Dr. N. Srikantamurthy, Dept.

of Chemistry Metal Finishing

Metal Finishing
The term metal finishing covers a wide range processes carried out to modify the
surface properties of a metal by deposition of a layer of another metal (or) polymer (or) by
the formation of an oxide film.
Definition:- Metal finishing is the process of deposition of a layer of the metal on the surface
of substrate.
Technological Importance of Metal Finishing:- Metal Finishing is carried out to obtain
technologically important surface properties, these properties are;
 A decorative appearance.
 An improved corrosion & heat resistance.
 An improved surface hardness.
 To provide good electrical and thermal conducing surface.
 To increase thermal resistance & optical reflectivity.
 In the manufacturing of electrical and electronic components.
Important Techniques of Metal Finishing:-
1. Electroplating.
2. Electroless plating.
Principles of Metal Finishing:- The fundamental principles governing metal finishing are;
a. Polarization
b. Decomposition potential
c. Overvoltage.

a. Polarization:- Polarization is an electrode phenomenon.

The decrease in EP due to insufficient supply of ions from bulk of the solution to surface of
the electrode is called polarization. The electrode potential is given by Nernst’s equation;

When the current is passed through an electrolytic bath, the electrolyzed products
deposit on the surface of the electrodes, results in the decrease in metal ion concentration in
the vicinity of cathodic surface.
If the diffusion of ions is slow from the bulk of the solution to electrode surface, a
concentration gradient is build up due to difference in concentration of the metal ion in the
vicinity of the electrode to bulk of the solution, the electrode potential changes and the
electrode is said to be polarized.

b. Decomposition Potential:- Decomposition potential is defined as “the minimum

external potential required for the continuous electrolysis of an electrolyte”.

If dilute solution of acid (or) base taken in the cell, at low voltages no reaction is found to
occur and when the voltage is slightly higher than 1.7v, a sudden evolution of H 2 and O2 at
the electrode is noted. This is accompanied by increase in the current. Thus the applied
voltage of 1.7v is the decomposition potential for dilute acids and bases.

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Dr. N. Srikantamurthy, Dept. of Chemistry Metal Finishing

c. Over Voltage:- Over voltage is defined as “the excess voltage that has to be applied
above the theoretical potential for continuous electrolysis”.
OV (η) = Experimental decomposition potential - Theoretical decomposition potential
Ex:- The theoretical potential of oxygen at platinum electrode is 1.23v but the actual
decomposition potential of oxygen is 1.68v. The excess 0.45v is the overvoltage of oxygen
on platinum electrode surface.

Electroplating:- “Electroplating is a process of electrolytic deposition of a metal on the

surface of another metal by electrolysis”. (OR)
Electroplating is the deposition of a metal by electrolysis over the surface of a substrate. The
substrate may be a metal, a polymer or a composite.

Theory of Electroplating:-Electroplating is achieved by passing an electric current through

an electrolytic solution containing metal ions and electrodes.
The process of electroplating is made of four important parts.
a. Electroplating bath solution:- It contains a suitable salt solution of the metal being plated.
It also contains other additives.
b. Anode:- It is positive elect rode in the electrolysis, where metal ions are created. It may be
inert electrode, it should be electrically conducting.

c. Cathode:- It is negative electrode in the electrolysis, where metal ions gets deposited and
it is an article to be plated.

d. DC-power supply:- The +ve terminal of the power supply is connected to the anode and
the -ve terminal is connected to the cathode. The electricity that passes from the anode
to the cathode.

Factors influencing the nature of electrode deposit:-

1. Current Density:- Current density is the current per unit area generally expressed in mill
amperes per square centimeter [mAcm-2] of the electrode surface.
 At low current density a bright, crystalline deposit is produced but rate of deposition is
slow.
 At high current density loose and bad deposit is obtained because the metal atoms may
not reach the most favorable positions.
 At very high current densities, mass transport of ions predominates in solution resulting in
a bad deposit of metal hydroxides.
Hence optimum current density b/w 10-70 mAcm-2 is generally maintained.

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Dr. N. Srikantamurthy, Dept. of Chemistry Metal Finishing
2. Metal-ion concentration & Electrolytes:-
 The decrease in metal ion concentration decreases the crystal size and results in good
deposit.
 The increase in metal ion concentration increase mass transfer leading results in bad
deposit.
So that to get good & thin coating films, metal ion concentration is 1-3 mol/dm3 is
preferred.
 The electrolyte used should be a good conductor of electricity.
 Electrolytes used don’t participate in the electrode reaction but increase the conductivity
of the plating bath.
 Generally mixture of electrolytes is used as single electrolyte doesn’t satisfy all the
required characteristics.
Ex:- Mixture of CuSO4 and H2SO4 electrolytes are used in the electroplating of copper.

3. Temperature:-
 At low temperature, electroplating results in a powdery, non-coherent deposition.
 At high temperature, the rate of evolution of hydrogen gas at cathode increases, results
loose deposit takes place.
 Increase in temperature cause corrosion of equipment and decomposition of the organic
additives.
Therefore a moderate temperature range of 35°C-60°C is used for most of the plating
processes.

4. PH:-
 At the lower pH, (acidic medium) hydrogen evolution takes place at cathode and affects
the nature of the deposit.
 At the higher PH, (alkaline medium) insoluble metal hydroxides deposits on the article.
Therefore optimum PH is maintained from 4 to 8 by using buffer solution.
Ex:- i) Borate buffer used in nickel plating. ii) Citrate buffer used in gold plating.

5. Throwing power of the plating bath:- “The ability of a plating bath to give a uniform
and even deposit on the entire surface of the substrate is known as Throwing power”.
 It is used as a measure of the distribution of the deposit.
 This property is particularly important when the article is of an irregular shape.
This can be improved by:
 High conductivity of the electrolyte
 Agitating the solution to minimize high local electrolytic resistance.

6. Organic Additives:- To improve the quality of electro deposits certain organic

compounds are added to the electrolytic bath. These are Brighteners, Levelers, Structure
Modifiers, and Wetting agents.
a. Brighteners:-
 Brighteners are the chemical substances added to get bright and lustrous deposit.
 They produced microscopically fine deposits.

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Dr. N. Srikantamurthy, Dept. of Chemistry Metal Finishing
 They usually cause the formation of even, fine grained deposit by the modification of
nucleation process.
Ex:- Aromatic sulphones (or) sulphonates and molecules containing C═N, N═C═S (or) C═O
groups are used as brighteners.
b. Levelers:-
 Levelers are added to get a level deposit.
 They produce a leveled deposit by preferentially getting absorbed at the places where
rapid deposition of metal takes place.
Ex: - Sodium Allyl Sulphonate is used as a leveler for Nickel deposition.
c. Structure Modifiers:-
 Structure modifiers are added to change the orientation of the crystals with respect to
surface of the substrate and also to decrease stress on the surface of the metal.
Ex:- Saccharin.
d. Wetting agent:-
 Wetting agents are added to release the gas bubbles from the surface of the substrate and
also improve the leveling and uniformity of the deposit.
Ex: - sodium lauryl sulphate.

Electroplating of Chromium:-
The surface of the object is cleaned thoroughly; organic substances are removed by
solvent cleaning and alkali cleaning. Inorganic substances are removed by mechanical
cleaning and picking. Finally the surface is washed with deionized water. Then chroming
plating is done under the following conditions.
In the field of electroplating two types of chromium are employed: decorative & hard.
Sl. Plating conditions Decorative chromium Hard chromium plating
NO. plating
1 Plating bath Chromic acid (H2CrO4) + Chromic acid (H2CrO4) +
composition H2SO4 in the weight ratio 100 H2SO4 in the weight ratio 100
:1 :1
2 Operating temp. 45-55°C 45-55°C
3 Current density 145 – 430 A/ft2 290 – 580 A/ft2
4 Current efficiency 10 – 15 % 17 – 21 %
5 Anode Insoluble anode: Pb-Sb or Pb- Insoluble anode: Pb-Sb or Pb-
Sn alloy coated with PbO2 Sn alloy coated with PbO2
6 Cathode Object to be plated Object to be plated
7 Anodic reaction Liberation of oxygen: Liberation of oxygen:
H2O 1/2 O2 + 2H+ + 2e- H2O 1/2 O2 + 2H+ + 2e-
8 Cathodic reaction Cr3+ + 3e- Cr Cr3+ + 3e- Cr
The plating bath contains chromic acid, during electroplating of chromium;
Cr (IV) is reduced to Cr (III) in the presence of SO42- catalyst. Cr (III) is reduced to Cr (0),
which gets deposited on the substrate.

For a good deposit, the Cr3+ concentration must be low. The PbO2 oxidizes a part of Cr3+ to
Cr6+ thus reducing the concentration of Cr3+.

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Dr. N. Srikantamurthy, Dept. of Chemistry Metal Finishing

Chromium anodes are not used in Cr-plating, because;

 If chromium dissolves at anode, there will be a high concentration of Cr 3+ in solution; in
such case a black deposit is obtained.
 In acidic solutions, chromium may undergo passivation.

Electroless Plating:-Electroless plating is the deposition of a metal without the use of

electrical energy.
It is defined as “the process in which metal is depositing over a substrate by controlled
chemical reduction of metal ions by a suitable reducing agent without using electrical
energy”.
Composition of Electroless Plating bath:-
 A source of electroactive metal in the form of a soluble salt. Ex:- NiCl2, CuSO4
 Reducing agent to reduce metal ions into metal atoms.
Ex:- sodium hypophosphite, Formaldehyde.

Distinctions b/w Electroplating and Electrolessplating:-

Property Electroplating Electrolessplating
Driving Force Electric Current Autocatalytic Redox Reaction
Anode Separate Anode Catalytic surface of substrate
Cathode Article to be plated Catalytically active surface
Reducing agent Electrons Chemical reagent
Anode reactant Metal (or) H2O Chemical reagent
Applicability Only to conductors Conductors and non-conductors.
Throwing Power Low High.

Electroless Plating of Copper:-Before Electroless plating the plastic board is degreased and
etched in acid. It is activated by dipping in SnCl2 / HCl at 25°C followed by dipping in PdCl2.
Electroless plating is done under the following conditions,
 Plating bath solution - Copper Sulphate,
 Reducing agent - Formaldehyde
 Complexing agent – EDTA, Buffer - Sodium Hydroxide [PH=11] & Tempr. - 25°C.
The plating is carried out at room temp. by dipping the activated plastic board in the bath
solution. The metallic copper obtained as a reduced product in the bath deposit on the metal
surface. Reactions:

Typical application of Electroless copper plating is printed circuit boards, particularly double
sided boards in which plating through holes is required.
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Dr. N. Srikantamurthy, Dept. of Chemistry Metal Finishing
Electroless Copper Plating on PCB:-The process involved is known as Subtractive method.
 A thin layer of copper is first coated over the PCB [Printed Circuit Board].
 The selected areas are protected by employing electroplated image and the remainder
of the plated copper is etched away so as to get required type circuit track.
 More number of components may be packed in a small space by making double sided
tracks.
 The connection b/w the two sides of PCB is provided by drilling holes, followed by
Electroless Cu-plating through holes.

Fig. Schematic representation of Electroless Cu-Plating through holes on PCB.

Electroplating of Nickel
Nickel is widely plated metal in plating industry, for both decorative and protective
applications. To electroplate nickel on other surfaces different bath compositions are used.
An all-purpose bath, used both for decorative and protective applications of nickel deposit, as
well as for making up worn out parts and for electroforming is Watt’s bath.

Watt’s bath
240g of NiSO4 + 45g of NiCl2 + 30g of boric acid /L. About
Bath composition
0.15g of sodium lauryl sulphate is also added.
pH 4 – 4.5
Operating Temperature 25 – 65oC
Current density 10 – 60 A/ft2
Addition agents Coumarin, sulfonic acid, aldehydes, thiomalic acid, saccharine
Current efficiency 95 – 100%
High purity Nickel pellets, or pieces in titanium mesh basket /
Anode
cotton / terylene cloth.
Cathode Article to be plated

Reaction

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