UNIT III - (b) METAL FINISHING

Syllabus-Technological importance, significances of polarization, Decomposition potential &

overvoltage in electroplating, theory of electroplating. Effect of plating variables on the nature of
electrodeposit - electroplating process, Electroplating of gold, Introduction to Electro less plating-Cu

Definition: Metal finishing is a group of procedures employed in industries to modify the surface
properties of materials and also to induce desired properties in the materials.
The articles used in our daily life would have undergone one or the other methods of metal finishing,
indicating its importance in modern life.
Technological importance of metal finishing
Metal finishing involves alteration of surface properties of a metal by providing a coat of a metal / metal
compound / composite in order to impart
 corrosion resistance
 wear resistance
 electrical and thermal conducting surface
 optical & thermal reflectivity
 decorative value
 hardness
Following techniques are extensively used in metal finishing:
i) Electroplating
ii) Electrolessplating
iii) Chemical conversion coating (like anodizing and phosphating etc.)
iv) Immersion plating (Used in colour coatings)

Theory of Electroplating

Definition: “Electroplating is defined as the process of deposition of a layer of a metal by electrolysis, over
the surface of a substrate, by passing current for a known period of time”.
Electrodeposition can be carried out on;
i) single metals like copper, nickel, chromium, zinc etc.
ii) Alloys like Cu – Zn, Cu – Sn, Pb – Sn, Ni – Cr etc.
iii) Composites like SiC, WC, etc.
The electroplating device is essentially an electrolytic cell, consisting of two electrodes connected to an
external source, dipped in a suitable electrolyte. Anode is a pure metal rod and the cathode is the object
being plated. Upon electrolysis the anode metal M, dissolves as M n+ ions and at cathode reduction of Mn+
from the electrolyte takes place to form metal deposit on the surface of the substrate. Reactions during
electroplating are;

Anode; M → M n+ + n e - anodic dissolution (oxidation) of the metal

Cathode; n e - + M n+ → M cathodic reduction of Mn+ from Solution

In an ideal solution both the processes takes place at the same rate and concentration of M n+ ions in
solution remain constant. Usually anode would be the same metal as the metal ion to be plated, but in
some cases, inert anode is used (for example Chromium plating). In such cases the M n+ ion concentration
decreases during plating and to maintain constancy of Mn+ concentration the electrolyte is added
externally from time to time. Some times anode may be rods, plates or even pellets (like in Nickel
plating).During electroplating electrodes are placed so as to achieve uniform current distribution.

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 The amount of metal being deposited can be calculated with the help of faradays laws of electrolysis.
Faraday’s first law of electrolysis: According this law ”The amount of metal deposited or liberated at an
electrode directly proportional to the quantity of electricity passed through the electrolyte during
electrolysis”
If Q (in coulombs) is the amount of electricity supplied then the amount of metal deposited or liberated
is given by;
WαQ

But Q = I x t

Therefore W α I x t, where I is in amperes and t in seconds

W = ZIt, where Z is known as electrochemical equivalent

When I = 1 amp and t = 1seconds, then W = Z, that is electrochemical equivalent is the amount of the
metal deposited or liberated when one ampere of current is passed for one second. Thus we can calculate
the amount of metal deposited by knowing current value and time.
Since electroplating process is all about electrolysis, three important factors namely Decomposition
potential, Polarization and Overvoltage govern electroplating process, therefore it is necessary to
understand them.

Characteristics of Good & Poor Deposit

Good deposit Poor deposit
Good adhesion, uniform and non-porous Has poor adhesion, is non-uniform and porous
Hard, ductile Has burnt powdery structure and is brittle
fine grained structure Is coarsely crystalline
bright and lustrous Is dull
It is formed by definite spiral, block or layer arrangement It is formed by step, ridge and poly crystalline block growth

Plating bath variables

The morphology and composition of electrodeposits vary significantly, and depend on following
variables:

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1. Metal salt concentration & electrolyte conductivity: Highly soluble & conducting metal salt provides
metal ions to electrolyte bath and its concentration has to be carefully monitored. If conductivity of
electrolyte bath is low then addition of inert electrolyte/s enhances conductivity. In case of insoluble
anode, depletion of metal ions is replenished by the addition of metal salt at regular intervals.
2. Metal ion concentration: If concentration of free metal ions is high, the deposit is bulk, uneven and
coarse grained. Use of complexing agent will help to control concentration of free metal ions. In some
instances, metal ion concentration can be controlled by common ion effect. For example, copper plating
from sulphate bath, H2SO4, a stronger electrolyte than CuSO4 suppresses the dissociation of later due to
SO42− common ion effect and monitors Cu2+ ion concentration.
3. Current density: The deposition rate certainly increases with increase in current density (current
flowing per unit area). For a given plating bath composition, the applied current density should be well
below limiting value. Around & above limiting current density the deposit may be spongy or powdery or
burnt or poorly adherent. Very low current density provides better crystal growth but poor coverage.
Hence, an optimum current density (above the low current density but well below limiting value) is
preferred.
4. Temperature: With increase in temperature, deposition rate increases due to increase in ionic mobility
& current distribution. At higher temperature, evolution of H 2 is more pronounced and affects the
stability of additives (especially organic additives are susceptible to decomposition). Hence, at moderate
temperature, metal deposition takes place rapidly without suffering quality.
5. pH: pH of aqueous electrolyte bath gets altered during electroplating process. Addition of a suitable
buffer resists the change in pH and gives required quality deposit.
6. Agitation: Gentle agitation not only decreases electrode polarization, but also, brings ions to the
electrode surface & enhances current distribution of plating bath solution. Also, it helps in dislodging
gaseous bubbles (like H2, O2) adhering to the electrode surface. Avoid vigorous stirring, which in turn
contaminate the deposit with impurities.
7. Complexing agents: Cyanide, hydroxide & sulphamate ions act as complexing ions in alkaline
medium. Complexing agent also prevents passivation of active (soluble) anode & unwanted reaction
between metal ions & cathode material. For example, in copper plating from cyanide bath, CN − ions
controls concentration of copper (I) ions by forming complex. The complex releases copper ions when
its concentration decreases below certain level.
Cu+ + 2CN− → [Cu (CN)2] –
8. Additives: Presence of additives in plating bath will certainly improve the quality of deposit. The
added additive may act as brightener / leveler / structural modifier / wetting agent.
a. Brighteners – Bright & lustrous deposit results due to small metal crystals (fine grains).
Brightener gets adsorbed on the substrate & controls grain size. E.g. Coumarin, Thiourea
b. Levelers – gets adsorbed at points where rapid deposition & facilitate at places where deposition
is slow or poor and helps to get leveled deposit. E.g. Sodium alkyl sulphonate and some
brighteners function as levelers also.
c. Structural modifiers – modifies orientation of atoms in the crystal, avoids crystal defects and
prevents introduction of stress. E.g. Saccharin
d. wetting agent – helps to dislodge H2 gas bubbles adhering to the cathode and prevents hydrogen
embrittlement. E.g. Sodium lauryl sulphate
Throwing power: It is the ability of an electroplating bath to deposit metal uniformly on an irregularly
shaped substrate (cathode). It is determined using Haring-Blum cell. Two identical cathodes C 1 & C2 are
placed at markedly different distances d1 and d2 from a single anode & electroplating is carried out. The
increase in weights, w1 and w2 on the two cathodes is noted. The throwing power (in percentage) is
calculated using the following equation:
Throwing power = 100 (X – Y) / (X + Y – 2)

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Where; X = d2 / d1 and Y = w2 / w1

The magnitude of throwing power depends on the distance between anode & cathode, current density,
electrolyte conductivity, pH, temperature, additives, agitation, etc.

Haring-Blum cell

The throwing power of an electroplating bath is decided by the following factors;

a) Position of electrodes
The position of anodes and cathodes in a plating bath during plating is very important because, the
distance between the electrodes yield better and uniform deposit, which can be evaluated from Harring-
Blum cell.
b) Conductivity of the electrolyte
If the electrolyte is highly conductive, the current distribution on the cathodic surface is uniform and
hence the metal is also deposited uniformly. Thus the solution with higher conductivity will have higher
throwing power.
c) Presence of addition agents
The presence of additives like levelers and brighteners ensure an even deposit and hence increase the
throwing power. Some organic compounds are used as levelers to get a level deposit. They get adsorbed
at places where rapid deposition of metal takes place. The adsorbed levelers will reduce the rate of
deposition at these points.

Surface preparation
Surface preparation is a series of cleaning treatments of the substrate surface prior to the coating
operation, intended for ensuring strong and uniform adhesion of the coating to the substrate. The
impurities generally observed on the substrate are: rust protection oils, cutting fluids (coolants), greases,
paints, lubricants, oxides, scale, rust, etc.
1. Solvent cleaning: Rust protection oils, cutting fluids (coolants), greases, paints, lubricants are
removed by dissolving them in a suitable organic solvents like toluene, xylenes, chlorinated
hydrocarbons, etc. The solvent may be used in the liquid state, when the substrate is either immersed
into the solvent or sprayed by it. For effective cleaning, solvent is used in the gaseous state (vapor
degreasing).

2. Alkaline cleaning: Fats, mineral oils and wax are removed from substrate by treating with hot alkaline
solutions (50–80°C) either immersion or spraying method, followed by water rinse. Sodium hydroxide,
sodium carbonate, sodium phosphate are common alkalis, used in combination with soaps, detergents
and chelating agents for effective cleaning.
3. Pickling: Pickling remove firmly adhering impurities like scale, rust or stains with acid / acid mixture
as pickling agent, followed by water rinse. Mild acids (citric and phosphoric acids) are used for

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activation of aluminum, zinc castings and other sensitive alloys. Strong acids (hydrochloric and
sulphuric acids) are used for activation of steels and stainless steels.
4. Mechanical cleaning: It involves removal of solid impurities like oxides, rust, etc by grinding, buffing
or polishing with abrasive materials or sand blasting.
5. Electrocleaning (Electropolishing): Electrocleaning helps to remove organic soils, oxides and solid
particles adhered to the surface and provide a fresh surface for plating. It is an electrolytic process
conducted in an alkaline / acid electrolyte, through the passage of electricity. The part to be cleaned may
act as anode or cathode. The process combines effects of the alkaline / acid cleaning and strong agitation
provided by the liberation of gas bubbles at anode (O2) or cathode (H2).

Electroplating of Gold
Gold plating is widely used in the following applications;
i) In semiconductors.
ii) In Printed or etched circuits.
iii) In Contacts and Connectors.
Based on the PH range maintained during plating, gold plating has been classified into three baths
namely;
a) Acid cyanide bath b) Alkaline cyanide bath c) Neutral cyanide bath

a) Acid cyanide bath

Plating bath : Potassium gold cyanide 8-16g/l,
Citric acid 90g/l
H
P : 3.8-4.3
id : 100-400 ASF
Temperature : 210c-490c
Anode : Platinum clad
Cathode : Specimen/ Article
Duration : 15 seconds at 400 ASF
Application : Used in the manufacture of PCBs and Connectors

Alkaline bath gives thin & porous deposit and preferred for decorative purposes. Neutral bath is less
porous and used in manufacture of PCBs. Acidic bath gives nonporous, pure and ductile deposit and
used in electronic industry.
 In gold plating, insoluble anode is preferred over soluble anode, because, anode efficiency is
greater than that of cathode and leads to bulk deposit.
 Direct gold plated silver / copper surface tarnish due to diffusion of silver / copper atoms to the
surface; an undercoat is preferred.
Applications: Gold plating is used in jewelry, printed circuits, electrical contacts, transistors, IC parts,
reactors and heat exchangers, etc.

Electroless plating
“Electroless plating is an autocatalytic reduction of metal ions with the help of a reducing agent on a
catalytically active substrate without using electricity”. It is an autocatalytic reaction as the deposited
metal atoms catalyses further reduction of metal ions. To initiate electroless plating, substrate surface
should be catalytically active.
Catalytically active surfaces: Pd, Pt, Cr, Ni, Fe, steel
Catalytically inactive surfaces: Cu, Al, brass, insulators

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 Metal ion + Reducing agent catalytically activated surface Metal(d) + Oxidized product

Inactive surface can be converted into active Pd surface by treating with a solution of palladium chloride
(in HCl) followed by stannous chloride solution (in HCl).
Comparison between electroplating and electroless plating

Factor Electroplating Electroless plating

Driving force Applied external potential Autocatalytic reduction reaction
Anode and Cathode Anode – Soluble / insoluble Substrate acts both as anode and
Cathode – substrate cathode
Nature of substrate Must be conductor Conductor / semiconductor /
insulator
Throwing power Low High
Nature of deposit Relatively pure and does not Impart unique surface (mechanical,
exhibit unique surface electrical and magnetic) properties
properties due to incorporation of oxidized or
reduced product

Advantages of electroless plating are

 Plating can be carried out on any kind of substrate (conductors / semiconductors / insulators)
 Impart unique mechanical, electrical and magnetic properties
 High throwing power
 Does not require electrical energy
Bath composition of electroless plating
Metal salt : Suitable quantity of metal salt is added to furnish metal ions
Reducing agent : Responsible for reduction of metal ions & plays vital role in imparting
unique surface properties
Complexing agent : Monitor the free metal ion concentration
Buffer : Prevent alteration in pH and helps to get desired quality deposit
Stabilizer : Enhances the stability of the bath by preventing unwanted reaction/s
Exaltant / Accelerator : Increase the deposition rate

Copper electroless plating

Copper electroless plating provides highly conducting, corrosion resistant, nonporous surface. If, the
substrate surface is catalytically inactive, then treatment with palladium chloride and stannous chloride
in acid medium provides active Pd surface. Plating is generally carried out in alkaline medium and
plating bath composition depends upon the quality and thickness of the deposit. Following bath gives a
thick, rapid deposit.
Plating bath Metal salt – Copper sulphate ( g / L) 30
composition Reducing agent – Formaldehyde ( mL / L) 170
Buffer – Sodium hydroxide ( g / L) 40
– Sodium carbonate (g / L) 25
Complexing agent – Rochelle salt ( g / L) 140
– EDTA (g / L) 17
Stabilizer – Methanol (mL / L) 125
Temperature Room
PH 11.5 – 12.0
Deposition rate ( m / h) 20

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Reactions:
2HCHO + 4OH− → 2HCOO− + 2H2O + H2 + 2e (oxidation)
Cu2+ + 2e → Cu (reaction)

Application of electroless copper plating in PCB production

Copper clad plastic board is printed with etch resistant pattern of the circuit or the tracking required on
both the sides. On etching with suitable etchant the copper below the printed pattern is etched away,
leaving the circuit pattern. The connection between two sides is made by drilling hole followed by
activation and plating through holes by electroless plating. The step by step process of developing PCB
is as shown below;

Applications
It is used for
 manufacture of PCBs
 through-hole connection for double sided PCBs
 base coat on metals for subsequent electroplating
 decorative coating
 metalizing plastic