NICKEL AND CHROMIUM PLATING

AIM:

To electroplate the given copper specimen with nickel and chromium and find the current efficiencies of
their electrodeposition.

PRINCIPLE:

The decorative and protective coating of steel is most commonly done with a combination of copper,
nickel and chromium electroplating. Chromium plating is used to produce hard (wear-resistance), bright
and corrosion resistance surfaces. However, the chromium is usually porous and hence the plated object
will be open to corrosion. To increase the corrosion resistance, an undercoat of nickel is usually done.
Moreover, nickel coating alone gets tarnished after some time giving a yellowish tint and requires a non-
tarnishing & durable surface finish. Since nickel plating is not strongly adherent to steel objects, a pre-
coating of copper will achieve its adequate adhesion. Thus, a common way to produce a decorative and
protective surface of steel objects involves successive electroplating of copper, nickel and chromium
from their respective baths. (In the present experiment a copper object is provided directly for its nickel
and chromium plating).

PROCEDURE:

1. Polish the given copper plate by emery paper to remove the previous coatings and make it as smooth
as possible.
2. Wash, degrease, dry and weigh the sample.
3. Put a mark on the plate up to which nickel will be electrodeposited. Find this area and calculate the
current required taking a c.d. of 1 asd.
4. Electro-deposit nickel on the copper plate from Watts Bath for 20 minutes using a nickel anode at
room temperature.
5. Wash the plate, dry and weigh it.
6. Electro-deposit chromium on the nickel-plated copper from the chromic acid path at 15 asd c.d. for
10 minutes at 45°C using lead anode.
7. Wash the plate, dry and weigh it.
8. Calculate the current efficiencies for both the electro depositions.

OBSERVATIONS (ON L.H.S.):

Record for each electroplating

a) bath composition; b) electrodes used; c) temperature; d) current density;

e) voltage and f) time of plating.

RESULT AND DISCUSSION:

 ANODIZING OF ALUMINIUM

AIM:

To anodize the given aluminium sample and to colour it with a dye and to measure the thickness of the
anodic film.

PRINCIPLE:

Anodizing refers to the development of an oxide coating of desired characteristics on the surface of a
metallic object by making it the anode of an electrolytic cell containing a suitable electrolyte. The
anodized surface of aluminium is composed of a hard, nonporous and adherent coating of Al2O3. It affects
remarkable resistance to wear and corrosion. Any desired colour can be imparted to the anodized object
by dipping it into a suitable dye.

When a current is passes through a acidified electrolyte, hydrogen is liberated at the cathode and nascent
oxygen at the anode. This nascent oxygen reacts with the object which is made the anode, forming an
impervious oxide coating. The initially formed oxide coating is attacked by the electrolyte and further
oxidation continues and ultimately a thick and porous film of the oxide is formed. The overall oxide
coating comprises of a thin nonporous passive layer and a thick porous outer layer depending on the
nature of metal, electrolyte and operating conditions.

PROCEDURE:

1. Polish the given aluminium plate using chemical polishing method. For this, dip the plate in the given
bath for about 2 minutes at 80°C.
2. Prepare a lead cathode.
3. Anodize the sample in the sulphuric acid (20%) bath at 10V to 20V for 10, 20, 30 & 40 minutes
taking care that the temperature does not rise during the process.
4. Wash the plate immediately in ammonical water (1%) followed by distilled water only and weigh it.
5. Keep the specimen in a dye solution for 20 minutes at 60°C.
6. Keep the object in a beaker of boiling water for 15 minutes. Wash and dry the plates.
7. For the determination of thickness of oxide coating, dissolve the oxide film in the given solution at
95-100°C for 5 minutes. Thickness of the oxide film in micron = (10000 G)(2.5xA).
8. Where, A = total surface area in cm2, G= difference in weigh in g.

OBSERVATIONS (ON L.H.S.):

Bath composition and operating conditions.

RESULTS AND DISCUSSION:

 CORROSION CELLS

AIM:

To understand the principles underlying galvanic and oxygen concentration cells.

(A) GALVANIC CORROSION CELL:

PRINCIPLE:

If a noble metal and a base metal are in contact electrolytically and electronically, they form a galvanic
cell, where the former acts as cathode and the latter as anode. Thus, the base metals of this pair gets
corroded. This is illustrated by means of the following experiments:

PROCEDURE:

1. Join a strip of copper to one of iron.

2. Immerse the couple in a beaker containing 'ferroxyl' indicator [NaCI-5gm, K3Fe (CN)6- 0.5gm, H₂O-
25ml, Phenolphthalein -1ml. (dissolve a pinch of phenolphthalein in 1cc alcohol and add this
solution)].
3. Leave the beaker and its contents undisturbed and observe after 2 hrs.

RESULT:

(B) OXYGEN CONCENTRATION CELL:

PRINCIPLE:

It is well known that oxygen in excess concentration causes passivity, whereas, at low concentration it
acts as stimulant in the corrosion of metals. Thus, that portion of a structural metal which is least
accessible to oxygen is most likely to corrode. This can be illustrated by the following experiment.

PROCEDURE:

1. Polish, degrease and dry a sheet of mild steel.

2. Place a drop of ferroxyl solution about 2-3 cm in diameter.
3. Observe the initial distribution of anodic and cathodic areas.
4. Keep the specimen undisturbed for 1-2 hours and prevent undue evaporation of the drop by covering
the specimen with a large watch glass or beaker.
5. Watch the distribution of anodic and cathodic areas with time.

RESULTS AND DISCUSSION:

 EFFECT OF CURRENT DENSITY ON METAL DEPOSITION

AIM:

To study the influence of current density on current efficiency and nature of deposit in the
electrodeposition of copper from copper sulphate bath.

PRINCIPLE:

In the industrial practice it is necessary to produce electroplated objects in large numbers with required
properties in the shortest possible time. Current density (C.D.) is one of the important factors which affect
the rate of the deposition and properties of the electrodeposits. As C.D. increases (up to a certain limit),
the time for production is cut down with consequent saving in space and investment. Further with higher
C.D., the deposition rate and cathode polarization are higher and consequently the grain size of the
deposit is smaller. Above a limiting C.D. for a given bath operating under fixed conditions, the deposits
become dull, burnt and non-adherent. Use of relatively higher C.D. may be beneficial in case of base
metal plating whereas in the case of noble metal it may not be advantages. High C.Ds are used for
electrodeposition of metal powders.

PROCEDURE:

1. Prepare a copper sulphate bath of the given composition.

2. Prepare 4-5 copper plates for use as cathodes and a thick copper plate for use as anode.
3. Checkup electrical connection and polarities of the terminals. Suspend the anode plate and a weighed
cathode plate firmally from the support provided for the purpose.
4. Perform 4 or 5 deposition experiments at room temperature under staying for 10 minutes at various
chosen current densities.
5. Wash, dry and weigh all the cathode plates at the end of each electrodeposition.
6. Note the appearance, adherence and brightness of the deposit for each plate in the observation column.
7. Calculate the current efficiency at different current densities.

OBSERVATIONS (L.H.S.):

(a) Bath Composition (b) Electrodes used (c) Voltage

(d) Temperature of plating (e) Time of plating (f) Make a Table as given below.

C.D. Weight of Cathode Actual Theoretical Current Apparent nature of

(a.s.d.) Weight of weight of efficiency deposition
deposition deposition
Before After Adherence Brightness
deposition deposition - - -

RESULTS AND DISCUSSION:

Draw a plot of current efficiency versus C.D. and discuss the results.
 THROWING POWER

AIM:

To study the throwing power of copper and nickel sulphate baths.

PRINCIPLE:

Throwing power refers to the ability of solution to give uniform deposition on irregular surfaces. For a
given bath operating under specific conditions, throwing power is influenced by the cathode polarization
characteristics of the bath, conductance of the solution on the change of current efficiency with change
of current density. T is quantitatively expressed as the variation of the metal distribution rate from the
primary current distribution ratio expressed as a percentage of the latter.

Three formulae have been proposed to express throwing power (T. P.) of the electrolytic baths.
𝑷−𝑴
1. 𝑻. 𝑷. = x 100 (Blum and Harring),
𝑷

𝑷−𝑴
2. 𝑻. 𝑷. = x100 (Heatley)
𝑷−𝟏

𝑷−𝑴
3. 𝑻. 𝑷. = x100 (B.S.S.)
𝑷+𝑴−𝟐

(𝒅𝟏) (𝒘𝟐)
Where, P-Primary Ratio , M-Metal Ratio
(𝒅𝟐) (𝒘𝟏)

Of the three formulae given above, the last one is more reasonable one.

PROCEDURE:

1. Prepare cathode plates and 1 perforated anode.

2. Weigh the cathode plates.
3. Arrange the experimental set up in the throwing power box using copper sulphate bath and find out
weight increase of cathodes at distance ratio of 1:3 after plating under fixed conditions.
4. Change the distance ratio to 1: 2 and find the weight increased on cathode under above conditions.
5. Repeat the above experiments with nickel sulphate baths.
6. Calculate the throwing power of both the baths.

RESULTS AND DISCUSSION:

 ELECTRO POLISHING

AIM:

To electropolish the given specimens of copper and brass.

PRINCIPLE:

The process of electropolytic polisiting consists in anodic treatment of the metal or alloy to be polished
at high current densities in relatively concentrated acid baths. Brightening of the surface results from
more rapid attack of the elevated portion of the rough surface than of the depressions. The theory of
electrolytic polishing assumes the presence or formation of viscous high-resistance film at anode which
tends to fill in depressions and thereby reduce the anodic current densities that would otherwise prevail
in these depressions. Because there is more opportunity for removal and replenishment of the film at the
high spots or peaks, as a result of higher current density and evolution of gas there, the attack is more
rapid on these sports.

PROCEDURE:

1. Grind the specimen (Cu) up to 3/0 and degrease it. Select a suitable cathode material and polish it.
Clean the anode support.
2. Prepare the necessary phosphoric acid bath. Arranging the polishing set-up ensuring a distance of
about 1 cm between the specimen and the cathode.
3. Increase the voltage with regular increment of 0.2V up to about 3 volts and note down the
corresponding current values.
4. From the voltage versus current values, determine the voltage required for electropolishing the
specimen.
5. Electropolish the specimen at the above voltage for different time intervals (e.g.2,4,6....minutes) and
determine the optimum time required to get the best results.
6. Repeat the above experiment with the other specimen (brass).

RESULT:

Plot graphs of voltage versus current for both the specimens and record the description of the sample of
the polished specimen.

DISCUSSION:
 OXIDATION OF COPPER/IRON

AIM:

To establish the relationship between the rate of oxidation of copper /iron and the thickness of oxide film.
Also, to determine the activation energy of the process.

PRINCIPLE:

Oxidation of a metals is its reaction with air or oxygen in the absence of water or an aqueous phase.
Scaling, tarnishing and dry corrosion are also sometime used to describe this phenomenon. As the
temperature is increased, the importance of metal oxidation also increases as it is considered for most
metallurgical applications at elevated temperatures. The oxidation resistance of metals is related to the
volume ratio of the metal and its oxide per gram of the metal known as Pilling -Bedworth ratio. According
to this ratio, a volume ratio of less than 1 produces insufficient oxide to cover the metal and is not
protective. Similarly, for ratio greater than 1 tends to introduce large compressive stresses in the oxide,
which also causes poor oxidation resistance due to cracking and spalling. The ideal ratio would be close
to l.

The lighter metals form an oxide which takes up less volume than the metal from which it is formed.
Therefore, film formation tends to be non-protective and continues at a constant rate. These metals (e.g.
K, Ca & Mg) tend to be very reactive and burn in air.

Heavier metals may form an oxide which takes up more volume than the metal from which it was formed.
Therefore, film formation slows up as the tightly packed film increases in thickness and growth is
protective, e.g. copper and irons. The relationship between thickness of film y and time t, can be parabolic
or logarithmic according to the properties of the oxide film, e.g. Copper in air at high temperature obeys
a parabolic relationship whereas iron at room temperature obeys a logarithmic relationship.

Parabolic Equation: y2 = k1t+k2

Logarithmic Equation: = k1 log (k2t+k3)

k1,k2 and k3 are constants.

The oxidation of copper, the metal ions diffuse out through the oxide lattice (via vacant lattice sites) to
form copper oxide at the surface. The thicker the film, the further the ions have to travel before being
oxidized, so that the oxidation rate slows down in a manner resembling an electric current which is
inversely proportional to the resistance.

dy/dt=k/y and ydy=kdt

Therefore, on integration, y² = k₁ t+k2

In the oxidation of aluminium, alumina has no vacant lattice sites so that the film is more protective than
the oxide of copper.

PROCEDURE:

1. Calibrate the spring of thermogravimetric balance by suspending standard weights from 0-3 grams at
an interval of 500 mg.
2. Draw a graph between the extension of spring and weight suspended.
3. Clean the given metal piece with emery paper and weigh.
4. Heat the furnace to the required temperature and bring it to such a position that metal piece hangs in
the Centre of the furnace.
5. Mark a reference point on the suspension wire through the cathetometer and take reading on vertical
scale.
6. Continue to take cathetometer readings at an interval of 5 minutes till there is no further change in
reading.
7. Remove the metal piece from furnace, cool and weigh it again.
8. Repeat the above experiment at other two temperatures.
9. Make a plot of weight gain versus time for all three temperatures.
10. Find the rate law and activation energy of the oxidation process.

RESULTS AND DISCUSSION:

 STUDY OF ELECTRODE POTENTIALS

AIM:

To determine electrode potentials of the given metal electrodes against the standard Calomel electrode
and to construct the e. m. f. series of metals.

PRINCIPLE:

When an electronic conductor (say a pure metal) is in contact with an electrolytic conductor containing
the concerned ions (at unit activity) a half cell or an electrode is obtained. At each cell a characteristic
potential known as "single electrode potential" is developed. Such potentials when measured against a
standard hydrogen electrode at 25°C are referred to as "standard electrode potentials'. The e. m. f. series
(or electrode chemical series) of materials is formulated on the basis of these standard electrode potentials
by arranging them in order of increasing cathodic behavior (from top to bottom). The series is of great
help in understanding many electrode processes such as electrowinning, electroplating, electroforming,
electrorefining, electropolishing and corrosion and protection, cementation etc.

PROCEDURE:

The electrode potential of the given metal is determined with reference to a Calomel Electrode (electrode
potential: +0.246 V) using a Digital Microvoltmeter instrument, which is as follows.

1. Clean and degrease the given metal samples.

2. Prepare 1M solutions of sulphate of Cu, Ni, Al, Mg, Zn, Cd, Fe etc.
3. Switch on the Digital Microvoltmeter and short the positive (red) and negative (black) terminals for
zero adjustment.
4. Set zero reading in the lowest range (1mV) with zero setting knob.
5. Keep the selector switch at the highest range (10V) which can be lowered as per the voltage of the
cell for better accuracy.
6. Connect calomel electrode to positive terminal and metal electrode to negative terminal and insert
both the electrodes in the concerned 1M electrolyte (avoiding connecting clips to come in contact
with the electrolyte). Note down the initial voltage reading.
7. Remove and wash the electrodes.
8. Repeat the experiment with other metal electrodes.

RESULTS:

The measured values are w. r. t. Calomel electrode (+0.246 V). The electrode potentials w. r. t. hydrogen
electrode can be calculated by subtracting the above values from 0.246 V. Compare these values with
Standard Electrode Potentials in the form of a Table.

DISCUSSION: