Electroplating

Prof. S. G. Warkar
 Electroplating
•Electrodeposition of metals on metals, non-metals and
alloys.
•Electroplating is done for decoration, protection and superior
engineering performance at lower cost comparable to the
articles formed by any other methods.
 Purpose of Electroplating
Main purpose of electroplating is to alter the surface
characteristics in order to achieve:
• improved appearance,
• improved protection from corrosion,
• improved frictional behavior,
•wear and chemical attack and
•improved hardness.
 Electroplating
•Electroplating of common metals include process in which
ferrous & non-ferrous base metals are electrodeposited
with Nickel, Chromium, Cadmium, Aluminum, Iron, Lead,
Zinc, Copper, brass, bronze etc.
•Electroplating of precious metals include process in which
ferrous & non-ferrous base metals are electrodeposited with
Silver, Gold, Platinum, Palladium, Indium, Iridium, Rhodium,
Ruthenium, Osmium etc.
 Electroplating
Basic electrolytic reaction in electroplating is electro-deposition of
metal ion from its solution.
There are two ways in which concentration of metal ions in
electrolyte is maintained :
1. Addition of electrolyte externally followed by analysis. In this
case inert anode such as graphite is used. Ex. Electroplating of
Chromium & Rhodium.
2. By using continuously dissolving anode of the metal ion to be
coated. Ex. Electroplating of Silver, Zinc, Nickel & Copper.
 Electroplating
•Although the later type of process would appear to maintain
a balanced concentration of metal ion in solution because
the same amount of current flows from anode to cathode.
• But, however, in practice there are several factors which
upset this balanced concentration of metal ion in solution.
Factors which disturb the balanced concentration
of Metal ion in Electrolyte solution:
i. Difference in anodic and cathodic current efficiencies.
ii. Passivation of anode by the formation of obstructive film
e.g. oxide, chloride, sulphide etc.
•When anodic current efficiency is lower than cathodic
current efficiency and when the anode passivates, a balance
concentration of metal ion cannot be maintained.
 Electroplating
•Since electroplating is done not only for decoration but also
for protection,
•It is very important in plating technology to secure a coating
which is adherent, coherent, uniform, decorous and
continuous.
•Thus in any plating process quality of plating is given first
importance and the economic factors become secondary.
 Plating Solutions
There are many plating solutions are in vogue but very few of
them are explored commercially.
They are classified as:
I. Acid sulphate solution of metal ion used for Zinc, Copper,
Tin & Nickel particularly for plating relatively simple
shapes.
II. Cyanide solutions which are popular for Copper,
Cadmium, Zinc, Silver, Gold & Brass.
III. Non cyanide alkaline solution containing small amount of
pyrophosphate are used for Copper & Zinc.
 Faraday’s Laws of Electrolysis
• Two basic laws which govern electrolysis were discovered by
Faraday (1833) are as follows:
1. Faraday’s first law states that the amounts of primary
product formed by electrolysis are directly proportional to
the amount of electricity flowing.
2. Faraday’s second law states that the passage of given
quantity of electricity causes the amounts of primary
products formed by electrolysis to be in the ratios of the
chemical equivalents of those products.
 Important characteristics of Electroplating
1. If electroplating is done for decoration, thin film is deposited but if
done for protection, thick coating is desired.
• In actual practice for protection against corrosion multiple coatings
are given on metal surface.
❖ E.g. When thin film of Ni coating is desired on iron or steel surface
and if this coating is not uniform and some pores are left behind then
heavy corrosion may take place at the pores because Ni is highly
cathodic to iron.
• So in order to prevent this type of corrosion a thin film of Copper is
coated (which is more resistant to corrosion) before depositing Ni
and then Ni is coated over Cu.
 Important characteristics of Electroplating
2. Adhesion
• Coating must adhere strongly to the surface otherwise the film
may get removed by peeling off.
• Maximum adhesion can be achieved by the removal of dust, dirt,
extraneous matter such as oil, grease, surface formed
compounds e.g. oxides etc. from the base metal surface.
3. Hardness
• If protection from abrasion is desired, the coating must be hard.
• Hardness is measured in Brinels. Ex. For Pb coating hardness is 5
Brinels and for Cr coating it is 1000 Brinels.
 Important characteristics of Electroplating
4. Brightness:
• Coating must be bright. Brightness of the film depends upon the
smoothness of the surface and natural reflectance of the coated
metal.
 Important characteristics of Electroplating
5. Current Density:
Defnition: Current required for coating per unit area of the object
and it is expressed in A/cm2 or mA/cm2 .
• It should be of proper strength.
• If the current density is too high it will result in loose and brittle
film while if it is too low the rate of deposition will be very low.
• Hence the optimum current densities should be used.
• However the upper limit of current density in electroplating can
be raised by keeping the electrolytic bath at elevated
temperature and also by agitating the bath.
Important characteristics of Electroplating

6. Metal ion Concentration:

• Should be low to prevent high electrolytic resistance.
• Low metal ion concentration does not mean that dilute solutions
are to be used.
• Those electrolyte solutions which undergo slow ionization or
whose ionization is suppressed by the addition of another salt
having common ion or which produces metal ion not by primary
ionization but by secondary ionization are to be used.
Important characteristics of Electroplating

7. Throwing Power:
• Ability of electrolytic bath to give a deposit of uniform thickness
over the entire irregularly shaped cathode area.
• Maximum throwing power is shown by such a cell system in
which all cathodes no matter how irregularly shaped receive a
uniform coating.
• While electrolytic bath with Poor throwing power produces an
article which is virtually uncoated in crevices and corners.
 Factors affecting throwing Power:
1. Optimum displacement of electrodes:
• In case of irregularly shaped object throwing power can be
improved by optimum displacement of anodes together with the
use of auxiliary anodes.
2. High conductance of electrolytic solution:
• Causes uniform distribution of current over even a complex
surface.
• In other words, high conductance results in uniform rate of
deposition over the entire cathode.
 Factors affecting throwing Power:
3. Additives:
• Throwing power is usually enhanced in presence of additives
such as complexing agents and levelers.
• Function of Levelers is to produce a level deposit by getting
itself adsorbed at regions where rapid diffusion of ions takes
place
• i.e the adsorbed leveler decreases the electron transfer rate at
such regions.
• Ex. For Nickel plating, Sodium allyl sulphate is employed as
leveler.
 Factors affecting throwing Power:
4. Hydrogen evolution:
•When electrode reactions are competed simultaneously by
hydrogen evolution, the metal deposition takes place at
high overpotential.
•This in turn causes reduction in the overpotential at these
points, thereby resulting in more uniform deposits.
 Determination of Throwing Power
• Throwing power is determined by using ‘Haring-Blum cell’,
which consists of a electrolytic cell containing the plating bath
solution under test.
• It has an anode at the centre and two cathodes (on two sides),
whose surfaces away from the anode are insulated.
• These electrodes are placed at respective distance of d1 and d2
(d1 > d2) from the anode.
• Electroplating is carried out for an appropriate time and weights
of metal (w1 and w2) respectively deposited on the two
electrodes are determined, then
 Haring-Blum cell

Haring-Blum cell is used to

determine throwing power.
It is basically a rectangular
(15x5x5cm) PVC box with an
open top.
Typically it has 2 cathodes
(5x5x0.2 cm) one at each end,
with a single anode perforated
of the same size placed
between them.
Determination of Throwing Power
• Studies on the Throwing Power can be carried out for different
compositions of electrolyte solutions.
• Deposits are produced on Cathodes positioned at both ends of
rectangular cell with some specific distance ratio from the
anode.
• Plating can be carried out for specific time period.
• From the weight of the deposits obtained at the near cathode
(Cn) W1 & far cathode (Cf) W2, throwing power can be
calculated.
• Field’s formula, a modified term of Haring and Blum formula is
the one greatly used, since the values it gives are more realistic
and range from + 100 % to –100%
Determination of Throwing Power
•
 Process of Electroplating
• Electroplating is carried out in electrolytic cell.
• Following points should be taken into consideration for getting good
results:
1. Article to be electroplated should be well-cleaned and pre treated
for getting long service life of the protective coating on a metal
surface.
2. Thus the article to be electroplated is first cleaned with organic
solvents to remove oils, grease etc and then treated with dil. HCl
(e.g. for copper & nickel plating) and dil. H2SO4 (for chrome plating)
to remove oxide.
 Process of Electroplating
• Cathode - Cleaned article
• Anode - Coating metal or an inert material
like graphite.
• Electrolyte solution - Metal salt solution
to be coated on cathode
• Anode and cathode are suspended in the electrolyte solution.
• Direct current is passed when coating metal ions migrate to the
cathode and get deposited there.
• Thus a thin coating of metal is deposited on the article made as
cathode.
 Process of Electroplating
• In order to have brighter and smoother deposits, low temperature,
medium current density and low metal ion concentration etc are
used.
 Theory of Electroplating
• Metal salt aqueous solution i.e. electrolytic solution undergoes
ionization forming ions.
• When a potential difference is applied to this salt solution by
dipping two electrodes in the solution -
• Metal ions migrate from the solution and get deposited on the
cathode (the article to be electroplated).
• Now there are two cases:
Theory of Electroplating
•
 Theory of Electroplating
•
 Theory of Electroplating
Case 2 When the anode is inert material like graphite –
• Electrolyte salt is continuously added to the electrolytic
bath in order to maintain proper concentration of the
coating metal ions.
•In such case, the process of electroplating is continuous
because anode is not consumed and hence its
replenishment is not required.
 Preparation of Basis Material
• Before a metal or non-metal is electroplated, the surface must
be physically, chemically and mechanically clean.
1. Physical clealiness: freedom from Oils, greases, superficial dirt
associated with polishing, buffing operations and atmospheric
dust.
2. Chemical cleanliness: freedom from oxides or other surface
formed compounds of the basis metal,
3. Mechanical cleanliness: freedom from surface skin of
damaged material e.g. loose fragments, scratches & strains
produced by mechanical operation.
 Series of operations in Electroplating
Steps involved in succession:
1. Pickling (Removal of scales)
2. Mechanical preparation of surface
3. Cleaning for physical cleanliness
4. Rinsing
5. Acid dipping for chemical cleanliness
6. Rinsing
7. Electroplating
8. Rinsing
9. Drying
 Pickling
• Involves the removal of relatively heavy scales of oxides formed
from hot rolling, casting and heat treatment and
• Also involves removal of rust or tarnish due to exposure to
atmosphere.
• This operation usually precedes polishing & buffing.
• Pickling consists of immersing the article in dil. HCl or dil. H2SO4.
• For cleaning copper, nickel & brass article the pickling bath
consists of a dil. HNO3 or a mixture of dil. HNO3 & dil. H2SO4.
 Mechanical Preparation

•To achieve better appearance and better surface protection

from corrosion and superior engineering properties.
•Rough surfaces are made smooth by mechanical methods
such as –
✔ Grinding with the help of grinding stone or grinding wheel
and
✔ Scratch rubbing either with the help of wire brush or
abrasive paper of cloth.
 Physical Cleanliness
•Involves the removal of oil, grease, atmospheric dust or
polishing and buffing compounds.
•Done by using organic solvent such as trichloroethylene or
perchloroethylene.
•Followed by cleaning with aqueous cleaning agents such as
sodium carbonate, sodium hydroxide and sodium silicate.
 Rinsing
•Rinsing the article with clean running water is important
between different steps in electroplating.
•Rinsing is done either by dipping the article in clean running
water
•&/or By spray rinsing or both depending upon the shape and
drag out characteristics of the article being plated.
Acid dipping for chemical cleanliness
• Done by dipping the article in 10-30% by vol. dil.HCl or dil.H2SO4
.
• This operation removes any tarnish film produced during
cleaning process and also neutralizes any alkaline film formed
which cannot be completely removed by rinsing.
• This is essential to ensure that the pH of the plating bath is not
affected.
• Subsequent to the acid dip and the rinse following it,
neutralization by dipping the article in dilute cyanide solution
may be desirable to prevent rusting.
Preparation of non-metallics:
• Non-metallics must be rendered clean, smooth and conducting
before subjecting to electroplating.
• Synthetic plastics such as vinyl chloride, vinylidine chloride, bakelite,
cellulose derivatives & laminated phenolics can be polished by
methods comparable to those used in case of metals.
• Leather, Paper, Cloth etc. are cleaned to remove oil, grease and wax
and are then rendered non porous by coating with shellac or lacquer.
• A conducting surface is produced by depositing a continuous coating
of Cu or Ag by chemical reduction or metal spraying.
 Constituent of Plating Bath
1. Salt solution of desired metal to be coated.
2. Conducting salt, whose function is to increase conductivity of
the bath, if the above salt is not sufficiently conductive?
3. Salt for promoting smooth anode corrosion and prevent its
passivity, if the metallic ion salt solution does not serve so?
4. Buffer solution, if the bath be operative successfully only over
a narrow pH range?
5. Suitable Additives for production of bright leveled pit-free
deposits.
 Constituent of Plating Bath
Ex. Brightener system in case of Nickel plating is –
✔ Mixture of Primary Brightener (saccharin or
p-toluenesulphonamide),
✔ Secondary Brightener (butynediol),
✔ Leveling agent (coumarin) and
✔ Wetting or Anti pitting agent (sodium lauryl sulphate).
• All these additives function on the principle of adsorption and
usually inhibit the metal deposition more strongly than hydrogen
evolution.
• However, a leveling agent is preferentially adsorbed on peaks and
hence causes metal deposition to take place preferentially at
recesses.
 Constituent of Plating Bath
• Some baths may contain all of these;
• Others may not, in that one substance may have more than one
function.
• For example, a common Ni plating solution will have –
✔ Metal ion in NiSO4.7H2O,
✔ NH4Cl or (NH4)2SO4 is used to increase the conductivity of the
bath,
✔ NiCl2.6H2O to assist anode corrosion and
✔ H3BO3 which acts as a buffer to maintain the pH of the solution.
 Constituent of Plating Bath

•In case of tin bath,

✔ Tin salt would be furnished by Na2SnO3,
✔ Conducting salt by NaOH which also assist anode corrosion,
✔Addition agent to affect the deposit being glucose or other
organic materials.
 Constituent of Plating Bath
• From industrial point of view the plating baths may be divided
into number of types
• E.g. Sulphate baths, cyanide, chloride, perchlorate and the
solutions from which precious metals are deposited.
• In most cases, a metal anode is the source of the plating metal.
• However in number of cases, the electrolyte constituents are the
source and reservoir of ions for the cathode deposit.
• In such cases insoluble anodes are employed.
 Constituent of Plating Bath

• In still other cases a combination of insoluble and active anode

may be used –
• As in the Cadmium cyanide baths where both cadmium which
dissolves and form Cd++ ions and steel, the one which does not
dissolve, are employed as anodes.
• Such a set up is made to balance anodic solution and cathodic
deposition which occur at different rates.
 Electroplating Methods

Electroplating method depends upon:

i. Type of metal to be electroplated
ii. Size and type of article to be electroplated
iii. Its main objectives
iv. Economics involved
 Fixtures

Some of the fixtures used are:

I. Jigs or Rock mountings for large scale electroplating of
routine articles.
II. Barrel plating for large number of small articles.
III. Individual mounting for electroplating of a single large
part like Car part.
IV. Wire mounting.
 Vat Plating Process
1. Plating tank:
Plating tank is a Vat (or rectangular tank) made of wood or steel with a
ceramic or polymer lining so as to provide thermal insulation.
Volume of the tank varies between 25 to 2000 liters.
2. Plating Bath Solution:
Highly conducting salt solution of the metal to be electroplated.
To enhance the conductivity as well as the Throwing power, usually non
participating electrolytes are added to bath solution.
To maintain proper pH and to get bright & compact deposits, buffer and
other additives are added respectively.
Level of plating bath solution in the Vat (tank) must cover completely the
surface area of cathode as well as anode.
 Vat Plating Process
3. Heating Arrangement:
Most of the electroplating processes are carried out at moderate
temperatures.
Heating the plating bath solution is usually carried out by using heating
coils or hot gases.
4. Convection current (Agitation):
In order to introduce convection current in the plating bath solution,
Air sparger (if oxygen does not interfere) or nitrogen sparger is
employed.
 Vat Plating Process
5. DC voltage arrangement:
For the plating operation, DC motor generators or DC rectifiers are
employed.
These are usually provided with arrangement to regulate both voltage
and current.
Initial nucleation stage requires high over potential.
After that the current is maintained at the optimum value so as to get
a good deposit.
For most plating operation, a voltage of 8-12V at operating current of
1-200 mA cm-2 is required.
 Vat Plating Process

6. Provision of Filters:
In large plating operations, filters are employed so as to filter out
regularly the metallic particles.
Otherwise these hinder in smooth deposition.
 Vat Plating Process
7. Power supply to electrodes:
Copper, Brass or Aluminum bus bars - for supplying power to
electrodes.
Anodes and cathodes are suspended alternatively from the bus bars
through the entire width of the tank.
Usually anodes are made of the plating metal but in some cases
insoluble anodes (e.g. Pb-Sn coated with PbO2 in Cr plating) are used.
Anodes can be rod-type, plate-type or even as pallets kept in titanium
mesh basket (e.g. Ni pallets in Ni plating).
Cathodes are either articles to be electroplated or Jigs connected to
the bus bars to hold objects to be electroplated.
Vat Plating Process
Vat Plating Process