SYNTHESIS AND CHARACTERISATION OF MANGANESE

DOPED TITANIUM DIOXIDE NANOPARTICLES

A Project Report submitted to the Department of Physics,
PSG College of Arts and Science (Autonomous), Affiliated to Bharathiar University
In partial fulfilment of the requirements for the award of the Degree of

MASTER OF SCIENCE IN PHYSICS

Submitted by

PRIYADHARSHINI R
18MPH019
Under the guidance of

Dr. M.ELANGO M.Sc., M.Phil., Ph.D.,

Assistant Professor of Physics
DEPARTMENT OF PHYSICS

PSG COLLEGE OF ARTS AND SCIENCE

An Autonomous college-Affiliated to Bharathiar University

Re-Accredited with ‘A’ Grade by NAAC (Third Cycle)
College with Potential for Excellence
(Status awarded by the UGC)
An ISO 9001:2008 certified institution
Coimbatore- 641014
APRIL-2020
1
 DECLARATION

I PRIYADHARSHINI R, hereby declare that the dissertation entitled “SYNTHESIS

AND CHARACTERISATION OF Mn DOPED TiO2” is submitted to the PSG
COLLEGE OF ARTS & SCIENCE affiliated to Bharathiar university in partial
fulfillment of the requirements for the award of the degree of MASTER OF SCIENCE in
PHYSICS is a record of original project work done by me during the period 2019-2020,
under the guidance of Dr. M.ELANGO M.Sc., M.Phil., Ph.D., Assistant professor in
Department of Physics, PSG College of Arts & Science Coimbatore-14 and it has not
formed the base for the award of any Degree/Diploma/Fellowship/Associateship or other
similar title to any candidate of any university.

Place: Coimbatore

Date: Signature of the student

Name of the student: PRIYADHARSHINI R

Roll No : 18MPH019

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 CERTIFICATE

This is to certify that this project report entitled “SYNTHESIS AND

CHARACTERISATION OF Mn DOPED TiO2 NANOPARTICLES” is submitted to
the PSG COLLEGE OF ARTS & SCIENCE affiliated to Bharathiar university in the
partial fulfillment of the requirement for the award of the degree of MASTER OF
SCIENCE in PHYSICS is a record of original project work done by
PRIYADHARSHINI R (18MPH019) during the period (2019-2020) of his study in the
DEPARTMENT OF PHYSICS, PSG COLLEGE OF ARTS AND SCIENCE,
COIMBATORE-14, under my supervision and guidance.

Place: Coimbatore

Date:

Faculty Guide Head of the Department

Submitted for the Viva Voce Examination held on

Internal Examiner External Examiner

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 ACKNOWLEDGEMENT

I am grateful to God for the good health and well- being that were necessary to
complete this project.

I am extremely thankful and I owe a special depth of sincere gratitude to my research

guide Dr. M.ELANGO M.Sc., M.Phil., Ph.D., Assistant professor, Department of
Physics, PSG College of Arts and Science for suggesting this interesting topic for my
project work and for her excellence guidance and valuable advice throughout the course of
my project work.

I take this golden opportunity to render my deep sense of gratitude to

Dr. V. VEERAVAZHUTHI, M.Sc., MS., MPhil., PhD., Associate Professor and Head
of the Department, Department of Physics, PSG College of Arts and Science for providing
his valuable guidance throughout our entire project work.

I express my heartfelt thanks to Dr. D.BRINDHA, Principal, PSG College of Arts and
Science, for her motivation in taking up project activities. My sincere thanks to
Thiru. Dr.T. KANNAIAN, Secretary, PSG College of Arts and Science, for his
magnanimous support throughout the project period.

I genuinely thank all the teaching and non-teaching staff members of Department of
physics, PSG College of Arts and Science, for their constant encouragement and support.
My hearty thanks to Ms. J.VARUNA Research Scholar, for her constant support and his
valuable guidelines in my project work.

I am left with no words to express my gratitude to my most beloved family members for
their pillar support both mentally and financially throughout my project work.

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 I thank all my friends for their help and motivation in all various levels for the
completion for my project work.

PRIYADHARSHINI R

(18MPH019)

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 CONTENTS

CHAPTER CONTENT PAGE NO

1 INTRODUCTION TO NANOTECHNOLOGY 7

2 LITERATURE REVIEW 23

3 MATERIAL INTRODUTION & 28

METHODOLOGY

4 CHARACTERIZATION TECHNIQUE 36

5 RESULT AND DISCUSSION 53

6 SUMMARY AND CONCLUSION 58

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CHAPTER-1

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 INTRODUCTION TO NANOTECHNOLOGY

1.1 INTRODUCTION

The word nano is a scientific prefix that stands for or 1 billionth; the word comes from

the Greek word nanos, meaning dwarf. To put this into perspective, a strand of human hair is roughly
75,000 nm across. On the flipside of the concept, you’d need ten hydrogen atoms lined up end-to-end to
make up 1 nm. Nanotechnology involves research and technology development at the 1 nm to 100 nm
range which creates and uses structures that have novel properties because of their small size. Industries
such as materials manufacturing, computer manufacturing, and healthcare will benefit — both directly
and indirectly from advances made by fellow players in the nano field. (Imagine, for example, quantum
computers simulating the effectiveness of new nanobased).Many fields of endeavor contribute to
nanotechnology, including molecular medicines physics, materials science, chemistry, biology, computer
science, electrical engineering, and mechanical engineering.

Nanomaterials with critical dimensions less than 100 nm may exhibit superior chemical,
biological, mechanical, electronic, magnetic, and optical properties that are often significantly different
from their corresponding micro counterparts. [1].They contain just a few atoms to a few thousand atoms
called quasi zero-dimensional mesoscopic systems, quantum dots, quantized or Q-particles, etc., This
difference is what causes nano materials to have unique characteristics, including how they react with
other materials, their color, and even how they melt at high temperatures. These unique properties depend
on the atomic structure, size confinement, composition, microstructure, defects, and interfaces, all of
which can be tailored by synthesis and other processes.

Nanotechnology makes it possible to achieve several benefits when you manufacture materials.
For example, nanomaterials can be stronger and more lightweight than their non-nanocounterparts. Nano
also makes it possible to make materials smaller, a key aspect of building computer chips. In addition,
nanoparticles can help fibers resist stains and repel water. Used as catalysts in chemical reactions,
nanoparticles can make processes more efficient and reduce the amount of energy they require. It could
extend our lives in a couple of ways: by helping to eradicate life-threatening diseases such as cancer,
heart disease, and diabetes and by making it possible to repair damage to our bodies at the cellular level.

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 Nanotechnology has achieved tremendous progress in the past several decades.It is expected
that the Nanotechnology will change the human life, medical and scientific field more profoundly than
many developments of the past.

Figure: 1.1 Size comparisons, from you (1.75 meters, or approximately 5 ft. 7 in.) all the way down to the
hydrogen Atom (0.1 nm).[1]

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1.2 HISTORY
Nanoparticles have been used by people for thousands of years, but they didn’t know it.
Researchers report that a lead-based hair dye used in ancient. Egypt created nano crystals during the
chemical reaction involved in the dyeing process. As early as the tenth century, many European church
windows got their color from gold nanoparticles embedded in glass.

The example of earlier use of nanomaterials are the Lycurgus cup from the 4th century AD on
display in the British museum in London. When light shines from the outside on the antique roman cup,
the cup looks olive green, when illuminated from the inside it shines ruby red. Colloidal nanoparticles of
silver and gold are responsible for this phenomenon.

The modern nanotechnology was the brain child of Richard P. Feynman, an American theoretical
physicist. He presented a lecture titled “There’s Plenty of Room at the Bottom” in 1959 at the California
Institute of Technology (CalTech) in which he introduced the concept of manipulating matter at the
atomic level.

The Japanese Scientist Norio Taniguchi of the Tokyo University of Science was the first to use the
term “Nano-Technology” in a 1974 conference, to describe semiconductor processes such as thin film
deposition and ion beam milling exhibition characteristic control on the order of a nanometer. His
definition was (Nanotechnology mainly consists of the processing of, separation, consolidation and
deformation of materials by one or molecules.

In 1986, K.Eric Drexler in his book “Engines of Creation” discussed the future of nanotechnology,
particularly the creation of larger objects from their atomic and molecular components, so called ‘bottom
top approach’. He proposed ideas for ‘molecular nanotechnology’ which is the self-assembly of
molecules into an ordered and functional structure. The invention of the scanning tunneling microscope
by Gerd Binnig and Heinrich Rohrer in 1981, provided the real breakthrough and the opportunity to
manipulate and image structures at the nanoscale.

Subsequently, the atomic force microscope was invented in 1986, allowing imaging of structures
at the atomic scale. Another major breakthrough in the field of nanotechnology occurred in 1985 when
Harry Kroto, Robert Curl and Richard Smalley invented a new form of carbon called fullerene(Bucky
balls),a single molecule of 60 carbon atoms arranged in the shape of a soccer ball. This led to a Nobel
Prize in chemistry in 1996.

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 One of the first scientific reports is the colloidal gold particles synthesized by Michael Faraday as
early as 1857.Nanostructured catalysts have also been investigated over 70 years. By the early 1940’s,
precipitated and furned silica nanoparticles were being manufactured and sold in USA and Germany as
substitute for ultrafine carbon black for rubber reinforcement.

Today nanophase engineering expands in a rapidly growing number of structural and functional
materials, Inorganic and organic, allowing to manipulating mechanical, catalytic, electric, magnetic,
optical and electronic properties.

1.3 NANO MATERIALS

Nano materials are a field that makes a materials science based approach to nanotechnology. It studies
materials with morphological features on the nanoscale, and especially those that have special properties
stemming from their nanoscale dimensions. The properties of nanostructured materials depend on the
following micro-structural features,

• Fine grain size distribution(<100nm).

• Chemical composition of the constituent phase.

• Interaction between constituent domains.

1.4 NANOSTRUCTURE

Nanostructure is a structure of intermediate size between microscopic and molecular structures.

Nanostructure detail is microstructure at nanoscale. In describing nanostructures it is necessary to
differentiate between the numbers of dimensions on the nanoscale.

1.5 CLASSIFICATION OF NANOSTRUCTURES

Classification is based on the number of dimensions, which are not confined to the nanoscale
range (<100 nm).

• 0-D nanostructures: Nanoparticles, quantum dots, nanodots

• 1-D nanostructures: Nanowires, nanorods, nanotubes
• 2-D nanostructures: Thin film-multilayer

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 • 3-D nanostructures: Bulk, powders, other nanostructures, including fractal structure.

Fig.1.2 Classification of nanoparticles

1.5.1 ZERO-DIMENSIONAL NANOSTRUCTURES

The definition of nanoparticle differs depending upon the materials and application concerned.
Thus particle smaller than 10-20nm, where the physical properties of solid materials themselves would
drastically change. These are crystals made of metals, with size below 100nm free standing or suspended
in a fluid or embedded in another material.

0-D Nanoparticles can be

• Amorphous or crystalline
• Single crystalline or poly crystalline
• Composed of single or multi-chemical elements
• Exhibit various shapes and forms
• Exist individually or incorporated in a matrix

1.5.2 ONE –DIMENSIONAL NANOSTRUCTURES

The nanowires with thickness below 100nm free standing or suspended in a fluid or embedded in
another material. Several chemical strategies are developed for 1D nanowires with different levels of
control over the growth parameter. One dimensional hat is outside the nanoscale. This leads to needle
like-shaped nanomaterials.1-D materials include nanotubes, nanorods and nanowires.

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1-D Nanomaterials can be

• Chemically pure or impure

• Standalone materials or embedded in within another medium.

1.5.3 TWO-DIMENSIONAL NANOSTRUCTURES

Two dimensional nanostructures included coatings made of nanocrystalline metals or

nanocomposite. The structural analysis of this coating will seen grains (single crystal) of metal with
diameter in nanoscale, joined by grain boundaries. Two of the dimensions are not confined to the
nanoscale, 2-D nanomaterials exhibit plate-like shapes. Two-dimensional nanomaterials include
nanofilms, nanolayers and nanocoating.

2-D Nanomaterials can be

• Make up of various chemical compositions

• Used as a single layer or a multilayer structures
• Deposited on a substrate
• Integrated in a surrounding matrix material.

1.5.4 THREE-DIMENSIONAL NANOSTRUCTURES

Bulk nanomaterials are materials that are not confined to the nanoscale in any dimension. These
materials are thus characterized by having three arbitrarily dimensions above 100nm. Materials possess a
nanocrystaline structure or involve the presence of features at the nanoscale. In terms of nanocrystalline,
bulk nanomaterials can be composed of a multiple arrangement of nanosize crystals, most typically in
different orientations. With respect to the presence of features at the nanoscale, 3-D nanomaterials can
contain dispersions of nanoparticles, bundles of nanowires and nanotubes as well as multi nanolayers.

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1.6 PROPERTIES OF NANO MATERIAL

1.6.1 MECHANICAL PROPERTIES

• The mechanical properties of nanomaterials increase with decrease in size, because smaller the size,
lesser is the probability of finding imperfections such as dislocations, vacancies, grain boundaries.

• Strength of material improves significantly as the particle size decrease due to perfect defect free
surface.
• Hardness, elastic modulus, toughness and yield strength of material also increases as particle size is
decreased.

1.6.2 MAGNETIC PROPERTIES

• As the size of these systems reaches the typical length of few nanometers it is expected that the
response of the system depends on the boundary (which are no longer periodic but determined by
the particle size).
• In magnetic properties the energy of magnetic anisotropy may be that small the vector of
magnetization fluctuates thermally, this is called super paramagnetism.
• Such a material is free of reminisce and coactivity. Touching super paramagnetic particles are
losing this special property by interaction, except the particles are kept at distance.

1.6.3 OPTICAL PROPERTIES:

• With the growing technology of these materials, it is essential to detailed basis for photonic
properties of nanoparticles.
• The linear and non-linear properties of such materials can be finely tailored by controlling the
crystal dimensions, and the chemistry of their surfaces.
• Distributions of non-agglomerated nanoparticles in a polymer are used to tune the index of
refraction.
• Additionally, such a process may produce materials with non- linear optical properties.

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1.6.4 CATALYTIC PROPERTIES

• Due to their large surface, nanoparticle made of transition element oxides exhibit interesting
catalytic properties.
• In special cases, catalysis may be enhanced and more specific by decorating these particles with
gold or platinum clusters.
• Essentially, increase in the surface area provides increase adsorption of reactant molecules on its
surfaces, which results higher catalytic activity.

1.6.5 PHYSICAL CHEMICAL PROPERTIES

• The size of the nanoparticle is comparable to the Bohr’s radius of the excitons. This significantly
alters the optical, luminescent and redox properties of nanoparticle when compared to the bulk
material.
• The surface of atoms constitute a considerable fraction of the total number of atoms of the
nanoparticles.
• The natural size of the nanoparticle with the size of the nanoparticle. This determines the
peculiarities of the kinetics of the chemical processes on the surface of the nanoparticle

1.6.6 ELECTRICAL PROPERTIES

• The electrical properties of nanomaterials vary between metallic to semiconducting materials.

• It depends on the diameter of the nanomaterials. The very high electrical conductivity of
nanomaterial is due to minimum defects in the structure.

1.6.7 THERMAL PROPERTIES

• The thermal conductivity of nanomaterials are very high, is due to the vibration of covalent bonds.
• Its thermal conductivity is 10 times greater than the metal. The very high thermal conductivity of
nanomaterial is also due to minimum defects in the structure.

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 1.7 SYNTHESIS OF NANO MATERIAL

There are large number of techniques available to synthesis of different types of nanoparticle in
the form of colloids, clusters, powders, tubes, rods, wires and thin film etc., some of them already existing
conventional techniques to synthesis different types of materials are optimized to get novel nanomaterials
and some new techniques are developed.

For the synthesis of nanoparticles, the processing conditions need to be controlled in such a
manner that the resulting nanoparticles have the following characteristics:

1. Identical size of all particles,

2. Identical shape,

3. Identical chemical composition and crystal structure, and

4. Individually dispersed with no agglomeration.

Two general ways are available to control the formation and growth of the nanoparticles. One is called
arrested precipitation and depends on either on exhaustion of one of the reactants or on the introduction of
the chemical that would block the reaction. Another method relies on the physical restriction of the
volume available for the growth of the individual nanoparticles by using templates.

The nanoparticles are prepared by the following methods:

1. Sol-Gel method
2. Precipitation method
3. Hydrothermal method
4. Chemical vapor deposition method
5. Co-precipitation method

The preparation of nanoscale structures and devices can be accomplished commonly through two
methods.

➢ TOP-DOWN APPROACH
➢ BOTTOM-UP APPROACH

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 In both methods, two requisites are fundamental: control of the fabrication conditions and control
of the environment conditions (presence of dust, contaminants, etc.). For these reasons, nanotechnologies
use highly sophisticated fabrication tools that are mostly operated in a vacuum in clean-room laboratories.

1.7.1 TOP DOWN

In the top down method nanomaterials are derived from a bulk substrate and obtained by the
progressive removal of material, until the desired nanomaterial is obtained ie) the large objects are
modified to give smaller features. For example: film deposition and growth, lithography, etching
technology, mechanical polishing etc.

1.7.2 BOTTOM UP
In the bottom-up approach, molecular components arrange themselves into more complex-
assemblies atom-by-atom, molecule-by-molecule, and cluster-by -cluster from the bottom (e.g., growth of
a crystal).This approach plays a very important role in preparing nanomaterials having very small size
where the top-down process cannot deal with the very tiny objects. The bottom-up approach generally
produces nanostructures with fewer defects as compared to the nanostructures produced by the top-down
approach.

Fig.1.3 Top-down and Bottom-up method

1.7.3 SOL GEL METHOD

Sol-gel method is a long established industrial process for generating colloidal nanoparticles from
liquid phase. It has been further developed for the production of advanced nanomaterials and coatings.

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Sol-gel process is a chemical method which is based on hydrolysis or condensation reactions. With the
correct amount of reactants, nanosized particles precipitate. Sol-gel techniques show many advantages
like low temperatures during processing, versatility and easy shaping and embedding. Common
precursors which are used for the production of oxides are alkoxides, due to their availability and to the
high liability of the M-OR bond allowing facile tailoring in situ during processing. This method lucks the
risk for nanoparticle release after the drying of the solution.[5,6]

Fig.1.4 Sol-Gel method

1.7.4 CO-PRECIPITATION METHOD

In chemistry, co-precipitation (CPT) is carrying down by a precipitate of substances normally
soluble under the conditions employed. Analogously, in medicine, co-precipitation is specifically the
precipitation is specifically the precipitation of an unbound “Antigen along with an Antigen-Antibody
complex “.

Co-precipitation is an important issue in chemical analysis, where it is often undesirable, but in

some cases it can exploited. In gravimetric analysis, which consists on precipitating the analyte and
measuring its mass to determine its concentration purity, co-precipitation is a problem because undesired
impurities often co-precipitate with the analyte, resulting in excess mass. This problem can often be
mitigated by “digestion” (waiting for the precipitate to equilibrate and form larger, purer particles) or by
redissolving the sample and precipitating it again.

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 There are three main mechanisms of co-precipitation inclusion, occlusion and adsorption. An
inclusion occurs when the impurity occupies a lattice site in the crystal structure of the carrier, resulting in
a crystallographic defect; this can happen when the ionic radius and charge of the impurity are similar to
those of the carrier. An adsorbate is an impurity that is weekly bound (adsorbed) to the surface of the
precipitate. An occlusion occurs when an adsorbed impurity gets physically trapped inside the crystal as it
grows.

Besides its applications in chemical analysis and in radiochemistry, co-precipitation is also

“Potentially important to many environment issues closely related water resources, including acid mine
drainage, radionuclide migration in fouled waste repositories, metal containment transport at industrial
and defense sites, metal concentrations in aquatic systems and waste water treatment technology”.[6]

1.7.5 CHEMICAL VAPOUR DEPOSITION

Chemical vapour deposition (CVD) is referred to activating chemical reactions between a
substrate surface and a gaseous precursor in order to a thinfilm be deposited onto the substrate. Activation
can be achieved either with increased temperatures (Thermal CVD) or with plasma (PECVD: Plasma
Enhanced Chemical Vapour Deposition); decreasing significantly the process temperature compared to
the thermal CVD process. This technique is a widely used materials-processing technology due to its low
set-up cost, high production yield, and ease of scale-up. Chemical vapour deposition has been developed
as a novel manufacturing process in many industrial sectors such as semiconductor and ceramic industry.
The working process of CVD, thus the gases are delivered into a reaction chamber operated at a suitably
determined high temperature (500–1200 °C). Also, inert gases, such as argon and nitrogen, are usually
used as carrier gases. The gases pass through the reactor coming into contact with the heated substrate;
they react and form a solid layer deposited onto the substrate’s surface. The temperature and pressure
system are the critical operation parameters of this process. A laboratory scale CVD system is depicted in
Figure.CVD is widely used for the production of CNTs.[3,4]

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 Fig.1.5 chemical vapour deposition method

1.7.6 PRECIPITATION METHOD

The precipitation of solids from a metal ion containing solution is one of the most frequently
employed production processes for nanomaterials. Metal oxides as well as non-oxides or metallic
nanoparticles can be produced by this approach. The process is based on reactions of salts in solvents. A
precipitating agent is added to yield the desired particle precipitation, and the precipitate is filtered out
and thermally post-treated. In precipitation processes, particle size and size distribution, crystalline and
morphology (shape) are determined by reaction kinetics (reaction speed).

1.8 APPLICATIONS OF NANOMATERIALS

Below we list some key applications of nanomaterials. Most current applications represent
evolutionary developments of existing technologies: for example, the reduction in size of electronics
devices.

1.8.1 MAGNETIC

Nanoparticles have the potential to increase the density of various storage media, and also when
magnetized they can improve the detail and contrast of MRI images as previously allowed to Specifically
engineered particles could improve the transfer of heat from collectors of solar energy to their storage

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tanks. They could also enhance the coolant system currently used by transformers in these types of
processes.

1.8.2 SUNSCREENS AND COSMETICS

The traditional chemical UV protection approach suffers from its poor long-term stability. A
sunscreen based on mineral nanoparticles such as titanium dioxide offer several advantages. Titanium
oxide nanoparticles have a comparable UV protection property. Nanosized titanium dioxide and zinc
oxide are currently used in some sunscreens, as they absorb and reflect ultraviolet (UV) rays and yet are
transparent to visible light and so are more appealing to the consumer.Nano sized iron oxide is present in
some lipsticks as a pigment. The use of nanoparticles in cosmetics has raised a number of concerns about
consumer safety.

1.8.3 PAINTS

Incorporating nanoparticles in paints could improve their performance by making them lighter and
giving them different properties. Thinner paint coatings (‘lightweighting’) used on aircraft, would reduce
their weight, which could be beneficial to the environment.

1.8.4 DISPLAYS

The huge market for large area, high brightness, flat-panel displays, as used in television screens
and computer monitoring, is driving thedevelopment of some nanomaterials. Nanocrystalline zinc
selenide, zinc sulphide, cadmium sulphide and lead telluride synthesized by sol gel techniques are
candidates for the next generation of light-emitting phosphors.

1.8.5 BATTERIES

With the growth in portable electronic equipment (mobile phones, laptop computers, remote
sensors), there is great demand for lightweight, high energy density batteries. Nano crystalline materials
synthesized by sol–gel techniques are candidates for separator plates in batteries because of their foam-

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like (aerogel) structure, which can hold considerably more energy than conventional ones. Nickel–metal
hydride batteries made of nano crystalline nickel and metal hydrides are envisioned to require less
frequent recharging and to last longer because of their large surface area.

1.8.6 NANOTECHNOLOGY IN MEDICINE

With the help of nano medicine early detection and prevention, improved diagnosis, proper
treatment and follow-up of disease is possible. Certain nano scale particles are used as tags and labels,
biological applications can be performed quickly, the testing has become more sensitive and more
flexible. Gene sequencing has become more efficient with the invention of nano devices like gold nano
particles, these gold particles when tagged with short segments of DNA can be used for detection of
genetic sequence in a sample.

1.8.7 MEMORY STORAGE

The floppy diskdrive, which is also known as diskette, a removable magnetic storage medium that
allows recording of data in 90s founded by IBM, which was 8-in and had a very low storage. But at this
modern era with the help of nanotechnology we can use the memory storage of about 1-TB, which was
not greater than 1-inch.

1.8.8 OPTIC

Nanoparticles could be engineered and used for anti-reflection product coatings, producing a
refractive index for various surfaces and also providing light based sensors for use in diagnosing cancer.

1.9 APPLICATIONS OF NANOTECHNOLOGY

The nanotechnology which occupies its role in many of the modern emerging technology.
1.9.1 PRESENT DAY APPLICATIONS
• Flexible solar panels
• Self-cleaning windows
• Self-cleaning concrete using catalytic TiO2
• Wi-Fi paint
• Selective absorbing–reflecting solar windows

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 • Scratch-resistant flooring
• Antimicrobial steel surfaces
1.9.2 FUTURE APPLICATIONS OF NANOTECHNOLOGY
• Disaster-resistant materials
• Intelligent materials (e.g., self-repairing, self-adjusting)
• Superior moisture barrier materials
• Resource-efficient materials
• Superior insulating materials
• Superior weather-resistant capability (e.g., low maintenance)
• Fibre-cement siding (self-cleaning, thin layer of silica)

1.10 OBJECTIVE OF MY WORK

The present work deals with the preparation and characterization of the TiO₂: Mn nanoparticle. In
this regard, the development of a novel cost effective and less complicated route for the synthesis of the
above nanomaterials. The co-precipitation methods being chosen for the preparation of the materials. The
structural and phase purity of the prepared material is being evaluated with the standard and classical
XRD method. The optical behavior of the product is too analyzed with optical absorption methods
namely UV- Visible absorption studies.

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CHAPTER-2

24
 LITERATURE REVIEW

Weeraman Buraso et.al.,(2018) had studied that Titanium dioxide nanoparticles with narrow size
distribution and negligible agglomeration were prepared by a simple precipitation method using titanium
isopropoxide as a starting material. The results from XRD showed that the samples calcined in air at the
temperature of 400 and 500 °C possessed pure anatase structure, while the sample calcined at above 600
°C had anatase-rutile structure. Slight enlargement of TiO2 nanoparticles from 11.3 to 27.4 nm was
achieved by increasing calcination temperature from 400 to 700 °C. From UV-Vis spectra, the optical
band gap of the samples was determined and the result showed that the direct and indirect transition
energy gap decreased with increasing calcination temperature. Photocatalytic activity measurements
indicated that the monophasic anatase TiO2 nanoparticles exhibited better photocatalytic activity
compared to the anatase-rich nanoparticles. The proper value of Eg = 3.30 eV and average particle size of
11.3 ± 1.3 nm, appropriated to the highest photocatalytic activity, could be achieved when calcining the
sample at 400 °C.

Ziquan Liu et,al.,(2014) had reported that Nano titanium dioxide(TiO2) powder was prepared with five
different methods separately. By conducting XRD detection of these five titanium dioxide samples, test
showed that the grain diameter of nano particle prepared by hydro-thermal method was the smallest. TEM
picture displayed that the actual grain was about 10 nm and was relatively well-distributed. Detection of
the photocatalytic activity of the five samples suggested that samples prepared by the hydro-thermal
method had the best property in these test, it could completely decompose the prepared helianthine
solution in about 2 h. Through the experiment, the test datum showed that the best sintering temperature
scope of hydrothermal method was between 500 to 550 °C.

P.B. Rathod et.at,.(2015) had successfully synthesized TiO2 nanoparticles by co precipitation method.
An average particle size of the resulting TiO2 nanoparticles was found to be 24 nm computed from XRD
analysis by using scherer's equation. An indirect band gap of TiO2 nanoparticles was found to be 3.1 eV.
The optical constants absorbance coefficient and extinction coefficient of these sample was determined
using absorbance spectra. The estimated optical band gap energy is an accepted value for the
photocatalytic activities in visible light and also for application in the photovoltaic and optical devices.
The co-precipitation used in this paper is a simple, useful, and an economic method to synthesized TiO2
nanoparticles.

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Guangping Zeng et.al.,(2019) had stated that a high-gravity precipitation method for the synthesis of
nano-TiO2 was developed through the exploration of the synthesis process, TiO2 with anatase crystals,
smaller particle sizes, better dispersion and average particle sizes of 12.5 nm was obtained in IS-RPB.
When the calcination temperature was 500 °C, nano-TiO2 had a better anatase crystal and maintained a
smaller particle size. The results show that the Fe-TiO2 anatase phase remains intact, and the variation of
the Raman peak width and intensity shows evidence of the existence of iron. XPS and EDX mapping
shows that iron was uniformly distributed in TiO2 and exists in the positive trivalent form. When the
Fe3+ was increased from 0.5% to 5.0%, the band gap energy of the catalyst was reduced from 3.06 eV in
undoped Fe to 2.86 eV and 2.26 eV. Fe3+ not only broadens the photoresponse range but also effectively
suppresses the recombination of the electron and hole. As a result, the catalytic activity was enhanced.
The degradation rate of 1.0%Fe-TiO2 to toluene of 105 ppm reached 95.7% after 4 h under UV light.

Gupta, et al., had reported the titanium dioxide (TiO2) nanocrystals were prepared electron microscopy
(TEM), Raman Scattering (RS) and photoluminescence (PL). The X-ray diffraction shows the formation
of nanocrystalline TiO2 of average series~7nm and ~15nm for two samples. The x-ray diffraction,
transmission electron microscopy (TEM) and Raman scattering shows that the TiO2 nanocrystals has
anatase crystal structure for both samples. The PL intensity of the smaller particle is more, which has
been attributed to defects and particle size variation.

Ahmad, et al., had discussed the nanocrystalline semiconductor metal oxides have achieved a great
importance in our industrial world today. They may be defined as metal oxides with crystal size between
1 and 100nm. TiO2 nanosize particles have attracted significant interest of materials scientists and
physicists due to their special properties and have attained a great importance in several technological
applications such as photo catalysis, sensors, solar cells and memory devices. TiO2 nanoparticles can be
produced by a variety of techniques ranging from simple chemical to mechanical to vacuum methods,
including many variants of physical and chemical vapour deposition techniques. From this we report the
synthesis of TiO2 nanoparticles by Sol-gel techniques. The importance and applications of these
nanoparticles are discussed.

Robert Liu et.al.,(2012) had studied that the photocatalysts of TiO2 and Ag-TiO2 were successfully
prepared by coprecipitation method annealed at 550°C.The composition of Ag-TiO2 prepared is about

26
Ag : Ti = 1 : 99 (molar), and particle size is 0.25 μm. The silver-deposited TiO2 photocatalysts enhanced
the inactivation of E. coli by visible irradiation when compared to that by using TiO2. The similar 100%
of high antibactericidal efficiencies and six times of rate of reaction compared to the usage of TiO2 were
obtained for either using visible light or UV light or even no light irradiation by the application of Ag-
TiO2.The study of mineralization of E. coli shows that better results of TOC removal percentage obtained
for visible light application than the irradiation of UV light.The visible light may effectively be applied
for the disinfection unit of water and wastewater treatment system by using photocatalysts of Ag-TiO2.

Sunderishwary et.al.,(2017) in her study, mesoporous anatase TiO2 nanoparticles were synthesised
using a green chemistry approach. This visible-light active photocatalyst was prepared via a simple and
solvent free precipitation method at low temperatures using titanium tetraisopropoxide (TTIP) as a
precursor and soluble starch as the template. The effect of initial solution pH and concentration of TTIP
on surface morphology and photocatalytic activities of TiO2 nanoparticles were evaluated. Based on the
results obtained, the TiO2 nanocatalyst prepared using 0.01 mol of TTIP under basic conditions revealed
the best photocatalytic activity. The as-synthesised nanoparticles were further characterised using X-ray
powder diffraction (XRD), scanning electron microscopy (SEM) and nitrogen adsorption analysis (NAA).
The XRD spectrum confirmed that the catalyst was composed of anatase tetragonal TiO2 phase. The
Brunauer–Emmett–Teller (BET) surface area of 81.59 m2 g1 proved the presence of mesopores (average
pore size ¼ 8.7 nm) which partially contributed to and catalysed the photodegradation process of
methylene blue (MB) solution under sunlight. The effects of various parameters such as initial dye
concentration, catalyst dosage and recyclability of the catalyst were evaluated to determine the best
conditions. Results obtained suggest that TiO2 nanoparticles synthesised through the green chemistry
approach under optimum conditions exhibited an effective photodegradation process of MB solution
under sunlight.

Hossein Mahmoudi et.al.,(2017) had been stated that TiO2 nanoparticles have been synthesized by the
sol-gel method using titanium alkoxide and isopropanol as a precursor. The structural properties and
chemical composition of the TiO2 nanoparticles were studied using X-ray diffraction, scanning electron
microscopy, and X-ray photoelectron spectroscopy. The X-ray powder diffraction pattern confirms that
the particles are mainly composed of the anatase phase with the preferential orientation along [101]
direction. The physical parameters such as strain, stress and energy density were investigated from the

27
Williamson- Hall (W-H) plot assuming a uniform deformation model (UDM), and uniform deformation
energy density model (UDEDM). The W-H analysis shows an anisotropic nature of the strain in
nanopowders. The scanning electron microscopy image shows clear TiO2 nanoparticles with particle
sizes varying from 60 to 80nm. The results of mean particle size of TiO2 nanoparticles show an inter
correlation with the W-H analysis and SEM results. Our X-ray photoelectron spectroscopy spectra show
that nearly a complete amount of titanium has reacted to TiO2 .

Hayle et.al.,(2014) had reported that the TiO2 powders were synthesized by sol-gel method using TiCl4
solution as a precursor. The synthesized TiO2 nanoparticles were characterized by XRD,UV-Vis
spectrophotometer, Transmission electron microscope (TEM), Scanning electron microscope(SEM),
Energy dispersive spectroscopy (EDS). XRD shows the particles size with high crystallinity and purity
which is in good agreement with the temperatures of 250oc,400oc and 600oc were 9.22 nm,14.33 nm and
36.72 nm respectively calculated from XRD result. The absorption edge was found to be 350 nm and the
corresponding calculated band gap energy was 3.54 eV. The average particle size of TiO2 investigated
from TEM using histograms at calcination temperatures of 250oc, 400oc and 600oc were found (8.55 ±
0.25) nm, (13.82± 0.41) nm and (36.06 ± 2.03) nm respectively. The polygonal structure of TiO2
nanomaterials were studied by SEM. The EDS result showed that at calcination temperatures of 250oc,
400oc and 600oc, the concentrations of titanium were 33.34%, 32.6% and 31.89%,and the concentrations
of chlorine were 2.64%,0% and 0%,and the concentration of oxygen were 64.02%,67.4% and 68.11% in
the synthesized TiO2 nanopowder respectively which is qualitatively confirmed by dispersive x-ray
spectroscopy results.

Thangavelu, et al., have reported the comparison between nano sized TiO2 powders prepared via two
different acidic conditions (i)pH 2 (ii)pH 4. The study presents the synthesis of nano sized TiO2 powder
with anatase structure was derived from Sol-gel process. Data concerning the effect of pH towards the
development of Ti22 nanoparticles is reported. The samples were examined by SEM-EDAX, XRD, and
FT-IR analysis. Surface morphological studies obtained from SEM micrograph. The crystalline size of
TiO2 powder has obtained for (i) pH 2 is ~3nm (ii) pH 4 is ~6nm at 400ᵒ C by controlling the acidity. In
FT-IR, all the peaks observed were around 460-560 cm-1 due to stretching and bending vibrations of –
OH groups. It was also found the pH of the solution affect the agglomeration of the particles.

28
Fatemeh Mostaghni et.al.,(2016) stated that Co/TiO2 nanocomposite was prepared by sol-gel method.
The structural and optical properties of nanocomposite were studied using, X-ray diffraction (XRD) and
diffuse reflectance UV-VIS spectrometry. The XRD spectra revealed its tetrahedral anatase structure. The
grain size and optical properties of composite are also reported. Syntesied Co/TiO2 photocatalyst showed
excellent activity for the photodegradation of Methyl orange whether under visible and ultraviolet light
irradiation

29
CHAPTER-3

30
 MATERIAL INTRODUCTION AND METHODOLOGY

3.1 MATERIAL INTRODUCTION

TiO₂, the oxide of the metal titanium, occurs naturally in several kinds of rock and mineral sands.
Titanium is the ninth most common element in the earth’s crust. TiO₂ is typically thought of as being
chemically inert. Titanium dioxide has been used for many years (ca. 90 years) in a vast range of
industrial and consumer goods including paints, coatings, adhesives, paper and paperboard, plastics and
rubber, printing inks, coated fabrics and textiles, catalyst systems, ceramics, floor coverings, roofing
materials, cosmetics and pharmaceuticals, water treatment agents, food colorants and in automotive
products, etc. The importance and variety of such applications have spurred enormous interest in the
fundamental knowledge, the fabrication and the characterization of TiO₂ based nanomaterials, leading to
an unprecedented level of understanding for a metal oxide.

Titanium oxide TiO₂ is available in the form of nanocrystals or nanodots having a high surface
area. They exhibit magnetic properties. Titanium belongs to Block D, Period 4 while oxygen belongs to
Block P, Period 2 of the periodic table. Titanium oxide is also known as flamenco, rutile, titanium dioxide
and dioxotitanium. Titanium oxide nanoparticles are known for their ability to inhibit bacterial growth
and prevent further formation of cell structures.
Titanium dioxide, also known as titanium (IV) oxide or titania, is usually occurring oxide of
titanium, chemical formula TiO₂. When used as a Pigment, it is called titanium white, Pigment White 6 or
CI77891. Generally it is sourced from ilmenite, rutile and anatase. It has wide range of applications, from
paint to sunscreen to food colouring, it has E number E171.
Titanium was once considered a rare metal, but now-a-days it is one of the most important metals
in the industry. The element was first discovered by Gregor in England in 1970, the mythological first
sons of the earth, the titans, in 1975. Chemically, Titanium is one of the transition elements in group IV
and period IV of Mendeleev’s periodic table. It has the atomic number 22 and atomic weight 47.9. Being
a transition element, titanium has an incompletely filled d shell in it is electronic structure.
Titania (TiO₂) is a cheap and innocuous inorganic material extensively employed in industrial and
commercial applications such as pigment in the paint industry, as sun blocking material in cosmetics, as a
binder in medical fields. For instance, more than 4 million tones of the white pigment are annually
consumed by the paint industry worldwide, being the pigment most widely used because of its brightness,
high refractive index and low-cost.

31
 Titanium dioxide is classified as a wide band-gap semiconductor, the anatase form having a band
gap of 3.2 eV [43]. Much of the bio-toxicity of TiO₂ is attributed to photo effects wherein the material is
illuminated with ultraviolet light. Band gap illumination produces an electron–hole pair excited state that
is a much stronger oxidant and reductant than is the ground state. Under standard conditions the excited
electron has a reduction potential of about 0.0 V vs. NHE while the hole has an oxidizing power of about
3.2 V.

3.2 STRUCTURE OF TiO₂

TiO₂ is a wide bandgap semiconductor that presents photo activity upon near UV or Higher
irradiation, absorbing photons and transforming them into chemical redox energy. Although TiO₂is inert
and do not promote chemical reactions without irradiation, the handling of very finely divided
TiO₂particles requires taking safety measures

Fig.3.1 Structure of TiO₂

Titania (TiO₂) has three crystalline structures namely,

➢ Anatase
➢ Rutile
➢ Brookite
Anatase and Rutile have tetragonal unit cell.

Rutile structure is thermodynamically stable while other two are in metastable state.

Rutile contains two TiO₂ molecules per unit cell, where a=4.59Å c=2.95Å.

Anatase contains four TiO₂ molecules per unit cell, where a=3.78Å c=9.51Å.

32
 PHASE CRYSTAL SPECIFIC LIGHT MOHR’S
GRAVITY
ABSORPTION(nm) HARDNESS
SYSTEM

Rutile Tetragonal 4.0 6.5 to 7

λ ≤ 415 nm
Anatase Tetragonal 3.9 5.5
λ ≤ 385 nm
Brookite Orthorhombic 4.12 λ ≤ 632 nm 5 ½ to 6

3.3 PROPERTIES OF TiO₂:

Chemical formula : TiO₂

Molar mass : 79.866 g/mol

Appearance : white solid

Density : (Rutile) - 4.23g/cm³, (Anatase) - 3.78g/cm³

Solubility in water : insoluble

Band gap : 3.05 eV

Refractive index : (Anatase) - 2.488, (Rutile) - 2.58, (brookite) - 2.583

3.4 PHYSICAL PROPERTIES:

Density : 4.23g/cm³

Molar mass : 79.9378g/mol

Magnetic susceptibility : +5.9× /mol

33
3.5 CHEMICAL PROPERTIES:

CAS no: 1317-80-2

Group: Titanium 4: Oxygen 16

Electronic configuration : Titanium [Ar] 3d²4s²: Oxygen [He] 2s²2p4

Chemical composition : Titanium : 59.9: Oxygen : 40.55

3.6 THERMAL PROPERTIES:

Melting point : 1843°c

Boiling point : 2972°c

3.7 APPLICATIONS:

Given below some of the chief applications of titanium oxide:

❖ Titanium oxide exhibits good photocatalytic properties, hence is used in antiseptic

compositions.
❖ Degrading organic contaminants and gems.
❖ As a UV-resistant material
❖ Manufacture of printing ink, self cleaning ceramics and glass , coating, etc,.
❖ Making of cosmetic products such as sunscreen creams, whitening creams, morning and night
creams, silk milks, etc,.
❖ Used in paper industry for improving the opacity of paper.

3.8 INTRODUCTION ABOUT DOPANTS:

To increase the UV-Visible light absorption of TiO2 addition of Transition metals can improve
the photocatalytic activity by decreasing the energy band gap or preventing (e-,h+) pair combination by
(e-,h+) trapping.

34
3.8.1 MANGANESE:

In steels, manganese improves the rolling and forgiving qualities as well as strength, toughness,
stiffness, hardness and hardenability. In aluminium and antimony, manganese addition forms highly
ferromagnetic compounds, especially in the presence of small amounts of copper.

Manganese is the fifth most abundant metal in the Earth’s crust. Its minerals are widely distributed, with
pyrolusite (manganese dioxide) and rhodochrosite (manganese carbonate) being the most common. The
main mining areas for manganese are in China, Africa, Australia and Gabon. The metal is obtained by
reducing the oxide with sodium, magnesium or aluminum, or by the electrolysis of manganese sulfate.
Manganese nodules have been found on the floor of the oceans. These nodules contain about 24%
manganese, along with smaller amounts of many other elements.

CHEMICAL DATA:

Symbol : Mn

Type :Transition metal

Appearance : A hard brittle, silvery white

Atomic weight : 51

Relative atomic mass : 54.938

Density : 7.3 g/cm³

Melting point : 1246°c

Boiling point : 2061°c

APPLICATIONS:

1. Manganese is too brittle to be of much use as a pure metal. It is mainly used in alloys, such as steel.
Steel contains about 1% manganese, to increase the strength and also improve workability and resistance

35
to wear. Manganese steel contains about 13% manganese. This is extremely strong and is used for railway
tracks, safes, rifle barrels and prison bars.

2. Drinks cans are made of an alloy of aluminum with 1.5% manganese, to improve resistance to
corrosion. With aluminum, antimony and copper it forms highly magnetic alloys.

3. Manganese (IV) oxide is used as a catalyst, a rubber additive and to decolorize glass that is colored
green by iron impurities. Manganese sulfate is used to make afungicide. Manganese (II) oxide is a
powerful oxidizing agent and is used in quantitative analysis. It is also used to make fertilizers and
ceramics.

3.9 METHODOLGY:

3.9.1 SYNTHESIS OF TiO₂ BY CO-PRECIPITATION METHOD:

MATERIALS USED:

Titanium tetraisopropoxide (TTIP), ethanol, deionized water.

3.9.2 PREPARATION OF MANGANESE DOPED TITANIUM DIOXIDE

NANOPARTICLES

This topic discuss about the synthesis of Manganese doped Titanium dioxide nanoparticles from
Titanium isopropoxide Ti{OCH(CH3)2}4. TiO2 nanoparticle was synthesized by Co-Precipitation method.
The beaker was washed with acetone and Deionized water to remove the impurities. Then 3.6 ml of
precursor was dissolved in 100 ml of DI water using magnetic stirrer, a transparent solution was formed.
The pH-6, 8 and 10 was maintained at room temperature by adding ammonia drop by drop. To remove
the isopropyl alcohol and other impurities, the precipitate was centrifuged for 10 mins. After the
centrifugation process, the precipitate was dried at 300°C in hot air oven for 3 hrs. to remove the excess
water. Then it was grinded to fine powder and preserved in air tight container for characterization.
Finally, the Mn doped TiO2 nanoparticles were formed.

36
3.9.3 FLOWCHART OF SYNTHESIS OF MANGANESE DOPED TITANIUM
DIOXIDE NANOPARTICLES

Titanium isopropoxide

Ti{OCH(CH3)2}4

100 ml of distilled water

Ammonia was added to
maintain pH-6,8,10
Stirred for 3 hr at room
temperature

Transparent solution was formed

Centrifuge at 2000 rpm for 10

minutes

Calcinated at 300°C for 3 hrs

Mn doped TiO2 nanoparticles was

obtained

37
PREPERATION OF FUNGAL MEDIUM
The fungal medium is prepared by stirring 3.6g of potato dextrose broth and 3g of agar
into 150 ml of water and the mixture is allowed to autoclave. The autoclaved Petri dish is kept in
UV for few mintues. Aspergillus is striked over the media and wells are made. The Mn doped
TiO2 of 0.05 g stirred into 4 ml of deionised water and ultrasonificated for 10 minutes with
irradiation time of 2 minutes. 6 micro litre of sample is poured into the well using micropipette
and kept at room temperature for three days.

38
CHAPTER-4

39
 CHARACTERIZATION TECHNIQUES

4.1 INTRODUCTION
Instrumentation helps us understand the specific properties of the substances, to be studied in a rapid
manner accurately as well as reliable to understand measured values. The grown nanoparticles are subjected to
various studies. Structural, Optical and compositional studies on the nanoparticles (which are grown) could be
made precisely using sophisticated techniques such as X-ray Diffraction (XRD), Fourier Transform- Infrared
Spectroscopy (FT-IR), Ultra-Violet (UV) spectroscopy.

4.2 X-RAY DIFFRACTION (XRD)

Von Laue in 1912 discovers the x-ray diffraction method. This x-ray diffraction studies gives
known about the arrangement and the spacing of atom in crystalline materials. The X-ray is
electromagnetic radiation of wavelength about 1Angstrom, which is about the same size as an atom. They
occur in that portion of the electromagnetic spectrum between gamma-ray and ultraviolet.

X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of crystalline material and can provide information on unit cell dimensions. It is a versatile,
non-destructive technique that reveals detailed information about the chemical composition and
crystallographic structure of natural and manufactured materials. By varying the θ, the Bragg's Law
conditions are satisfied by different d-spacing in polycrystalline materials.

nλ = 2dsinθ

Where,

n is an integer referring to the order of reflection.

λ is wavelength of the radiation.

d is the spacing between diffracting planes in Å.

θ is the incident angle.

40
 The x-ray diffraction is one of the most important characterization tools used in solid state
chemistry and material science. We can determine the size and the shape of the unit cell for any
compound very easily using the diffraction of x-rays.

PRINCIPLE

X-ray diffraction is based on constructive interference of monochromatic X-rays and a crystalline

sample. These X-rays are generated by a cathode ray tube, filtered to produce monochromatic radiation,
collimated to concentrate, and directed toward the sample. The interaction of the incident rays with the
sample produces Constructive interference (and a diffracted ray) when conditions satisfy Bragg's Law.
This law relates the wavelength of electromagnetic radiation to the diffraction angle and the lattice
spacing in a crystalline sample.These diffracted X-rays are then detected, processed and counted.

By scanning the sample through a range of 2θangles, all possible diffraction directions of the
lattice should be attained due to the random orientation of the powdered material. Conversion of the
diffraction peaks to d-spacing allows identification of the mineral because each mineral has separate d-
spacings. Typically, this is achieved by comparison of d-spacings with a standard reference patterns.

Figure 4.1 Bragg’s reflection from a crystal

When a beam of X-rays directed at a crystal interacts with the electrons of the atoms in the crystal.
The electrons oscillate under the impact and become a new source of electromagnetic radiation. The
waves emitted by the electrons have the same frequency as the incident rays and the emission is in all the
directions. There are millions of atoms in the crystal; the emission in a particular direction is the

41
combined effect of the oscillations of electrons of all the atoms. The emission will be in phase and
reinforce one another only in certain specific directions, there is destructive interference of the emissions
from different sources.

INSTRUMENTATION

X-ray diffractometer consists of three basic elements an X-ray tube, a sample holder, and an X-ray
detector. X-rays are generated in a cathode ray tube by heating a filament to produce electrons,
accelerating the electrons toward a target by applying a voltage, and bombarding the target material with
electrons. When electrons have sufficient energy to dislodge inner shell electrons of the target material,
characteristic X-ray spectra are produced. These spectra consist of several components, the most common
being Kα and Kβ. Kα consists, in part of Kα1 and Kα2. Kα1 has slightly shorter wavelength and twice the
intensity as Kα2. The specific wavelengths are characteristic of the target material. Filtering by foils or
crystal Monochromators, is required to produce monochromatic X-rays needed for diffraction. Kα1 and
kα2 is sufficiently close in wavelength such that a weighted average of the two is used.

Fig 4.2 X-ray diffractometer

As the sample and detector are rotated, the intensity of the reflected X-rays are recorded. When
the geometry of the incident X-rays impinging the sample satisfies the Bragg equation, constructive
interference occurs and a peak in intensity occurs. A detector records and processes this X-ray signal and
converts the signal to a count rate which is then output to a device such as a printer or computer monitor.

The geometry of an X-ray diffractometer is such that the sample rotates in the path of the
collimated X-ray beam at an angle θ while the X-ray detector is mounted on an arm to collect the

42
diffracted X-rays and rotates at an angle 2θ. The instrument used to maintain the angle and rotate the
sample is termed a goniometer. For typical powder patterns, data is collected at 2θ from ~5◦ to ~70◦
angles that are present in the X-ray scan.

APPLICATIONS

X-ray powder diffraction is most widely used for the identification of unknown crystalline materials.
Determination of unknown solids is critical to studies in geology, environmental science, material
science, engineering and biology. Other applications include

➢ Characterization of crystalline materials.

➢ Identification of fine-grained minerals such as clays and mixed layer clays that are difficult to
determine optically.

➢ Determination of unit cell dimensions and measurement of sample purity.

4.3 ULTRAVIOLET-SPECTROSCOPY

Ultraviolet–visible spectroscopy or ultraviolet-visible spectrophotometry (UV-Vis or UV/Vis)

refers to absorption spectroscopy or reflectance spectroscopy in the ultraviolet-visible spectral region.
This means it uses light in the visible and adjacent (near-UV and near-infrared [NIR]) ranges. The
absorption or reflectance in the visible range directly affects the perceived color of the chemicals
involved. In this region of the electromagnetic spectrum, molecules undergo electronic transitions. This
technique is complementary to fluorescence spectroscopy, in that fluorescence deals with transitions from
the excited state to the ground state, while absorption measures transitions from the ground state to the
excited state.

The Ultraviolet spectroscopy is useful as an analytical tool for two reasons. First it can be used to
identify some functional group in molecules and secondly, it can be used for determining the current
strength of the substance is extremely useful. Ultraviolet spectroscopy is used mostly in chemical and
biochemical laboratories for variety purposes. When the visible or ultraviolet light is absorbed by the
substances, the electron in the ground state gets excited from ground to higher energy state.

43
PRINCIPLE

The Principle of ultraviolet-visible absorption is that the Molecules containing π-electrons or non-
bonding electrons (n-electrons) can absorb the energy in the form of ultraviolet or visible light to excite
these electrons to higher anti-bonding molecular orbitals. The more easily excited the electrons (i.e. lower
energy gap between the HOMO and the LUMO), the longer the wavelength of light it can absorb.

INSTRUMENTATION AND WORKING

Instrumentation and working of the UV spectrometers can be studied simultaneously. Most of the
modern UV spectrometers consists of the following parts.

Light Source: Tungsten filament lamps and Hydrogen-Deuterium lamps are most widely used
and suitable light source as they cover the whole UV region. Tungsten filament lamps are rich in red
radiations; more specifically they emit the radiations of 375 nm, while the intensity of Hydrogen-
Deuterium lamps falls below 375 nm.

Monochromators: Monochromators generally composed of prisms and slits. The most of the
spectrophotometers are double beam spectrophotometers. The radiation emitted from the primary source
is dispersed with the help of rotating prisms. The various wavelengths of the light source which are
separated by the prism are then selected by the slits such the rotation of the prism results in a series of
continuously increasing wavelength to pass through the slits for recording purpose. The beam selected by
the slit is monochromatic and further divided into two beams with the help of another prism.

Sample and reference cells: One of the two divided beams is passed through the sample solution
and second beam is passé through the reference solution. Both sample and reference solution are
contained in the cells. These cells are made of either silica or quartz. Glass can't be used for the cells as it
also absorbs light in the UV region.

Recording devices: Most of the time amplifier is coupled to a pen recorder which is connected to
the computer. Computer stores all the data generated and produces the spectrum of the desired compound.

44
 Fig 4.3 Schematic diagram of Ultraviolet- Visible spectrometer

Detector: Generally two photocells serve the purpose of detector in UV spectroscopy. One of the
photocell receives the beam from sample cell and second detector receives the beam from the reference.
The intensity of the radiation from the reference cell is stronger than the beam of sample cell. This results
in the generation of pulsating or alternating currents in the photocells.

Amplifier: The alternating current generated in the photocells is transferred to the amplifier. The
amplifier is coupled to a small servometer. Generally current generated in the photocells is of very low
intensity, the main purpose of amplifier is to amplify the signals many times so we can get clear and
recordable signals.

Beer- Lambert’s Law

UV spectroscopy obeys the Beer-Lambert law, which states that, when a beam of monochromatic
light is passed through a solution of an absorbing substance, the rate of decrease of intensity of radiation
with thickness of the absorbing solution is proportional to the incident radiation as well as the
concentration of the solution. The expression of Beer-Lambert law is-

45
 A = log (I0/I) = ε. C. L

Where,

A = absorbance

I0 = intensity of light incident upon sample cell

I = intensity of light leaving sample cell

C = molar concentration of solute

L = length of sample cell (cm.)

ε = molar absorptivity

APPLICATIONS

Quantitative Analysis:

➢ The change in absorbance for a given concentration change is greater, leading to greater
sensitivity and accuracy in measurement
➢ The relative effect of other substances or impurities is smaller
➢ The rate of change of absorbance with wavelength is smaller, and the measurement is not so
severely affected by small errors in the wavelength setting.

Qualitative Analysis

➢ It is used to study the transition of electron.

➢ To determine chemical structure of complex molecules.

4.4 FOURIER TRNSFORM INFRARED SPECTROSCOPY (FTIR)

FT-IR spectroscopy is the study of interaction of infrared radiation with matter as a function of
photon frequency. It provides information about the vibration and rotation of the chemical bonding and
molecular structures. FTIR spectroscopy is used to find whether the functional group is present or not.
Requirements for the absorption of IR radiation,

46
 1. A molecule absorbs radiation only when natural frequency of vibration of molecule is same as
frequency of incident radiation.

2. The molecule can absorb IR radiation when its absorption causes change in its electric dipole.

IR light absorption due to change in rotational and vibrational energy in the molecule. After the
absorption of IR radiation, the molecule of the chemical substance vibrate at many rates of vibration,
because of this vibrations we get IR absorption spectrum. Different bands may be found in IR spectrum
which will correspond to the characteristics functional groups and bonds present in chemical compounds.
IR spectrum is the finger prints to identify the chemical substance. No two compounds provide the exact
same infrared spectrum. Heart of the FTIR is Michelson Interferometer. The FT in FTIR gives the
wavelength selection method (Fourier Transform).

In 1949 Peter Fellgett obtained the first IR spectrum by using FTIR spectrometer. IR spectrum has
two regions they are,

1. Fingerprint region (600 cm-1 to 1200 cm-1)

2. Functional group region (1200 cm-1 to 3600 cm-1)

Information from FTIR

➢ Identify unknown materials

➢ Determine quality or consistency of sample
➢ Determine amount of components in mixture
➢ Widely used for quantitative analysis.
➢ All molecular species except ‘homo nuclear di-atomics’ O2, H2, N2 detectable.

Instrumentation

FT-IR spectrometer consists of three important components, they are

1. Radiation source

2. Interferometer

3. Detector

47
Source

Infrared energy is emitted from the black-body source and then this beam passes through the
aperture which controls the amount of energy presented to the sample.

Interferometer

Where the ‘spectral encoding’ taking place. The resultant interferogram signal exits the
interferometer.

Detector

After irradiating with the sample the beam finally passes to the detector. The detectors are
specially designed to measure the special interferogram signal. The final signal sent to the computer
where the Fourier transform takes place.

Fig 4.4 Schematic representation of FT-IR system

Advantages

✓ Better sensitivity
✓ FT-IR needs less energy from the source
✓ It takes less time to scan

48
CHAPTER-5

49
 RESULT AND DISCUSSION

5.1 XRD ANALYSIS

The structural properties of 10% Mn doped TiO₂ nanoparticles of pH=6,8,10 synthesized by

co-precipitation method are measured using X-Ray diffraction with Cu-Kα radiation (λ=1.5406 A0) at
scan speed of 100/minute.

The X-Ray diffraction pattern of 10% Mn doped TiO₂ nanoparticles are shown in figure-5.1. The
XRD pattern and these samples were compared with the standard JCPDS (card no-89-4921). The position
and their relative peaks of all the samples are in good agreement with the standard XRD pattern, with the
characteristic peaks correspondingly to [1 0 1], [1 0 3], [1 0 5], [1 1 6] as the most prominent peaks. These
values also matches well with the XRD pattern of 10% Mn doped TiO₂ nanoparticles. All the observed
peaks can be indexed in agreement with the expected Tetragonal structure of TiO₂ nanoparticles. The
peaks are narrow and sharp, which indicates the high crystallinity.

The crystallite size of 10% Mn doped TiO₂ nanoparticles of pH=6,8,10 is obtained by De-bye
Scherrer’s equation are shown in table-1.The crystallite sizes of 10% Mn doped TiO₂ nanoparticles of
pH=6,8,10 are 6.18 nm, 6.20 nm and 6.50 nm respectively. The crystallite size of nanoparticles decreases
with increase in pH.

5.1.1 PARTICLE SIZE ANALYSIS

Average crystallite size has been calculated from the recorded XRD pattern using well known Debye
Scherrer Equation,

d=
Where,
λ = 1.514Å
β = F.W.H.M
θ = position corresponding to peak

5.1.2 UNIT CELL DETERMINATION

For tetragonal structure, the inter planar spacing between the two closest parallel planes with the
Miller indices given by d is given by

50
 = + =
Using above formula the calculated values of lattice parameters a,c are as follow:

Full Width d spacing Crystallite Average Lattice

Sample 2θ Half Hkl (A0) Size D(nm) Crystallite parameter
(Degree) Maximum Size D(nm) Observed
(FWHM) (A0)
10% Mn 25.37815 1.07587 004 2.3992 7.56892
doped TiO₂ a=3.9604
30.87055 0.88447 200 1.9802 9.31806
pH=6 6.1808 c=9.5971
48.04924 1.31187 107 1.2945 6.63005

54.68285 1.91179 312 1.1474 4.67802

10% Mn 25.34876 0.92977 101 6.3371 8.75776

doped TiO₂ a=3.7852
37.98137 2.28526 004 9.4953 3.67641
pH=8 6.2040 c=9.4685
48.03363 1.23454 200 12.0084 7.04492

69.78522 1.87276 220 1.3465 5.17177

10% Mn 25.3296 0.88359 101 3.5133 9.21513

doped TiO₂ 12.664805 3.513390248 101 a=3.7864
38.03411 1.98326 004 2.3639 4.23691
pH=10 6.5018 c=9.4558
48.0169 1.15525 200 1.8932 7.5279

69.49386 2.01036 220 1.3515 4.80927

Table.1 Determination of crystallite size and lattice parameter

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 2θ θ DISLOCATION
SAMPLE (Degree) (Degree) DENSITY( ) STRAIN
g/
25.37815
10% MN 12.68907 17.45549 20.84909
DOPED TiO₂ 30.87055
15.43527 11.51724 13.97722
pH=6 48.04924
24.02462 22.74917 12.84171
54.68285
27.34142 45.69570 16.13322
25.34876
10% MN 12.67438 13.03808 0.91235
DOPED TiO₂ 37.98137
18.99069 73.98606 3.43159
48.03363
pH=8 24.01682 20.14870 2.40020
69.78522 34.89261 37.38702 5.69892

25.32961 12.66480 11.77597 17.15684

10% MN
DOPED TiO₂ 38.03411 19.01705 55.70578 25.10761

pH=10 48.0169 24.00845 17.64595 11.31717

69.49386 34.74693 43.23548 12.64601

Table.2 Determination of dislocation density and strain

The lattice parameter values of 10% Mn doped TiO₂ nanoparticles of pH=6,8,10 also matches
well with the standard JCPDS data. A slight enhancement in the lattice parameter values of Mn doped
TiO₂ nanoparticles are observed when comparing with the lattice parameter values of pure TiO₂
nanoparticles.

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Fig 5.1 XRD Analysis of 10% Mn doped TiO₂ Ph=6

Fig 5.2 XRD Analysis of 10% Mn doped TiO₂ Ph=8

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 Fig 5.3 XRD Analysis of 10% Mn doped TiO₂ Ph=10

5.2 UV-VISIBLE INTERPRETATION

UV-Visible absorption spectral study may be assisted in understanding the electronic structure of
the optical bandgap of the material. Absorption in the near ultra violet region arises from electronic
transition associated with the sample. The optical properties of the synthesized TiO₂ nanoparticles using
UV-Visible spectroscopy were studied and the spectrum recorded is shown in figure-5.4, 5.5, 5.6.The
optical absorption of Mn doped TiO₂ nanoparticles were measured in the scanning range of the
wavelength 200-800nm.

BANDGAP CALCULATION

The absorption peak is related to the bandgap energy and hence using maximum absorbed
wavelength, peak wavelength can be converted into bandgap energy. This conversion is carried out using
Einstein-Planck relation E=hc/λ .

For 10% Mn doped TiO₂ nanoparticles of pH=6,8,10, the absorption peaks are observed at 305.47
nm, 306.19 nm and 307.52 nm respectively. Their corresponding band gap energies are 4.05 eV, 4.06ev
and 4.03ev respectively. From this result, it is observed that the band gap energies of Mn doped TiO₂
nanoparticles are higher than that of the pure TiO₂ nanoparticles.. Thus, there is a red shift in the

54
absorption spectra of Mn doped TiO₂ nanoparticles, which indicates that their crystallite sizes must be
smaller than that of the pure TiO₂ nanoparticles.

Fig 5.4 UV Spectrum of 10% Mn doped TiO₂ Ph=6

Fig.5.5 UV Spectrum of 10% Mn doped TiO₂ Ph=8

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 Fig 5.6 UV Spectrum of 10% Mn doped TiO₂ Ph=10

5.3 FTIR ANALYSIS

Fig 5.7 FTIR Analysis of 10% Mn doped TiO₂ pH=6

56
Fig 5.8 FTIR Analysis of 10% Mn doped TiO₂ pH=8

Fig 5.9 FTIR Analysis of 10% Mn doped TiO₂ pH=10

57
 The vibrational bands and the functional groups present in the prepared nanoparticles were
analysed by taking the FTIR spectrum at room temperature. The FTIR spectrum of Mn doped TiO₂
(10%) nanoparticles are shown in figure. The strong bands in the wave number range 400-800 cm-1 are
evident in FTIR spectra of Metal oxide . The bands at 447 cm-1, 454 cm-1 , 517 cm-1, 552 cm-1 are
attributed to the bending vibration of O-Ti-O. The broad band around ⁓3400cm-1 is attributed to O-H
stretching vibrations and the absorption peak at 3401.64 cm-1, 3415.59 cm-1 originates due to the O-H-
O bending vibration of water present in the moisture absorbed from the atmosphere. The absorption
peaks at 1627.52 cm-1 , 1627.90 cm-1may be due to the presence of Manganese acetate dopant.

5.4 ANTIMICROBIAL ACTIVITY:

5.4.1 ANTIFUNGAL ACTIVITY:
The results of antifungal activity against Aspergillus shows a good variation with variation in
pH of Mn doped TiO2 nanoparticles, fig 5.4.1, 5.4.2 and 5.4.3 shows antifungal activity of pH 6,
pH 8 and pH 10 of Mn doped TiO2 nanoparticles.
The antifungal activity is done using ultra sonification method.The dispersion of metal oxide
nanoparticles without ultra sonication the activity was feeble as indicated by figure 5.4.4 for pH
10 Mn doped TiO2 nanoparticles (there is no zone of inhibition found in this case).

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5.4.2 ANTIBACTERIAL ACTIVITY:

The synthesised TiO2 nanoparticles showed only very feeble antibacterial activity which doesn’t
vary with the pH of the dopant.

59
 CHAPTER-6

CONCLUSION

TiO₂ nano particles were prepared using co-precipitation method. The pH of the growth medium
was fixed at 6, 8 and 10. The TiO₂ matrix was (doped) with Mn ions at of 10 wt %. The prepared Mn
doped nano particles were subjected to analytical techniques for material confirmation.
The UV visible spectra shows a strong red shift in band edge absorption further confirms the nano
dimensional state of the material prepared. From the XRD analysis it was inferred that the Mn doped TiO₂
prepared at pH=6,8 and 10 nanoparticles are in anatase phase with lattice constants a = 3.9604Å, 3.7852
Å, 3.7864 Å and c =9.5971Å, 9.4655 Å, 9.4558 Å respectively. From the XRD observations, the
crystallites were in nano dimensional state.
The UV-Visible spectra shows that there was an increase in wavelength with increase in pH
concentration leading to decrease the band gap energy. The broad envelope of peaks revealed the poly
dispersed state of nanoparticles with the particle size ranged from 6.18 nm to 6.50 nm
The FTIR study reveals the presence of Mn doped TiO₂ through the analysis of the fingerprint
region. From all the above discussions, it is evident that the Mn ions successfully incorporated inside the

60
TiO2 lattices by obeying Vegard’s law. This Mn doped TiO2 samples are propitious for the both industrial
and biological applications.The antimicrobial activity shows that the increase in pH of TiO₂ increases the
antifungal activity.

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