The parts of the metal exposed to a higher
concentration of oxygen become cathodic while parts of the metal exposed to a relatively
lower concentration of oxygen become anodic and get corroded. Example: If a metal
like Zn is partially immersed in a dilute solution of a NaCl solution is not agitated
properly, then, the parts above are more strongly aerated and hence, become cathodic.
On the other hand, parts immersed to greater depth show a smaller oxygen concentration
and thus, become anodic. So a difference of potential is created, which causes a flow of
current between the two differentially-aerated areas of the same metal. Zinc will dissolve
at the anodic areas, and oxygen will take up electrons at the cathodic areas to form
hydroxyl ions.

Zn Zn2+ + 2e-
½O2 + H2O + 2e- 2OH-

Zn rod
Cathode
½O2 + H2O + 2e- 2OH-
Anode
NaCl solution

Differential aeration corrosion caused by partially immersion of Zn rod

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(iii) Pitting Corrosion:
Pitting corrosion is a localized accelerated attack; it is usually the result of
breakdown or cracking of the protective film on a metal at specific points. Breakdown of
the protective film may be caused by : (i) surface roughness or non-uniform finish (ii)
scratches or cut edges (iii) local straining of metal, due to non-uniform stresses.
More oxygenated Cathodic part
½O2 + H2O + 2e- 2OH-

Iron Pit (Anodic)


Fe Fe2+ + 2e-

Pitting corrosion on the surface of Iron


The presence of the extraneous impurities like sand, dust, scale etc., embedded on
the surfaces of metals also lead to pitting. Owing to the differential amount of oxygen in
contact with the metal, the small part underneath the dust or sand becomes the anodic
areas and the surrounding large parts become the cathodic area. Intense corrosion
therefore starts underneath the impurity. Once a small pit is formed, the rate of corrosion
will be increased.
(iv)Crevice corrosion:
Crevice corrosion is formed between different metallic objects or between a metal and
non-metallic material joined by blot, nuts, rivets and washers. The crevice on coming
into contact with a liquid becomes anodic region as the oxygen supply to this area is less
compared to other parts and gets corroded preferentially.

==== Anode

Crevice Corrosion

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Factors influencing the corrosion

The rate and extent of corrosion mainly depends on

1. Nature of the metal 2. Nature of the environment.

1. Nature of the metal

(i) Purity of metal:

Impurities present in the metal generally form minute or tiny electrochemical cells
and the anodic parts get corroded. For example Zinc metal containing impurity such as
Pb or Fe undergoes corrosion of Zn due to the formation of electrochemical cells.
Consequently, corrosion resistance of a metal may be improved by increasing its purity.
(ii) Oxidation potential of the metal:

The position in the electrochemical series is indicative of the natural tendency of


the metal to undergo corrosion. When two metals are in contact with each other and
simultaneously with an electrolyte, a galvanic cell is set up and the metal higher in the
series undergoes corrosion.
(iii) Overvoltage:
When a metal, which occupies a high positon in galvanic series for example Zn is
placed in 1N H2SO4, it undergoes corrosion forming a film and evolving hydrogen gas,
the initial rate of reaction is quite slow, because of high overvoltage of zinc metal, which
reduces the effective electrode potential to a small value. However, if a few drops of
copper sulphate are added, the corrosion rate of zinc is accelerated, because some copper
gets deposited on the zinc metal, forming minute cathodes, where the hydrogen
overvoltage is only 0.33 V. Thus reduction in overvoltage of the corroding metal
accelerates the corrosion rate.
(iv) Passivity of the metal:
Iron dissolves readily in very dilute nitric acid. However at higher concentration
acid directly oxidizes the metal to its oxide on the surface. The layer of the oxide formed
on the surface makes iron resistant to dissolution, a phenomenon known as passivity.
Passive iron is not easily corroded as the oxide film is self-healing, that is, a ruptured film
repairs itself on re-exposure to oxidizing conditions.

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(v) Physical state of metal:
The rate of corrosion is influenced by physical state of the metal such as grain
size, orientation of crystals, stress etc. The smaller the grain-size of the metal or alloy,
greater will be the corrosion. Also, the area under stress, tend to act as anodic and
corrosion takes place at these areas.
(vi) Relative areas of cathodic and anodic regions:
The rate of corrosion is more with the combination of a large cathodic region and
a small anodic region, because the greater demand for electrons at the larger cathodic
region has to get a greater current density which is supplied by the smaller anodic region.

2. Nature of the corroding environment


(i) Temperature:
With increase of temperature of environment, corrosion rate is generally
enhanced.
(ii) Humidity in the atmosphere:
Humidity of the air surrounding the metal influences corrosion, the greater the
humidity higher being the rate of corrosion. Critical humidity is the humidity of the air
above which the rate of atmospheric corrosion of the metal increases sharply and depends
on the nature of the metal and the nature of the corrosion products.
(iii) Presence of impurities in atmosphere:
In presence of gases like CO2, H2S, SO2 the acidity of he liquid, adjacent to the
metal surfaces, increases and its electrical conductivity also increases, resulting in higher
rate of corrosion.
(iv) Presence of suspended particles in atmosphere:
If the suspended particles are chemically active in nature (NaCl) they absorb
moisture and act as strong electrolytes, thereby causing enhanced corrosion.
(v) Effect of pH:
The pH of the surrounding medium plays an important role in influencing the rate
of corrosion. In general acidic media are more corrosive compared to neutral or mildly
alkaline media.

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Corrosion Control
1. Proper designing:
(i) Avoid the contact of dissimilar metals in the presence of a corroding solution.
(ii)When two dissimilar metals are to be in contact, the anodic material should have as
large area as possible.
(iii) Whenever the direct joining of dissimilar metals is unavoidable an insulating fitting
may be applied in between them to avoid direct metal-metal electrical contact.
(iv) A proper design should avoid the presence of crevices between adjacent parts of the
structure.
(v) It is desirable that the design allows for adequate cleaning and flushing of the critical
parts of the equipment. Sharp corners and recesses should be avoided as they favor the
formation of stagnant areas and accumulation of solids.
2. Using pure metal:
Impurities in a metal cause heterogeneity, which decreases corrosion-resistance of
the metal. Thus, the corrosion resistance of a given metal may be improved by increasing
its purity.
3. Using metal alloys:
Corrosion resistance of most metals is best increased by alloying them with
suitable elements, but for maximum corrosion resistance, alloy should be completely
homogeneous. Chromium is the best suitable alloying metal for iron or steel.
4. Cathodic protection:
In this method the metal to be protected is forced to behave like a cathode,
thereby corrosion does not occur. There are two types of cathodic protections:
(i) sacrificial anodic protection method (ii) Impressed current cathodic protection

(i) Sacrificial anodic protection method:


The metallic structure to be protected is connected by a wire to a more anodic
metal, so that all the corrosion is concentrated at this more active metal. The more active
metal itself gets corroded slowly, while the parent structure is protected. The more active
metal so-employed is called “sacrificial anode”. The corroded sacrificial anode block is

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replaced by a fresh one, when consumed completely. Metals commonly employed as
sacrificial anodes are magnesium, zinc, aluminium and their alloys. Important
applications of sacrificial anodic method include protection of buried pipelines,
underground cables, marine structures, ship-hulls, water tanks etc.
e-
>

Mg

Iron pipe
Sacrificial anode

Sacrificial anode –cathodic proctection

(ii) Impressed current cathodic protection:


In this method the object to be protected is made the cathode of an electrolytic
cell by connecting it to the negative terminal of a DC source. The positive terminal of the
DC source is connected to scrap iron, platinum, graphite, nickel or lead anode and buried
or immersed in a conducting medium adjacent to the metal to be protected. The anode is
usually in a backfill so as to increase the electrical contact with the surrounding soil.
This type of cathodic protection has been applied to open water-box coolers, water tanks,
buried oil or water pipes, condensers
e-

Iron pipe

Impressed current-cathodic protection

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Corrosion Inhibitors
Inhibitors are inorganic or organic chemical substances which when added a small
quantity to the corrosive environment, effectively decrease the corrosion rate.
Inhibitors are classified into (i) Anodic inhibitors (ii) Cathodic inhibitors (iii) Vapour
phase inhibitors
(i) Anodic inhibitors:
Oxidizing agents such as sodium chromate and sodium nitrite function as
inhibitors of corrosion by repairing the protective oxide film or by oxidation of corrosion
products to less soluble chemicals, which plug anodic sites. These are known as anodic
inhibitors because they inhibit anodic oxidation of the base metal. Anodic inhibitors such
as chromates, phosphates, tungstates or other ions of transition elements with high
oxygen content retard the corrosion of metals by forming a sparingly soluble compound
with newly produced metal cations at the anodic sites. This compound will then adsorb
on the corroding metal surface forming a passive film or barrier thereby reducing the
corrosion rate.
(ii) Cathodic inhibitors:
(a) In acidic solutions, the main cathodic reaction is evolution of hydrogen.
2H+ + 2e- H2(g)
Consequently, corrosion may be reduced either by slowing down the diffusion of
hydrated H+ ions to the cathode. The diffusion of H+ ions is considerably decreased by
organic inhibitors like amines, mercaptans, heterocylic nitrogen compounds, substituted
ureas and thioureas, which are capable of being adsorbed at the metal surfaces.
(b) In neutral solutions, the cathodic reaction is
½O2 + H2O + 2e- 2OH-
The corrosion can be controlled either by eliminating oxygen from the corroding
medium by adding reducing agents like Na2S or Na2SO3 or by retarding its diffusion to
the cathodic areas by adding Mg, Zn or Ni salts.
Vapor Phase Inhibitors (VPI):

These inhibitors readily vaporize forming a protective layer on the metal surface. VPIs
are used in the protection of storage containers, sophisticated equipment etc. Ex : Dicyclohexyl
ammonium nitrate, benzotriazole (BTA) etc.,

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Protective coatings
Pretreatment of metal surface to be plated or coated:
For proper adhesion of plating or coating the metal surface to be plated should be free
from greases, oils, rusts and other corrosion products. Removal of theses impurities are
carried out in the following ways:
(i) Degreasing: Organic solvents such as CCl4, acetone, trichloro-ethylene are used to
remove oils, greases present on the metal surface.
(ii) Alkali cleaning: This method is used to remove old paint coating. The base metal
containing old paint coating is removed by keeping it in an alkali cleaning agent. This
treatment is always to be followed by a thorough rinsing with water.
(iii) Sand blasting: In this method oxide scale present on the steel surface is removed by
introducing sand into air stream under the pressure o 25-100 atmosphere.
(iv) Pickling: In this process the base metal is immersed in an acid solution. This
treatment dissolves any corrosion products present on the surface.

Organic coatings – Paints:


Paint is a mechanical dispersion mixture of one or more pigments in a vehicle.
The vehicle is a liquid, consisting of non-volatile, film-forming material, drying oil and a
highly volatile solvent, thinner. When a paint is applied to a metal surface oxidizes
forming a dry pigmented film.
Requisites of a good paint:
1. It should be fluid enough to spread easily over the protected surface.
2. It should possess high covering power
3. It should form a quite tough, uniform, adherent and impervious film
4. Its firm should not get cracked on drying.
5. It should protect the paint surface from corrosion effects of environment.
6. It should form film and the colour remain quite stable.
7. Its film should be glossy.

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Constituents of paints:
A paint essentially consists of the following ingredients (i) pigments (ii) vehicle or drying
oil (iii) thinner (iv) driers (v) fillers or extenders (vi) plasticizers and (vii) antiskinning
agents.
1. Pigment: Pigment is a solid substance, which is an essential constituent of paint. Its
functions are to (i) provide capacity to paint (ii) provide strength to paint (iii) provide
desire colour to paint (iv) gives aesthetical appeal to the paint film.
Examples: Pigments used are whites- white lead, zinc oxide, titanium oxide
Red – red lead, ferric oxide, chrome red
Blue-Prussian blue,
Black – carbon black
Brown – Brown umbre
2.Vehicle or drying oil: Drying oil is a film-forming constituent of the paint. These are
glyceryl esters of high molecular weight fatty acids, generally present in animal and
vegetable oils. Functions of drying oil, it’s a main film forming constituent, acts as a
medium, gives toughness, adhesion, durability and water-proofness.
Examples: The most widely used drying oil, are linseed oil, soyabean oil and dehydrated
castor oil.
3.Thinners: It reduces viscosity of the paint, suspend the pigments, increase the elasticity
of the paint film, help the drying of the paint film as they evaporate.
Examples: Turpentine, xylol, kerosene etc.
4. Driers: Driers are oxygen-carrier catalysts. They accelerate the drying of the oil-film
through oxidation, polymerization and condensation.
Examples: resonates, linoleates, tungstates and naphthenates of Co,Mn, Pb and Zn.
5. Extenders or fillers: it increases durability of the paint, help to reduce the cracking of
dry paint film.
Examples: BaSO4, talc, asbestos, china-clay, magnesium silicate, calcium sulphate etc.
6. Plasticizers: it provides elasticity to the film and to minimize its cracking.
Examples: tricresyl phosphate, triphenyl phosphate, tributly phthalate.
7. Antiskinning agents: it prevents gelling and skinning of the paint film.
Example: polyhydroxy phenols.

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Mechanism in drying of oils:
The oil film, after it has been applied on the protected surface absorbs oxygen at
the double bonds, forming peroxides, diperoxides and hydroperoxides which isomerise,
polymerize and condense to form a characteristic tough, coherent, hard elastic, infusible
highly cross linked structured macromolecular film.

Wet paint (oil + pigment + film of oil + pigment pigmented film


extender + drier + thinner) + drier crossed linked structure
Evaporation of thinner oxidation and
Polymerization of

Base material Base material Base material

Conjugated double bonds

CH2COO(CH2)7-CH=CH-CH2-CH=CH-(CH2)4-CH3

n CH COO(CH2)7-CH=CH-CH2-CH=CH-(CH2)4-CH3

CH2COO(CH2)7-CH=CH-CH2-CH=CH-(CH2)4-CH3

Glyceride of linolenic acid (drying oil)


Air oxidation
and polymerization

CH2COO(CH2)7-CH - CH-CH2-CH=CH-(CH2)4-CH3

O O

CH COO(CH2)7-CH - CH-CH2-CH - CH-(CH2)4-CH3

O O

CH2COO(CH2)7-CH - CH-CH2-CH - CH-(CH2)4-CH3

ether crosslink O O

CH2COO(CH2)7-CH - CH-CH2-CH - CH-(CH2)4-CH3

O O

CH COO(CH2)7-CH - CH-CH2-CH - CH-(CH2)4-CH3

O O

CH2COO(CH2)7-CH - CH-CH2-CH - CH-(CH2)4-CH3

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O O

Metallic coatings – Principle and methods of electroplating

Principle of Electroplating:

This process involves coating of a thin layer of one metal over another metal by
passing direct current through an electrolytic solution. The base metal to be plated is
made of cathode whereas the anode is made of either coating metal itself or an inert
material in the electrolytic cell.
Procedure:

The article to be electroplated is first treated with organic solvent to remove oils, greases
etc. then, it is made free from surface scales, oxides, etc., by treating with dil. HCl or
H2SO4. The cleaned article is then made cathode of an electrolytic cell. The anode is
either the coating metal itself or an inert material of good electrical conductivity. The
electrolyte is a solution of a soluble salt of the coating metal. The electrolytic solution is
kept in an electroplating tank. The anode and cathode are dipped in the electrolytic
solution. When direct current is passed, coating-metal ions migrate to the cathode and
get deposited there. Thus, a thin layer of coating-metal is obtained on the article, made as
the cathode. For brighter and smooth deposits, favourable conditions such as low
temperature, medium current-density and low metal-ion concentration are used.
Electrolyte to (+) (-)
replenish the loss

Direct current source

Cathode

Anode

Electroplating

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Factors affecting the electrodeposit:

1. Cleaning of the article to be plated: Pretreatment of the surface of any material to be


electroplated is essential. Maximum coating adhesion can be obtained only, if the base
metal surface is free from dirt and grease.
2. pH of the bath liquid: For a good electrodeposit the pH of the bath must be properly
maintained.
3. Thickness: For decorative purposes, thin deposit is done, while for corrosion
resistance, thick plating is required.
4. Composition of the electrolytic bath: Low metal ion concentrations re preferred, since
they give rise to very adherent coating films.
5. Throwing power: Throwing power is the ability of electrolytic cell to give a deposit of
uniform thickness over the entire cathodic area. When the cathode is regular in shape
maximum throwing power is exhibited by an electrolytic system
6. Temperature: Most of the electroplating bath solutions should be used at room
temperature. However, warm baths are also used to increase the solubility of electrolyte
thereby increases the concentration and current density of the bath.

Electroplating of gold:

Gold plating is a method of depositing of thin layer of gold on the surface of other metals,
most such as copper or silver.
Copper or silver is first electroplated with a suitable barrier metal like Sn, Ni or bronze to
provide leveling and brightening to the substrate and to inhibit the migration of copper or
silver into the gold layer.
Process: The electroplating of gold is carried out by using either neutral cyanide bath or
acid cyanide bath.
Anode: inert metal Cathode:Cu or Ag or Cd.
Electrolyte: Gold potassium cyanide K[Au(CN)2]
Temperature: 70-80˚C
pH= 6-8

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Current density : 1-40 mA/cm2
Additives / Salts /Acids: Citrate, phosphate, phosphoric acid.

Mechanism: during electrolysis, the electrolyte is decomposed into Au+ ions.

K[Au(CN)2] K+ + [Au(CN)2]-

[Au(CN)2]- Au+ + 2 CN-

At cathode, deposition of Au+ occurs

Au+ + e- Au

Applications : Gold plating is often used in electronic industries for making printed
circuit boards, semiconductor lead-out connection because of high electrical conductivity
(ii) gold plating of silver is used in the manufacture of jewelry.
Electroless plating:

Definition: The process of producing a thin, uniform and hard deposit of metal on an
activated substrate (Metal or non-metal) by using suitable soluble reducing agents
without any electrical energy, and the driving force for the deposition is auto catalytic
redox reactions.
The reducing agent reduces the metallic ions to metal, which gets plated over the
catalytically activated surface giving a uniform thin coating.

Metal ions + Reducing agent Metal + Oxidised products

Process:

The process involves

1. Pretreatment or activation of work piece to be plated.

2. Preparation of bath composition.

1. Pretreatment or activation of work piece to be plate

(i) Metals like Cu, Ag etc. are known as non-catalytic metals. Surface of such metals
need activation. They are activated by using steel or iron pieces for initiating the
reactions.

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(ii) Non-metals like glasses, ceramic, plastics are activated by dipping in SnCl2, PdCl2
in HCl. This process produces a thin film of palladium coating on non-metal surfaces
which in turn causes the work piece to get activate for electroless plating.
2. Preparation of bath composition

Name of the ingredient Function Examples

Coating metal ion To provide metal ion for NiCl2, NiSO4, CuSO4 etc.
deposition
Reducing agent To liberate electrons for the Sodium hypophosphite,
reduction of metal ion sodium boron hydride
Buffer To maintain pH Sodium acetate, NaOH,
Roschelle salt
Complexant To improve the quality of Sodium acetate, sodium
deposit. citrate
Exaltant To increase the rate of Succinate, Maleate, Lactate
deposition
Stabilizer to prevent decomposition of Cations like Pb, Ca etc.,
the plating bath
Brightener To improve the brightness Thiourea, Sodium benzoate
of the deposit

Electroless plating of nickel:

1. Pretreatment and activation of surface

The surface to be plated is first degreased by using organic solvents or alkali,


followed by acid treatment.
Example (i) The surface of the stainless steel is activated by dipping in hot solution of
50% dil H2SO4
(ii) Metals and alloys of Aluminum, copper, Iron etc., can be directly Nickel plated
without activation.
2. Preparation of plating bath composition

NiCl2,.6H2O 20g/l - coating solution


NaH2PO2H2O 20 g/l - reducing agent
(Sodium hypophosphite)
Sodium acetate 10 g/l - Buffer
Sodium succinate 15 g/l - complexing agent
Temp 85-95˚C

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pH 4-6
Mechanism:

The pretreated object is immersed in the plating bath for the required time.

At Anode:

The reducing agent, NaH2PO2 in solution, moves toward the activated substrate
and liberates electrons by anodic oxidation.

H2PO2- + H2O H2PO3- + 2 H+ + 2e-

At Cathode:

The salt solution containing Ni2+ ions gain electrons and get deposited

Ni2++ 2e- Ni

The over all reaction at the surface of work piece is

Ni2+ + H2PO2- + H2O Ni + H2PO3- + 2 H+

Condition during Electroless plating:

(a) During the redox reaction, both Ni ions and sodium hypophosphite are consumed,
so these are replenished periodically.
(b) Maximum plating obtained at 93C, still higher temperature may cause the
decomposition of the bath.
(c) H+ ions are liberated in the redox reaction so pH of the bath solution decrease
during the process, so addition of buffer is essential to get quality plating.

Advantages of electroless nickel plating:

1. It gives rise to harder surface with better wear resistance due to plating of Ni-P
alloy.
2. Free from pores and possess better corrosion resistance property.
3. Due to excellent throwing power the object having intricate part with irregular
shapes can be plated.

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Applications:

(i) Electroless Ni-P coatings are used in various electronic applications.

(ii) Electroless nickel deposition on polymers find preferred decorative as well as


functional applications.
(iii) Heat treated electroless nickel coatings finds applications in hydraulic
compressors, pressure vessels, pumps and fuel injection assemblies.
(iv) Plastic cabinets coated with copper and nickel finds applications in digital as
well as electronic instruments.
Advantages of electroless plating:
(i) Does not require electrical power source.
(ii) It has better throwing power.
(iii) Intricate parts with irregular shapes can be uniformly coated.
(iv) By adding complexes and additive agents the quality of electroless deposit can
be improved.
(v) Electroless deposit is less porous hence it gives better chemical, mechanical
and magnetic properties.

References:
(a) Engineering Chemistry, Jain and Jain, Dhanpat Rai Publishing Co., 15th Edition.
(b) Engineering Chemsitry, B. Sivasankar, Tata McGraw Hill Co.,

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