METAL FINISHING

The term metal finishing covers a wide range of processes carried out to modify the surface
properties of a metal by deposition of a layer of another metal, a polymer or by the formation
of an oxide film.

Metal Finishing Techniques

1) Electroplating of metals, alloys.

2) Electrolesspating of metals, alloys.

3) Immersion plating of metals.

4) Electrophoretic painting involving painting on electrically charged conducting surface.

5) Chemical conversion coatings. Ex: Anodizing, Phosphating.

Importance of Metal Finishing

Metal finishing finds extensive applications in industries, electronics, engineering and
metal processing companies.The technological importance of metal finishing is

1.To give decorative surfaces.

2. To impart abrasion and wear resistance.

3. To offer corrosion resistance.

4. Imparting hardness

5. To impart thermal resistance.

6. To offer the surface a thermal or optical reflectivity

7. To provide electrical or thermal conduction

8. In the manufacture of electrical and electronic components such as printed circuit

boards, capacitors and contacts.

9. To manufacture metal articles by electroplating

10. To produce gramophone records.

11. In electrochemical machining, polishing and etching.

Principles of Metal Finishing
.

1. Polarization,

2. Decomposition potential.

3. Over voltage.

1. Polarization

Polarization is an electrode phenomenon. The electrode potential is determined by the nernst

equation

E = Eo + 0.0591/n log(Mn+)

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 in the vicinity of
the electrode surface decreases owing to the reduction of metal ions. Therefore, there is a shift
in the equilibrium and a change in the electrode potential.

The concentration gradient between the bulk of the solution and the area surrounding the
electrode surface leads to diffusion of ions from the bulk of the solution towards the electrode
surface. This reestablishes the equilibrium.

If the diffusion is slow, the electrode potential changes and the electrode is now said to be
polarized.

Polarization is defined as a process in which there is a variation in electrode potential due to

slow supply of ions from the bulk of the solution to the electrode.

Polarization depends on

 Nature of the electrode i.e. size, shape and composition. 


 Electrolyte concentration. 

 Temperature. 

 Products formed at the electrodes. 

 Rate of stirring of the electrolyte 

Effect of polarization can be minimized by stirring the electrolyte continuously and by using
electrodes of larger surface area and electrolytes of higher conductivity.
2) Decomposition Potential

It is defined as the minimum voltage that must be applied to bring about continuous
electrolysis of an electrolyte.

Decomposition potential can be determined by using an electrolytic cell. The cell consists of
two platinum electrodes immersed in a dilute solution of an acid or a base. The voltage is varied
by moving the contact maker D along the wire AB 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. On increasing the voltage to slightly above 1.7V, there is an abrupt
increase in the current and sudden evolution of H2 & O2. The applied voltage of 1.7V is the
decomposition voltage for dilute acids & bases.

A plot of the current flowing between the electrodes against the applied voltage is shown in the
fig.

There is a very slight increase in the current at low voltages. Beyond the decomposition voltage
electrolysis begins and there is an abrupt increase in the current.
Consider the electrolysis of a 1M solution of ZnI2 which produces Zn and I2 at the respective
electrodes. For this electrolysis, the decomposition potential is found to 1.30V which is in
agreement with theoretical value. The products accumulated at the electrodes and the setup of
the following cell is as follows;

Zn | Zn22+|| I2 |I-

This cell exerts a back emf and offers resistance to the flow of current. For electrolysis to occur,
the applied voltage (Eo) should be at least equal to the back emf.

3) Over-Voltage

It is defined as the excess voltage that has to be applied above the theoretical decomposition
potential for continuous electrolysis.

This is denoted by η. The applied voltage has to exceed the theoretical value by at least of 1V
for continuous electrolysis. This is known as over-voltage or over potential.

η= Experimental decomposition potential - theoretical decomposition potential

ED = ECathode - EAnode + η

Over Voltage depends on several factors:-

 Nature and physical state of the metal electrodes. 


 Nature of the substance deposited. 

 Current density. 

 Temperature. 

 Rate of stirring of the electrolyte 

Hydrogen overvoltage is the overvoltage required for the liberation of hydrogen at the
cathode during electrolysis. It is large for soft metals like lead; mercury shows the
highest overvoltage among metals. 

Hydrogen overvoltage is a measure of the liberation of hydrogen gas from the electrode
surface; a lower overvoltage indicates a quick release of hydrogen gas. The liberation of
H2 on electrode surface takes place in three steps 

H3O+ H+ + H2O

H+ + e H

H + H H2

The deposition of metals over electrode surface takes place in one step
 Mn+ + e M

Therefore the overvoltage for metal deposition is small compared to hydrogen

overvoltage.

Electroplating
The electroplaing device is essentially an electrolytic cell, in which two electrodes,
anode and cathode are dipped in an electrolyte solution. The principle com[ponents of
an electroplating process are given below.

The components include

1) An electrochemical bath containing a conducting salt and the metal to plated in a

soluble form as well as a buffer and additives.

2) The electronically conducting cathode ie 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 inert vessal to contain the above mentioned materials made of either rubber
lined steel, plastic, concrete or wood.

5) A D.C- electrical power source

Electrolysis reaction

Electroplating is the process of electrolytically depositing a layer of metal on to a

surface. The object to be plated is made the cathode in an electrolytic bath
containing a metal ion Mn+ . so the cathode reaction is

Mn+ + ne M
 The preferred anode reaction is the dissolution of the same metal in the solution

M Mn+ + ne

However , if the anode is made of some inert material thet does not pass into the
solution, the electrolytic salt is added continously 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 Cu 2+ ions,, replenishing the Cu2+ ions deposited at
the cathode. CuSO4 solution can be used as electrolyte, which ionizes as

CUS04 CU2+ + SO42-

On passing current, Cu2+ ions migrate to the cathode and get deposited there. At
cathode:

Cu2+ +2e Cu and at anode copper enters into the solution as cu2+ ions.

EFFECTS OF PLATING VARIABLES ON THE NATURE OF ELECTRODEPOSIT

1) Current density

Current density is the current per unit area of the electrode surface. It is expressed in
mA/cm2 (or) A/dm2 (or) A/m2 ‘

when the current density is low, metal is deposited slowly and the deposits produced are
gross grained.when the current density is increased ,the rate of electrodeposition
increases,but depositon is loose,rough and brittle.

In general, it is desirable to use as high current density as practicable and thereby to increase
the rate of electroplating.

* When the current density is above the optimum limiting value, one more possibility is the
formation of a burnt and spongy deposit.

* This is caused by the occurrence of hydrogen discharge at the cathode. Therefore, an

optimum current density should be applied to obtain a fine and smooth deposit.

2) Metal ion concentration

In general, a decrease in metal ion concentration decreases the crystal size and results in a fine
adherent coating films.

* This can be achieved either by the addition of a compound with a common ion or by the
formation of complex compounds and ions.

* For example, when copper is deposited from copper sulphate bath, sulphuric acid is added to
the solution.

CuSO4 Cu2+ + SO42-

H2SO4 2H+ + SO42-

Due to common ion effect of SO42- from sulphuric acid, the concentration of cupric ions in the
solution is reduced.

Using a solution of sodium cuprocyanide,

CuCN + NaCN [NaCu(CN2)]

[NaCu(CN2)] Na+ + [Cu(CN)2]-

[Cu(CN)2]- Cu2+ + 2CN-

Low concentration of cuprous ions is formed through the formation of [Cu(CN) 2]-and this
releases cuprous ions continuously for the deposition of copper.

3) Electrolyte Concentration: Normally, the metal salt concentration is

kept high and various electrolytes are added in high concentration to
increase the conductivity of the solution.

4) Throwing power of a plating bath

It is defined as the degree of uniformity of metal distribution or evenness of deposit

thickness obtained on a cathode of irregular shape.

The throwing power depends on the shape of the cathode. It is maximum in regular shaped
cathode whereas it is minimum, if the cathode shape is irregular.

Factors affecting throwing power:-

1. Conductivity of the electrolyte- Solutions with higher conductivity will have higher
throwing power.
2. Presence of addition agents- Additives like levelers and brighteners ensure an even
deposit and hence increase the throwing power.
3. Agitation

Haring Blum Cell:-

The cell consists of a box of PVC or similar insulating materials of 15x5 cm dimension. Sheet
metal cathodes are fitted at both ends of the box and are connected by a rod. An anode is plated
between the cathodes at different distances X1 & X2 from the cathodes.
The cathodes are weighed initially. Electro-deposition is carried out for a known period of time.
At the end of the test, the cathodes are weighed again.

Throwing power is calculated by using the equation

TP% = (K-M)/[K+M-2] x 100 where

K=X1/X2 & M= W2/W1
W1 & W2 are the weights of the metal deposited on the cathodes.When W1=W2, that is the
amount deposited is same irrespective of the placement of the electrodes, throwing power is
100% and is considered to be very good.

5) pH of the electrolyte bath

* For a good electrodeposit, the pH of the bath must be properly maintained at a definite range.
* In general, the cyanide baths are alkaline with pH values varying from about 9 for silver to
about 13 for cadmium.
* For non-cyanide baths, slightly basic or acidic conditions are preferred.
* At a higher pH, precipitation of hydroxides of the metal may take place .
* At very low pH. More hydrogen evolution takes place on the cathode, giving burnt deposit.
* Therefore, the required pH is maintained by using suitable buffers by having optimum pH
value of 4-8 .
Ex:- Electroplating of nickel
Buffer- Borate
pH: 4.0 --- 4.5

6) Addition Agents
1. Complexing agents.
2. Brightners.
3. Levelers.
4. Structure modifiers.
5. Wetting agents.
i) Complexing Agents

Complexing agents are used for the following purposes:-

1. To maintain low metal ion concentration.
2. To prevent the chemical reaction between cathode metal & plating ions.
3. To prevent the passivation of anode.
4. To improve the throwing power of the plating bath.
 5. To enhance the solubility of the slightly soluble metal salts.

The most common complexing agents used in electroplating are Hydroxide, Cyanide and
sulphate ions.

ii) Brighteners
In order to obtain a bright and lustrous deposit, specific chemicals are added to plating baths.
These addition agents are called brighteners.If they are absent ,it yields dull deposits.
Ex:- Aromatic,Sulphones, Sulphonates, Thiourea are used as brighteners in nickel plating.
The molecules of the brighteners are adsorbed on the metal nuclei, preventing the freshly
discharged ions from depositing over the earlier nuclei.
*Concentration of the brighteners added should be maintained at an optimum range.
* Aryl Sulphonic acid may not themselves produce bright deposits but they increase the
brightening power of other compounds.
iii) Levelers
Certain organic compounds are used as levelers in order to get a level deposit.
Levelers produce a level deposit by preferentially getting adsorbed at places where rapid
depostion of metal takes place.

Many brighteners act as levelers.Sodium allyl sulphonate is used as a leveler for nickel
deposition.

iv) Structure Modifiers

These additives modify the structure of the deposit in such a way as to alter the deposit
properties. Sometimes,the electrodeposits are internally stressed resulting in microcracking of the
deposit.They are also called as stress relievers.
Ex:- Saccharine.
v) Wetting Agents
During electroplating process, H2 gas released at cathode may entrap on the cathode surface and
later on may escape resulting in porous and brittle deposit.Wetting agents are added to release
the gas bubbles from the surface on immediate formation.
Wetting agents, sometimes improve the uniformity of the deposit.
Ex:- Sodium Lauryl Sulphate [CH3(CH2)11 OSO3Na]

ELECTROPLATING

Electroplating can be defined as a process in which a base metal is coated with a thin and
uniform layer of another metal by electrolytic deposition.

Pretreatment Process

1) Solvent cleaning:-Solvent cleaning involves the cleaning of the metal surface by using
inorganic solvents such as carbon tetrachloride, toluene, etc. These solvents remove the organic
impurities such as oil, grease etc.
2) Alkali cleaning:-

Solvent cleaning removes most of the soil and grease. but minute residues are left behind. It is to
remove these residues that alkali cleaning is used.

Ex: Sodium carbonate, Sodium hydroxide, sodium phosphate.

3) Mechanical cleaning:-

Mechanical cleaning involves removal of the oxide layer or rust and other inorganic deposits on
the metal surface by using silicon carbide abrasion wheels. This is followed by sand blasting.

4) Pickling:-

Pickling refers to severe or continued treatment. Pickling of steel involves dipping steel in
dil.HCl or dil.H2SO4 solution which contain some inhibitors which retard the dissolution of steel
itself. For copper and its alloys, the pickling solution is dil.H2SO4 (or) dil.HNO3 & dil.H2SO4.

Electroplating of Chromium
Plating bath: Chromic Acid (CrO3 & H2SO4) 100:1 Proportion.
Operating Temperature: 45-60oC
Current Density: 100-200 mA/cm2
Current Efficiency: 8-12%
Anode: Insoluble anodes; Pb-Sb (or) Pb-Sn coated with Pbo2 (or) stainless steel.
Cathode: Object to be plated; Pretreated.
Application: Decorative & corrosion resistance finish.
The plating bath contains CrO3 in which Cr is +6 oxidation state. This is reduced to +3 oxidation
state by a series of complex reactions in the presence of SO42- furnished by H2SO4. Cr3+ ions are
reduced to elemental Cr which gets deposited on the substrate. The reactions taking place during
chromium plating are given below:
Cr03 + H20 H2Cr04 Cr042- + 2H+
The amount of Cr3+ ions should be restricted in order to obtain good deposit. Insoluble anodes
PbO2 which oxidises Cr3+ to Cr6+ oxidation state are used thus controlling the Cr3+ ion
concentration.
Chromium anodes are not used in Cr plating because chromium metal passivates strongly in acid
sulphate medium. Further, Chromium anode gives rise to Cr3+ ions on dissolution.
(A black deposit of chromium is obtained in the presence of large concentration of Cr3+ ions.
Applications:-
i. Decorative chromium provides a durable finish on cylces, automobiles, furniture’s,
surgical & dental instruments.
ii.Black chromium is used in optical instruments, machine tools, electronic parts.

Electroless Plating

It is defined as the controlled deposition of a continuous film of a metal from its salt solution on
to a catalytically active surface by a suitable reducing agent without using electrical energy.
Mn+ + Reducing agent M + oxidized product
Pretreatment Process- preparation of catalytically active surface:
1) Acid Treatment- The substrate surface is given an acid treatment with Cr2072- and H2S04.
2) Electroplating a thin layer of the metal to be plated.
3) For non conducting surfaces such as plastics (or) PCB or glass the surface is treated with
Stannous Chloride solution containing hydrochloric acid at 250c followed by dipping in
palladium solution.The surface is dried to get a layer of Pd.

Electroless plating of Copper

Copper from its solution gets deposited spontaneously in presence of a suitable reducing agent
on metals such as gold, silver, platinum, palladium, rhodium. Insulators like plastics & glass are
to be activated before subjecting to electroless plating.
An important application of electroless copper plating is in Printed Circuit Boards(PCB).

Plating Bath

Plating bath solution: Solution of copper sulphate.

Reducing Agent: Formaldehyde

Buffer: NaOH & Rochelle Salt.

Complexing Agent: EDTA

pH: 11

Temperature: 25oC
Cathode: Cu2+ + 2e Cu

Anode: 2HCHO + 4OH- 2HCOO- + 2H2O + H2 + 2e

Overall Reaction: Cu2+ + 2HCOO- + 2H2O +
2HCHO 4OH- Cu + H2

The PCB base made of polymeric material is initially cladded with thin foils of copper on both
sides. Then it is etched as per circuit specifications to get circuit track. Holes are drilled through
the circuit tracks as per circuit specifications for double sided PCB. The holes are given
pretreatment and are catalytically activated by dipping in stannous chloride and palladium
chloride.The catalytically activated PCB is dipped in plating bath solution for electroless plating
of holes.The holes are coated with thin layer of copper resulting in double sided PCB

Distinction between Electroplating and Electrolessplating

Electroplating Electrolessplating
Driving force Current Autocatalytic redox
reaction

Anode Separate anode Catalytic surface of

Substrate

Cathode Object to be plated(treated to remove Object to be plated(treated

surface impurities) to make surface
catalytically active)

Reducing electrons Chemical reagents

agent

Applicability Only on conductors Conductors and non

conductors
Throwing Not Satisfactory with irregular shape Satisfactory in all parts
power
Cost Not economical Most economical

Reactions Oxidation takes place at anode and Both oxidation and

reduction at cathode reduction takes place at
catalytically active surface