MODULE – 2

CORROSION

Introduction

Corrosion is an undesirable process. Due to corrosion there is limitation of

progress in many areas. The cost of replacement of materials and equipments lost
through corrosion is unlimited.
Metals and alloys are used as fabrication or construction materials in engineering.
If the metals or alloy structures are not properly maintained, they deteriorate
slowly by the action of atmospheric gases, moisture and other chemicals.
This phenomenon of destruction of metals and alloys is known as corrosion.
Corrosion of metals is defined as the spontaneous destruction of metals in the
course of their chemical, electrochemical or biochemical interactions with the
environment.
Thus, it is exactly the reverse of extraction of metals from ores.
Example: Rusting of iron A layer of reddish scale and powder of oxide (Fe 3O4) is
formed on the surface of iron metal.
A green film of basic carbonate [CuCO3 + Cu (OH)2 ] is formed on the surface of
copper, when it is exposed to moist-air containing carbon dioxide.
Definition

❖ Corrosion* “The spontaneous destruction and consequent loss of a

metal/alloy due to unavoidable chemical/electrochemical attack by the
environment”

Example:
1. When Cu is exposed to the industrial environment it forms an adherent
protective green deposit which isolates the metal from the environment, hence
the further action is very slow.

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 2. When iron metal is exposed to the industrial environment, the metal forms a
loosely adherent product of hydrated ferric oxide called rust, which is relatively
non-protective.
Hence, the fundamental approach to the phenomena of corrosion, the structural
features of the metal, reactions which occur at the interface and nature of the
environment are to be considered.

ELECTROCHEMICAL THEORY OF CORROSION

• Most of the corrosion cases are electrochemical in nature, taking place by an

electrochemical attack on the metal in the presence of moisture/conducting
medium- called wet corrosion.
• According to the theory, when a metal is in contact with the conducting
medium or when dissimilar metals/alloys are either immersed
partially/completely in a solution, a large number of galvanic cells with the
existence of anodic and cathodic area on the metal, are formed.
• In this corrosion, oxidation of the metal and reduction of species present in
solution takes place at anodic and cathodic parts, respectively.
• The electrons are transferred through the metal from anode to cathode.
• The anodic part of the metal suffers from corrosion and cathode is protected
from corrosion.
• Corrosion reactions are:
At anode (oxidation reaction): M →Mn+ + ne-
The reaction at cathode (reduction reaction) depends on the nature of the
environment:
If the medium is acidic,

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 (a) In the presence of dissolved oxygen : 2H+ + ½O2 + 2e-→H2O

(b) In the absence of dissolved oxygen: 2H+ + 2e-→ H2

If the medium is alkaline/neutral,

(a) In the presence of dissolved oxygen : H2O+½ O2 + 2e-→2 OH 

(b) In the absence of dissolved oxygen : 2H2O+2e-→2 OH + H2



Example: Rusting of an Iron in the presence of moist air

At anode: Fe→Fe+2 + 2e-

At cathode: H2O+½ O2 + 2e-→2 OH 

Net reaction: Fe+2 +2 OH →Fe(OH)2



In the presence of excess of oxygen: 2Fe(OH)2+ ½ O2→Fe2O3.2H2O

(rust)

In the limited supply of oxygen: 3Fe(OH)2+½ O2→Fe3O4.3H2O

(black rust)

FACTORS AFFECTING THE RATE OF CORROSION

NATURE OF THE METAL

• The position of the metal/alloy in the galvanic series decides the rate and extent
of corrosion.
• The metals with lower electrode potential values are more reactive and more
susceptible for corrosion than the metals with higher electrode potential values.
• The rate of corrosion depends upon the difference in the position of the metals
in the galvanic series. Greater the difference, faster is the corrosion at anode.

Exception: metals and alloys which show passivity are exception for this general
trend.
Such metals form a protective coating on surface which prevent corrosion

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 NATURE OF THE CORROSION PRODUCT

• In aerated atmosphere almost all metals get covered with a thin surface film of
metal oxide(corrosion product).
• The thickness of the oxide layer varies with respect to the nature of the metal
and the environment.
• If the oxide film (corrosion product) is nonporous, protective in nature, prevents
the further corrosion. The layer acts as a barrier between the fresh metal surface
and corrosive environment.
• If the oxide film (corrosion product) is porous, unstable in nature, continues the
corrosion processes.

Example: Aluminium Titanium and chromium form a protective film of metal

oxide on the surface. Stainless steel forms a protective film of Cr2O3 on the
surface. But in the case of Zinc and Iron, the corrosion product formed do not
have a protective value.

pH OF THE MEDIUM

• Acidic media are generally more corrosive than alkaline/neutral media. The pH
of the solutions decides the type of cathodic reaction.
• The corrosion of iron in oxygen free water is slow, until the pH<5, the
corresponding corrosion rate is much higher in presence of oxygen.
• The metals which are amphoteric in nature viz. Al, Zn, etc., dissolve in alkaline
solutions as complex ions.
• Corrosion of metals readily attacked by acid can be reduced by increasing the
pH of the environment. Example: Zn suffers from severe corrosion even in the
presence of mild acidic medium, whereas corrosion is minimum at pH=11.
TEMPERATURE

• The velocity of a chemical reaction increases with increase in temperature.

• If the medium is acidic, hydrogen evolution takes place at cathode. The rate of
diffusion of H+ towards cathode increases with increase in temperature and
enhances the rate of corrosion.

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 • If the medium is alkaline / neutral, oxygen absorption takes place at cathode.
Since the solubilities of the dissolved gases decreases with increase in
temperature, the rate of corrosion also decreases.
• Passive metals becomes active at high temperature and increases the rate of
corrosion with increasing temperature. Ex. Caustic embrittlement in high
pressure boilers.

ANODIC AND CATHODIC AREA EFFECT

• The rate of corrosion (x) is directly proportional to the ratio of area of cathode
to the area of anode. i.e., x = area of cathode/ area of anode
• Higher the value of x, greater is the rate of corrosion..
• When anode is small and cathode is large all the electrons liberated at anode,
are consumed at the cathodic region. Therefore, the rate of anodic reaction is
greater and increases the extent of corrosion.

Example: A broken coating of Tin on Iron surface results in intense corrosion at

the broken region. Iron is anodic to tin. Exposed region has small area and acts
as anode.Tin acts as a cathode which has a large area.

TYPES OF CORROSION

Differential metal Differential aeration Stress

corrosion corrosion corrosion
Ex: Galvanic corrosion Ex: Pitting corrosion Ex:Caustic
Waterline corrosion embrittlement

DIFFERENTIAL METAL CORROSION

• When two dissimilar metals are in direct contact with one another and exposed
to a corrosive conducting medium, the metal higher up in the electrochemical
series behaves as anode and suffers from corrosion, whereas the metal lower in
the electrochemical series becomes cathode and protected from corrosion. This
type of corrosion is also known as Galvanic corrosion.
• If the potential difference between the electrodes is high, greater the extent of
corrosion.

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 • Oxidation /reduction takes place at anode/cathode respectively.
• The reduction at cathode depends on the nature of the corrosive environment. In
acidic medium, corrosion occurs by hydrogen evolution; while in
alkaline/neutral solution, oxygen absorption takes place.
• When Zn and Cu metals are electrically connected and exposed to an
electrolyte, Zn (higher in electrochemical series) forms anode and suffers from
corrosion whereas Cu (lower in electrochemical series) forms cathode and
protected from corrosion.
• Examples: Steel screws in a brass marine hardware
Steel pipe connected to copper plumbing

DIFFERENTIAL AERATION CORROSION

• This type of corrosion is due to the formation of differential aeration cell or

oxygen concentration cell.
• When a metal surface is exposed to differential air or oxygen concentrations-
forms differential aeration cell.
• The more oxygenated part of the metal behaves as cathode and less oxygenated
part becomes cathode.
• Differential aeration of metal causes a flow of current called the differential
current and the corrosion is called differential aeration corrosion.

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 • Example (a): Rusting of an iron.
• Example (b): Consider a piece of Zn metal is partially immersed in a dilute
solution of neutral salt (NaCl), and the solution is not agitated properly.
The part of the metal above and closely adjacent to the water-line are more
oxygenated, because of easy access of oxygen and hence become cathodic. The
part of the Zn metal immersed to greater depth, which have less access of
oxygen and becomes anode. Hence a difference in potential between the
electrodes is created, which causes a flow of current between the two
differentially aerated areas of the same metal and causes corrosion at anode.
• Differential aeration accounts for the corrosion of metals partially immersed in
a solution, just below the water line. This type of differential aeration corrosion
is also known as water line corrosion.
• Consider a steel tank containing water. The maximum corrosion takes place
along a line just beneath the level of water meniscus. The area above the
waterline is highly oxygenated and acts as the cathodic and completely
unaffected by corrosion. (Eg. Marine plants attacking themselves in the sides).

Poor oxygenated more oxygenated

Area (anode) area (cathode)

PITTING CORROSION
• It is a localized accelerated attack in which only small areas of the metal surface
are attacked whilst the remainder is largely unaffected. This localised attack
results in pitting. The pits may initiate and propagate to a certain depth resulting
in the formation of cavities and becomes inactive.
• Pitting is very destructive and frequently ruins the tubes, pipes etc.
Pitting is due to breakdown or cracking of the protective film on a metal at
specific points.

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 • The presence of impurities like sand, dust, scale, etc., on the surface of metal
leads to pitting.

• Pitting corrosion is due to the formation of differential aeration cell.

• This attack becomes more intensified with time.

STRESS CORROSION
• It is a highly localised attack on the metal.
• This corrosion occurs only in the presence of specific corrosive environment
and the presence of tensile stress on the metal.
• Stress may be produced on the metal during fabrication of the article or during
etching, drawing, servicing etc.
• This corrosion involves an attack along the narrow paths forming local anodic
areas with respect to more cathodic area of the metal surface.
• The stress produces strains, resulting localised zones, which are chemically
active and easily attacked even by a mild corrosive environment results in the
formation of fissures.
• The fissures lead to crack in the presence of stress.
• The crack grows and propagates perpendicular to the operating stress, and
failure occurs after progressing a finite distance.
• Example: Caustic embrittlement

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 • It is a stress corrosion occurring in mild steel when exposed to alkaline
solutions at high temperature and stress.
• The boiler water, usually contains a certain proportion of sodium carbonate
added for water softening purposes.
• In high pressure boilers, the carbonates breaks up to give respective hydroxide
and carbon dioxide, and make boiler water alkaline.
Na2CO3+H2O→NaOH+CO2
• This very dilute alkaline water flows into the minute hairline cracks and
crevices by capillary action.
• The water evaporates and increases the concentration of the alkali.
• This concentrates alkali dissolves iron as sodium ferroate in crevices, cracks
and the metal under stress.
• The sodium ferroate decomposes into magnetite and alkali is regenerated in
the process as per the following reactions.
NaOH +Fe→ Na2FeO2+H2

Na2FeO2+H2O→ NaOH +Fe3O4

• This type of stress corrosion in boilers in the presence of alkaline medium,

called caustic embrittlement.

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 • This can be prevented by the addition of the substances such as sodium
sulphate, tannin, etc., which blocks the cracks and crevices, thereby prevents
the penetration of alkali.

CORROSION CONTROL
Corrosion can be completely avoided only under ideal conditions. Since it is
impossible to attain such conditions, it can be minimized by using various
corrosion control methods. They are:
a) by protective coatings
b) by corrosion inhibitors
c) by cathodic protection

CATHODIC PROTECTION:

The principle is to force the metal to be protected, to behave as cathode. There are
two types of cathodic protections namely,
1) Sacrificial anodic protection
2) Impressed current cathodic protection

SACRIFICIAL ANODIC PROTECTION

• The metallic structure to be protected is connected to a more anodic metal

using a metallic wire.
• The more active metal gets corroded, while the parent structure is protected
from corrosion.
• The more active metal so employed is called sacrificial anode.
• The sacrificial anodes to be replaced by fresh ones as and when it is required.
• Commonly used sacrificial anodes are: Mg, Zn, Al etc.

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 • This method is generally used for the protection of buried pipelines, ship
hulls, water tanks, etc.
Example: steel pipe is protected by connecting it to a block of Mg or Zn. In
such cases steel acts as a cathode and is unaffected Mg or Zn acts anode and
undergoes sacrificial corrosion

IMPRESSED CURRENT CATHODIC PROTECTION

• The metallic structure to be protected is made as cathode by impressing the

current.
• The current is applied in the opposite direction to nullify the corrosion current.
• The impressed current is obtained from a source like battery.
• An insoluble anode (ex: graphite, high silicon content iron, etc.) is buried in
the soil, and connected to the structure to be protected.

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 • The anode is usually placed in a backfill, to provide a better electrical contact
with the surroundings.
• This method is suitable for large structures and for long term operations

ANODIC PROTECTION
• The principle is to force the metal to be passive, to behave as anode.

• Metals like titanium, chromium, iron, nickel and their alloys show passivity.

• Metals become passive on applying potential greater than passivating

potential by maintaining constant current using potentiostat.

• Passivity is due to the formation of oxide film on the surface in an oxidizing

environment

• The passivation can be explained by plotting a graph

• The plot of corrosion current as a function of applied potential shows as the

potential is increased the corrosion current increases first(region AB),then
decreases (region BC),then remains constant(region CD),then increases
again(region DE)

• Region CD is passive region at this region rate of corrosion is very slow, but

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 PROTECTIVE COATINGS
• Corrosion is prevented by the application of protective coating on the surface of
metal, thereby the metal surface is isolated from the corrosive environment.
• The coatings being chemically inert to the environment under specific
conditions of temperature and pressure, forms a physical barrier between the
coated surface and its environment.
• Coatings are not only preventing corrosion but also decorate the surface of the
metal.
• Important types of protective coatings are:

(i) Metal coatings

(ii) Inorganic coatings and
(iii) Organic coatings

METAL COATINGS
• Metal coatings can be applied on the base metal by hot dipping process.
• This method is used for producing a coating of low melting metals such as
Zn,Al, Sn etc., on iron / steel metals which have relatively high melting
point.
• The process involves immersing of the base metal in a molten bath of
coating metal covered by a flux layer.
• The flux cleans the surface of the metal base metal and prevents the oxidation
of molten coating metal.
• The coating metal may be anodic or cathodic to the base metal.

Example: Galvanising and Tinning

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 GALVANISING: (HOT DIPPING METHOD)

▪ Coating of zinc on iron or steel, by hot dipping process is called galvanising.

(M.P of Zn = 419oC)
▪ The article is washed with organic solvents to remove oil/grease, with sulphuric
acid to remove scale/rust, then with water and dried, before coating.
▪ Coating metal is anodic to iron/steel, called anodic coating.
▪ The molten metal bath is covered with a flux of Ammonium chloride, which
prevents the oxidation of the coated metal.
▪ The article is dipped in a molten bath of Zn. The excess of coated metal is
removed by passing through a pair of hot rollers and cooled gradually.
▪ Galvanising is applied to nails, bolts, pipes, roofing sheets etc.
▪ Galvanised sheets cannot be used for preparing/storing food stuffs, since Zn
dissolves in acidic medium and forms toxic compounds.
▪ If any crack is produced on the galvanised sheets, causes severe corrosion on
the coated Zn metal and the base metal is protected.
▪ Zn is chosen as a protective coating for iron/steel because of its natural
resistance against corrosion in most atmospheric conditions, and Zn is
electronegative to iron and can protect it sacrificially.

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 TINNING

• Coating of tin on iron or steel, by hot dipping process is called tinning. (M.P of
Sn = 232oC).
• The metal surface is washed with organic solvents to remove oil/grease, with
sulphuric acid to remove scale/rust then with water and dried, before coating.
• Coating metal is cathodic to iron/steel, called cathodic coating.
• The molten metal bath is covered by a flux of Zinc chloride.
• The clean and dry sheet is passed through flux layer, molten tin, finally
removed out through palm oil, which prevents the oxidation of the coated tin.
• It possesses more resistance against atmosphere.
• It is non-toxic in nature and more noble than the base metal.
• Tinning is widely used for coating the steel sheets, Cu and brass sheets used for
manufacturing containers for storing/packing food materials, cooking utensils,
refrigeration equipments, etc.
• If any crack is produced on the tinned sheets, causes severe corrosion of the
base metal.

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 • Tin coatings form a useful preparation for protective painting in general
applications
INORGANIC COATINGS (CHEMICAL CONVERSION COATINGS)
• These coatings are produced at the surface of the metal by chemical /
electrochemical reactions.
• These coatings are applied on the article for decorative effect and to increase
the corrosion resistance of the base metal.
• These serves as an excellent base coating for paints and enamels.
• Examples: Anodising and Phosphating

ANODISING OF ALUMINIUM

• These coatings are generally produced on non-ferrous metals like Al, Zn, Mg
and their alloys by anodic oxidation (electrochemical) process.
• The base metal is made as anode.
• Anodising of Al: It is carried out to produce a porous/nonporous coating.
• The porous coating is obtained by anodic oxidation. The electrolysis is
conducted in an acid bath, at moderate temperature 30-40oC, using moderate
current densities, in which the base metal is made as anode. The commonly
used baths are H2SO4 / Chromic acid / Phosphoric acid /oxalic acid.

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 • The thickness of the film increases with progressive oxidation. Outer most
layer of the oxide film is very porous and soft, these pores are sealed by
exposing to the boiling water.
• In this process the metal oxide layer changes into its mono hydrate.
The non porous coatings are produced by using non-corrosive electrolytes like
boric acid and borax.
• These coatings are applied on electrolytic condensers.
• The anodised coatings are thicker than the natural oxide film and possess
improved corrosion resistance as well as resistance to mechanical injury.

PHOSPHATING

• These coatings are generally applied frequently to iron, steel and zinc and to a
lesser extent on Al, Cd and Sn.
• These are produced by the chemical reaction of the base metal with aqueous
solution of phosphoric acid(pH-1.8-3.2) and phosphate of Fe, Mn or Zn.

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 • The reactions are slow, hence it is enhanced by using accelarators along with
the phosphating mixture.
• The most common mode of acceleration is by addition of oxidizing agents,
such as nitrate, nitrite, chlorate and hydrogen peroxide.
• The chemical reaction between the base metal and the phosphating mixture
results in the formation of surface film consisting of crystalline Mn-Fe
Phosphate, Zn-Fe Phosphate etc. These coatings are applied by immersion or
spraying or brushing.
• These coatings do not offer complete resistance to the atmospheric corrosion.
• These are used as a primer coat for paints, enamels, etc.

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 MODULE – II

METAL FINISHING

INTRODUCTION

Every manufactured product made of metal or having metal components will

feature some type of metal finishing. Many industries use metal finishing in their
manufacturing processes including aerospace, automotive, electronics, hardware,
appliances, telecommunications and jewelry. Electrolytic plating, electroless
plating, and chemical and electrochemical conversion are typically used in the
surface finishing process. Other supporting processes can include degreasing,
cleaning, pickling, etching, and polishing. The use of metallic compounds in
electroplating and the application of organic solvents in all manner of metal
finishing are the primary materials subject to extensive environmental regulations.
In the U.S., the metal finishing industry is one of the largest users of many toxics
chemicals. The rinsing process and periodic disposal of spent chemicals are the
primary source of wastewater generated in metal finishing operations. The major
contaminants of concern can include Ag, Cd, CN, Cr, Cu, Ni, Pb, Sn, Zn and COD.

Like many other manufacturing industries, metal finishing shops have to confront
the immediate challenges of various water supply issues. Among which is the
severe shortage of water for production, quality and treatment of water from
contaminated sources, and ever-increasing water cost.

All these factors are the drivers steering the metal finishers to implement on-site
wastewater recycle program to meet both the operational and economic
requirements

❖ Metal finishing covers the wide range of processes carried out in order to
modify the surface properties of a metal. These processes involve deposition

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 of a layer of another metal or a polymer, conversion of a surface layer of
atoms into oxide films which ultimately modify the surface of the metal.

The principle of metal finishing are used in electroplating of metals, alloys and
composites, manufacture of electronic components such as PCBs, capacitors,
connectors etc.

❖ Definition: “It is a process of modifying surface properties of metals by

deposition of a layer of another metal or polymer on its surface, by the
formation of an oxide film”.

TECHNOLOGICAL IMPORTANCE OF METAL FINISHING

The main technological importance of metal finishing include

1. Imparting the metal surface to higher corrosion resistance.

2. Imparting improved wear resistance.
3. Providing electrical and thermal conducting surface.
4. Imparting thermal resistance and hardness.
5. Providing optical and thermal reflectivity.
6. In the manufacture of electrical and electronic components such as PCB’s,
capacitors contacts, etc.
7. In electro framing of articles, electrochemical machining, electro polishing
and electrochemical etching.
8. To increase the decorativeness of metal surface.
9. In electrotyping and to build up material or restoration.
10. To improve wear resistance or solder ability.

PRINCIPLES OF METAL FINISHING

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 POLARIZATION
The polarization is an electrode phenomenon. The electrode potential is
determined by the Nernst equation,

0.0591
𝐸 = 𝐸𝑜 + log[𝑀𝑛+ ]
𝑛

Where Mn+ is the concentration of the metal ions surrounding the electrode surface
at equilibrium. When there is a passage of current, the metal ion concentration near
the electrode surface decreases due to the reduction of some of the metal ions into
metal atoms. There exist a concentration gradient between electrode surface and
bulk concentration. Therefore there is a shift in the equilibrium and a change in
electrode potential.

As a result there will be a change in the electrode potential; however equilibrium is

re-established due to the diffusion of metal ions towards the electrode. If the
diffusion is slow the electrode potential changes and the electrode is said to be
polarized. Polarized electrode uses more negative potential than required in order
to maintain given current.

M n+ + n e- M

Therefore polarization can be defined as the process where there is a variation of

electrode potential due to the inadequate supply of species from the bulk of the
solution to the electrode is known as “polarization”.

Factors which affect polarization

• Nature of the electrode (i.e. size, shape, composition).

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 • Electrolyte concentration and its conductivity.
• Temperature.
• Rate of stirring of the electrolyte.
• Product formed at the electrode.

Significance of polarization

1) Polarization is a condition caused by changes in bath concentration or

changes within either the anode or cathode films. It is caused by the
movement and discharge of ions.
2) Polarization is always present during electrolysis of a solution but is of
concern when its effect becomes excessive. It is caused by a depletion of the
electrode surface, as in concentration polarization, or resistance polarization
which is caused by the formation of a diffusion layer surrounding the
electrode.

DECOMPOSITION POTENTIAL

It is defined as “the minimum voltage that must be applied in order to bring

about continuous electrolysis of an electrolyte”.

Electrolysis of an electrolyte occurs only when applied voltage is above certain

value below which electrolysis do not occur. This can be determined by an
electrolytic cell, if dilute acid or bases are used as electrolytes ,it required more
than 1.7V. The decomposition potential for Zn and iodine cell is experimentally
found to be 4.3 volts. The decomposition potential is represented as

ED = Ecathode - Eanode

Determination of decomposition potential

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 The decomposition potential is determined using an electrolytic cell as shown in
the figure.

The cell consists of two platinum electrodes immersed in a dilute solution of an

acid or a base. The voltage is varied along the wire and the current passing through
the cell is measured using an ammeter. At low voltage no reaction occurs and there
is a very slight increase in the current & small amount of hydrogen & oxygen are
liberated at the cathode & anode respectively.. This hydrogen gas adsorbed on the
cathode electrode & produces back emf which opposes the applied emf. On
increasing the voltage to slightly above 1.7V, there is an abrupt increase in the
current and process of electrolysis begins. A plot of the current against the applied
voltage as below.

Significance of decomposition potential:

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 • Minimum external voltage that must be applied in order to bring about
electrolysis of electrolyte.
• It is impossible to predict the order of discharge of ions from an electrolytic
solution containing several ions.

OVER VOLTAGE

It is defined as “The excess voltage that has to be applied above theoretical

decomposition potential to bring the continuous electrolysis of an electrolyte” is
known as over voltage.

The theoretical voltage required for the decomposition of aqueous solution of an

acid is equal to the emf of the reversible cell with hydrogen and oxygen gases at
one atmosphere. This is known to be about 1.23 volt at ordinary temperature with
platonised platinum electrodes. It is however found that the observed
decomposition potential is always higher than the theoretical value. Thus with
platinum and lead electrodes, a voltage of 1.7 and 2.2 is respectively required for
the electrolysis of dilute sulphuric acid as against a theoretical value of 1.23 volt.
This difference between the observed and theoretical decomposition potential is
called “over voltage”.

Over voltage = (Experimental decomposition potential – theoretical

decomposition potential)

Over voltage of an electrolyte depends on

1) Nature and physical state of the metal employed for the electrodes.
2) Nature of the substance deposited.
3) Current density.

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 4) Temperature.
5) Rate of stirring of electrolyte.

ELECTROPLATING

Definition: “it is a process of deposition of a metal by electrolysis, over the surface

of substrate. The substrate may be another metal, polymer, ceramic, or a
composite”.

Theory of electroplating

Electroplating process being electrolysis, the amount of metal getting deposited

and the amount of current passing through the electrolytic cell are related to each
other by the law of electrolysis called Faraday’s laws.

The principal components of electroplating process are:

1) Electroplating bath 2) Cathode 3) Anode 4) Electroplating tank 5)

Reactions at anode and cathode

1) Electroplating bath: The plating bath contains solution for plating process.
It is normally a mixtures of metal ion solution, other electrolytes,

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 complexing agents and various organic additives added to improve the
nature of deposit.

2) Cathode: The substrate to be plated is made as cathode and suspended as

separate bars. These cathode electrodes are placed in electrolytic bath
solution.

3) Anode: The metal which is to be plated on the other metal is made as anode.
Anode is used in the form of a rod, a plate or pellets. The anode is enclosed
inside an anode bag to retain impurities.

4) Electroplating tank: It is made of wood or steel. If steel tanks are used

these are thermally insulated with ceramic or polymeric materials. The
volume of tank may vary from 20 – 100 dm3.

5) Reaction at anode and cathode: Electroplating is the process of

electrolytically depositing a layer of metal on a surface. The anode metal
undergoes oxidation liberating metal ions and electrons. The electrolytic
bath containing metal ions undergoes reduction to metal atoms and gets
deposited on the metal or substance to be plated.

At cathode: M n+ + n e- M
At anode: M M n+ + n e-

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 FACTORS (PLATING VARIABLES) INFLUENCING NATURE OF
ELECTRODEPOSITS

The nature of the electrodeposit is affected by numbers of factors which are

discussed below.

1) Metal ion concentration.

2) Electrolyte concentration.

3) Complexing agents.

4) Organic additives.

5) Current density.

6) pH.

7) Temperature.

8) Throwing power of plating bath.

1) Metal ion concentration

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 A higher concentration of metal ion increases the mass transfer leading to poor
deposit. For a good adherent deposit, the metal ion concentration should be low; it
is normally 1-3 mol dm-3. The low metal ion concentration can be achieved by
adding compounds having common ions or by the formation of complex
compounds and ions. In general a decrease in metal ion concentration decreases the
crystal size and result in a fine adherent coating films.

Example: when copper is deposited from CuSO4 bath, H2SO4 is added to the
solution. Due to the common ion effect of SO42- , the concentration of Cu2+ ion in
the solution is reduced.

CuSO4 Cu2+ + SO42-

H2SO4 2H+ + SO42-

2) Electrolyte concentration:

A good adherent deposition can be obtained with higher electrolyte concentration.

The electrolytes used do not participate in the electrode reactions but increases the
conductivity of the plating bath and cathode efficiency. It also controls the change
in pH.

3) Complexing agents:

These are added

1) to maintain low metal ion concentration.

2) to prevent the chemical reaction between the cathode metal and plating ions.
3) to improve the throwing power the plating bath.
4) to increase the solubility of slightly soluble metal salts.
5) to prevent the passivation of anode so that anode dissolves easily and
improve the current density.
Ex: Cyanides, hydroxides, sulphamates.

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 4) Organic additives:

These are added to improve the nature of electrodeposits. They modify the
structure, morphology and properties of the electrodeposits. The different organic
additives used are as follows:

a) Brighteners c) Structure modifiers

b) Levelers d) Wetting agents

a) Brighteners:

These are added to obtain a bright and microscopically fine deposit. The
brighteners are adsorbed on the nuclei of the metal and forms new nuclei, i.e., large
number of smaller crystals resulting in the formation of good deposit.

Ex: Aromatic sulphones or sulphonates & compounds containing C=O, N=C=S,

etc.

b) Levelers:

Levelers are added to produce an even (level) deposit by getting adsorbed at

regions where rapid deposition takes place. The levelers reduce the rate of
deposition at those points.

Ex: Sodium alkyl sulphonates.

c) Structure modifiers or Stress relievers:

These additives modify the structure of the deposit and orientation in such a way as
to alter the deposit properties. These substances avoid the development of internal
stress in the deposits.

Ex: Saccharin.

d) Wetting agents:

Wetting agents are used to release hydrogen gas bubbles from the surface. The
wetting agents also improve the uniformity of the deposit.

Ex: Sodium lauryl sulphate.

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 5) Current density:

Current density is the current per unit area expressed in amperes per m2. At low
current density, a bright, crystalline deposit is produced but the rate of deposition is
slow. At higher current density, hydrogen evolution occurs and deposits are
spongy, irregular and loosely held. Deposits may have a burnt appearance.

For good deposit the current density should be optimum . (10- 70 A m-2.)

6) PH:

The nature and appearance of the electrodeposit depends on p H of the plating

solution. If pH of the medium is low H2 gas is evolved at the cathode causing brittle
and burnt deposit. At higher pH values, deposits of metallic oxides or hydroxides
may form. Hence an optimum pH (4- 8) is employed.

7) Temperature:
A good deposit is formed at slightly higher temperature (35-60oC). At very low
temperature hydrogen evolution takes place at the cathode forming a burnt deposit.
Therefore moderate temperature is used to get good deposit.

8) Throwing Power of a plating bath:

The ability of a plating bath to give a uniform and even deposit on the entire
surface of the object, irrespective of its shape is known as “throwing power”.

Throwing power of plating bath can be determined by using “Haring Blum Cell”.

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 Haring Blum cell consists of plating bath solution whose throwing power is to be
determined. Anode is placed at the centre and two cathodes are placed on the either
side of the anode at a distance x1 and x2. Electroplating is carried out and weight of
electro deposit on the two cathodes is weighed. The weight of electro deposit (w1)
on x1 which is placed far from anode is less than another x2, which is very nearer to
the anode. Then throwing of plating bath is calculated from the equation.

% throwing power =
 K M 
  100
 (K  M )  2 

Where K = x1 / x2 (when x1 > x2); M = w2 / w1

Throwing power is said to be very good (100%) when w1 ═ w2

REQUIREMENTS OF ELECTROLYTE SOLUTION FOR

ELECTROPLATING

• Metal content should be high but metal ion concentration should be low.
• Conducting power of solution should be high.
• Electrolyte solution should be stable under operating condition.

Application of electroplating:

• For better appearance

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 • Plating for protection
• Plating for special surface
• Plating on non metals
• Plating for engineering effect

ELECTROPLATING OF CHROMIUM

Chromium is one of the widely used metal for electroplating. In the field of
electroplating two types of Chromium are employed, decorative Chromium and
hard Chromium.

Pretreatment: Before the application of the electroplated coatings, it is essential to

clean the surface of the base metal. The impurities present on the surface like
grease, oil, oxide layer, dust etc are removed by solvent cleaning or alkali cleaning
or mechanical cleaning.

DECORATIVE / HARD CHROMIUM

Bath composition : 250g Chromic acid + 2.5g H2SO4 proportion/dm3

Temperature : 45-60°C. / 45-55°C for hard chromium

Current Density : 145- 430 A m-2 / 290-580 A m-2 for hard

chromium

Anode : Insoluble anodes like pb-sb

Cathode : Object to be electroplated. (Pre-treated).

Mode of plating - The plating bath contains CrO3 in which Cr is in +6 oxidation

state. This is reduced to +3 oxidation state in the presence of SO42- furnished by
H2SO4. Cr3+ ions are reduced to elemental Cr which gets deposited on the surface
of cathode. The reactions taking place are given below.

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 2H2CrO4 H2Cr2O7 + H2O
H2Cr2O7 Cr2O72- + 2H+
Cr2O72- + 14H++ 6 e- 2Cr3+ + 7H2O
Cr3+ + 3e- Cr
Applications

Decorative chromium provides a durable finish on cycles, automobiles, furnitures,

household fittings, air craft, surgical instruments etc

Hard chromium is used in the manufacture of cutting tools, Piston rings,

cylindrical liners etc.

Note - Chromium anodes are not used in Chromium plating because

1) Chromium metal deactivates strongly in acid medium.

2) Cr anodes gives rise to Cr3+ ions on dissolution and a black deposit of Cr is

obtained in the presence of large concentration of Cr3+ ions.

3) The wide difference between the anode and cathode efficiencies. The anode
efficiency is 100%, the cathode efficiency is at best around 20%. This results
in building up of excessive chromic acid concentration.

ELECTROLESS PLATING (AUTO CATALYTIC)

Definition: “The process of depositing a metal over substrate by controlled

chemical reduction of metal ion by a reducing agent without using electric current
is called electroless plating”

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 Metal ions + reducing agent Metal + oxidized product

DIFFERENCES BETWEEN ELECTROPLATING AND ELECTROLESS

PLATING

Electro plating Electroless plating

1) Driving force Passage of current Auto catalytic redox

reaction

2) Anode A separate anode is used Catalytic surface of the

substrate acts as anode

3) Reducing agent Electrons bring about Chemical reagents bring

reduction about reduction

4) Applicability Applicable only to Applicable to both

conductors conductors and
nonconductors

Components of electroless plating bath solution

▪ Metal salts to provide metal ions

▪ Reducing agents for reduction of metal ions to metal
▪ Buffer to control pH.
▪ Other additional agents

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 Advantages of electroless plating over electroplating

• Does not require electrical power source and accessories.

• Deposition can be made on non-conductors such as plastics, ceramics etc.
• Plating baths have excellent throwing power.
• The electroless deposits possess unique characteristic chemical, mechanical
and magnetic properties.
• Does not require levelers.
• Electroless deposits are less porous.

ELECTROLESS PLATING OF NICKEL

Electroplating of nickel involves the following features.

1) Pretreatment and activation of the surface:

The surface to be plated is first degreased by using organic solvents
followed by acid treatment.

2) Metals and like Al, Cu, Fe, and Brass etc be directly nickel plated without
any activation.
3) Stainless steel surface is activated by dipping in hot solution of 50% dilute
H2SO4.
4) Activation of Mg alloy surface is carried out by giving a thin coating of Zn
and Cu over it.
5) Activation of nonmetallic articles is carried out by first dipping in Sncl 2
solution containing Hcl, followed by dipping in palladium chloride solution.

COMPOSITION OF BATH

Acid nickel bath

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 Coating solution : NiCl2 solution 20g/L

Reducing agent : Sodium hypophosphite 20g/L

Buffer : Sodium acetate 10g/L

Complexing agent : Sodium succinate 15g/L

pH : 4.5

Temperature : 93°c

Alkaline nickel bath

Coating solution : NiCl2 solution 30g/L

Reducing agent : Sodium hypophosphite 20g/L

Buffer : Ammonium chloride 50g/L

Complexing agent : Ammonium citrate 55g/L

pH : 8 – 10

Temperature : 90°c

Chemical Reactions

Anodic Reaction : H2PO2- + H2O H2PO3- + 2H+ + 2e-

Cathodic reaction : Ni 2+ + 2 e- Ni

Net Reaction : Ni2+ + H2PO2- + H2O Ni + H2PO3- + 2H+

Note: Buffer is added because

The above redox reaction involve the liberation of H+ ions, so pH of the solution
goes down as the reaction proceeds, there by adversely affecting the quality of the
deposit as well as plating rate.

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 Advantages

1) Electroless nickel deposits are free from pores and possess better corrosion
resistance than electro plated nickel deposit.
2) It gives rise to harder surface with better wear resistance.

Applications

1) Used to plate on industrial components such as pumps and valves, shafts,

gears, reaction vessels and other tools.
2) Electroless nickel coated polymers finds preferred decorative applications.
3) Electroless plating of nickel finds applications in domestic as well as
automotive fields.

Bright[4] Semi-bright[4]
Chemical
Formula
Name
Metric US Metric US

150–300 20–40 225–300 30–40

Nickel sulfate NiSO4·6H2O
g/L oz/gal g/L oz/gal

60–150 8–20
Nickel chloride NiCl2·6H2O 30–45 g/L 4–6 oz/gal
g/L oz/gal

Boric acid H3BO3 37–52 g/L 5–7 oz/gal 37–52 g/L 5–7 oz/gal

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 ELECTROLESS PLATING OF COPPER OVER PCB

Electroless plating of copper involves the following features.

1) Pretreatment and activation of the surface

The surface to be plated is first degreased by using organic solvents
followed by acid treatment.

2) Metals like Fe, Co, Ni etc can be directly copper plated without
pretreatment.
3) PCBs are activated by first dipping in Sncl2 solution containing Hcl,
followed by dipping in palladium chloride solution.
Procedure

A thin layer of copper is first electroplated over the PCB.Then selected areas are
protected by employing electroplated image and the remainder of the plated copper
is etched away so as to get required type of circuit pattern. Usually double sided
tracks are made in order to pack more number of components in a small space.
Finally, the connection between 2 sides of PCB is made by drilling holes, followed
by electroless copper plating through holes.

COMPOSITION OF THE BATH

Coating solution : CuSO4.5H2O + 15g/L

Reducing Agent : Formaldehyde 8g/L

Buffer : NaOH 15g/L+ Rochelle salt14g/L

Complexing agent : EDTA solution 20g/L

pH : 11.0

Temperature : 25°c

Chemical Reactions

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 Anodic Reaction : 2HCHO + 4OH- 2 HCOO - + 2H2O + H2 + 2e-
Cathodic Reaction : Cu2+ + 2 e- Cu

Net reaction : Cu2+ + 2HCHO + 4 OH- Cu + 2HCOO- +

2H20 + H2
Note: Buffer is added because,

The above redox reaction involves the consumption of OH- ions, so the pH of
the solution decreases as the reaction proceeds.

Application

• Widely used for metalizing printed circuit boards.

• For producing through hole connections.
• For plating on non-conductors.
• As an undercoat for electroplating.
• For decorative plating on plastics

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