UNIT-V

ELECTROLYTIC PROCESSES
Electrodeposition

Electrodeposition  is an electrochemical process that allows the accumulation of metal

ions on the electrode surface by electrolytic and electrophoretic deposition. A three-electrode setup
composed of working, counter, and reference electrodes used for electrodeposition. The working
electrode is the substrate where the deposition of metal ions takes place through the chemical reaction
governed by applied current or potential.
An electrolytic deposition of MnO 2 was carried out by using MnSO 4 and
Mn(OAc)2 solutions. In contrast, the electrophoretic deposition occurs through the electrolytic deposition
of suspended particles (non-conductive charged particles) on the working electrode under the applied
electric potential. The electrodeposition process requires a stable suspension containing well-dispersed
nanoparticles with desired electrophoretic mobility and additive for stabilizing the suspension.
Concentration of the electrolyte, pH and the dispersing medium are the key factor for
the electrodeposition processes. It can be divided into two parts based on the particle charge - anodic and
cathodic deposition. The oxidation of negatively charged particles on anode results in an anodic
deposition process whereas the cathodic deposition results when positive ions get deposited on the
cathode.

Electrolysis:
Electrolysis is a process by which electric current is passed through a substance to effect a chemical
change. The chemical change is one in which the substance loses or gains an electron (oxidation or
reduction).

Laws of Electrolysis

The laws state that

Faraday’s First Law of Electrolysis states that the chemical deposition due to the flow of current
through an electrolyte is directly proportional to the quantity of electricity (coulombs) passed through it.
i.e. mass of chemical deposition:
m∝ Q
m=Z Q
Where, Z is a constant of proportionality and is known as electro-chemical equivalent of the substance.

Faraday’s second law of electrolysis states that, when the same quantity of electricity is passed through
several electrolytes, the mass of the substances deposited are proportional to their respective chemical
equivalent or equivalent weight.
Chemical Equivalent or Equivalent Weight
The chemical equivalent or equivalent weight of a substance can be determined by Faraday’s laws of
electrolysis, and it is defined as the weight of that subtenancy which will combine with or displace the
unit weight of hydrogen.
The chemical equivalent of hydrogen is, thus, unity. Since valency of a substance is equal to the number
of hydrogen atoms, which it can replace or with which it can combine, the chemical equivalent of a
substance, therefore may be defined as the ratio of its atomic weight to its valency.

Process of Electrodeposition:

Electroplating is a process that uses electric current to reduce dissolved metal cations so
that they form a coherent metal coating on an electrode. The process used in electroplating is called
electro-deposition. It is analogous to a galvanic cell acting in reverse. The part to be plated is the cathode
of the circuit. In one technique, the anode is made of the metal to be plated on the part. Both components
are immersed in a solution called an electrolyte containing one or more dissolved metal salts as well as
other ions that permit the flow of electricity. A power supply supplies a direct current to the anode,
oxidizing the metal atoms that it comprises and allowing them to dissolve in the solution.
At the cathode, the dissolved metal ions in the electrolyte solution are reduced at the
interface between the solution and the cathode, such that they "plate out" onto the cathode. The rate at
which the anode is dissolved is equal to the rate at which the cathode is plated, i.e. the current through the
circuit. In this manner, the ions in the electrolyte bath are continuously replenished by the anode. Other
electroplating processes may use a non-consumable anode such as lead or carbon. In these techniques,
ions of the metal to be plated must be periodically replenished in the bath as they are drawn out of the
solution. The most common form of electroplating is used for creating coins such as pennies, which are
small zinc plates covered in a layer of copper.

Process of Electrodeposition:

The cations associate with the anions in the solution. These cations are reduced at the
cathode to deposit in the metallic, zero valence state. For example, in an acid solution, copper is oxidized
at the anode to Cu2+ by losing two electrons. The Cu 2+ associates with the anion SO 42− in the solution to
form copper sulfate. At the cathode, the Cu 2+ is reduced to metallic copper by gaining two electrons. The
result is the effective transfer of copper from the anode source to a plate covering the cathode. The plating
is most commonly a single metallic element, not an alloy. However, some alloys can be electrodeposited,
notably brass and solder.
Many plating baths include cyanides of other metals (e.g., potassium cyanide) in
addition to cyanides of the metal to be deposited. These free cyanides facilitate anode corrosion, help to
maintain a constant metal ion level and contribute to conductivity. Additionally, non-metal chemicals
such as carbonates and phosphates may be added to increase conductivity. When plating is not desired on
certain areas of the substrate, stop- offs are applied to prevent the bath from coming in contact with the
substrate. Typical stop-offs include tape, foil, lacquers, and waxes.
Application of electro-deposition:

Since its invention in 1805 by Italian chemist, Luigi Brugnatelli, electroplating has become an extensively
used industry coating technology.
Its applications are mainly in the following four groups:
1. Decoration: Coating a more expensive metal onto a base metal surface in order to improve the
appearance. Applications are jewellery, furniture fittings, builders’ hardware and tableware.
2. Protection: Corrosion-resistant coatings such as chromium plating of automobile parts and
domestic appliances, zinc and cadmium plating of nuts, screws and electrical components. Wear-
resistant coatings such as nickel or chromium plating of bearing surfaces and worn shafts and
journals.
3. Electroforming: Manufacture of sieves, screens, dry shaver heads, record stampers, moulds, and
dies.
4. Enhancement: Coatings with improved electrical and thermal conductivity, solderability,
reflectivity etc.

Electro-deposition-clearing:

Cleanliness is essential to successful electroplating, since molecular layers of oil can prevent adhesion of
the coating. ASTMB322 is a standard guide for cleaning metals prior to electroplating. Cleaning
processes include solvent cleaning, hot alkaline detergent cleaning, electro-cleaning, and acid treatment
etc. The most common industrial test for cleanliness is the water break test, in which the surface is
thoroughly rinsed and held vertical. Hydrophobic contaminants such as oils cause the water to bead and
break up, allowing the water to drain rapidly. Perfectly clean metal surfaces are hydrophilic and will
retain an unbroken sheet of water that does not bead up or drain off. ASTM F22 describes a version of
this test. This test does not detect hydrophilic contaminants, but the electroplating process can displace
these easily since the solutions are water-based. Surfactants such as soap reduce the sensitivity of the test
and must be thoroughly rinsed off.

Deposition of metals:
It is possible to deposit alloys also provided the electrode potentials of the constituent metals are not
much different. Electroplating of brass and bronze are the best examples. For this, the anode is made up
of an alloy to be deposited and the electrolyte consists of a mixture of electrolytes and which would have
been employed for separate deposition of metal consumed. For brass plating solution of double cyanides
of zinc and potassium and copper and potassium is used as electrolyte and current density of 25 – 40
Ampere/ square meter is used.

Electro-polishing or electro-buffering:
Electro-polishing, also known as electrochemical polishing or electrolytic polishing (especially in the
metallography field) or electro-buffering, is an electrochemical process that removes material from a
metallic work piece. It is used to polish, passivate, and deburr metal parts. This process basically makes
the surface smoother. It may be used in lieu of abrasive fine polishing in microstructural preparation.
Typically, the work piece is immersed in a temperature-controlled bath of electrolyte and serves as the
anode; it is connected to the positive terminal of a DC power supply, the negative terminal being attached
to the cathode. A current passes from the anode, where metal on the surface is oxidized and dissolved in
the electrolyte, to the cathode. At the cathode, a reduction reaction occurs, which normally produces
hydrogen. Electrolytes used for electro-polishing are most often concentrated acid solutions having a high
viscosity, such as mixtures of sulfuric acid and phosphoric acid. Other electro-polishing electrolytes
reported in the literature include mixtures of perchlorates with acetic anhydride and methanolic solutions
of sulfuric acid. To achieve electro-polishing of a rough surface, the protruding parts of a surface profile
must dissolve faster than the recesses. This process, referred to as anodic leveling, is achieved by a mass
transport limited dissolution reaction. Anodic dissolution under electro-polishing conditions deburrs metal
objects due to increased current density on corners and burrs. Most importantly, successful electro-
polishing should operate under diffusion limited constant current plateau, achieved by following current
dependence on voltage (polarization curve), under constant temperature and stirring conditions.

Factors affecting electrodeposition:

1. Nature of Electrolyte:
The formation of smooth deposit largely depends upon the nature of electrolyte employed. The electrolyte
from which complex ions can be obtained, such as cyanides, provides a smooth deposit.

2. Current Density:
Electrodeposition depends upon the rate at which crystals grow and the rate at which fresh nuclei are
formed, therefore, at low current densities the deposits are coarse and crystalline in nature. The deposit of
metal will be uniform and fine-grained if the current density is used at rate higher than that at which the
nuclei are formed. In case the rate of formation of nuclei is very high due to very high current density,
there is a chance that the limiting value of the electrolyte is exceeded. At such instances, the deposit will
be spongy and porous.

3. Temperature:
A low temperature of the solution favours formation of small crystals of metal; and a high temperature,
large crystals. In some cases this is very marked, a difference of only 15°C resulting in a 50% decrease in
strength of the metal deposited. On the other hand, high temperature may give beneficial results due to (a)
increased solubility of the salts, permitting greater metal concentration and higher current densities; (b)
increased conductivity, which also permits higher current densities and reduces the tendency to form
trees; (c) decreased occlusion of hydrogen in the deposited metal, which in many cases is the case of bad
deposits. Since both (a) and (b) tend to decrease crystal size, they may in some cases counteract the
tendency of temperature alone to increase the crystal size.

4. Conductivity:
The use of a solution of good conductivity is important from the standpoint of view of economy in power
consumption and also because it reduces the tendency to form trees and rough deposits.

5. Electrolytic Concentration:
Higher current density, which is necessary to obtain uniform and fine-grain deposit, can be achieved by
increasing the concentration of the electrolyte.
6. Additional Agents:
The addition of acids or other substances to the electrolyte reduces its resistance, as already mentioned.
There is another class of additional agents which takes little or no direct part in the chemical reactions but
influences the nature of deposit, sometimes even making an otherwise unworkable process into one of
practical importance. Such additional agents are glue, gums, dextrose, dextrin, gelatin, agar, alkaloids,
albumen, phenol, glycerin, sugar, glucose, rubber etc. The crystal nuclei absorb the additional agent
added in the electrolyte. This prevents it to have large growth and thus deposition will be fine-grained.
For obtaining satisfactory deposit of zinc from zinc sulphate solution addition of glucose or certain types
of sugar is necessary.

7. Throwing Power:
This is the ability of electrolyte to produce uniform deposit on an article of irregular shape and is one of
the most important characteristics of plating or deposition bath. The distance between the various portions
of cathode and anode will be different due to irregular shape of the cathode. Due to unequal distance, the
resistance of the current path through the electrolyte for various portions of the cathode will be different
but the potential difference between the anode and any point on the article to be plated (cathode) will, of
course be the same and the result will be that the current density will be more on the portion nearer to
anode and it will cause uneven deposit of the metal.
Throwing power can be improved in two ways—firstly by increasing the distance between the anode and
cathode and secondly by reducing the voltage drop at the cathode surface. In some cases decrease of
current density causes a decrease in voltage drop at cathode, leaving more voltage available for
overcoming the resistance of the electrolyte, thus tending to counteract any change in current
concentration. This is the reason that solutions of the cyanides of metals usually have a better throwing
power than solutions of the sulphates.

8. Polarization:
The rate of deposition of metal increases with the increase in electroplating current density up to a certain
limit after which electrolyte surrounding the base metal becomes so much depleted of metal ions that the
increase in current density does not cause increase in rate of deposition. Use of current density beyond
this limit causes electrolysis of water and hydrogen liberation on the cathode. This hydrogen evolved on
the cathode blankets the base metal which reduces the rate of metal deposition.
This phenomenon is called the polarization. Blanketing effect can be reduced by agitating the electrolyte.
With reverse current electroplating, in which at regular intervals plating current is reversed for a second
or so, sufficient electron concentration is established around the base metal and the polarization effect
becomes negligible even with very high overall speed of plating.

Principle of Galvanizing and its application:

Galvanizing is the process which employs an electrochemical action for providing a coating of highly
corrosion resistant material on the surface of another metal. The galvanizing process is widely used for
providing a coating of zinc on iron and steel.
It is very much low cost process and widely used for corrosion resistant coating on sheet metal, household
items for daily used made from iron and steel e.g. buckets, tubs and other containers. Galvanized is also
done on machine parts, tools, ships tanks and wires etc.
Galvanized pipes, metal sheets and wires are probably the most popular galvanized items which find wide
applications both in industrial use as well as in articles made for domestic use. There are number of
techniques can be employed for galvanizing of zinc to the metal surface.

Techniques Used in Galvanizing:

The following are the main techniques used for galvanizing of zinc:

Hot-Dipping Galvanizing:
It is the cheapest of the galvanizing techniques employed in mass production.

Procedure:
The first step in applying this process is thorough cleaning of the items to be galvanized. This involves
decreasing etc. depending upon the condition of work-surfaces. The main idea is to obtain an absolutely
clean surface. If the item to be galvanized is sheet metal, it is annealed after surface cleaning and then
cooled in an oxide free atmosphere. The sheet is then dipped in the bath.
If uniform thickness of coating is required then sheets are drawn through set of rollers immediately
following the coating process. This process drives away the excess zinc and allows only the required
amount of zinc to remain on the surface. Without this process the coating thickness cannot be controlled.
This is followed by drying, and then the sheets are ready for shipment.
In another method of galvanizing instead of dipping the article in hot zinc bath, hot zinc is made to flow
over the surface of the article. This process suits well for galvanizing extremely large surface of iron and
steel sheet.

Applications of Galvanizing
1. To galvanized sheet metal.
2. To galvanized house-hold items such as buckets, tubs and other containers.
3. To galvanized machine parts, tools, ships, tanks and wires.
4. Metal pipes and wires are most popular galvanized items which find application in industrial use as
well as in articles made for domestic use.

Principle of Anodizing and its application:

It is the process in which a film of oxide is provided on metal surface is known as anodising.

(i) The give a protective coating on the metal surface like aluminium, zinc, copper and bronze
etc.
(ii) To provide a decorative appearance on the surface.
(iii) To provide a bright and smooth surface on aluminium articles prior to electroplating.
(iv) To provide specific colour base for subsequent painting on the surface.
(v) To improve the corrosion resistance of aluminium and aluminium products.

The anodised is achieved by using different electrolytes varying current and temperature of
solution etc. Anodising process is neither a purely electrical process nor purely chemical process; it is a
combination of both hence called electrochemical process.
The following steps are involved in the completion of electrochemical process:

(i) Cleaning and preparing the surface through different cleaning method.
(ii) It consists of anodising i.e. converting metal surface into an oxidized film.
(iii) The third stage consists of providing of desired colour.

For anodising aluminium and its alloys products acid solution used are sulphuric acid,
chromic acid and oxalic acid. The selection of particular acid solution depends upon the type of colour
shade required. Aluminium anodising is a process in which a film of oxide is formed on the surface of
aluminium. The oxide coating is very hard and is highly resistance to corrosion.

The coating is of good appearance. The aluminium article is made the anode and electrolyte
is an aqueous solution of sulphuric acid and chromic acid. A dc supply of voltage of 10 to 60 volts is
required for the process. It is possible to anodise other metals such as steel galvanised iron, brass, zinc,
silver and copper etc.

This is particularly of special application in aircraft, in which aluminium is used for

stressed members. The colour of the film is generally of light grey and gives a decorative finish.

Applications of Anodising:
Some of the applications of anodising:
1. To provide a protective coating on the metal surface.
2. To anodising on steel for producing a black film on various steel parts used a decorative article.
3. Several galvanized iron and steel articles and machine parts are anodised to improve the
resistance of galvanised coating to rusting, abrasion, wear and increase its life.
4. To anodising zinc to give distinct colour coatings.
5. Anodising is done on silver jewellery and show pieces made of silver.

Electroplating on non-conducting materials:

Non-conductive materials, also known as insulators, are materials that either prevent or block
the flow of electrons. These materials exhibit this trait because the atoms inside these insulators do not
contain the extra electrons needed to pass an electric charge --- this makes it incredibly difficult to pass a
charge through the material.

The key to electroplating non-conductive materials is with a process called electroless

plating. Unlike electroplating, which relies on depositing a thin layer of metal using an electric current,
electroless plating deposits a light coating of metal without the use of electricity. Instead, the electroless
plating process adheres the coating using an autocatalytic reaction. We’ll explain the steps in more detail
below.

Cleaning: Before applying any chemicals, the surface of the substrate must be clear of any oils, greases
and particulates — any of these could interfere with the etching or plating process and result in a sub-
standard coating. Typically, cleaning involves the application of several acids and bases, interspersed
with several rinses to clear away any chemical residues.

Etching: Once the surface of the material is clean, a procedure called etching prepares it for plating. In
this process, the plastic or ceramic workpiece gets submerged in a chrome-sulfur etching solution, which
eats away at the surface of the substrate. This process creates texture on the surface of the piece, which
allows the metal to easily adhere to the substrate. After completing this step, you must clean the substrate
thoroughly to neutralize any excess chromic acid.

Electrolyte bath: The next step after etching is to immerse the object in an electrolyte bath of palladium
and tin salts. The object then gets coated with an electroless plating solution of either nickel or copper.
The palladium and tin salt solution acts as a catalyst, causing a reaction that forces the nickel or copper to
form a thin coat on the substrate.

Paint alternative: If you prefer a method other than the electrolyte bath, you can add a conductive paint
to the surface of the substrate.

Copper Electroplating: Once the electroless layer is ready, a thin layer of copper metal gets
electrodeposited on the surface of the workpiece.