ADVANCED MATERIAL CHEMISTRY

MALLA REDDY COLLEGE OF

ENGINEERING & TECHNOLOGY
(An Autonomous Institution – UGC, Govt. of India)
Recognizes under 2(f) and 12(B) of UGC ACT 1956
(Affiliated to JNTUH, Hyderabad, Approved by AICTE –Accredited by NBA & NAAC-“A” Grade-ISO
9001:2015 Certified)

ADVANCED MATERIAL CHEMISTRY

B.Tech – I Year – I Semester

DEPARTMENT OF HUMANITIES AND SCIENCES

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD)

 ADVANCED MATERIAL CHEMISTRY

Preface
Chemistry as a basic science plays a vital role in making a foundation for engineering students
and ensuring security by shaping a fruitful superstructure for their entire career. Chemistry is
the back bone in designing an understanding the nature of various engineering materials.
Moreover, thorough knowledge of chemistry provides the requisite expertise to deal with
challenges in disciplines of engineering related to design an development of new materials.
Material Science and Engineering is a key aspect of most companies the world over. In the race
to make things stronger, cheaper, lighter, more functional and more sustainable, the
manipulation of materials, their properties and processes is key. The field of materials science
and engineering is important both from a scientific perspective, as well as towards applications.
Materials are of the utmost importance for engineers (or other applied fields), as the usage of
the appropriate materials is crucial when designing systems.

Advanced material Chemistry is a textbook exclusively designed for the needs of

undergraduate students of all disciplines of engineering and technology. The scope of the
subject is very wide and writing a book for a heterogeneous variety of students across the
country was a challenging assignment. The needs of the students are diversified and incorporate
a combination of the both traditional topics and the latest trends in the subject including
emerging areas like functional materials, smart materials and nanomaterials.

This book has been organized to meet syllabi requirements of both JNTUH and AICTE. It
serves as an introductory text to first year students, enabling them to understand basic
principles and updating them on the advancements in the ever-growing field of chemistry. The
aim of this text is to enable the student to develop capabilities in self learning and
understanding.
Keeping these objectives in mind the book has been written in very simple language. All
chapters are provided with highly descriptive and well labeled figures. A simple look at a figure
will enable the student to grasp the underlying description.
Organization of the book
The book has been organized into Five Units. This text book emphasizes on the basic concepts
an engineering applications of advanced materials It begins with topics of common interest
like electrochemistry, batteries, corrosion, photochemistry followed by functional and
advanced materials like polymers, fiber reinforced plastics, nanomaterials and smart materials.

• Unit I-Electrochemistry provides through understanding of electrochemical cells,

batteries and fuel cells.

• Unit II-Corrosion provides sufficient knowledge on fundamentals of corrosion and

development of different techniques in corrosion control.

• Unit III-Functional materials includes various polymeric materials and composites which
have increasing applications in all fields of engineering due to their low cost and ease of
manufacture.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD)

 ADVANCED MATERIAL CHEMISTRY

• Unit IV-Advanced Materials includes nano and smart materials which represents a fast
growing set of advanced materials that have excellent engineering applications.

• Unit V-Photochemistry explains the principles and applications of photochemistry in

engineering field.

We would like to extend our sincere gratitude to Dr. VSK Reddy, Principal, Malla Reddy
College of Engineering and Technology (autonomous) under whose patronage we were able to
write this book. We are also indebted to our Dr. V. Madhusudhana Reddy, Head of the
Department, Humanities & Sciences for his constant support and motivation for our academic
growth. With great pleasure we acknowledge the compatible environment shared by our
colleagues.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD)

 ADVANCED MATERIAL CHEMISTRY

MALLAREDDY COLLEGE OF ENGINEERING AND TECHNOLOGY

(UGC AUTONOMOUS)

B.TECH I YEAR – I SEM (MECH & ANE) L T/P/D C

3 -/-/- 3

ADVANCED MATERIAL CHEMISTRY

COURSE OBJECTIVES: The students will be able to

1. Apply the electrochemical principles for construction of batteries and fuel cells.
2. Analyze engineering problems related to corrosion and develop different corrosion control
techniques.
3. Identify different types of polymers, composites and their applications in various
engineering fields.
4. Gain knowledge on wide variety of advanced materials like nano and smart materials which
have excellent engineering properties.
5. Explain the principles and applications of photochemistry in engineering field.

Unit I Electrochemistry: (8 hours)

Introduction- Electrochemical cells - electrode potentials, construction and working of a
galvanic cell, EMF and its applications - potentiometric titration; Nernst equation and its
applications; electrochemical series and its applications. Batteries -classification of batteries,
primary cell - lithium cells; secondary cells - lead acid battery and lithium ion battery; Fuel
cells - H2-O2 fuel cell; applications and advantages of fuel cells.

Unit II Corrosion: (8 hours)

Introduction- Causes and effects of corrosion; Theories of corrosion- chemical (oxidation
corrosion) and electrochemical corrosion, Corrosion control methods - cathodic protection -
sacrificial anodic protection and impressed current cathodic protection; protective coatings -
galvanizing and tinning, electroplating (Cu plating) and electroless plating (Ni plating) -
advantages and applications of electroplating/electroless plating.

Unit III Functional Materials: (10 hours)

Polymers: Introduction- thermoplastic and thermosetting resins, preparation, properties and
engineering applications of Polyvinylchloride (PVC), Teflon (PTFE), Polymethyl methacrylate
(PMMA), Polycarbonate, Bakelite. Conducting polymers-classification of conducting
polymers-conduction mechanism in polyacetylene and applications of conducting polymers.
Composite materials: Introduction-Fibre reinforced plastics (FRPs) - Glass fibre reinforced,
Carbon fibre reinforced plastics and their applications.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD)

 ADVANCED MATERIAL CHEMISTRY

Unit IV Advanced Materials: (8 hours)

Nanomaterials: Introduction and classification of nanomaterials; preparation of nanomaterials
- Sol-gel and Chemical vapour deposition method; applications of nanomaterials (industrial and
medicinal). Carbon nanotubes (CNTs) - applications.

Smart materials: Introduction- types of smart materials - examples and applications of

piezoelectric materials, shape memory alloys, magnetostrictive materials and electrostrictive
materials.

Unit V Photochemistry: (8 hours)

Introduction- Laws of photochemistry- Stark-Einstein law, Beer-Lambert’s law; Photochemical
processes – Photosensitization; Photophysical processes - Fluorescence and Phosphorescence -
Jablonski diagram, applications of fluorescence and phosphorescence.

Suggested Text Books:

1. Engineering Chemsitry by P.C. Jain & M. Jain: Dhanpat Rai Publishing Company (P) Ltd,
New Delhi. 16thEdition.
2. Engineering Chemistry by Prasanta Rath, B. Rama Devi, C. H. Venkata Ramana
Reddy, Subhendu Chakroborty, Cengage Learning Publication, India Private Limited,
2018.
3. Principles and Applications of Photochemistry by Brian Wardle Manchester Metropolitan
University, Manchester, UK, A John Wiley & Sons, Ltd., Publication, 2009.
4. Engineering Analysis of Smart Material Systems by Donald J. Leo, Wiley, 2007.

Reference Books:
1. Engineering Chemistry by Shashi Chawla, Dhanpat Rai Publishing Company (P) Ltd, New
Delhi.
2. Engineering Chemistry, by S. S. Dara, S. Chand & Company Ltd, New Delhi.
3. P.W. Atkins, J.D. Paula, “Physical Chemistry”, Oxford, 8th edition (2006).
4. B.R. Puri, L.R. Sharma and M.S. Pathania, “Principles of Physical Chemistry”, S. Nagin
Chand & Company Ltd.,46th edition(2013).

COURSE OUTCOMES: The student will be able to

1. Relate the knowledge of operating principles of various types of electrochemical cells,
including fuel cells and batteries, to optimize the need for sustainable development.
2. Analyze and develop technically sound, economic and sustainable solutions for complex
engineering problems related to corrosion and its effects.
3. Identify, formulate and develop polymeric compounds used in various engineering
materials for futuristic engineering applications.
4. Apply the knowledge of nanotechnology and smart materials to find solutions for
various engineering problems.
5. Evaluate the photochemical and photophysical processes to reach substantiated
conclusions in the technological arena.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD)

ADVANCED MATERIAL CHEMISTRY

INDEX

UNIT-I: Electrochemistry 1-19

UNIT-II: Corrosion 20-32

UNIT-III: Functional Materials 33-46

UNIT-IV: Advanced Materials 47-64

UNIT-V : Photochemistry 65-76

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD)

 ADVANCED MATERIAL CHEMISTRY

UNIT I: ELECTROCHEMISTRY

Introduction:
Electrochemistry is the branch of chemistry which deals with the transformation of
electrical energy to chemical energy and vice versa. In brief it deals with the chemical
applications of electricity.

Electrical Energy Chemical Energy

Electric current is a flow of electrons generated by a battery, when the circuit is completed.
Electrolysis is one process where electrical energy causes chemical changes. It is carried out in
an apparatus called electrolytic cell. The cell contains electrolyte and electrodes. The electrode
connected to the positive pole of the current source is called anode. The electrode connected to
the negative pole of the current source is called cathode. When an electric current is passed
through the electrolytic solution, cations move towards cathode (-ve electrode and anions move
towards anode (+ve electrode)
Ex: Electrolysis of water yields H2 and O2

In other process, certain chemical reactions takes place in a vessel and produce electric energy.
The device is called electrochemical cell. Eg. Galvanic cell, batteries and fuel cells
Broadly we can classify the cells as electrolytic cells and electrochemical cells.

Electrolytic cell: A device which converts electrical energy to chemical energy

Electrochemical cell: A device which converts chemical energy to electrical energy

Types of Conductors:
Electrical Conductors: Substances which allow electric current to pass through them are
known as electrical conductors. Eg. All metals, graphite, fused salts, aqueous solutions of acids
and bases and salts.
Semi conductors: The substances which partially conduct electricity are called semi-
conductors. The conducting properties of semi-conducting properties are increased by the
addition of certain impurities called “dopping”.
Ex: ‘Si’ and Ge on addition of V group elements like P produces n-type semi-conductor.
On addition of III group element like B, Al, produces p-type of semi-conductor.

Non-conductors or Insulators: The substances which do not allow electricity are called non-
conductors. . Eg. Rubber, wood, paper, all non-metals except carbon.

Conductance: The capacity of a conductor to allow the passage of current through it called
conductance. It is a property of conductor which facilitates flow of electricity through it.
1
Conductance (C) =
𝑅

i.e. The reciprocal of resistance is called conductance. Units: Ohm.-1

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 1

 ADVANCED MATERIAL CHEMISTRY

Conductor: The substance which allows the passage of electric current through it is called
conductors. E.g.:- all metals, graphite, aqueous solution of acids and bases.

Band Theory of Electrical Conductivity

Electric conductors are two types

Metallic conductor Electrolytic conductors

Conductance due to the migration of Conductance due to the migration of ions in

electrons. a solution of fused electrolyte.
E.g.: metals, graphite. E.g.: Acids and bases
Passage of current due to electron flow. No Passage of current due to movement of
chemical reaction takes place. ions. Some chemical reaction takes place.
Free electrons are responsible for electrical Free ions are responsible for electrical
conduction. conduction.
Mass is not transferred Mass is transferred.
With increase of temp resistance increases With increase of temperature resistance
and conductance decreases decreases and conductance increases.

Electrolytes are classified into two types:

Strong electrolytes: The electrolytes which completely dissociates in solution at all
concentrations. Their conductance is very high. Eg. NaCl, HCl, NaOH.

Weak Electrolytes: The electrolyte which partially dissociates at moderate concentration.

Their conductance is low as they dissociate only to a small extent even at very high dilutions.
Eg: CH3COOH, NH4OH, sparingly soluble salts like AgCl, AgBr, AgI, BaSO4, PbSO4 etc

CONDUCTANCE:
Ohm’s Law: Ohm’s law states that the current (I) flowing through a conductor is directly
proportional to potential difference (E) applied across the conductor and is inversely
proportional to the resistance of conductor.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 2

 ADVANCED MATERIAL CHEMISTRY

Thus,
EαI

Where I is the current in amperes, and E is potential difference applied across the conductor in
volts.

Thus E = IR

or
E
R=
I

Where R is the proportionality constant and is known as the resistance of conductor in ohms.
Thus, the resistance of a conductor is directly proportional to the potential difference applied
across the conductor and inversely proportional to the current carried by the conductor.

SPECIFIC RESISTANCE: The resistance of a uniform conductor is directly

proportional to its length (l) and inversely proportional to the area of the cross- section (a).
Thus
R α l/a

R = ρ l/a

The proportionality constant (ρ) is called as the specific resistance of an electrolytic solution
of 1cm in length and 1cm2 area of cross section. i.e. resistance of 1cm3 of the electrolytic
solution.
UNITS: specific resistance units: Ohm cm

Cell constant:
It is a constant, characteristic of the cell in which the electrolyte is taken and its value depends
on the distance between the electrodes and area of cross-section of the electrodes.
Distance between the electrodes
Cell constant =
Area of cross − section of each electrode

𝒍
𝒙=
𝒂
1 l
And specific conductance, K= ×
R a

Cell constant
∴ Specific conductance =
R

𝐾
or 𝑥 = 𝐾 × 𝑅; or 𝑥 = ( ∵ 𝑐 = 1/𝑅)
𝐶

If area of cross-section is in cm2 and distance between the electrodes is in cm, the unit of cell
constant is cm-1.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 3

 ADVANCED MATERIAL CHEMISTRY

ELECTRODE POTENTIAL:
• When a metal rod is dipped in its salt solution (electrolyte), the metal atom tends either to
lose electrons (oxidation) or to accept electrons (reduction).
• The process of oxidation or reduction depends on the nature of metal.
• In this process, there develops a potential between the metal atom and its corresponding
ion called the electrode potential.
• It is a measure of tendency of a metallic electrode to lose or gain electrons when it is in
contact with its own ions in solution.
• Reduction potential: The tendency of an electrode to gain electrons and to get reduced is
called reduction potential, its value is +x volts.
• Oxidation potential: Similarly the tendency of an electrode to lose electrons and to get
oxidized is called oxidation potential, its value is –x volts
• The potential develop between electrode and electrolyte by the formation of charges and
these charges are formed Helmholtz electrical double layer, through which potential
develop between electrode and electrolyte.

+ _
+ + + + + +
_ + _
_ + _
_ + _
_ + _
_ + _
_ + _
_ + _
Anode Cathode
Helmholtz Electrical Double LayeR

Single electrode potential:

Each electrochemical cell is made up of two electrodes, at one electrode electrons are
evolved and at other electrode electrodes used up. Each electrode which is dipped in its salt
solution is called Half Cell. The potential of half-cell i.e. the potential difference between the
metal and its salt solution in which it is dipped is called single electrode potential. It cannot be
measured directly.

The total cell E.M.F is equal to the sum of the single electrode potentials. Each electrode is
affixed with a symbol corresponding to the reaction that takes place near the electrode.

E cell = E (anode) + E (Cathode)

The half-cell reactions are as follows; the half-cell reaction which corresponds oxidation is

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 4

 ADVANCED MATERIAL CHEMISTRY

Zn → Zn2+ + 2e-

The electrode is called oxidation electrode and potential of the electrode is oxidation potential
or the potential of left hand electrode which is represented as EOX or EL . The cell reaction
of the electrode where reduction takes place is given below

Cu2+ + 2e - → Cu

The electrode is called reduction electrode or right hand electrode and the potential of this
electrode is reduction potential and represented as E (Red) or E (R).

The total cell reaction is Zn+ Cu2+→ Zn2++ Cu.

E (cell) = E (OX) + E (Red)

E.M.F of the cell is equal to the sum of the oxidation potential and reduction potential, also
expressed as the reduction potential of the right hand electrode minus reduction potential of the
left hand electrode.

GALVANIC CELL: A galvanic cell is a system in which a spontaneous oxidation and

reduction reaction occurs and generates electrical energy. Eg. Daniel cell

Construction of Galvanic Cell

A galvanic cell is made up of two half cells. One is oxidation or anodic half- cell and
other one is reduction or cathodic half cell. Daniel cell is an example of galvanic cell having
zinc and copper electrodes. The first half cell consists of zinc electrode dipped in ZnSO4
solution and the second half is made of copper electrode dipped in copper sulphate solution.
Both half cells are connected externally by metallic conductor and internally by a bent glass
tube having saturated solution of a strong electrolyte (KCl) called salt bridge. It acts as a bridge
between the two half cells.

Working of Galvanic cell:

When two half cells are connected externally by a wire through a voltmeter, spontaneous redox
reaction takes place at the electrode.

At anode: Oxidation takes place with the liberation of two electrons.

Zn Zn+2 + 2e- (oxidation or de-electronation)

At cathode: Reduction occurs and cuprous ion is reduced to metallic copper.

Cu+2 + 2e- Cu (reduction or electronation)

The overall reaction is Zn + Cu+2 Zn+2 + Cu

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 5

 ADVANCED MATERIAL CHEMISTRY

As the connection is complete, the flow of electrons will be externally from

anode to cathode and internally from cathode to anode through the salt bridge. The flow of
current is due to the difference in electrode potentials of both the electrodes. The potential
difference in the cell is called the EMF and is measured in volts. It can be measured by the
potentiometer. The flow of current becomes slow after using the electrodes for a long time
because of the polarization of the electrodes.
At this stage, the salt bridge comes to the aid and restores the electrical neutrality of the
solution in the two half cells. When the concentration of Zn2+ ions around the anode increases,
sufficient number of Cl- ions migrate from the salt bridge to the anode half cell. Similarly,
sufficient number of K+ ions migrate from the salt bridge to cathode half cell for neutralizing
excess negative charge due to the additional SO42- ions in the cathodic half cell. Thus it
maintans the electrical neutrality of the two solutions in the half cells.

Representation of a galvanic cell:

1. The electrode showing oxidation reaction is anode and the other electrode where reduction
occurs is cathode.
2. As per IUPAC convention, the anode is always represented on the left and cathode always
represented on the right side of the cell.
Anode Half-Cell || Cathode Half-Cell

Electrode | Anode Soln || Cathode Soln | Electrode

Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)

3. The electrode on left (i.e, anode) is written by writing the metal first and then the electrolyte.
The two are separated by a vertical line or a semicolon. The electrolyte may be represented by
the formula of the whole compound or by ionic species and concentration may also be
mentioned in bracket.

Examples of representing anode half-cell as:

Eg: Zn/Zn2+ or Zn;Zn2+ or Zn/ZnSO4(1M).

4. The cathode of the cell (at which reduction takes place) is written on the right hand side. In
this case, the electrolyte is represented first and then the metal. The two are separated by a
vertical line or a semicolon.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 6

 ADVANCED MATERIAL CHEMISTRY

Examples of representing cathode half-cell as:

Cu2+/Cu or Cu2+; Cu or CuSO4(1M)/Cu.

5. A salt bridge is indicated by two vertical lines, separating the two half-cells.

Zn;Zn2+(1M) // Cu2+(1M); Cu.

Electromotive Force or Cell Potential (EMF):

The flow of electricity from one electrode to another electrode in a galvanic cell
indicates that the two electrodes have different potentials. The difference of potentials between
the electrodes of a cell which causes flow of current from an electrode at higher potential to
other electrode at lower potential is known as electromotive force or cell potential.

The EMF of the cell depends on (a) temperature (b) nature of reactants and (c) concentration
of solutions in two half cells.
Mathematically:

EMF or Ecell = Ecathode− Eanode or

E(cell) = E(right) – E(left)

Where
E(cell) = e.m.f of cell
E(right) = reduction potential of right hand side electrode (cathode)
E(left) = reduction potential of left hand side electrode (anode)

Ecell = Eox (anode) + ERed (cathode)

Ecell = ER - EL (both are reduction potentials)
Ecell = EL (anode) - E R (cathode) (both are oxidation potentials)

Salt bridge: Salt bridge is a U shaped glass tube containing concentrated solution of an inert
electrolyte such as KCl, KNO3 and K2SO4 or paste of inert electrolyte (whose ions do not take
part in redox reaction and do not react with the electrolyte) in agar–agar medium or gelatin.

Functions of salt bridge:

1. Salt bridge helps to complete the circuit by allowing the ions to flow from one solution to
the other without mixing the two solutions.
2. It helps to maintain electrical neutrality of the solution in the half cells.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 7

 ADVANCED MATERIAL CHEMISTRY

Applications of EMF
Potentiometric Titration:
A potentiometric titration is one in which the end point is detected by measuring changes in
the potential of a suitable electrode (after coupling it with a standard reference electrode) during
the course of reaction. No indicator is used in this titration. The electrode whose potential
varies during the reaction and which depends upon the concentration of ionic species is called
the indicator electrode.
The potentiometric titrations are subdivided in terms of the type of chemical reaction involved
in the titration, e. g. acid-base titration, redox titration, precipitation titration
and complexometric titration.

Acid-Base titration: The acid solution whose strength has to be determined is taken in a beaker
and the hydrogen electrode and calomel electrode were dipped in the solution. The electrodes
were connected to the potentiometer and the e.m.f. is measured.
Reference Electrode: Saturated Calomel Electrode (SRP = 0.242 V) [Anode]
Indicator Electrode: Quinhydrone Electrode [Cathode].
Cell Notation:
(-) Pt / Hg, Hg2Cl2 / KCl (sat) // H+ Test Sol. / Q, QH2 / Pt (+) Cell Reactions:
Anode: 2Hg + 2Cl-→Hg2Cl2 + 2e-
Cathode: Q + 2H+ + 2e-→ QH2
Ecell= Ecathode- Eanode= [0.0990 – 0.0591 pH] – 0.242 i.e. E Cell is a function of pH.
During titration, as base is added to the acid, the H+ ion concentration in the half cell containing
Quinhydrone will decrease. Correspondingly, there will be a decrease in the EQE and E Cell
values also. ECell values are noted, graph is plotted, where equivalence point is located and
concentration of test solution is calculated.

The steepest portion of the curve indicates the equivalent point of the titration. Instead ΔE/ΔV
is plotted against the volume of the base.
Electrode potential

E/ V
End Point

End Point

Volume of titrant
Volume of HCl solution

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 8

 ADVANCED MATERIAL CHEMISTRY

Nernst equation:
Derivation of Nernst equation: Nernst found that the single electrode potential varies
with the change in concentration of ions and temperature and hence the EMF of the cell also
varies. He derived a mathematical relationship between the standard electrode potential,
temperature and the concentration of ions. This relationship is known as the Nernst equation.

Consider the redox reaction: M n+ + ne- M

In the above reversible reaction the free energy change (G) and its equilibrium constant
(K) are related by the following equation which is popularly known as Van’t Hoff reaction
isotherm.
product
∆ G = RT ln K + RTln
reactant

product
∆ G = ∆G0 + RTln
reactant

When ∆ G0 is the standard free energy change

The free energy change is equivalent to the electrical energy –nFE

Where n = valency

F = Faraday (96500 coloumbs)

E = Electrode potential

R = 8.314 Joules K-1 mole-1(Gas constant)

T = Temperature (K)

-nFE = - nFE0 + RTln([M])/([Mn+]) (Concentration of M is unity)

-nFE = - nFE0 – RTln [Mn+]

= - nFE0 – RT2.303 log10 [Mn+]

Dividing the equation by – nF

2.303𝑅𝑇
E = E0+ + log10 [Mn+]
𝑛𝐹

Put the values of R, T and F then

2.303𝑅𝑇 0.0591
=
𝑛𝐹 𝑛

0.0591
E = E0 + log10 [Mn+]
𝑛

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 9

 ADVANCED MATERIAL CHEMISTRY

APPLICATIONS OF NERNST EQUATION:

1. It can be used to study the effect of electrolyte concentration on electrode potential.
E = Eo – RT/nF ln[1/Mn+]
2. It can also be used for the calculation of the potential of a cell under non-standard
conditions.
For example,
Cu(s)/Cu2+(aq)(0.50M)//H+(0.01)/H2(0.95atm)
0.0591
Ecell = Eocell − log(Cu2+)PH2/[H+]2
2
3. Determination of unknown concentration of one of the ionic species in a cell is possible
with the help of Nernst equation, provided Ecell and concentration of other ionic species are
known.
4. The pH of a solution can be calculated from the measurement of EMF and Nernst equation.
5. Nernst equation can also used for finding the valence of an ion or the number of electrons
involved in the electrode reaction.

ELECTROCHEMICAL SERIES:
A series in which various metals and elements have been arranged in increasing order
of their standard reduction potential or decreasing order of their standard oxidation potential as
compared to that of standard hydrogen electrode is called electrochemical series. These
standard electrode potentials are measured at 250C

In this series, iron lies above hydrogen and copper lies below it. Hence, if an iron rod is dipped
in CuSO4 solution a layer of copper metal will get deposited on the surface of the iron rod.
Fe → Fe++ + 2e-
Cu++ + 2e-→ Cu
Fe + Cu++→ Fe++ + Cu.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 10

 ADVANCED MATERIAL CHEMISTRY

The reverse of this reaction is not possible, i.e. a copper rod dipped in FeSO 4 solution will not
show redox reaction.

Applications of Electrochemical Series:

1) Comparison of oxidizing and reducing power: It gives information about the relative
ease with which oxidation and reduction of metal occurs. Based on the electrochemical
series the element with higher reduction potential have a greater tendency to get reduced
and act as good oxidizing agents. Whereas the elements with lower reduction potential
have a tendency to get oxidized and act as good reducing agents.
Ex: F2 can be reduced easily than Li+ ions. So it is a good oxidizing agent.

2) Relative activities of metal: Provides information about the replacement tendencies of

metals. The greater the O.P of a metal, more easily it can lose electrons and greater is
its reactivity, i.e. the metal with higher O.P can displace the metal with lower O.P. in
their salt solution.
Ex: Mg > Zn > Fe > Cu > Ag. Zn has lower reduction potential than Cu. Hence Zn can displace
copper from CuSO4 solution.

3) Any metal above hydrogen will displace hydrogen from dil. acid solution. For example,
Na reacts with water to liberate hydrogen because
E0 (Na+/Na) = -2.714 V is less than E0(H+ / H2 = 0).

2Na + H2SO4 → Na2SO4 +H2

2K + H2SO4 → K2SO4 + H2

Ca + H2SO4 → CaSO4 +H2

4) Provides information about the relative corrosion tendencies of metals. Metals above
hydrogen undergo corrosion easily as they have higher oxidation potentials.

5) Predicts spontaneity of redox reaction. Spontaneity of a redox reaction can be predicted

from EMF of the cell reaction. If EMF of a cell is –ve, the reaction is non spontaneous
and if EMF is +ve then the reaction is spontaneous.

6) When a cell is constructed anode should be a metal higher in the series and cathode
should be a metal lower in the series. Eg. When a cell is constructed using Zn and Cu,
Zn higher in the series will be the anode and Cu will be the cathode.
7) This series is also helpful in direct calculation of the EMF of cell formed between
electrodes.
E0= -0.76V (reduction potential)
E0= 0.34V (reduction potential)
E0 = ER-EL
= 0.34 - (0.76) = 1.10V

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 11

 ADVANCED MATERIAL CHEMISTRY

BATTERIES
Battery is an electrochemical cell or often several electrochemical cells connected in series that
can be used as a source of direct electric current at constant voltages. A device which converts
chemical energy to electrical energy is called battery cells, connected together electrically in
series. Batteries are commercial electrochemical cells.

ADVANTAGES OF BATTERIES:
(1) Batteries act as a portable source of electrochemical energy.
(2) The portability of electronic equipment in the form of handsets has been made possible by
batteries.
(3) A variety of electronic gadgets have been made more useful and popular with the
introduction of rechargeable storage batteries having reliability, better shelf life and
tolerance to service.
(4) For all commercial applications, batteries are constructed for their service. For example
batteries for automotives and aircrafts, stand by batteries etc.

Requirements of Battery:
A useful battery should fulfill the following requirements

1. It should be light and compact for easy transport.

2. It should have long life both when it is being used and when it is not used.

3. The voltage of the battery should not vary appreciably during its use.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 12

 ADVANCED MATERIAL CHEMISTRY

Differences between Primary, Secondary and Fuel cells:

Primary cell Secondary cells Fuel Cell
It acts as a simple It acts as a galvanic cell while It acts as a simple galvanic
galvanic cell. discharging and electrolytic cell cell.
while charging.
Cell reaction is not Cell reaction can be reversed. Cell reaction is not
reversible. reversible
Cannot be recharged. Can be recharged Do not store energy
Can be used as long as Can be used again and again by Energy can be withdrawn
the materials are active recharging the cell indefinitely as long as
in their composition. outside supply of fuel is
maintained
E.g: E.g: E.g:
Leclanche or dry cell. 1. Lead storage cell 2. Nicol or H2-O2, CH3OH-O2
Zn/NH4Cl (20%), ZnCl2/ Nickel cadmium battery emf
MnO2/C. emf =1.5V. =1.4 Applications:
Applications: Applications: Electronic Space vehicles due to their
Radios, torches, calculators, electronic flash light weight and the bi
transistors, hearing aids. units & cordless electronic product H2O produced is a
shavers etc. valuable source of fresh
water for astronauts.

PRIMARY CELLS:
Lithium cells:
Lithium cells are primary cells in which lithium acts as anode and the cathode may
differ. Lithium metal is used as anode because of its light weight, high standard oxidation
potential (≥3V) and good conductivity. As the reactivity of lithium in aqueous solution is more,
lithium cells use non-aqueous solvents as electrolyte.
Lithium cells are classified into two categories:

(a) Lithium cells with solid cathode:

The electrolyte in this system is a solid electrolyte. The most widely used cell is lithium
– manganese dioxide cell (3V). MnO2 should be heated to over 3000C to remove water before
keeping it in the cathode, thereby increasing the efficiency of the cell.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 13

 ADVANCED MATERIAL CHEMISTRY

Anode: Lithium Metal,

Cathode: MnO2 as an active material.

Electrolyte: LiBF4 salt in a solution of propylene carbonate and dimethoxy ethane.

Reactions:

At anode: Li⟶ Li + + e-

At cathode: e- + MnO2 ⟶ MnO2-

Net reaction: Li + MnO2⟶ LiMnO2

Applications:
1. The coin type cells are used in watches and calculators.
2. Cylindrical cells are used in fully automatic cameras.

(b) Lithium cells with liquid cathode: Lithium–sulphur dioxide cell is an example of liquid
cathode. The co-solvents used are acrylonitrile or propylene carbonate (or) mixture of the
two with SO2 in 50% by volume.

Cell reaction: 2Li + 2SO2⟶ Li2S2O4.

Lithium thionyl chloride cell is another example of liquid cathode. It consists of high surface
area carbon cathode, a non – woven glass separator. Thionyl chloride acts as an electrolyte and
as a cathode.

Cell reaction:

At anode: Li ⟶ Li+ + e-

At cathode: 4Li+ 4e-+ 2SOCl2⟶ 4LiCl + SO2 + S

Net reaction: 4Li + 2SOCl2⟶ 4LiCl + SO2 + S

SOCl2 (cathode)

Li (anode)

Electrolyte

In this cell no co-solvent is required as SOCl2 is a liquid with moderate vapor pressure. The
discharging voltage is 3.3 -3.5V.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 14

 ADVANCED MATERIAL CHEMISTRY

USES:
1. They are used for military and space applications.
2. In medicinal devices such as neuro-stimulators, drugdelivery system, lithium batteries are
widely used.
3. They are also used in electric circuit boards for supplying fixed voltage for memory
protection and standby functions.

Advantages:
1. The energy output of a lithium cell is 2-4 times better than that of conventional zinc anode
batteries.
2. Lithium batteries can work over temperature range of 40-700C.
3. They have higher voltages of about 4V when compared to other primary cells with 1.5 V
only.

Secondary cell: E.g.: Lead – Acid cell:

If a number of cells are connected in series, the arrangement is called a battery. The lead storage
battery is one of the most common batteries that are used in the automobiles. A 12 V lead
storage battery is generally used, which consists of six cells, each providing 2V. Each cell
consists of a lead anode and a grid of lead packed with lead oxide as the cathode. These
electrodes are arranged alternately, separated by a thin wooden piece and suspended in dil.
H2SO4 (38%), which acts as an electrolyte. Hence, it is called lead acid battery.

Anode: Pb

Cathode: PbO2

Electrolyte: H2SO4 (20-22%)

EMF = 2 V

Lead storage cells: To increase the current output of each cell, the cathode and the anode
plates are joined together, keeping them in alternate positions. The cells are connected parallel
to each other.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 15

 ADVANCED MATERIAL CHEMISTRY

The cell is represented as

Pb/PbSO4(s), H2SO4/PbSO4(s),Pb

In the process of discharging, i.e., when the battery produces current, the reactions at the
electrodes are as follows:

Discharging reactions:
At anode: Pb → Pb2+ + 2e-
Pb2+ + SO42- → PbSO4

At cathode: PbO2(s) + 4H+ + 2e-→ Pb2++2H2O

Pb2+ + SO42- → PbSO4

Therefore, the overall reaction is:

Pb(s) +PbO2+4H2SO4(aq) → 2PbSO4(s) + 2H2O + Energy

During discharging the battery, H2SO4 is consumed, and as a result, the density of H2SO4 falls.
When it falls below 1.20 g/cm3, the battery needs recharging. In discharging, the cell acts as a
voltaic cell where oxidation of lead occurs.

Recharging:
During recharging, the cell is operated like an electrolytic cell, i.e. electrical energy is
supplied to it from an external source. The electrode reactions are the reverse of those that
occur during discharge.

PbSO4 + 2e- → Pb + SO42- (Reaction at cathode)

PbSO4 + 2H2O → PbO2 + 2H2SO4 + 2e- (Reaction at anode)
-------------------------------------------------------------------------
2PbSO4 + 2H2O + Energy → Pb + PbO2 + 2H2SO4

During this process, lead is deposited at the cathode, PbO2 is formed at the anode and
H2SO4 is regenerated in the cell.

Applications and Advantages:

Lead-acid batteries are used for supplying current to railways, mines, laboratories,
hospitals, automobiles, power stations, telephone exchange, gas engine ignition, UPS. Other
advantages are its recharge ability, portability, and relatively constant potential and low cost.

Disadvantages: Use of conc. H2SO4 is dangerous. Use of lead battery is fragile.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 16

 ADVANCED MATERIAL CHEMISTRY

Lithium-ion batteries (or) Lithium-ion cells:

Lithium-ion battery is a secondary battery. As in lithium cell, it does not contain metallic
lithium as anode. As the name suggests, the movement of lithium ions are charging '&
discharging. Lithium-ion cell has the following three components.

1. A positive electrode (Layers of lithium-metal oxide) (cathode).

2. A negative electrode (Layers of porous carbon) (anode).
3. An electrolyte (Polymer gel) (separator)

Construction:
The positive electrode is typically made from a layers of chemical compound called lithium-
cobalt oxide (LiCoO2). The negative electrode is made from layers of porous carbon (C)
(graphite).Both the electrodes are dipped in a polymer gel electrolyte (organic solvent) and
separated by a separator, which is a perforated plastic and allows the Li+ ions to pass through.

Working
Charging Reaction:
During charging, Li+ ions flow from the positive electrode (LiCoO2) to the negative electrode
(graphite) through the electrolyte. Electrons also flow from the positive electrode to the
negative electrode. The electrons and Li+ ions combine at the negative electrode and deposit
there as Li.

LiCoO2 + C→ Li1-xCoO2 + CLix

Charging Mechanism Discharging Mechanism

charger
load
electrons electrons

seperator seperator
Anode Cathode Anode Cathode

C LiCoO2
graphite
Li+ Li+
Li+ Li+ Li+ Li+ Li+ Li+
Li + C Li + LiCoO2
graphite +
Li + +
Li+ Li+ Li+ Li Li
Li+ Li+

Li+ Li+ Li+ Li+

Li+ Li+

Electrolyte (gel polymer electrolyte) Electrolyte (gel polymer electrolyte)

Discharging Reaction:
During discharging, the Li+ ions flow back through the electrolyte form negative electrode to
the positive electrode. Electrons flow from the negative electrode to the positive
electrode. The Li+ ions and electrons combine at the positive electrode and deposit there as Li.
Li1-xCoO2 + CLix → LiCoO2 + C

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 17

 ADVANCED MATERIAL CHEMISTRY

Advantages (or) Characteristics:

1. Lithium-ion batteries are high voltage and light weight batteries.
2. It is smaller in size.
3. It produces three time the voltage of Ni-Cd batteries.
4. It has none of the memory effect seen in Ni-Cd batteries.
Uses:
It is used in cell phone, note PC, portable LCD TV, semiconductor driven audio, etc.

FUEL CELLS

Definition: A fuel cell is an electrochemical which converts chemical energy contained in

readily available fuel oxidant system into electrical energy.

Principle: The basic principle of fuel cell is as same as that of an electrochemical cell. The
fuel cell operates like a galvanic cell. The only difference is that the fuel and the oxidant are
stored outside the cell. Fuel and oxidant are supplied continuously and separately to the
electrodes at which they undergo redox reaction. Fuel cells are capable of supplying current as
long as reactants are replenished.

Fuel + Oxidant → Oxidation products + Electric Energy

Examples: 1. H2-O2 fuel cell

2. CH3OH-O2 fuel cell

Hydrogen Oxygen Fuel Cell:

This cell is a common type of fuel cell. Similar to a galvanic cell, fuel cell also have
two half cells. Both half cells have porous graphite electrode with a catalyst (platinum, silver
or a metal oxide). The electrodes are placed in the aqueous solution of NaOH or KOH which
acts as an electrolyte. Hydrogen and oxygen are supplied at anode and cathode respectively at
about 50 atmospheric pressure, the gases diffuse at respective electrodes. The two half-cell
reactions are as follows.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 18

 ADVANCED MATERIAL CHEMISTRY

At anode: 2H2 (g) + 4OH- (aq) → 4H2O (l) + 4e-

At cathode: O2 (g) + 2H2O (l) + 4e- → 4OH- (aq)

The net reaction: 2H2 (g) + O2 (g) → 2H2O (l)

The EMF of this cell is measured to be 1.23V. A number of such fuel cell are stacked together
in series to make a battery.

Advantages:
1. The energy conversion is very high (75-82%).
2. Fuel cell minimizes expensive transmission lines and transmission losses.
3. It has high reliability in electricity generation.
4. The byproducts are environmentally acceptable.
5. Maintenance cost is low for these fuels.
6. They save fossil fuels.
7. Noise and thermal pollution are very low.
8. They have low maintenance cost.
9. They have quick start system.

Disadvantages:
1. The major disadvantage of the fuel cell is the high cost and the problems of durability and
storage of large amount of hydrogen.
2. The accurate life time is also not known.

APPLICATIONS:
1. The most important application of a fuel cell is its use in space vehicles, submarine or
military vehicles.
2. The product H2O is valuable source of fresh water by the astronauts.
3. It is hoped that fuel cell technology will bring a revolution in the area of energy production.
4. Fuel cell batteries for automotive will be a great boom for the future.

Limitations:
1. The life time of fuel cells is not accurately known
2. It cannot store electricity
3. Electrodes are expensive ad short lived.
4. Storage and handling of H2 gas is dangerous because it is inflammable.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 19

 ADVANCED MATERIAL CHEMISTRY

UNIT II: CORROSION

Introduction:
Metals and alloys are used as fabrication or construction materials in engineering. If the metals
or alloy structures are not properly maintained, they deteriorate slowly by the action of
atmospheric gases, moisture and other chemicals. This phenomenon of destruction of metals
and alloys is known as corrosion.
The surface of almost all the metals begin to decay more or less rapidly when exposed to
atmospheric gases, water or other reactive liquid medium.

Corrosion
➢ The process of decay of metal by environmental attack is known as corrosion.
➢ Metals undergo corrosion and convert to their oxides, hydroxides, carbonates, sulphides,
etc.
➢ Examples:-
➢ i) Rusting of iron – when iron is exposed to the atmospheric conditions, a layer of reddish
scale and powder of Fe3O4 is formed.

➢ ii) Formation of green film of basic carbonate- [CuCO3 + Cu(OH)2] on the surface of copper
when exposed to moist air containing CO2.
➢ The corrosion of metals is measured in the units of milli/inches/year or mm/year.

Corrosion-Oxidation
Metal Metallic Compound + Energy
Metallurgy-Reduction

Corrosion is an oxidation process and it is reverse of metal extraction.

Causes of corrosion:
1. The metals exist in nature in the form of their minerals or ores in the stable combined forms
as oxides, chlorides, silicates, carbonates and sulphides.
2. During the extraction of metals, these ores are reduced to metallic state by supplying
considerable amount of energy.
3. Hence the isolated pure metals are in excited states than their corresponding ores.
4. So metals have natural tendency to go back to their combined state (minerals/ores).
5. When metal is exposed to atmospheric gases, moisture, liquids etc, the metal surface reacts
and forms more thermodynamically stable compounds.

Effects of corrosion:
1. Wastage of metal in the form of its compounds.
2. The valuable metallic properties like conductivity, malleability, ductility etc. are lost due
to corrosion.
3. Life span and efficiency of metallic parts of machinery and fabrications is reduced

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 20

 ADVANCED MATERIAL CHEMISTRY

Theories of corrosion:
1. Dry corrosion
2. Wet corrosion

Dry corrosion or Chemical corrosion: The direct chemical action of environment on the
surface of metal in absence of moisture is known as dry corrosion.
This type of corrosion occurs mainly through the direct chemical action of atmospheric
gases like O2, halogens, H2S, SO2, N2 or anhydrous inorganic liquid with the metal surface.
Example: (i) Silver materials undergo chemical corrosion by Atmospheric H S gas.2

(ii) Iron metal undergo chemical corrosion by HCl gas.

There are three types of chemical Corrosion:

1. Oxidation corrosion
2. Corrosion due to other gases
3. Liquid metal corrosion

Oxidation Corrosion:
Direct action of oxygen at low or high temperatures on surface of metals in absence of moisture
is known as oxidation corrosion. Alkali metals and Alkaline earth metals are rapidly oxidized
at lower temperatures. At high temperature all metals are oxidized (except Ag, Au, Pt).
Mechanism:
1) Oxidation takes place at the surface of the metal forming metal ions M 2+
2) Oxygen is converted to oxide ion (O2-) due to the transfer of electrons from metal.
3) The overall reaction is of oxide ion reacts with the metal ions to form metal oxide film.

Reactions in oxidation corrosion

Mechanism: Initially the surface of metal undergoes oxidation and the resulting metal oxide
scale forms a barrier which restricts further oxidation. The extent of corrosion depends upon
the nature of metal oxide.

Nature of the oxide formed: It plays an important role in further oxidation corrosion process.

Metal + oxygen metal oxide (corrosion product)

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 21

 ADVANCED MATERIAL CHEMISTRY

When the oxide film formed is:

(a) Stable metal oxide layer

A stable layer is fine grained in structure and can get adhered tightly to the parent metal surface.
Such a layer will be impervious in nature and hence behaves as protective coating, thereby shielding
the metal surface. Consequently further oxidation corrosion is prevented.
E.g.: Al, Sn. Pb, Cu, etc. form stable oxide layers on surface thus preventing further oxidation.

Example:

Unstable metal oxide layer

The oxide layer formed decomposes back into metal and oxygen. Consequently oxidation
corrosion is not possible in such cases.
Eg: Ag, Au and Pt do not undergo oxidation corrosion.
Metal oxide Metal + oxygen

(c) Volatile Metal oxide layer

The oxide layer formed is volatile in nature and evaporates as soon as it is formed. There
by leaving the under lying metal surface exposed for further attack. This causes rapid continuous
corrosion, leading to excessive corrosion eg: Mo- molybdenum forms volatile MoO3 layer.

(d) Porous Metal oxide layer

If the metal oxide layer is porous, the oxide layer formed has pores or cracks. In this
case the atmospheric oxygen penetrates through the pores or cracks and corrode the underlying

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 22

 ADVANCED MATERIAL CHEMISTRY

metal surface. This cause continuous corrosion till conversion of metal into its oxide is
completed. Eg: Alkali and alkaline earth metals (Li, Na, K, Mg, Fe etc.)

Example:

Pilling Bedworth rule:

• To express the extent of protection given by the corrosion layer to the underlying metal
Pilling Bedworth rule was postulated.
• It is expressed in terms of specific volume ratio.

𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐦𝐞𝐭𝐚𝐥 𝐨𝐱𝐢𝐝𝐞 𝐥𝐚𝐲𝐞𝐫

• Specific Volume ratio =
𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐩𝐚𝐫𝐞𝐧𝐭 𝐦𝐞𝐭𝐚𝐥

• Smaller the specific volume ratio, greater is the oxidation corrosion

• Eg. The specific volume ratio of W, Cr, and Ni are 3.6, 2.0 and 1.6 respectively.
Consequently the rate of corrosion is least in Tungsten(W)

➢ If the volume of the corrosion film formed is more than the underlying metal, it is strongly
adherent, non-porous and does not allow the penetration of corrosive gases. No further
corrosion.
➢ If the volume of the corrosion film formed is less than the underlying metal, it forms
pores/cracks and allow the penetration of corrosive gases leading to corrosion of the
underlying metal.

Wet Corrosion or Electrochemical Corrosion

• The direct chemical action of environment on the surface of metal in presence of
conducting liquid with the formation of electrochemical cells.
• It a common type of corrosion which occurs usually in aqueous corrosive environment
• Occurs when metal comes in contact with a conducting liquid.
• Formation of galvanic cell on the surface of metal generating anodic and cathodic areas

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 23

 ADVANCED MATERIAL CHEMISTRY

• At anode oxidation takes place liberating electrons.

• Electrons at anode are transported to cathodic area where H+ or O2 and H2O consumes
the electrons generating non-metallic ions like OH- or O2-
• Metallic (M+) and non metallic (OH- or O2-) diffuse towards each other and results in
the formation of corrosion product in between the anodic and cathodic area.

Mechanism: Electrochemical corrosion involves flow of electrons between anode and cathode.
The anodic reaction involves dissolution of metal liberating free electrons.
n+
M M + ne-
The cathodic reaction consumes electrons with either evolution of hydrogen or absorption of
oxygen which depends on the nature of corrosive environment.

Wet corrosion takes place in two ways.

1. Evolution of Hydrogen
2. Absorption of Oxygen

Evolution of Hydrogen:
This type of corrosion occurs in acidic medium.
Eg: Rusting of iron metal in acidic environment takes place in the following way:

At Anode dissolution of iron to ferrous ion takes place with the liberation of electrons

2+ -
Anode: Fe Fe + 2e (Oxidation)

The electrons released at anode flow through the metal from anode to cathode, where as H+
ions of acidic solution take up these electrons and eliminated as hydrogen gas.

+ -
Cathode: 2H + 2e H2 (Reduction)

+ 2+
The overall reaction is: Fe + 2H Fe + H2

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 24

 ADVANCED MATERIAL CHEMISTRY

This type of corrosion causes “displacement of hydrogen ions from the acidic solution by metal
ions.
In hydrogen evolution type corrosion, the anodic areas are large and cathodic areas are small.

Absorption of Oxygen:
• This type of corrosion takes place in basic or neutral medium in presence of oxygen.
• For example, rusting of iron in neutral or basic aqueous solution of electrolyte in presence
of atmospheric oxygen.
• Usually the surface of iron is coated with a thin film of iron oxide.
• If the film develops cracks, anodic areas are created on the surface and the rest of the metal
surface acts as cathodes.
• It shows that anodic areas are small and the cathodic areas are large.
2+ -
Anode: Fe Fe + 2e (Oxidation)
The released electrons flow from anode to cathode through iron metal.

At cathode: ½ O2 + H2O 2OH-+ 2e- (Reduction)

Overall reaction: Fe2 + 2OH-

+
Fe(OH)2

If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide and then
to hydrated ferric oxide which is known as rust.

4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3

4 Fe(OH ) 2 + O2 + 2 H 2O ⎯⎯⎯⎯
oxidation
→ 4 Fe(OH )3 ⎯⎯⎯⎯
oxidation
→ Fe2O3 .3H 2O
Rust (hydrated ferric oxide)

The product called rust corresponds to Fe2O3.3H2O.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 25

 ADVANCED MATERIAL CHEMISTRY

Corrosion control methods:

1. Proper designing
2. Using Pure metals
3. Using metal alloys
4. Use of inhibitors
5. Modifying Environment
6. Cathodic protection
7. Application of protective coatings

Cathodic Protection:
The method of protecting the base metal by forcibly making it to behave like a cathode there
by corrosion does not occur is called as cathodic protection.
There are two types of cathodic protection
(a) Sacrificial anodic protection
(b) Impressed current cathodic protection

Sacrificial anodic protection

• In this protection method, the metallic structure to be protected (base metal) is connected
by a conducting wire to a more anodic metal so that all the corrosion is concentrated at this
more anodic metal.
• The more anodic metal itself gets corroded slowly, while the parent structure (cathodic) is
protected. The more active metal so employed is called sacrificial anode. The corroded
sacrificial anode is replaced by a fresh one, when consumed completely.
• The artificially made anode thus gets corroded gradually protecting the original metallic
structure. Hence the process is known as sacrificial anodic protection.
• Metals commonly employed as sacrificial anode are Mg, Zn, Al and their alloys which
possess low reduction potential and occupies higher end in electrochemical series.
Eg: A ship-hull which is made up of steel is connected to sacrificial anode (Zn-blocks) which
undergoes corrosion leaving the base metal protected.

Unprotecte
d
base metal

Figure1. Sacrificial anode method: Ship hull and underground water pipeline

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 26

 ADVANCED MATERIAL CHEMISTRY

Ground Level

Soil Mg Sacrificial anode

Mg

Base Metal Iron

(underground pipe line)
Buried pipe line protected to Mg block

Applications of Sacrificial anodic protection:

By referring to the electrochemical series, the metal with low reduction potential is connected
to the base metal which acts as anode.
1. To protect underground pipelines- Buried pipe line protected by connecting to Mg block
2. Protection of ship hulls and other marine devices.
3. Protection of water tank- by suspending Zn or Mg rods, body of the tank made cathode and
protected.

Advantages:
1. It is a simple method.
2. It does not require external power.
3. It has low maintenance and installation cost
4. Cathodic interferences are minimum.

Disadvantages:
1. More than one anode is required some times.
2. It does not work properly in high corrosive environment.
3. Sacrificial anode must be replaced periodically as and when it is consumed

Impressed current cathodic protection:

• In this method, an impressed current is applied in opposite direction to nullify the corrosion
current, and convert the corroding metal from anode to cathode.
• The impressed current is slightly higher than the corrosion current. Thus the anodic
corroding metal becomes cathodic and protected from corrosion.
• The impressed current is taken from a battery or rectifier on A.C. line.
• The metal to be protected is made cathode by connecting to an external battery (-ve
terminal)
• The anode is usually insoluble anode like graphite, stainless steel, or platinum connected
to +ve terminal of the battery. Usually a sufficient D.C current is passed on to the insoluble
anode kept in a black fill composed of coke or gypsum, so as to increase the electrical
contact with the surrounding soil.
• In impressed current cathodic protection, electrons are supplied from an external cell, so
that the object itself becomes cathodic and does not get oxidized.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 27

 ADVANCED MATERIAL CHEMISTRY

_ +
Rectifier
Ground Level

Soil

. .. . . .
.... ... Anode
Burried pipe .. . . .. (Graphite)
made cathode
..
. .. .. .
Black fill
(protected) (gypsum)

Applications:
1. The impressed current cathodic protection is used for the protection of water tanks, water &
oil pipe lines, transmission line towers etc.

Advantages
The method is mainly employed to protect large structures for long term operations.

Disadvantages
1. The method is expensive as it requires high current
2. Capital investment and maintenance costs are more
3. It is difficult to maintain uniform current over the entire metal surface as a result
localized corrosion may occur.
4. The metal should not be over protected, ie, use of much high potential is avoided
otherwise problems related to cathodic reactions like evolution of H 2 and formation of
OH- Ions talks place leading to corrosion of base metal

Metallic coatings:
The surface of the base metal coated with another metal (coating metal)is called metallic
coatings. Metallic coatings are broadly classified into anodic and cathodic coatings.

1. Anodic coating:
• The metal used for the surface coating is more anodic than the base metal which is to be
protected.
• For example, coating of Al, Cd and Zn on steel surface are anodic because their electrode
potentials are lower than that of the base metal iron. Therefore, anodic coatings protect the
underlying base metal sacrificially.
• The formation of pores and cracks over the metallic coating exposes the base metal and a
galvanic cell is formed between the base metal and coating metal. The coating metal
dissolves anodically and the base metal is protected.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 28

 ADVANCED MATERIAL CHEMISTRY

2. Cathodic coating:

• Cathodic coatings are obtained by coating a more noble metal (i.e. metals having higher
electrode potential like Sn, Au, Ag, Pt etc.) than the base metal. They protect the base metal
as they have higher corrosion resistance than the base metal due to cathodic nature.
• Cathodic coating protects the base metal only when the coating is uniform and free from
pores.
• The formation of pores over the cathodic coating exposes the base metal (anode) to
environment and a galvanic cell is set up. This causes more damage to the base metal.

Methods of application of metallic coatings:

1. Hot dipping:
• Hot dipping process is applicable to the metals having higher melting point than the coating
metal.
• It is carried out by immersing a well cleaned base metal in a bath containing molten coating
metal and a flux layer.
• The flux cleans the surface of the base metal and prevents the oxidation of the molten
coating metal. Eg: Coating of Zn, Pb, Al on iron and steel surfaces.
The most widely used hot dipping processes are
(a) Galvanizing
(b) Tinning

Galvanizing:
• Galvanizing is a process in which the iron article is protected from corrosion by coating it
with a thin layer of zinc.
• It is the anodic protection offered by the zinc.
• In this process, at first iron or steel is cleaned by pickling with dil.H2SO4 solution for 15-
20 minutes at 60-900C. In pickling any scale, dirt, oil, grease or rust and any other impurities
are removed from the metal surface.
• The article is washed well and then dried.
• It is then dipped in bath of molten zinc maintained at 425-430oC.
• The surface of bath is kept covered with ammonium chloride – flux to prevent oxide
formation. The article is covered with a thin layer of zinc when it is taken out of bath.
• It is then passed through a pair of hot rollers, which removes any excess of zinc and
produces a thin film of uniform thickness
• Then it is annealed and finally cooled slowly.

Applications: Galvanizing is widely used for protecting iron exposed to the atmosphere (roofs,
wire fences, pipes etc.) Galvanized metallic sheets are not used for keeping eatables because
of the solubility of zinc.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 29

 ADVANCED MATERIAL CHEMISTRY

Tinning
• The process of coating tin over the iron or steel articles to protect them from undergoing
corrosion is known as tinning.
• Tin is a noble metal and therefore it possess more resistance to chemical attack. It is the
cathodic protection offered by the tin. In this process, iron sheet is treated in dilute sulphuric
acid (pickling) to remove any oxide film, if present.
• A cleaned iron sheet is passed through a bath of ZnCl2 molten flux followed by molten tin
and finally through a suitable vegetable oil. The ZnCl 2 flux helps the molten metal to adhere
to the base metallic surface.
• Palm oil protects the tin coated surface against oxidation.
• Finally the sheet is passed through rollers to remove excess of tin and produce thin coat of
tin of uniform thickness

Applications:
1. Tin metal possess good resistance against atmospheric corrosion. Tin is non-toxic and
widely used for coating steel, copper and brass sheets
2. The containers coated with tin are used for storing food stuffs, ghee, oil etc and packing
food materials.
3. Tinned copper sheets are used for making cooking utensils and refrigeration equipment.

Electroplating:
• It is a process in which coating metal is deposited on the base metal by passing direct
current through an electrolytic solution containing the soluble salt of the coating metal.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 30

 ADVANCED MATERIAL CHEMISTRY

• The base metal is first

subjected to acid pickling to
remove any scales, oxides etc.
The base metal is made as
cathode of the electrolytic cell
and the coating metal is made
as anode.
• The two electrolytes are
dipped in the electrolyte
solution which contains the
metal ions to be deposited on the base metal.
• When a direct current is passed from an external source, the coating metal ions migrate
towards cathode and get deposited over the surface of base metal in the form of a thin layer.
• Low temperature, medium current density, low metal ion concentration conditions are
maintained for better electro-plating.

Objectives of Electroplating
1. To increase resistance to corrosion, chemical attack and wear resistance of the plated metal
2. To improve physical appearance and hardness
3. To increase the decorative and commercial values of metals
4. To increase the strength of non-metals like plastics, wood and glass etc.
5. To make surface conductive by using light weight non-metallic materials like wood and
plastics

Electroplating-Copper plating:
For example, for electroplating of copper on iron article the following are maintained
Electrolytic bath solution: CuSO4
Anode: Pure copper
Cathode: Base metal article
Temperature: 20-40oC (low temp for brighter and smooth surface)
Current density: 20-30 mA/cm2
When direct current is passed, the Cu2+ ions migrate to the cathode and deposit on the base
metal article.
Anode: Cu(s) Cu2+(aq) + 2e-
Cathode: Cu2+(aq) + 2e- Cu(s)

Electroless plating
• The method of deposition of a metal from its salt solution on a catalytically active surface
by a suitable reducing agent without using electrical energy is called electroless plating.
• This process is also called chemical plating or autocatalytic plating.
• The metallic ions (M+) are reduced to the metal with the help of reducing agents(R-1). When
the metal(M) is formed, it gets plated over a catalytic surface.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 31

 ADVANCED MATERIAL CHEMISTRY

Electroless-Ni plating:
It is an auto-catalytic chemical technique used to deposit a layer of nickel-phosphorus
or nickel-boron alloy on a solid work piece, such as metal or plastic. The process relies on the
presence of a reducing agent.
It involve the following features
Pretreatment and activation of the surface: The surface to be plated is activated by treatment
with organic solvents or alkali, followed by acid treatment

Composition of Bath:
Coating solution- NiCl2 solution
Reducing agent- Sodium hypophosphite (NaH2PO2.H2O)
Buffer- Sodium acetate
Complexing agent- Sodium succinate
Optimum PH- 4.5
Optimum temperature - 93

Advantages of Electroless plating:

1. Electrical energy is not required.
2. Even intricate parts (of irregular shapes) can be plated uniformly
3. There is flexibility in plating volume and thickness.
5. The process can plate recesses and blind holes with stable thickness.
6. Chemical replenishment can be monitored automatically.
7. Bright finishes can be obtained.
8. Plating on articles made of insulators (like plastics) and semiconductors can easily be carried
out.
9. Electroless plated Ni objects has better corrosion resistance, deposits are pore free, hard and
wear resistant.

Applications:
1) They are used in electronic industry for fabricating printed circuits and diodes.
2) It is used in domestic as well as automotive fields (eg. jewelry, tops of perfume bottles).
3) Its polymers are used in decorative and functional works.
4) Its plastic cabinets are used in digital as well as electronic instruments.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 32

 ADVANCED MATERIAL CHEMISTRY

UNIT III: FUNCTIONAL MATERIALS

Polymers
Introduction:
Polymers can be defined as the large molecules (macro molecules) formed by the linking
together of large number of smaller molecules called monomers. (In Greek language ‘poly’
means “many” & ‘mer’ means “units”)
E.g.:- polyethylene is a polymer formed by linking together of a large number of ethylene
molecules
Polymerisation
nCH2 =CH2 ( CH2−CH2 ) n

Thus the repeated unit of polymer is called monomer. The number of repeating units in a
polymer chain is called degree of polymerization. For e.g. if 100 molecules of ethylene
polymerize to give the polymer chain, the degree of polymerization is 100.
Polymers form very important components in our daily life. The polymers are highly
useful in domestic, industrial & medical fields. The following are the reasons for the extensive
use of polymers.
1) Most of the polymers are non-toxic & safe to use
2) They have low densities (light in weight), so transportation of polymers will be easy
3) They possess good mechanical strength
4) They are resistant to corrosion and will not absorb moisture when exposed to the
atmosphere
5) They can function as good thermal & electrical insulators
6) They can be moulded and fabricated easily
7) They possess esthetic colors
But the limitations for the use of polymers are:
• Some polymers are combustible.
• The properties of polymers are time dependent
• Some of them cannot withstand high temperatures.
• It is also interesting to note that many carbohydrates, proteins & enzymes, DNA &
RNA are natural polymers.
Plastics
Plastics are the polymers characterized by the property of plasticity (permanent
deformation in structure on applying some stress/force). They can be moulded to desired shape
when subjected to heat and pressure in the presence of catalyst.

Plastics as engineering materials:

Advantages of plastics over other engineering materials
1. Low fabrication cost, low thermal & electrical conductivities, high resistance to
corrosion & solvents.
2. The stress – strain relationship of plastics is similar to that of the metals.
3. Plastics reduce noise & vibration in machines.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 33

 ADVANCED MATERIAL CHEMISTRY

4. Plastics are bad conductors of heat and are used to make handles for hot objects, most
plastics are inflammable.
5. Plastics are electrical insulators & find large scale use in the electrical industry.
6. Plastics are resistance to chemicals.
7. Plastics are clear & transparent so they can be given beautiful colours.

Types of Plastic: 1) Thermoplastics

2) Thermosetting plastics

Difference between Thermoplastic & Thermoset resins:

Thermoplastic Resins Thermoset Resins
1. These resins become soft on heating and 1. They do not soften on heating and become
rigid on cooling by regaining original hard. On prolonged heating they decompose
properties. These can be reshaped and used. and cannot get back its structure. Hence
cannot be reshaped and used.
2. The heating and cooling do not alter the 2. These resins are permanent setting resins.
chemical nature of these resins but involves
changes in physical nature.
3.They are formed by addition 3. They are formed by condensation
polymerization polymerization.
4. Small molecular weight compounds with 4. Large molecular weight compounds with
linear structures. three dimensional networks.
5. They consist of long chain linear polymer 5. Highly cross-linked structure strong
with weak secondary vandarwaal’s forces covalent bonds are responsible for strength.
of attraction in between them.
6. They soften on heating readily because 6.The bonds retain their strength on heating,
the secondary force of attraction between hence do not soften on heating
the individual chain can break easily by
heat, pressure or both
7. These plastic can be reclaimed from 7. Cannot be reclaimed from waste
waste
8. They are soft, weak and less brittle 8. They are hard, strong and more brittle
9.These resins are usually soluble in 9. Due to strong bonds and cross links, they
organic solvents are insoluble in all organic solvents.
10. Curing by cooling 10. By applying heat and pressure
Eg: PE, PS, PVC, Teflon Eg: Bakelite, Polyester(Terylene)and
silicones

(1) Polyvinyl chloride (PVC):

Preparation: The monomer used for the manufacture of PVC is vinyl chloride. Vinyl chloride
is prepared by treating acetylene with HCl at 60-800C and in presence of a metal oxide catalyst.
Polyvinyl chloride is produced by heating vinyl chloride in presence of benzyl peroxide or
H2O2.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 34

 ADVANCED MATERIAL CHEMISTRY

Properties:
1. PVC is a colorless, non-inflammable and chemically inert powder
2. It has specific gravity 1.33 and melting point 148oC
3. Resistant to atmospheric conditions like O2, CO2 and moisture
4. They are rigid and flexible
5. It has resistance to light

Applications:
There are two kinds of PVC plastics
Rigid PVC (Unplasticized PVC):
• It is chemically inert & non-inflammable powder having a high softening temperature of
1480C.
• This PVC is used for making safety helmets, refrigerator components, tyres, cycle & motor
cycle mud guards.
Plasticized PVC:
• It is produced by mixing plasticizers like dibutyl phthalate with PVC resin uniformly.
• It is used for making rain coats, table-cloths, handbags, curtains & electrical insulators,
radio,
2) Teflon (Polytetrafluoro ethylene):
Preparation: Teflon is prepared by addition polymerization of tetraflouroethylene

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 35

 ADVANCED MATERIAL CHEMISTRY

Properties:
Teflon is also known as Fluon. Due to the presence of highly electronegative fluorine atoms,
Teflon has got:
• High melting point (350oC)
• The strong attractive force is responsible for high toughness & high chemical resistance
towards all chemicals except hot alkali metal & hot fluorine.
• High density 2.1-2.3gm/cc
• It is a very good electrical insulator
• It possess very good abrasion resistance
Engineering applications:
• It is used in making seals & gaskets, which have to withstand high temperature.
• It is also used for insulation of electrical items and for making non-sticky surface coating,
particularly for cooking utensils.
• Teflon used as insulating material for motors, transformers, cables, wires, fitting etc.,

3) Polymethyl methacrylate:
It is also known as acrylic or plexiglass as well as by trade name Plexiglas Acrylite lucite and
Perspex

Preparation
a) from cyanohydrin

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 36

 ADVANCED MATERIAL CHEMISTRY

b) from hydroxy propanol

Properties
PMMA polymer exhibits glass-like qualities – clarity, brilliance, transparency, translucence

Transmittance – PMMA (Acrylic) polymer has a Refractive Index of 1.49 and hence offers
high light transmittance. PMMA grades allow 92% of light to pass through it, which is more
than glass or other plastics. These plastic materials can easily be thermoformed without any
loss in optical clarity. As compared to polystyrene and polyethylene, PMMA is recommended
for most outdoor application thanks to its environmental stability.

Surface Hardness – PMMA is a tough, durable and lightweight thermoplastic. The density of
acrylic ranges between 1.17-1.20 g/cm3 which is half less than that of glass. It has
excellent scratch resistance when compared to other transparent polymers like Polycarbonate,
however less than glass. It exhibits low moisture and water absorbing capacity, due to which
products made have good dimensional stability.

UV Stability – PMMA has high resistance to UV light and weathering. Most commercial
acrylic polymers are UV stabilize for good resistance to prolonged exposure to sunlight as its
mechanical and optical properties fairly vary under these conditions, Hence, PMMA is suitable
for outdoor applications intended for long-term open-air exposure.

Chemical Resistance – Acrylics are unaffected by aqueous solutions of most laboratory

chemicals, by detergents, cleaners, dilute inorganic acids, alkalies, and aliphatic hydrocarbons .
However, acrylics are not recommended for use with chlorinated or aromatic hydrocarbons, esters,
or ketones.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 37

 ADVANCED MATERIAL CHEMISTRY

Engineering Applications of PMMA

Architecture and Construction
PMM is widely used in window and door profiles, canopies, panels, façade design, etc. It also
facilitates light transmission and provides good heat insulation, hence a suitable choice of
building green houses. PMMA is also used to build aquariums and marine centers.

Lighting
PMMA sheets are used for designing LED lights where it helps maximize light emitting
potential. It is also used for construction of lamps thanks to its transparency and optical
properties.

Automotive and Transportation

In vehicles, PMMA sheets are used in car windows, motorcycle windshields, interior and
exterior panels, fenders etc. Also colored acrylic sheets are used in car indicator light covers,
interior light covers etc. It is also used for windows of a ship (Salt resistance) and aviation
purposes. PMMA also open new design possibilities for car design possibilities for
manufacturers thanks to its pleasant acoustic properties, outstanding formability and excellent
surface hardness.

Electronics:
Due to its excellent optical clarity, high light transmission and scratch resistance, PMMA is widely
used in LCD/LED tv screens, laptops, smartphones display as well as electronic
equipment displays. PMMA also finds used in solar panels as cover materials thanks to its excellent
UV resistance and excellent light transmission allowing high energy conversion efficiencies.
Medical and Healthcare:

PMMA is a high purity and easy-to-clean material and hence used to fabricate incubators, drug
testing devices, storage cabinets in hospitals and research labs. Also, due to its high bio-

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 38

 ADVANCED MATERIAL CHEMISTRY

compatibility, PMMA is also applied as dental cavity fillings and bone cement.

Furniture
PMMA offers exception properties such as transparency, toughness and aesthetics to produce
chairs, tables, kitchen cabinets, bowls, table mats etc. in any shape, color or finishes

Polycarbonate:
Polycarbonates (PC) are a group of thermoplastic polymers containing carbonate groups in their
chemical structures. Polycarbonates used in engineering are strong, tough materials, and some grades
are optically transparent. They are easily worked, molded, and thermoformed. Because of these
properties, polycarbonates find many applications.

Preparation of polycarbonate
The polymer is usually formed by the reaction of bisphenol A and carbonyl chloride in a basic
solution. A solution of bisphenol A in sodium hydroxide (i.e. a solution of the sodium salt of
the phenol) is prepared. It is mixed with a solution of carbonyl chloride in an organic solvent
(dichloromethane).
The first step in the synthesis of polycarbonates starts out with the reaction of bisphenol A with
sodium hydroxide to get the sodium salt of bisphenol A

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 39

 ADVANCED MATERIAL CHEMISTRY

The sodium salt of bisphenol A is then reacted with phosgene a right nasty compound which
was a favourite chemical weapon in World War I to produce the polycarbonate

Properties:
Polycarbonates are strong, stiff, hard, tough, transparent engineering thermoplastics that can
maintain rigidity up to 140°C and toughness down to -20°C or special grades even lower.

Applications in Engineering :
Electronic components
Polycarbonate is commonly used in eye protection, as well as in other projectile-resistant
viewing and lighting applications that would normally indicate the use of glass, but require
much higher impact-resistance. Polycarbonate lenses also protect the eye from UV light.
Being a good electrical insulator and having heat-resistant and flame-retardant properties, it is
used in various products associated with electrical and telecommunications hardware. It can
also serve as a dielectric in high-stability capacitors.[

Construction materials
Polycarbonate sheeting in a greenhouse.
The second largest consumer of polycarbonates is the construction industry, e.g. for dome
lights, flat or curved glazing, and sound walls.

Data storage
CDs and DVDs
A major application of polycarbonate is the production of Compact Discs, DVDs, and Blu-ray
Discs. These discs are produced by injection molding polycarbonate into a mold cavity that has
on one side a metal stamper containing a negative image of the disc data, while the other mold
side is a mirrored surface.
It is also used in automotive, aircraft and security components’

3. Bakelite (or) Phenol Formaldehyde Resin:

Bakelite is an important thermosetting resin named after the scientist Bakeland, who
synthesized this resin in the year 1909. The condensation reaction of phenol & formaldehyde
in the presence of acid or alkali catalyst and at proper temperature produces the phenol
formaldehyde resin or Bakelite resin.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 40

 ADVANCED MATERIAL CHEMISTRY

Stage-I: The initial reaction of phenol & formaldehyde in presence of acid or alkali produces
o-hydroxy methyl phenol and p-hydroxy methyl phenol.

Stage-II: o-hydroxy methyl phenol undergoes self condensation in presence of acid or alkali
and forms a linear polymeric chain called novolac.

Stage-III: On further heating, in the presence of hexamethylenetetramine both o-hydroxy

methyl phenol and p-hydroxy methyl phenol undergoes self condensation and forms a 3D-cross
linked thermosetting polymer which is known as “Bakelite”.

Properties:
(1) Bakelites are hard, rigid and withstand very high temperatures.
(2) They have excellent heat and moisture resistance.
(3) They have good chemical resistance, resistance to acids, salts and many organic solvents,
but it is attached by alkalis due the presence of –OH group.
(4) They have good abrasion resistance.
(5) They have electrical insulation characteristics.
(6) It is a good anionic exchanging resin, exchange –OH group with other anion.
(7) Low molecular weight grades have excellent bonding strength and adhesive properties.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 41

 ADVANCED MATERIAL CHEMISTRY

Engineering Applications:
(1) It is used for making electric insulator parts like switches, plugs, switch boards etc.
(2) For making moulded articles like telephone parts cabinet of radio and television.
(3) As an anion exchanger in water purification by ion exchange method in boilers.
(4) As an adhesive (binder) for grinding wheels etc.,
(5) In paints and varnishes.
(6) For making bearings used in propeller shafts, paper industry and rolling mills.

Conducting Polymers:
Most polymeric materials are poor conductors of electricity because of the non-availability of
large number of free electrons for the conduction process. Thus most of the polymers are used
as insulators. However some polymers have electrical conductivity and can be used in place of
metals due to their light weight and low cost, Polymeric materials which possess electrical
conductivities on par with the metallic conductors are called conducting polymers. Special
polymers with conductivities as high as 1.5 x 107 ohm-1 m-1 have been made their conductivity
may be due to unsaturation or due to the presence of externally added ingredients to polymers.
Those polymers which conduct electricity are called conducting polymer. The conduction of
polymers is due to unsaturation or due to the presence of externally added ingredients to them.
Conducting polymers are classified into two types.

a) Intrinsic conducting polymers:

These are characterized by intensive conjugation of π-bonds in their structure. This is a polymer
whose back bones or associated groups consisting of delocalized electron pair or residual
charge, which increases their conductivity to a large extent. The conduction process is due to
the overlapping of orbitals containing conjugated π-electrons, resulting in the formation of
valence bands as well as conduction bands separated by significant Fermi energy gap. The
electrical conductivity is due to thermal or photolytic activation of the electrons, which gives
them sufficient energy to cross the Fermi gap and cause conduction. Important commercially
produced intrinsic conducting polymers are polyacetylene, polythiophene, polyaniline.

Conducting polymers having conjugation:

Polymers have alternating double and single bond along the polymer chain and each
carbon atom is in sp2 hybridized state. One valence 𝜋e- on carbon is in Pz orbital. The orbitals
of conjugated 𝜋e-s overlap the entire backbone of the polymer and result in the formation of
valence bands & conduction bands.
The valence band is filled band and conduction band is empty. When the energy gap between
these is low, the e-s from valence band are excited to conduction band become mobile
throughout the polymer and show conductivity.
E.g. trans-polyacetylene, polyaniline

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 42

 ADVANCED MATERIAL CHEMISTRY

Doped conducting polymers:

The conducting polymers having 𝜋e-s in their backbone can easily be oxidized or reduced because
they possess low ionization potential and high electron affinities. Hence their conductance can be
increased by introducing a positive charge or negative charge on polymer backbone by oxidation or
reduction. This process is similar to semiconductor technology and is called doping. Doping is again
two types.
(1) Creating a positive site on polymer backbone called p-doping.
(2) Creating a negative site on the polymer backbone called n-doping.
Oxidation process is done by adding some alkali metals or e- acceptor and conductivity is
enhanced by p-doping. Reduction process is done by adding reducing agents or electron donor
and conductivity is enhanced by n-doping.

p-doping:
p-doping is done by oxidation of a conducting polymer like polyacetylene with a Lewis
acid or iodine vapour. This is called oxidative doping.

During oxidation process the removal of 𝜋 electrons from polymer backbone lead to the
formation of a delocalized radical ion called polaron having a hole in between valence band
and conducting band.
The second oxidation of the polaron results in two positive charge carriers in each chain
called bipolaron, which are mobile because of delocalization. These delocalized charge carriers
are responsible for conductance when placed in electric field.

n-doping:
n-doping is carried out by reduction process by the addition of an electron to polymer
backbone by using reducing agents like sodium napthalide Na+(C10H8)-. Formation of polaron,
bipolaron takes place in two steps, followed by recombination of radicals, which yields two
charge carriers on the polyacetylene chain responsible for conduction
The electron added to polyacetylene by reductive doping doesn’t go into the conducting band
but goes into an intermediate electronic state within the band gap of radical anion. Bipolaron
contains electrons in the energy levels residing in the band gap.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 43

 ADVANCED MATERIAL CHEMISTRY

b) Extrinsic conducting polymers:

The conductivity of these polymers is due to the presence of externally added ingredients
in them. These polymers are two types.

Conducting element filled polymers:

The polymers acting as a binder to hold the conducting element such as carbon black,
metallic fibers, metallic oxides etc., minimum concentration of filler is added so that the
polymer starts conducting. This minimum concentration of conductive filler is called
percolation threshold. At this concentration of filler, a conducting path is formed in polymeric
material. The most preferred filler is the special conducting grade C-black has very high surface
area, more porosity and more of filamentous properties.

Advantages:
1. These polymers are low cost polymers
2. They are light in weight and mechanically durable.
3. These polymers are strong with good bulk conductivity.
4. They are fabricated very easily to any design.

Applications of conducting polymers:

• The conducting polymers are used in rechargeable batteries, small in size (bottom size),
producing current density up to 50glucos Conducting polymers are also used for
making analytical sensors for pH, O2, NOx,SO2, NH3 and glucose
• The conducting polymers are used for making ion exchangers. These membranes made
of conducting polymers show selective permeability for ions and gases hence they are
used for control release of drug.
• The conducting polymers are used for making electronic displays and optical fibres
• They are used for cancer chemotherapy
• The conducting polymers are applicable in photovoltaic devices, LED’s and data
storage.

Composite Materials:
A composite material (also called a composition material or shortened to composite, which is
the common name) is a material made from two or more constituent materials with significantly
different physical or chemical properties that, when combined, produce a material with
characteristics different from the individual components.

Fiber Reinforced Plastics (FRP):

• Combination of plastic material & solid fillers give hard plastic with mechanical strength
& impact resistant is known as reinforced plastic.
• The fiber polymers with solid/fillers to impart mechanical strength & hardness without
losing plasticity are known as fiber reinforced plastics (FRP).
• Fillers like carborandum, quartz & mica – impart hardness & strength.
• Barium salt impervious to x-rays.
• Asbestos provide heat & corrosion resistant for FRP.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 44

 ADVANCED MATERIAL CHEMISTRY

Nature of polymers used for FRP:

Composition of FRP – 50% of the mouldable mixture contain fillers.
• Addition of carbon black to natural rubber increase the 40% strength of rubber & used in
the manufacture of tyres.
• China clay improves the insulation property of PVC, Teflon.
• When CaCO3 is added to PVC, then they are used for insulation of tubing, seat covers,
wires & cables.
• Asbestos filled FRP → for electrical appliances’.
• FRP has good shock & thermal resistances, mouldability, dimensional stability &
reparability.

Applications
• Fiber reinforced plastics find extensive use in space crafts, aeroplanes, boat nulls, acid
storage tanks, motor cars and building materials.
• Melamine FRP is used for insulation & making baskets

Advantages of FRP
(a) Low efficient of thermal expansion
(b) High dimensional stability
(c) Low cost of production
(d) Good tensile strength
(e) Low dielectric constant
(f) Non inflammable & non-corrode and chemical resistance

Glass Reinforced Plastics:

Glass reinforced plastic (shortened as GRP) is made of synthetic resin as main basic material
and glass fiber or other product as reinforced material, processed into a solid material by
molding and setting
Fiberglass is a common type of fiber reinforced plastic using glass fiber. The fibers may be
randomly arranged, flattened into a sheet (called a chopped strand mat), or woven into a fabric.
The plastic matrix may be a thermoset polymer matrix—most often based on thermosetting
polymers such as epoxy, polyester resin or vinyl ester or a thermoplastic.

Applications:
1. Fiberglass is an immensely versatile material due to its light weight, inherent strength,
weather-resistant finish and variety of surface textures
2. During World War II, fiberglass was developed as a replacement for the molded
plywood used in aircraft radomes (fiberglass being transparent to microwaves).
3. fiberglass is also used in the telecommunications industry for shrouding antennas , due
to its RF permeability and low signal attenuation properties.
4. Because of fiberglass's light weight and durability, it is often used in protective
equipment such as helmets. Many sports use fiberglass protective gear, such as
goaltenders' and catchers' masks.
5. Storage tanks can be made of fiberglass with capacities up to about 300 tones.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 45

 ADVANCED MATERIAL CHEMISTRY

6. Glass-reinforced plastics are also used to produce house building components such as
roofing laminate, door surrounds, over-door canopies, window canopies and dormers,
chimneys, coping systems, and heads with keystones and sills
7. In rod pumping applications, fiberglass rods are often used for their high tensile strength
to weight ratio. Fiberglass rods provide an advantage over steel rods because they
stretch more elastically (lower young modulus) than steel for a given weight,
8. GRP and GRE pipe can be used in a variety of above- and below-ground systems.

Carbon Reinforced Fiber:

Carbon fiber reinforced polymer or carbon fiber reinforced plastic, or carbon fiber reinforced
thermoplastic, is an extremely strong and light fiber-reinforced plastic which contains carbon
fibers.
One method of producing CFRP parts is by layering sheets of carbon fiber cloth into a mold in
the shape of the final product. The alignment and weave of the cloth fibers is chosen to optimize
the strength and stiffness properties of the resulting material. The mold is then filled with epoxy
and is heated or air-cured.
Carbon Fiber Reinforced Plastics are very hard to machine, and causes significant tool wear.
The tool wear in CFRP machining is dependent on the fiber orientation and machining
condition of the cutting process. In order to reduce tool wear various types of coated tools are
used in machining CFRP and CFRP-metal stack.

Applications
Aerospace engineering
CFRP is widely used in micro air vehicles (MAVs) because of its high strength to weight ratio.

Automotive engineering
Many supercars over the past few decades have incorporated CFRP extensively in their
manufacture, using it for their monocoque chassis as well as other components.

Civil engineering
CFRP has become a notable material in structural engineering applications

Carbon-fiber microelectrodes
Carbon fibers are used for fabrication of carbon-fiber microelectrodes.
Carbon-fiber microelectrodes are used either in amperometry or fast-scan cyclic voltammetry
for detection of biochemical signaling.

Sports goods
CFRP is now widely used in sports equipment such as in squash, tennis, and badminton
racquets, sport kite spars, high-quality arrow shafts, hockey sticks, fishing rods, surfboards,
high end swim fins, and rowing shells.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 46

 ADVANCED MATERIAL CHEMISTRY

UNIT IV: ADVANCED MATERIALS

NANOMATERIALS

Introduction:
Nano science and technology is a broad and interdisciplinary area growing explosively
worldwide in the past few years. Nanomaterials are cornerstones of nanoscience and
nanotechnology. Now a days in research and development the major sectors are energy,
environment, water technology, pharmaceuticals etc. The usage of nanomaterials is enormous
as energy storage devices such as fuel cells, detection of threats in defense, navy, drug delivery
and water purification. Industrial revolution has made life easy and pleasant. Today’s high-
speed personal computers and mobile communications would not have certainly been possible
without the use of nanoscience and nanotechnology.
The size of the material ranging from 10nm to 100nm is called as Nano Scale. Here the
nanoscale is very important because many physical and chemical properties starts changing
significantly when the size of the material is below 100nm and reduction of the particle size to
nano level could improve the properties of the materials to high level .This resulted in the birth
of “Nano Science” and “Nano Technology” which has great potential to create many new
materials and devices which has great applications in many fields.
Nanotechnology deals with structures of the size 100nm or smaller and involves in developing
materials or devices within that size. It plays an important role in the fields of physics,
chemistry, biology, Engineering and technology. So, a nanomaterial is defined as a material if
the size of material is 100nm or below it.
The science and technology which deals with the particles in size between 1 to 100nm is known
as nano science and nanotechnology.

Nano Scale:
The size of the material ranging from 10nm to 100nm is called as Nano scale. Here the
nanoscale is very important because many physical and chemical properties starts changing
significantly when the size of the material is below 100nm and reduction of the particle size to
nano level could improve the properties of the materials to high level .This resulted in the birth
of “Nano Science” and “Nano Technology” which has great potential to create many new
materials and devices which has great applications in many fields.
Nanotechnology is the latest technology in which the materials are used in nano size, i.e. atoms
are in the order of 1 to 100nm.
Nanoscale: 1nm = 10-9m = 10-7cm
Nano means 10-9m i.e. a billionth part of a meter. Atoms are extremely small & the diameter
of a single atom can vary from 0.1 to 0.5nm depending on the type of the element.
Ex: Carbon atom – 0.15 in diameter, water molecule – 0.3nm
Red blood cell – 7,000nm, Human hair-80,000nm wide
White blood cell-10,000nm, Virus – 100nm, Hydrogen atom - 0.1nm
Bacteria range – 1,000 to 10,000nm, proteins – 5 to 50nm
DNA – 2nm Width, Quantum dots – 8nm
Nano particles – 1 to 100nm, Fullerenes – 1nm

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 47

 ADVANCED MATERIAL CHEMISTRY

Nanomaterials: The materials in which the atoms are in the order of 1 to 100nm and these
atoms will not move away from each other, called as nanomaterials.
Eg: C, ZnO, Cu – Fe alloys, Ni, Pd, Pt etc.
1. Materials that are nanoscale in one dimension called as nano layers [Thin films, surface
coatings].
2. Two dimensional nanomaterials are called as nano tubes and nanowires.
3. Three dimensional nanomaterials are called as nanoparticles.
Ex: Precipitates, Colloids & quantum dots, tiny particles of semi-conductor materials.

Nanomaterial is defined as a material if the size of material is 100nm or below it.

Nano materials are classified into three types. They are

1) Materials that are nanoscale in one dimension
2) Materials that are nanoscale in two dimension
3) Materials that are nanoscale in three dimension.

Examples of materials that are nanoscale in one dimension are layers, such as thin films or
surface coatings.

Materials that are nanoscale in two dimensions include nanowires and nanotubes.
Materials that are nanoscale in three dimension are particles for example precipitates, colloids
and quantum dots (tiny particles of Semiconductor materials)

So, based on this nano material generally fall into two categories, they are

1) Fullerenes
2) Nanoparticle

Fullerenes:
Afullereneisamoleculecomposedofcarbonintheformofahollowsphereortube.Fullerenes are also
classified into spherical and cylindrical fullerenes, spherical fullerenes are also called as bucky
balls and cylindrical ones are called as carbon nanotubes or bucky tubes. Fullerenes are similar
in structure to graphite.

The first fullerene discovered was Buckminster fullerene C60 in 1985. It was named after
Richard Buckminster fuller. Carbon nanotubes (CNTs) are allotropes of carbon with a
cylindrical nanostructure. Carbon nanotubes are again categorized into

(1) Single-Walled nanotubes (SWNTs)

(2) Multi-Walled nanotubes (MWNTs)

These are useful in many applications in nanotechnology, electronics, optics and material
science.

Nanoparticles:
Nanoparticles are available in different forms such as clusters, metal nanoparticles, colloids,
nano shells, quantum dots etc., They are made of metals, semiconductors or oxides.
Nanoparticles have been used as quantum dots and as chemical catalysts.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 48

 ADVANCED MATERIAL CHEMISTRY

Surface to Volume Ratio

In chemical reactions, this surface to volume ratio plays an important role. There is an
enormous change in the properties of materials due to increased surface area to volume ratio.
The nanomaterials have relatively larger surface area when compared to the same volume of
the material produced in larger form. So we know that material has high surface energy if it is
small in size and vice versa. Therefore, nanoparticles have large surface area to volume ratio
and they possess large surface energy. Due to high surface energy materials are more reactive
and also nanoparticles show enhanced stability and broader scope of applications. In some
cases, materials that are inert in their larger form are reactive when produced in their nanoscale
form. This affects their strength or electrical properties.

Fabrication
Nanomaterials or Nanostructures can be made mainly in two ways. They are
(1) Bottom-up fabrication
(2) Top-down fabrication

Bottom-up Fabrication is one in which the nanostructure is built atom by atom from small
components, whereas top-down fabrication is one in which an existing solid gradually reduced
in size using some external radiation.

Bottom-up Fabrication
Preparation: Now there are many known methods to produce nanomaterials. Let us study
briefly few these methods.

Sol Gel Method:

The solutions in which molecules of nanometer are dispersed appear clear. The colloids in
which molecules of size ranging from 20 nm to 100 nm appear milky. A colloid suspended in
a liquid is called as sol. A suspension that keeps its shape is called gel. Thus sol-gels are
suspensions of colloids in liquid that keep their shape. Sol-gel formation occurs in different

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 49

 ADVANCED MATERIAL CHEMISTRY

stages. The sol el process can be characterized by a series of distinct steps.

Step1: Formation of different stable solutions of the alkoxide or solvated metal precursor (the
sol).

Step 2: Gelation resulting from the formation of an oxide or alcohol bridged network (the gel)
by a poly condensation or poly esterification reaction. This results in a dramatic increase in
the viscosity of the solution.

Step 3: Aging of the gel(synthesis), during which the poly condensation reactions continue
until the gel transforms into a solid mass. This is accompanied by contraction of the gel
network and expulsion solvent from gel pores.

Step 4: Drying of the gel, when water and other volatile liquids are removed from the gel
network. If isolated by thermal evaporation, the resulting is termed a xerosal. If the solvent
(such as water) is extracted under super critical or near super critical conditions, the product
is an aerogel.

Step 5: Dehydration, during which surface bound M-OH groups are removed. This is normally
achieved by calcinations of the monolith at temperature’s up to 800 0 C.

Step 6: Densification and decomposition of the gels at high temperature (T>800 0 C). The
pores of the gel network are collapsed, and remaining organic species are volatilized.

The typical steps that are involved in sol gel processing are shown in fig. By different
process one can get either nan film coating or nano powder or dense ceramic with nanograins.
Advantages
1. The possibility of synthesizing nonmetallic materials like glasses, glass ceramics or
ceramic materials at very low temperatures.
2. One can mono sized nanoparticles.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 50

 ADVANCED MATERIAL CHEMISTRY

Disadvantages
1. Controlling the growth of the particle is difficult.
2. Stopping the newly formed particles from agglomeration is also difficult.

Ex-Nanoparticles prepared by sol gel method are Si(OR)3 , where R is alkyl groups ay various
types.

Chemical Vapour Deposition:

In this method nanoparticles are deposited from gas phase. Material is heated to form a gas and
then allowed to deposit on a solid surface, usually under high vacuum. In deposition by
chemical reaction new product is formed. Nanopowders of oxides and carbides of metals can
be formed if vapours of carbon or oxygen are present with the metal.

It involves pyrolysis of vapours of metal organic precursors in a reduced pressure atmosphere.

In the simplest form, a metal –organic precursor is introduced into the hot zone of the reactor
using mass flow controller. The precursor is vapourised either by resistive or inductive heating.
The carries gas such as Ar or Ne carries the hot atoms to the reaction chamber. The hot atoms
collide with cold atoms and undergo condensation through nucleation and form small cluster.
In side reaction chamber other reactants are added to control the reaction rate. Then these
clusters are allowed to condense on a moving belt arrangement with scrapper to collect the
nanoparticles. The particle size could be controlled by rate of evaporation (energy input), rate
of cluster formation (energy removal rate) and rate of condensation (cluster removal from the
reaction chamber).

Fig: Chemical Vapour Deposition

CVD method of synthesis of nanoparticles has many advantages.

1. The increased yield of nanoparticles.
2. A wider range of ceramics including nitrides and carbides can be synthesized.
3. More complex oxides such as BaTiO3 or composites structures can be formed.
4. In addition to the formation of single-phase nanoparticles by CVC of a single precursor
the reactor allows the synthesis of
a) Mixtures of nanoparticles of two phases or doped nanoparticles by supplying two
precursors at the front end of the reactor, and

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 51

 ADVANCED MATERIAL CHEMISTRY

b) Coated nanoparticles, i.e., n-ZrO2 coated with n-Al2O3 or vice versa, by supplying a
second precursor at a second stage of thereactor.

Applications of Nanomaterials:

In Production Technologies
• It is important and perspective now to use nanomaterials in composites as components of
various functions.

• In the production of steels and alloys adding nanopowders helps to reduce porosity and
improve the range of mechanical properties.

• Manifestation of super plasticity in nano structured aluminum and titanium alloys makes
their use promising in the manufacture of complex shapes details and for using as a
connecting layer in welding different solid-state materials.

In Military Engineering
• Ultra-fine powders are used in a number of radars absorbing coatings for aircraft, created
with the use of technology "Stealth", and promising types of explosives and incendiary.

• Carbon nanofibers are used in special ammunition intended for the scrapping of the enemy
power systems (so-called "graphite bomb").

In Nuclear Power Engineering

The beginning of nuclear power engineering was given by the ultra-fine powders. These
powders are commonly used in industrial processes for the separation of uranium isotopes.
Prospects for the development of nuclear energy by bringing the particles to the nano state are
mainly associated with a decrease in the average consumption of natural uranium. This happens
mostly at the expense of increasing the depth of the nuclear fuel combustion. To do this,
scientists are exploring the possibility of the creation of coarse-grained structures of nuclear
materials, which can be porous. These nanomaterials will promote a high retention of fission
products.

In Material Surface Protection

In some cases, for reliable operation, it is necessary to ensure the high water and oil repellency
properties of material surface. Some examples of such products may be car windows, glass
planes and ships, protective clothing, wall storage tanks for liquids, building construction, etc.
At present the titanium oxide nanoparticles coating with sizes of 20-50 nm and a polymer
binder have been developed. This coating greatly reduces the wettability of the surface with
water, oil and alcohol solutions.

In Medical
• Silver nanoparticles have good antibacterial properties are used in surgical instruments,
refrigerators, air-conditioners, water purifiers etc.
• Gold nanoparticles are used in catalytic synthesis of silicon nanowires, sensors carrying the
drugs and in the detection of tumors.
• ZnO nanoparticles are used in electronics, ultraviolet (UV) light emitters, piezoelectric

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 52

 ADVANCED MATERIAL CHEMISTRY

devices and chemical sensors.

• TiO2 nanoparticles are used as photocatalyst and sunscreen cosmetics (UV blocking
pigment).
• Antimony-Tin-Oxide (ATO), Indium-Tin-Oxide (ITO) nanoparticles are used in car
windows, liquid crystal displays and in solar cell preparations.
• Nanoscale structures and materials such as nanoparticles, nanowires, nanofibers, and
nanotubes have been explored in many biological applications e.g., biosensing, biological
separation, molecular imaging, and/or anticancer therapy because of their novel properties
and functions differ drastically from their bulk counter parts.
• Their high volume/surface ratio, surface tailor ability, improved solubility, and
multifunctionality open many new possibilities for biomedicine.
• The intrinsic optical, magnetic and biological properties of nanomaterials offer remarkable
opportunities to study and regulate complex biological processes for biomedical
applications in an unprecedented manner.

Carbon Nanotubes (CNTS):

A carbon nanotube is a tube-shaped material, made of carbon, having a diameter measuring on
the nanometer scale. To understand the structure of a carbon nanotube it can be first imagined
as a rolled-up sheet of graphene, which is a planar-hexagonal arrangement of carbon atoms
distributed in a honeycomb lattice. A single layer of graphite sheet is called graphene.

Carbon nanotubes have many structures, differing in length, thickness, and in the type of
helicity and number of layers. As a group, CNTs typically have diameters ranging from <1nm
up to 50nm. Their lengths are usually several microns, but recent advancements have made the
nanotubes much longer, and measured in centimeters.

There are two types of carbon nanotubes.

1. Single wall carbon nanotubes (SWCNT)

Single-wall nanotubes (SWNT) are tubes of graphite that are normally capped at the ends. They
have a single cylindrical wall. The structure of a SWNT can be visualized as a layer of graphite,
a single atom thick, called graphene, which is rolled into a seamless cylinder.

Most SWNT typically have a diameter of close to 1 nm. The tube length, however, can be many
thousands of times longer. SWNT are more pliable yet harder to make than MWNT. They can
be twisted, flattened, and bent into small circles or around sharp bends without breaking.

2. Multi wall carbon nanotubes (MWCNT)

There are two structural models of multi wall nanotubes. In the Russian Doll model, a carbon
nanotube contains another nanotube inside it (the inner nanotube has a smaller diameter than
the outer nanotube). In the Parchment model, a single graphene sheet is rolled around itself
multiple times, resembling a rolled-up scroll of paper. The simplest representative of a MWNT
is a double walled carbon nanotube (DWNT).
Multi wall carbon nanotubes have similar properties to single wall nanotubes, yet the outer
walls on multi wall nanotubes can protect the inner carbon nanotubes from chemical
interactions with outside materials. Multi wall nanotubes also have a higher tensile strength

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 53

 ADVANCED MATERIAL CHEMISTRY

than single wall nanotubes.

The diameters of MWNT are typically in the range of 5 nm to 50 nm. The interlayer distance
in MWNT is close to the distance between graphene layers in graphite, around 3.39A 0

MWNT are easier to produce than SWNT. However, the structure of MWNT is less well
understood because of its greater complexity and variety. Regions of structural imperfection
may diminish its desirable material properties.

Applications of Carbon Nanotubes:

1. Catalyst supports: CNTs can be sued a catalyst supports because they can provide higher
surface areas and high chemical stability and controlled surface chemistry.
2. Hydrogen storage: Recently carbon nanotubes have been proposed to store hydrogen in
hydrogen-oxygen fuel cell.
3. Drug Delivery: CNTs can be widely used as drug carriers for drug deliver, as they can
easily adapt themselves and enter the nuclei of the cell.
4. Actuator/Artificial Muscles: An actuator is a device that can induce motion. In the case
of a carbon nanotube actuator, electrical energy is converted to mechanical energy causing
the nanotubes to move.
5. Chemical Sensors/Biosensors: Devices used to detect changes in physical and chemical
quantities are called sensors. CNTs act as sensing materials in pressure, thermal, gas,
optical, mass, position, stress, strain, chemical and biological sensors.
6. Touch Screens: Very thin CNT films (10 or 20nm) are transparent to visible light and
can conduct enough electricity to make them useful for many applications which include
thin film solar cells, organic LEDs and touchscreens.
7. Structural and Mechanical Applications: CNTs are characterized with superior
mechanical properties such as stiffness, toughness and strength. These properties lead in
the production of very strong, lightweight materials that can be sued in areas such as
building, structural engineering and aerospace.
8. Aerospace Components: CNTs have good fatigue strength over a long time which makes
use of them as aircraft components.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 54

 ADVANCED MATERIAL CHEMISTRY

SMART MATERIALS

Introduction:
The world has undergone two materials ages, the plastics age and the composite age, during
the past centuries. In the midst of these two ages a new era has developed. This is the smart
materials era. According to early definitions, smart materials are materials that respond to their
environments in a timely manner. With the development of material science, many new, high-
quality and cost-efficient materials have come into use in various field of engineering. In the
last ten decades, the materials became multifunctional and required the optimization of
different characterization and properties. With the last evolution, the concept has been driving
towards composite materials and recently, the next evolutionary step is being contemplated
with the concept of smart materials. Smart materials are new generation materials surpassing
the conventional structural and functional materials. These materials possess adaptive
capabilities to external stimuli, such as loads or environment, with inherent intelligence.

Smart or intelligent materials are materials that have the intrinsic and extrinsic capabilities,
first, to respond to stimuli and environmental changes and, second, to activate their functions
according to these changes. The stimuli could originate internally or externally. The definition
of smart materials has been expanded to materials that receive, transmit, or process a stimulus
and respond by producing a useful effect that may include a signal that the materials are acting
upon it. Some of the stimuli that may act upon these materials are strain, stress, temperature,
chemicals (including pH stimuli), electric field, magnetic field, hydrostatic pressure, different
types of radiation, and other forms of stimuli

Smart materials
Smart materials, also called intelligent or responsive materials, are designed materials that
have one or more properties that can be significantly changed in a controlled fashion by
external stimuli, such as stress, moisture, electric or magnetic fields, light, temperature, pH, or
chemical compounds.
The several external stimulus to which the smart materials sensitive are:
• Stress
• Temperature
• Moisture
• pH
• Electric Fields
• Magnetic Fields

Three basic components of a smart system are:

 Sensor
 processor
 Actuator

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 55

 ADVANCED MATERIAL CHEMISTRY

Fig: Common smart materials and associated stimulus-response.

Example: Smart concrete building (suitable to earth quake areas)

Sensor : optical fibers (embedded in concrete)
Processor: smart wires (automatic shrink/expand)
Actuator: chemically active smart materials (fillers preventing crack propagation)

Classification of Smart Materials

Active and Passive Smart Materials:

Smart materials can be either active or passive. Fairweather (1998) defined active smart
materials as those materials which possess the capacity to modify their geometric or
material properties under the application of electric, thermal or magnetic fields, thereby
acquiring an inherent capacity to transduce energy. Piezoelectric materials, shape memory
alloys, and magnetostrictive materials are active smart materials. Being active, they can be
used as force transducers and actuators.
The smart materials, which are not active, are called passive smart materials. Although
smart, these lack the inherent capability to transduce energy. Fibre optic material is a good
example of a passive smart material. Such materials can act as sensors but not as actuators
or transducers.

Types of Smart Materials

1. Piezoelectric Materials
2. Shape Memory Alloys
3. Magnetostrictive Materials
4. Electrostrictive materials

Piezoelectric Materials
• The word originates from the Greek word “piezein”, which means “to press”.
Discovered in 1880 by Pierre Curie in quartz crystals

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 56

 ADVANCED MATERIAL CHEMISTRY

• Piezoelectrics are materials that can create electricity when subjected to a mechanical
stress.
• They will also work in reverse, generating a strain by the application of an electric
field.
• Piezoelectric effect: When subjected to an electric charge or a variation in voltage,
piezoelectric material will undergo some mechanical change, and vice versa. These
events are called the direct and converse effects.
All piezoelectric materials are non-conductive in order for the piezoelectric effect to occur and
work. They can be separated into two groups: crystals and ceramics.

Working Principle
Piezoelectric effect
Piezoelectric effect is the ability of certain materials to generate an electric charge in response
to applied mechanical stress

Direct Piezoelectric Effect

Piezoelectric material will generate electric potential when subjected to some kind of
mechanical stress.
Devices that use the direct piezoelectric effect include microphones, pressure sensors,
hydrophones, and many other sensing types of devices.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 57

 ADVANCED MATERIAL CHEMISTRY

Inverse Piezoelectric Effect

If piezoelectric material is exposed to an electric field (voltage) it consequently lengthens or
shortens proportional to voltage.
The piezoelectric effect can be reversed, which is referred to as the inverse piezoelectric effect.
This is created by applying electrical voltage to make a piezoelectric crystal shrink or expand.
The inverse piezoelectric effect converts electrical energy to mechanical energy.

Using the inverse piezoelectric effect can help develop devices that generate and produce
acoustic sound waves. Examples of piezoelectric acoustic devices are speakers (commonly
found in handheld devices) or buzzers. The advantage of having such speakers is that they are
very thin, which makes them useful in a range of phones. Even medical ultrasound and sonar
transducers use reverse piezoelectric effect. Non-acoustic inverse piezoelectric devices include
motors and actuators.

Fig: Piezoelectric effect

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 58

 ADVANCED MATERIAL CHEMISTRY

Examples of Piezoelectric materials

Natural Synthetic
Quartz Lead zirconatetitanate (PZT)
Rochelle salt Zinc oxide (ZnO)
Topaz Barium titanate (BaTiO3)
Sucrose Gallium orthophosphate (GaPO4)
Tendon Potassium niobite (KNbO3)
Silk Lead titanaate (PbTiO3)
Enamel Lithium tantalite (LiTaO3)
DNA Sodium tungstate (Na2WO3)

Applications of Piezoelectric material

Mechanical to Electrical Conversion Electrical to Mechanical Conversion
1. Phonograph cartridges 1. Valves
1. Microphones 2. Earphones and speakers
2. Vibration sensors 3. Ultrasonic cleaners
3. Accelerometers 4. Emulsifiers
4. Photoflash actuators 5. Sonic transducers
5. Gas igniters 6. Micro pumps
6. Fuses -

Electrostrictive Materials:
This material has the same properties as piezoelectric material, but the mechanical change is
proportional to the square of the electric field. This characteristic will always produce
displacements in the same direction.
Electrostrictive materials are materials that exhibit a quadratic relationship between mechanical
stress and an applied electric polarization (Fig). Electrostriction can occur in any material.
Whenever an electric field is applied, the induced charges in the material attract each other
resulting in a compressive force. This attraction is independent of the sign of the electric field.
The strain in the material lies along the axis of the induced polarization, which is preferably
the direction of the applied electric field. Electrostriction is a small effect and, in contrast to
piezoelectric materials, electrostrictive materials show a large effect near the Curie
temperature, especially for ferroelectric substances, such as members of the perovskite family.

Examples: Lead Lanthanum Zirconate Titanate (PLZT); Lead Magnesium Niobate (PMN).
Electrostriction is used in actuators for accurate and fine positioning. Electrostrictive translators
are less stable than piezoelectric devices with greater sensitivity to temperature.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 59

 ADVANCED MATERIAL CHEMISTRY

Applications of Electrostrictive Materials

• Sonar projectors for submarines and surface vessels
• Actuators for small displacements
• Lead Magnesium Niobate is a piezoelectric polycrystalline ceramic material with
applications in optoelectronics and acousto-optics.
• Lead zirconate titanate is used to make ultrasound transducers and other sensors and
actuators, as well as high-value ceramic capacitors and FRAM chips.
• PLZT is a piezoelectric ceramic material with applications in dielectric thin films,
CMOs, ceramic capacitors and resonators, ultrasound transducers, photovoltaic cells,
and energy storage.

Magnetostrictive materials:
Magnetostrictive materials are similar to piezoelectric and electrostrictive materials except the
change in shape is related to a magnetic field rather than an electrical field.
Magnetostrictive materials convert magnetic to mechanical energy or vice versa. The
magnetostrictive effect was first observed in 1842 by James Joule who noticed that a sample
of nickel exhibited a change in length when it was magnetised. The other ferromagnetic
elements (cobalt and iron) were also found to demonstrate the effect as were alloys of these
materials. During the 1960s terbium and dysprosium were also found to be magnetostrictive
but only at low temperatures which limited their use, despite the fact that the size change was
many times greater than that of nickel. The original observation of the magnetostrictive effect
became known as the Joule effect, but other effects have also been observed. The Villari effect
is the opposite of the Joule effect, that is applying a stress to the material causes a change in its
magnetization.

Working Principle
When subjected to a magnetic field, and vice versa (direct and converse effects), this material
will undergo an induced mechanical strain. Consequently, it can be used as sensors and/or
actuators.

Magnetic materials contain domains which can be likened to tiny magnets within the material.
When an external magnetic field is applied the domains rotate to align with this field and this
results in a shape change as shown in Figure 6. Conversely if the material is squashed or
stretched by means of an external force the domains are forced to move and this causes a change
in the magnetisation.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 60

 ADVANCED MATERIAL CHEMISTRY

Examples: Materials that have shown a response to a magnetic stimuli are primarily inorganic:
alloys of iron, nickel, and cobalt doped with rare earths.

The most common magnetostrictive material today is called TERFENOL-D (terbium (TER),
iron (FE), Naval Ordanance Laboratory (NOL) and dysprosium (D)). This alloy of terbium,
iron and dysprosium shows a large magnetostrictive effect and is used in transducers and
actuators.

Applications:
• Magnetostrictive materials can be used as both actuators (where a magnetic field is applied
to cause a shape change) and sensors (which convert a movement into a magnetic field).
• Early applications of magnetostrictive materials included telephone receivers,
hydrophones, oscillators and scanning sonar.
• The development of alloys with better properties led to the use of these materials in a wide
variety of applications. Ultrasonic magnetostrictive transducers have been used in
ultrasonic cleaners and surgical tools. Other applications include hearing aids, razorblade
sharpeners, linear motors, damping systems, positioning equipment, and sonar

Shape Memory Alloys:

Shape Memory alloys are metals that exhibit the properties of pseudo-elasticity and the Shape
Memory Effect.

• Shape memory alloys are smart materials

• A shape memory alloys (SMA) are metal alloys that can be deformed at one temperature
but when heated or cooled, return to their “original shape”.
• Shape Memory Alloys are materials that “remember” their original shape.
• If deformed, they recover their original shape upon heating.
• They can take large stresses without undergoing permanent deformation.
• They can be formed into various shapes like bars, wires, plates and rings thus serving
various functions.
• SMA also exhibits super elastic (Pseudoelastic) behaviour.
The high temperature causes the atoms to arrange themselves into the most compact and regular
pattern possible.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 61

 ADVANCED MATERIAL CHEMISTRY

Shape Memory Effect – unique ability of materials to be severely deformed and then return
to their original shape through stimulus
SME occurs due to the change in the crystalline structure of materials.

Working Principle
• SMAs have two stable phases are:
• Martensite: Low temperature phase, relatively weak
• Austenite: High temperature phase, relatively strong
• Martensite to Austenite transformation occurs by heating
• Austenite to Martensite occurs by cooling.
• A phase transformation which occurs between these two phases upon heating/cooling
is the basis for unique properties of SMAs.

When subjected to a thermal field, this material will undergo phase transformations which will
produce shape changes. It deforms to its ‘martensitic’ condition with low temperature, and
regains its original shape in its ‘austenite’ condition when heated (high temperature).

Examples: Nickel-Titanium alloys (NiTinol)

Copper -Aluminium- Nickel alloys
Copper-Zinc-Aluminium alloys
Iron -Manganese-Silicon alloys
Nickel–titanium alloys have been the most used shape memory material. This family of nickel–
titanium alloys is known as Nitinol, after the laboratory where this material was first observed
(Nickel Titanium Naval Ordinance Laboratory).

Applications of Smart memory Alloys

Nitinol has been used in military, medical, safety, and robotics applications. Specific
applications include hydraulic lines on F-14 fighter planes, medical tweezers and sutures,

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 62

 ADVANCED MATERIAL CHEMISTRY

anchors for attaching tendons to bones, stents for cardiac arteries, eyeglass frames, and
antiscalding valves in water faucets and showers

1) Aircraft
Alloys can be used to create flexible wings in aircrafts using Shape Memory wires.

2) Automotive
To reduces engine noise, some designers installs chevrons onto engines to mix the flow of
exhaust gases and reduces engine noise.

3) Robotics
Muscle Wires: SMAs are very good at mimicking human muscles and tendons so they can be
used to create humanlike movements in robots.

4) Civil Structures
SMAs find a variety of applications in civil structures such as bridges and buildings. One such
application is Intelligent Reinforced Concrete (IRC), which incorporates SMA wires embedded
within the concrete.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 63

 ADVANCED MATERIAL CHEMISTRY

5) Piping
The first consumer commercial application was a shape-memory coupling for piping, e.g. oil
line pipes for industrial applications, water pipes.

6) Medicine
Stent- A reinforced grafts for vascular application to replace or repair damaged arteries (25mm
diameter)

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 64

 ADVANCED MATERIAL CHEMISTRY

Unit V: PHOTOCHEMISTRY

Introduction:
Photochemical reactions occur all around us, being an important feature of many of the
chemical processes occurring in living systems and in the environment. The power and
versatility of photochemistry is becoming increasingly important in improving the quality of
our lives, through health care, energy production and the search for ‘ green ’ solutions to some
of the problems of the modern world. Many industrial and technological processes rely on
applications of photochemistry, and the development of many new devices has been made
possible by spin - off from photochemical research.

Photochemistry is the study of the chemical reactions and physical changes that result
from interactions between matter and visible or ultraviolet light.

Photochemistry:
The branch of chemistry which deals with the absorption of light radiations and its effect
(physical or chemical) on the substance is known as photochemistry.
Photochemistry is concerned with reactions which are initiated by electronically excited
molecules. The light radiations which are important from the photochemistry point of view are
those of visible and ultra-violet regions, i.e., those having wavelength between 2000 A 0 to 8000
A0. It is for this reason, photochemistry has made large contributions to the fundamental and
applied sciences.

Laws of Photochemistry:
Photochemistry has two basics laws, which describe the condition and efficiency of photo
absorption.
Grotthuss–Draper law:
• The first law of photochemistry called as Grotthuss-Draper law.
• This law states that radiation must be absorbed by the compounds in order for a
photochemical reaction to happen.
•
Stark-Einstein law:
• The second law of photochemistry called as the Stark-Einstein law.
• This law states that for each photon of radiation absorbed by a chemical system, no
more than one molecule is activated for a photochemical reaction.

Stark-Einstein Law: (Einstein law of photochemical equivalence)

“Each molecule of absorbing substance absorb one photon (or quantum) of the radiation in
primary process.”

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 65

 ADVANCED MATERIAL CHEMISTRY

Explanation:
A molecule acquire energy by absorbing photon as,

A + hυ ---------> A*

Thus energy of photon is,

E = hυ

Where υ = frequency of absorbing photon. h = plank’s constant = 6.624 × 10–34 J.s The
energy of 1 mol photon (ie. Einstein) is given by, E = N.h.υ

𝑵.𝒉.𝑪
But, υ = C/λ E=
𝛌

N= Avogadro’s no. = 6.023 × 1023 mol– . C= velocity of light. = 3 × 108 m/s.

A mole of photon can excite a mole of molecule. But if electromagnetic radiations are extremely
intense, molecule may absorb two or more photons.

A + 2 hυ ---------> A*

Hence this law is not valid for all condition.

The Beer –Lambert’s Law

The Beer–Lambert law, also known as Beer’s law, the Lambert–Beer law relates
the attenuation of light to the properties of the material through which the light is travelling.
When a monochromatic light of initial intensity Io passes through a solution in a transparent
vessel, some of the light is absorbed so that the intensity of the transmitted light I is less than
Io .There is some loss of light intensity from scattering by particles in the solution and reflection
at the interfaces, but mainly from absorption by the solution.

The relationship between I and Io depends on the path length of the absorbing medium, l or x,
and the concentration of the absorbing solution, c. These factors are related in the laws of
Lambert and Beer.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 66

 ADVANCED MATERIAL CHEMISTRY

Lambert’s Law:
When a monochromatic radiation is passed through a homogeneous absorbing
medium, the rate of decrease in the intensity of radiation with thickness of absorbing medium
is directly proportional to the intensity of the incident radiation.

−dI −dI
αI ie = k. I
dx dx

dI
➔ = −k. dx
I

On integrating above equation between respective limits,

I
log10 = −a. x
Io
I
➔ = 10−a.x
Io

Lamberts-Beer’s Law (or Beer’s Law):

When a monochromatic radiation is passed through a solution of absorbing
medium, the rate of decrease in the intensity of radiation with thickness of absorbing
medium is directly proportional to the intensity of the incident radiation and concentration
of the solution.

−dI −dI
α I. c. ie. = k′. I. c
dx dx

dI
➔ = −k′ . c. d
I
On integrating equation between respective limits,
I
log10 = −ε. c. x
Io

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 67

 ADVANCED MATERIAL CHEMISTRY

𝑰𝒐
A= = 𝜺𝒄𝒙
𝑰

A = Absorbance or optical density (OD)

I0 = Intensity of incident light
I = Intensity of transmitted light
 = molar absorption coefficient (L mol-1cm-1)
c = concentration of solution (mol/lit)
x = thickness of absorbing medium(cm)

The units of e require some explanation here as they are generally expressed as non-SI units
for historic reasons, having been used in spectroscopy for many years.

Concentration, c, traditionally has units of moles per litre, mol L-1

Path length, l, traditionally has units of centimetres, cm.
A has no units since it is a logarithmic quantity.

Limitations of Beer – Lambert’s Law

1. The law holds good only for monochromatic radiation.
2. The law governs the absorption behaviour of dilute solutions only.

Types of Photo Processes

The two main types of processes which we study under photochemistry are
1) Photophysical processes
2) Photochemical processes or Photochemical reactions

Photochemical Processes or Photochemical Reactions

Processes in which absorbed light causes some chemical change in the substance are called
photochemical processes.
Types of photochemical reactions:
a) Photodissociation
b) Photosynthesis: when a larger molecule is formed from simple ones
c) Photosensitized reactions: when an excited molecule supplies activation energy for the
reactants.

Processes of photochemical reactions: The overall photochemical reaction consists of

i) Primary reaction and ii) Secondary reaction.
In the primary reaction, the quantum of light is absorbed by a molecule A resulting in the
formation of an excited molecule.
A + h →A*

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 68

 ADVANCED MATERIAL CHEMISTRY

In the secondary reaction, the excited molecules react further to give the product of higher
quantum yield.
A*→B

All photochemical reactions take place in two steps. In the first step, the reacting molecules are
activated by absorption of light. In the second step, the activated molecules undergo a
photochemical change.

Examples:
Decomposition of HI: In the primary reaction, one HI molecule absorbs a photon and
dissociated to produce one H and one I. This is followed by the second reaction as shown below:
HI + h → H+ I............................Primary reaction

H + HI → H2 +I

I + I→ I2 ..................................Secondary reaction

Overall reaction: 2HI + h → H2 +I2

The overall reaction shows that the two HI are decomposed for one photon (h).

Formation of HCl: In the primary step, one Cl2 molecule absorbs a photon and discussed into
two Cl atoms. This is followed by the secondary reaction as shown below:

Cl2 + h → 2Cl ........................ Primary reaction

Cl + H2 → HCl + H

H + Cl2 → HCl + Cl....................Secondary reaction

Photosensitizations: In some photochemical reactions, the reactant molecules do not absorb

radiation and no chemical reaction occurs. However, if a suitable foreign substance (called
sensitizer), which absorbs radiation, is added to the reactant, the reaction takes place. The
sensitizer gets excited during absorption of radiation and transfers its energy to the reactants
and initiates the reaction.

Photosensitization: The foreign substance absorbs the radiation and transfers the absorbed
energy to the reactants is called a photosensitizer. This process is called photosensitized reaction
(or) photosensitization. Examples,

i) Atomic photosensitizers : mercury, cadmium and zinc.

ii) Molecular photosensitizers: benzophenone, sulphur dioxide.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 69

 ADVANCED MATERIAL CHEMISTRY

Examples:
A) Dissociation of Hydrogen: UV light does not dissociate H2 molecule, because the molecule
is unable to absorb the radiation. But, if a small amount of mercury vapour is added, dissociation
of hydrogen takes place. Here Hg acts as photosensitizer.

Hg + hυ Hg*

Hg* + H2 Hg + 2H

B) Photosynthesis in plants: During photosynthesis of carbohydrates in plants from CO 2 and

H2O, chlorophyll of plants acts as a photosensitizer. The energy of the light absorbed by the
chlorophyll (due to the presence of conjugation in chlorophyll) is transformed to CO2and
H2O molecules, which then react to form glucose.

hυ; chlorophyll
6CO2 + 6 H2O C6H12O6 + 6O2

Photophysical Processes
Generally atoms or molecules go to excited state by the absorption of suitable radiation. If the
absorbed radiation is not used to cause a chemical reaction, it will be re-emitted as light of
longer wavelength. This process is called as photophysical process.
These are processes in which a substance absorbs light and emits it without undergoing any
chemical change. These processes are again classified into three types depending upon the
nature of absorbed light and the manner in which it is emitted.

a) If the absorbed light is emitted instantaneously, the process is known as fluorescence.

b) If the absorbed light is emitted after time lag, the process is called phosphorescence.
c) If the absorbed light has sufficiently high energy, the electrons not only jump to the outer
levels, but may leave the atom completely. This process is called photoelectric effect.

Types of Photophysical process:

Photophysical process is of two types
1) Fluorescence
2) Phosphorescence

Fluorescence:
The phenomenon in which a substance absorbs light and emits a part of it instantaneously,
usually at a different wavelength is called fluorescence and the substance itself is called
fluorescent. Fluorescence stops as soon as light is cut off.

The phenomenon of fluorescence is explained on the basis of the fact that absorption of light
energy causes excitation of the electrons of the atoms of molecules of the substance. These
excited electrons immediately jump back to the lower level emitting a part of absorbed light in

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 70

 ADVANCED MATERIAL CHEMISTRY

the form of radiations of different wavelengths. Usually the emitted radiation has greater
wavelength than that of the absorbed light. This is due to the fact that the absorbed energy raises
the electron to a sufficiently higher level but the return of the excited electron to the original
level takes place in steps, through the intermediate levels. The energy thus produced in every
jump is smaller and hence the wavelength of the light emitted is larger than that of the absorbed
light.

Mechanism of Fluorescence

However in some cases (eg: mercury vapours) the emitted light has the same wavelength as that
of the absorbed light. This phenomenon is called resonance fluorescence. Further in certain
cases, light of shorter wavelength (i.e., of higher energy) is emitted. This is explained by
suggesting that the emitted light contains, in addition to the absorbed light, some energy is
already present in the system before absorption.

If a mixture is present i.e., it mercury vapours are mixed with the vapours of silver, thallium
lead or zinc, which do not absorb at the wavelength of mercury vapours, a part of the excitation
energy from mercury atoms gets transferred to the atoms of the foreign substances (Silver,
thallium, lead or zinc). These are then raised to higher energy states and emit, radiation when
they return to their lower energy states. This is termed as sensitized fluorescence.

On the other hand the intensity of fluorescent radiation is diminished ifa photo chemically
excited atom collides with another atom. This is known as quenching of fluorescence and is
because of the transfer of energy from the excited atom to the colliding atoms.

A few examples of fluorescent substances are listed below:

1. Certain organic dyes eg: fluorescein and eosin. If their solutions are kept in light,they
show fluorescence from green to violet color.
2. Fluorespar-fluorite (CaF2) fluoresces with blue light.
3. Vapours of sodium, mercury, iodine, etc.
4. Uranyl sulphate UO2SO4 (green light).
5. Chlorophyll (green colouring matter of plants) solution in ether, fluoresces blood red,
but appears green by transmitted light.
6. Petroleum
7. A solution of quinine sulphate emits blue light on irradiation with light.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 71

 ADVANCED MATERIAL CHEMISTRY

Applications of Fluorescence

• Used in testing the condition of food stuffs.

• Used for detecting ring worm.
• In industry for testing and identifying material. eg: in rubber industry.
• In analysis: Concentration of riboflavin (Vitamin B2) in chloroform can be examined
• Use of fluorescent microscopes: Fluorescope used in X - ray diagnosis is helpful in
testing condition of food stuff and detecting ring worms etc.
• In television: The cathode stream of the photoelectric effect is made visible in the
cathode ray tube by adding ZnS to which a little Ni Is added to cut off phosphorescence
which would make the picture blurred.
• For lightening purposes in fluorescence tubes.
• Using this phenomenon (fluorescence) invisible radiations like ultraviolet rays can be
viewed.
• The difference in the fluorescence caused by UV rays in different types of inks enables
police to detect forged documents.

Phosphorescence:
The phenomenon in which a substance absorbs light and emits it for some time even after the
external light is cut off is called phosphorescence and the substances exhibiting this
phenomenon are called phosphorescent. Thus phosphorescence may be regarded as slow or
delayed fluorescence. This phenomenon is observed mainly in solids because in solids,
molecules are tightly packed and have least freedom of motion, and thus the excited electrons
keep on jumping back slowly for quite some time.

The mechanism of phosphorescence is similar to fluorescence except that the electrons are
trapped in metastable excited state called triplet state with low probability of direct transition
to the lower level, giving rise to a slow emission of radiation. In this phenomenon the emission
of light of different wavelengths continues even after the source of light radiation has been
cutoff.

Fig: Mechanism of Phosphorescence

Sulphides of zinc and alkaline earth metals containing traces of heavy metal sulphide are best
examples of phosphorescent substances. Such mixtures are generally used for luminous paints,
for painting watch dials, electric switches etc. Further the fluorescent substances become

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 72

 ADVANCED MATERIAL CHEMISTRY

phosphorescent when fixed by suitable methods i.e., by fusion with other substances. For
example, many dyes which show fluorescence, when dissolved in fused boric acid or glycerol
followed by cooling, become phosphorescent.

Phosphorescence is rarely observed in gases, and almost never observed at room temperature.

Applications of Phosphorescence:
Phosphorescence finds applications in biology and medicine similar to that of fluorescence.
Some interesting applications are as follows.

One can carry out the determination of aspirin (acetyl salicylic acid) in blood serum with high
sensitivity by phosphorimetry at liquid nitrogen temperatures.

• Low concentration of procaine, cocaine, phenobarbital and chloropromazine in blood

serum have been determined by phosphorimetry in combination with extraction
procedures.
• Cocaine and atropine in urine have been determined by employing phosphorimetry in
combination with extraction procedures.
• Phosphorimetry has been employed in combination with thin layer or paper
chromatography for separating three tobacco alkaloids (nicotine, nor nicotine and
anabasine) from crude tobacco.

Differences between Fluorescence and Phosphorescence

Fluorescence Phosphorescence
It is the radiation emitted in a transition It is the radiation emitted in a transition
between states of different multiplicity between states of same multiplicity
Its decay period is much longer, 10-4-100 s. Its decay period is very short, 10-9-10-4sec.

It is not observed in solution at room It can be observed in solution at room

temperature. temperature.
Its spectrum is mirror image of the Its spectrum is not mirror image of the
absorption spectrum. absorption spectrum.
It is exhibited by some elements in vapour It is rarely observed in gaseous or
state. vapours.
Examples: uranium, petroleum, organic Examples: ZnS, sulphides of alkaline
dyes, chlorophyll, CaF2,etc. earth metals.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 73

 ADVANCED MATERIAL CHEMISTRY

Jablonski Diagram or Mechanism of Photophysical Process or Mechanism

of Fluorescence and Phosphorescence:
The phenomenon of fluorescence and phosphorescence are best explained with the help of the
Jablonski diagram. The Jablonski diagram is a pictorial representation of the energy transitions
caused by the absorption of a UV radiation by a molecule.

Fig: Jablonski Diagram

Modified Jablonski diagram shows transitions between excited states and the ground state.
Radiative processes are shown by straight line, radiationless processes by wave lines.
Most molecules possess an even number of electrons and all the electrons are paired in ground
state. The spin multiplicity of a state is given by 2S + 1, where S is the total electronic spin.

Fig: Spin orientation of absorption of light photon

i) When the spins are paired (↑↓), the clockwise orientation of one electron is cancelled by
the anticlockwise orientation of other electron. Thus,
S = s1 + s2 = (1/2) – (1/2) = 0
2S + 1 = 1, ie., spin multiplicity is 1. The molecule is in the singlet ground state.

ii) On absorption of a suitable energy, one of the paired electrons goes to a higher energy
level. The spin orientation of the two electrons may be either
a) Parallel (↑↑), then S= s1+s2 = (1/2)+(1/2) = 1, 2S +1= 3, ie., spin multiplicity is 3. The
molecule is in the triplet (T) excited state.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 74

 ADVANCED MATERIAL CHEMISTRY

b) or anti-parallel (↑↓), then S = s1 + s2 = (1/2) – (1/2) = 0, 2S + 1 = 1, ie., spin multiplicity

is 1. The molecule is in the singlet (S) excited state
Since the electron can jump from the ground state to any of the higher electronic states
depending upon the energy of the photon absorbed we get a series of
a) singlet excited states ie., S1, S2, S3, etc., (first singlet excited state, second singlet
excited state, third singlet excited state, etc.)and
b) triplet excited states ie., T1, T2, T3, etc., (first triplet excited state, second triplet excited
state, third triplet excited state, etc.).
Generally singlet excited state has higher energy than the corresponding triplet excited state.
Thus, the energy sequence is as follows: ES1> ET1> ES2> ET2> ES3> ET3 and so on.

When a molecule absorbs light radiation, the electron may jump from S0 to S1, S2 (or) S3 singlet
excited state depending upon the energy of the light radiation as shown in Jablonski diagram.
For each singlet excited state there is a corresponding triplet excited state, ie.

S1 → T1; S2 → T2; S3 → T3, etc.

Types of Transitions:

Absorbance

The first transition in the Jablonski diagrams is the absorbance of a photon of a particular energy
by the molecule of interest. Absorbance is the method by which an electron is excited from a
lower energy level to a higher energy level.

The excited species can return to the ground state by losing all of its excess energy by any one
of the following absorptions

1. Non-radiative Process
2. Radiative Process

Non-radiative transition: It does not involve the emission of any radiations, so these are also
known as non-radiative or radiation less transitions. It involves transition from, S2 → S1 or S3
→ S1 or T2 → T1 or T3 → T1. It only involves emission of heat. Non-radiative transitions
involve the following two transitions.

a) Internal Conversion (IC): These transitions involve the return of the activated molecule
from the higher excited states to the first excited states, ie. It involves transition from, S3 →
S2 or S2 → S1 Or T3 → T2 or T2 → T1 . In this process energy loss in the form of heat. It
occurs in less than 10-11second.

b) Intersystem Crossing (ISC): The molecule may also lose energy by another process called
inter system crossing (ISC). These transitions involve the return of the activated molecules
from the states of different spins ie. Different multiplicity ie., S2→ T2; S1 → T1. These
transitions are forbidden, occurs relatively at slow rates.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 75

 ADVANCED MATERIAL CHEMISTRY

Radiative transition: It involves the return of activated molecules from the singlet excited state
S1 and triplet state T1 to the ground state S0. These transitions are accompanied by the emission
of radiations. It involves transition from S1→ S0 or T1→ T0. Thus, radiative transitions involve
the following two radiations.

Fluorescence The emission of radiation due to the transition from singlet excited state S 1 to
ground state S0 is called fluorescence (S1 → S0). This transition is allowed transition and occurs
in about 10-8second.

Phosphorescence The emission of radiation due to the transition from the triplet excited state
T1 to the ground state S0 is called phosphorescence (T1 → S0). This transition is slow and
forbidden transition. In phosphorescence even after incident light radiation is cut off there is
emission of light for some time. It is also called slow Fluorescence. The substance which shows
Phosphorescence is called fluorescent substance. The name Phosphorescence is derived from
phosphorous which glows in dark.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 76