Department of Chemistry

ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

Introduction

The large numbers of metals used in most of engineering works/applications need an ideal metal or
alloy which can fulfill all the properties like corrosion resistance, wear and tear resistance, impact
resistance, mechanical, electrical and thermal properties, etc., But none of the metals possess all these
properties. Metal surfaces are modified in order to satisfy their lacking properties and this surface
modification is achieved by the technique known as “Plating Technique.”

Plating technique involves the deposition of a thin layer of a noble metal on a base metal or a
polymer or conversion of a thin layer of the surface into the oxide, chromate or phosphate of the metal.

Technological Importance:

Plating technique finds extensive applications in variety of industries, extending to many electronics,
engineering and metal processing companies as well as to both large and small specialist firms. The
technological importance of plating technique is in imparting certain additional properties to the
materials in addition to their intrinsic properties. So that, the utility of the materials is increased.

1. Provide a bright, shiny appearance.

2. Imparting higher corrosion resistance.
3. High resilience resistance to wear and tear.
4. Providing electrical and thermal conducting surface.
5. To increase abrasion and impact resistance.
6. To increase hardness of the surface.
7. Imparting improved solderability.
8. Providing optical or thermal reflectivity.
9. Imparting chemical and thermal resistance.
10. In the manufacture of metal articles entirely by electroplating.
11. In electroplating and in electrophoretic painting.
12. In electroforming of objects.
13. In electro machining.
14. In electro chemical etching, polishing and engraving.
15. Material restorations.

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

Types of plating
Two important methods of plating techniques are:
 Electroplating of metals or alloys and

 Electroless plating of metals or alloys

Electro Plating:

The term electroplating refers to the deposition of a metal on the surface of another metal, alloy or
any conductor in general, by the process of electrolysis. It consists of a process by which a metal is
deposited on another metal or alloy by passing a direct current through an electrolyte solution
containing the metal ions to be deposited. Therefore, electroplating can be defined as “A process in
which a base metal is coated with a thin and uniform layer of another suitable metal by electrolytic
deposition.”
The common coating metals used are Zn, Cu, Ni, Cr, Ag, Pt, Au, etc., Electro-deposition is an
important and frequently used method in industries for producing metal coating.
Electro Plating Process:
The electro-plating device is essentially an electrolytic cell, in which two electrodes, anode and
cathode are dipped in an electrolyte solution. The principal components of an electroplating process are
shown schematically in the following figure.

DC power

 Θ
Electroplating Tank
A C
N A
O T
D H
E Ionic transport O Electroplating Metal Layer
D
E

Electrolyte

Schematic representation of Electro-Plating unit

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

The essential components include:

1. An electroplating bath containing a conducting salt and the metal to be placed in a soluble form as
well as buffer and additives.
2. The electronically conducting cathode, i.e., the article to be plated.
3. The electronically conducting anode, the coating metal itself or an inert material of good electrical
conductivity like graphite.
4. An insert vessel to contain the above mentioned materials, made up of either rubber lined steel,
plastic, concrete or wood.

Electrolysis Reactions:
Electroplating is the process of electrolytically depositing a layer of metal onto a surface. The
object to be plated is made the cathode in an electrolytic bath containing a metal ion, Mn+ So that, the
simplest reaction at the cathode is:
Mn+ + ne-  M
Wherever possible, the preferred anode reaction is the dissolution of the same metal in the solution.
M  Mn+ + ne-
In such cases, there is a continuous replenishment of electrolyte during electrolysis.
However, if the anode is made up of an inert material that does not pass into the solution, the
electrolytic salt is added continuously in order to maintain optimum metal ion concentration in the
solution.
As an example, in the electroplating of copper, the coating metal copper itself is made anode,
which dissolves as Cu2+ ions, replenishing the Cu2+ ions deposited at the cathode.
CuSO4 solution can be used as electrolyte, which ionizes as,
Cu SO4  Cu2+ + SO42-
On passing current, Cu2+ ions migrate to the cathode and get deposited there.
At the cathode, Cu2+ + 2e-  Cu
At the anode copper enters into the solution as Cu2+ ions.
At the anode, Cu  Cu2+ + 2e-
Thus in the case, there is a continuous replenishment of electrolyte during electrolysis.

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

Characteristics of a Good Deposit:

1. The deposit should be continuous, uniform, non porous and adhesive.

2. It should be of fine gained nature.
3. It should be bright and lustrous.
4. It should be hard and ductile.
In general, for a given metal, fine grained deposits are smoother, brighter, harder, stronger but less
ductile than coarse grained deposits. However, some exceptions do exist.

Requirements of an electrolyte solution for electro plating:

The electrolyte solution used for electroplating should possess the following characteristics.

1. Metal content of the solution should be high and the free metal ion concentration should be
relatively low.
2. The conducting power of the solution should be high.
3. It should be stable under the operating conditions, without undergoing hydrolysis, oxidation,
reduction and other chemical changes.
4. The solution should dissolve the anode quite efficiently whenever an active anode is used and
should be able to maintain constant metal content of the solution.
5. It should possess good covering power and throwing power. Covering power is the measure of the
ability of the bath solution to deposit the metal over the entire surface of an article.

However, no single electrolyte satisfies all these requirements. Therefore, usually, a mixture of two
or more electrolytes is used along with suitable addition agents.

1. Current efficiency (or) weight of metal actually deposited

Cathode efficiency = ----------------------------------------------------------------------------------------- x 100
weight of metal calculated from the quantity of electricity passed

Weight of metal dissolved

2. Anode efficiency = ------------------------------------------------------------------------------------ x 100
weight of metal calculated theoretically from Faraday’s law

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

Plating Process
Electroplating of Gold
Gold plating was initially applied for decorative purposes on jewelry articles. But later it is found
applications in the industries, for various purposes.

Typically four bath compositions are used for gold plating. Two of them are alkaline cyanide
baths, one is neutral cyanide bath and fourth one is acidic cyanide bath. Rubber or plastic lined tanks
can be employed for the plating bath and the temperature being kept below 700C. Agitation in terms of
cathode movement or solution circulation is desirable.

Bath A and B are used primarily for decorative gold plating and for industrial uses. Bath A is
used for low thickness of gold (0.02 to 0.25 µm) and bath B is used for large thickness of gold (up to 40
µm for items subject to heavy wear and abrasion). These baths are not suitable for plating on PCBs.

Batch C is used for components where baths A and B cannot be used. The gold deposits from
this bath are less porous compared to those from baths A and B. Bath D is similar to bath C in use and
yields a gold deposit of 99.999% plus purity with highest ductility. Since insoluble anodes are used in
almost all gold baths, gold salt – the potassium gold cyanide complex, is periodically added to replenish
the gold.

When gold is directly plated on copper, the copper atoms have the tendency to diffuse through
the gold layer, causing tarnishing of its surface and formation of an oxide layer. Therefore, a layer of a
suitable barrier metal, usually nickel to be deposited on the copper substrate, before gold plating. The
nickel deposit also provides mechanical backing for the gold layer, improving its wear resistance. It also
reduces the effect of pores present on the gold layer.

When gold is plated on silver, silver atoms also diffuse through the gold layer, causing gradual
fading of its colour and tarnishing the surface. This process may take months to years, depending on the
thickness of the gold layer. Therefore, it is better to use a barrier metal layer underneath the gold
deposit.

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

Electroplating of Gold by acid cyanide bath

Constituents Bath D (Acidic)

(1) Plating bath Solutions:

(i) Potassium gold cyanide g/dm3 6.0 – 18.0

(ii) Mono potassium dihydrogen phosphate g/dm3 20.0
(iii) Potassium citrate g/dm3 50.0
(2) pH 3–6
(3) Temperature oC 40 – 70
(4) Current density (A / ft2) 1 – 20
(5) Cathode efficiency (%) 80 – 90
(6) Brightener Thiourea
(7) Leveler Sodium allyl sulphonate
(8) Anode Pt, Platinized Ti, Carbon
(9) Cathode Object to be electroplated (It must be free
from dirt. Oil and grease, etc., in order to
get a good deposit).

Applications:
Gold deposit is a shiny deposit with good tarnish and corrosion resistance. It has good electrical
conductivity, comparable with copper and silver, and has an ability to reflect IR radiation.
1. Gold deposit is used for decorative purposes in jewellery, watch cases, pen points, etc.,
2. In the electrical industry, printed circuits, contacts and connectors are gold plated.
3. In electronics, transistors and integrated circuit parts are gold plated.
4. In the aerospace industry, instrument coverings and external surfaces exposed to radiation in space
are gold plated.
5. Reactors and heat exchangers in the conductor tube for desalination are gold plated, because of
the high corrosion resistance nature of gold.
6. Because of its acid and corrosion resistance, it is used for decorative purpose especially in tombs of
temples.

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

THROWING POWER

The ability of plating bath to give a uniform and even deposit on the entire surface of the object is
measured by its throwing power. This is particularly important in object of complex shape. For Ex,
Plating in holes and recesses takes place less uniformly than on even surfaces. Throwing power is said
to be good if the distribution of the deposit is uniform. This is irrespective of the shape of the object.
Throwing power of plating bath is defined as “the ability of the bath to produce uniform and even
deposit on the entire surface of the substrate”. Experimentally the TP of a plating bath is determined
using ‘Haring-Blum cell’.

Haring Blum Cell

The Haring Blum Cell consists of plating bath solution and an anode (A) at the center of the cell. Two
cathodes (C1 & C2) are placed at different distances (d1 & d2 where d1>d2) from the anode as shown in
the fig.

Weight of cathodes Weight of cathodes Weight of metal

Article to be plated
before deposition after deposition deposited on cathodes

Cathode 1 (C1) m1 g m3 g W1 = (m3 – m1) g

Cathode 2 (C2) m2 g m4 g W2 = (m4 – m2) g

Initial weights of the cathodes are noted. Electro plating is carried out for a sufficient time and then at
the end, the cathodes are weighed again. Finally, the masses W1 and W2 of the metal deposited on the
cathodes (C1 & C2) are determined. The mass W1 deposited on the cathode C1 (away from the anode)
will be lesser than W2 deposited on cathode C2 (nearer to the anode) i.e., W1<W2.

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

The throwing power of the plating bath solution is calculated from the equation

% Throwing power = (X-Y) X 100

(X+Y-2)

Where, X = d1/d2 and Y = W2/W1.

The throwing power is considered a very good (100%) When W1 = W2, that is the amount deposited is
same irrespective of the placement of the electrodes. The throwing power is considered as very poor
when its value is -100%.

Although the TP does not directly determine the nature of the deposit, certain factors which influence
the uniformity of the plating is expressed in terms of TP. These include

(i) Conductance of the solution: In a solution of high conductance, the current distribution will be
uniform over a complex cathode surface and therefore the rate of deposition is uniform. i.e.,
Solutions with higher conductivity will have higher TP.

(ii) Anodes: By Optimum Placement of the anodes and use of auxiliary anodes uniform deposition
may be achieved.

(iii) Complexing agents: Presence of complexing and addition agents such as levelers improves the
throwing power.

Numerical problems on Throwing Power

1. Calculate the percentage of throwing power of plating bath in a Haring Blum cell if the distances
between the two cathodes are 6.6 cm and 4 cm from the anode and the masses of the plating on the
cathodes are 52 mg and 55 mg respectively.

Solution:
d1 = 6.6 cm; d2 = 4 cm; W1 = 52 mg ; W2 = 55 mg.
X = d1/d2 = 6.6/4 = 1.65
Y = W2/W1 = 55/52 = 1.0577
Percentage of Throwing Power = ((X-Y)/(X+Y-2)) * 100
Percentage of TP = {(1.65 – 1.0577) / (1.65 + 1.0577 – 2)} *100
Percentage of Throwing Power = (0.5923 / 0.7077) * 100
Percentage of Throwing Power = 83.69%

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

2. Calculate the percentage of throwing power of plating bath solution in a Haring - Blum cell if the
distances between the two cathodes are 7 cm and 5 cm from the anode and the masses of plating on
the cathodes are 88 mg and 90 mg respectively.

3. Calculate the percentage of throwing power of plating bath solution in a Haring-Blum cell if the
distances of the two cathodes from the anode are 6 cm and 5 cm and the quantities of metal
deposited on cathodes are 72 mg and 75 mg respectively.

4. Calculate the percentage of throwing power of plating bath solution in a Haring - Blum cell if the
distances between the two cathodes are 10 cm and 5 cm from the anode and the masses of the
plating on the cathodes are 70 mg and 75 mg respectively.

5. The throwing power of an electrolyte in a Haring Blum cell is 75%. In an experiment, 68 mg of the
metal was deposited at the nearest cathode kept at a distance of 4.8 cm from the anode. At what
distance must the cathode be kept from the anode if the metal deposited on it was 64 mg?

Solution:
Percentage of Throwing Power, TP = 75%
d1 =? d2 = 4.8 cm; W1 = 64 mg; W2 = 68 mg; X = d1/d2 = d1/4.8.
Therefore, d1 = 4.8 * X
Y = W2/W1 = 68/64 = 1.0625.
Percentage of Throwing Power, TP = ((X-Y)/(X+Y-2)) * 100
75 = {(X – 1.0625) / (X + 1.0625 -2)} * 100
75 = {( X – 1.0625) / (X – 0.9375)} * 100
75 * (X – 0.9375) = 100 * (X – 1.0625)
That is, 100 * (X – 1.0625) = 75 * (X – 0.9375)
100 X – 106.25 = 75 X – 70.3125
100 X – 75 X = 106.25 – 70.3125
25 X = 35.9375; Therefore, X = 35.9375 / 25

X = 1.4375
Now, d1 = 4.8 * X = 4.8 * 1.4375
d1 = 6.9 cm

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

6. Calculate the throwing power of a plating bath in a Haring - Blum cell if the distances of the two
cathodes from the anode are 6 cm and 5 cm and the quantities of metal deposited are 72 mg and 75
mg respectively. In the same cell if one of the cathode which was fixed at 6 cm was moved to 8 cm
from the anode, calculate mass of metal deposited on the electrode.

Solution A:
d1 = 6 cm; d2 = 5 cm; W1 = 72 mg ; W2 = 75 mg.
X = d1/d2 = 6 / 5 = 1.2
Y = W2/W1 = 75 / 72 = 1.042
Percentage of Throwing Power = ((X-Y)/(X+Y-2)) * 100
Percentage of TP = {(1.2 – 1.042) / (1.2 + 1.042 – 2)} *100
Percentage of Throwing Power = 65.29%
Solution B:
Percentage of Throwing Power, TP = 65.29%
d1 = 8 cm; d2 = 5 cm; W1 = ? ; W2 = 75 mg.
X = d1/d2 = 8 / 5 = 1.6
Y = W2/W1 = 75 / W1
Therefore, W1 = 75 / Y
Percentage of Throwing Power, TP = ((X-Y)/(X+Y-2)) * 100
65.29 = ((1.6 - Y) / (1.6 + Y - 2)) * 100
65.29 = ((1.6 - Y) / (Y – 0.4)) * 100
65.29 * (Y – 0.4) = 100 * (1.6 - Y)
65.29 Y – 26.12 = 160 – 100 Y
That is, 100 Y + 65.29 Y = 160 + 26.12
165.29 Y = 186.12
Therefore, Y = 186.12 / 165.29

Y = 1.126
Now, W1 = 75 / Y = 75 / 1.126

W1 = 66.61 mg

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

Electroless Plating
Electroless plating is a method of depositing a metal or alloy over a substrate (conductor or non-
conductor) by controlled chemical reduction of the metal ions by a suitable reducing agent without
using electrical energy.
The electroless plating process can be represented as,

Catalytic surface
Metal ions + Metal deposited over catalytic active
Reducing Agent surface + Oxidized Product

The reduction of metal ions by the reducing agent is catalyzed by the metal atoms being plated.
Therefore, electroless plating is also termed as autocatalytic plating.
The surface to be plated should be catalytically active so that in the beginning of the plating
reaction, the surface of the substrate catalyses the reduction. Once the substrate is covered by the
metal or alloy coating, the coating catalyses the reduction. The process continues with building of
successive layers of metal or alloy.
The catalytic metals such as, Ni, Co, Steel, Fe, Rh, Pd, Al, etc., do not require any surface
preparation before electroless plating on them. Non-catalytic metals such as Cu, Brass, Ag, etc., need
activation.
This can be achieved by rendering them cathodic for a short period by passing direct current or
by dipping in palladium chloride - hydrochloric acid solution. Non conductors like glass, plastics,
ceramics, etc., are first activated in a solution of SnCl2 and HCl. After rinsing, it is immersed in a solution
of PdCl2 and HCl.
Composition of Electroless Plating bath:
It consists of,
1. Soluble metal salts to provide metal ions for deposition.
2. Reducing agent for reduction of metal ions to metal atoms. Eg., Formaldehyde, Hypophosphite.
3. Complexing agents to complex metal ions to prevent bulk deposition. Eg., citrate, tartarate,
succinate.
4. Stabilizer to give more stability to the solution. Eg., Thiourea and cations of Pb, Ca & Thallium.
5. Exaltant or accelerator to increase the rate of plating. Eg., anions like succinate, glycinate & fluoride.
6. Buffer to control pH.
7. Additives like brighteners.

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The selection and concentration of complexing agent must be considered very carefully; because if
the metal is too-heavily complexed, sufficient free metal ions will not be available for deposition.

Advantages of Electroless Plating over electroplating:

1. Does not require electrical power source and accessories.

2. Electroless plating is applicable to conductors, semi conductors and insulators like plastics.
3. Throwing power of electroless plating bath is high and hence the objects of irregular shapes can be
plated uniformly.
4. Electroless plating are less porous & more compact than electroplating and have a unique chemical,
mechanical and magnetic properties.
5. No need of levelers.
6. Electroless deposits are hard.
7. H2 gas is not trapped.

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

Electroless plating of copper

Bath Composition

1. Plating bath : 12g. / lit. of CuSO4 solution

2. Reducing Agent : 8g. / lit. of Formaldehyde
Complexing agent &
3. : 20 g. / lit. of EDTA
exaltant
14g. / lit. of Rochelle Salt (sodium potassium tartarate) and
4. Buffer :
12g. / lit. of NaOH
5. pH : 11 – 12
6. Temperature : 25oC
7. Cathode : Article to be plated which is catalytically active

Reactions:
At Cathode: Cu2+ + 2e-  Cu
8. 2HCHO + 4OH-  2HCOO- + 2H2O + H2 + 2e-
At Anode:
Net Reaction: Cu2+ + 2HCHO + 4OH-  Cu + 2HCOO- + 2H2O + H2

9. Plating rate : 1-5 µm/h

10. Applications  Widely used for metalizing printed circuit boards
 For Producing through – hole connections
 For plating on non conductors
:
 As a base for subsequent conventional electro plating
 Applied on wave guides and for decorative plating on
plastics.
Note:
 Since Cu2+ ions and HCHO are consumed during the redox reactions, so these are replenished
periodically.
 The redox reaction involves the consumption of OH- ions, so the pH of the solution decreases, as the
reaction progresses. That is why addition of buffer is essential.

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ENGINEERING CHEMISTRY, 22ECHB102– UNIT 2 - CHAPTER 4: PLATING TECHNIQUES

Preparation of PCB

Through hole connections are necessary when double sided printed circuit boards are
fabricated. The electrical connections between two sides of the board are made by drilling hole and then
plating through holes by electroless plating.

Steps involved in the manufacture of double sided PCB

For the manufacture of double sided printed circuit boards, the plastic board is initially covered
with copper layers by cladding thin layers of electroformed copper foils. i.e., the plating is carried out at
room temperature by dipping the activated plastic board in the bath solution.

The temperature is maintained at about 25oC. The process is continued till a layer of
5 to 10 mm thickness is obtained. The rate of plating is maintained at 1 to 5 µm h-1.

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Selected areas are then protected by a photo-resist or electroplated image and the rest of the
copper is etched away to produce the circuit pattern or the track. On etching with suitable etchant the
copper except below the printed pattern is etched away, leaving the circuit pattern.

Double-sided copper clad laminates with tracks are preferred because of feasibility of packing of
more components in a smaller space.

The connection between two sides is made by drilling hole followed by activation and plating
through holes by electroless plating.

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