1.1 Nanoscience and Nanotechnology: Optical Characteristics of Barium Titanate Polyethylene Nanocomposites
1.1 Nanoscience and Nanotechnology: Optical Characteristics of Barium Titanate Polyethylene Nanocomposites
1.1 Nanoscience and Nanotechnology: Optical Characteristics of Barium Titanate Polyethylene Nanocomposites
CHAPTER 1
INTRODUCTION
This chapter consists of a brief introduction regarding the study done in this
dissertation work. First a little description about nanotechnology then a little
information about nanofiller, nanocomposites and polymers and different of its types.
Then the classification, properties, methods of synthesis and application of polymer
nanocomposites. Also, future motivation and purpose of work are included.
1.2 Nanofillers
Nanofillers are basically additives in solid form, which are added in polymer matrix
and differ from it in terms of their composition and structure. They are generally
inorganic materials and a very example of rarely organic materials. Inactive fillers
play an important role by raising the quantity and lower the prices, while on the other
hand active fillers carry out improvements in certain mechanical and physical
properties of the particles.
Classification of Nanofillers
1. One-dimensional nanofiller: It is found in the form of films, coatings and
multilayers
2. Two-dimensional nanofiller: tubes, fibres, plates, wires, rods
3. Three-dimensional nanofiller: it is generally in particles, quantum dots and
hollow spheres
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1.3 Composites
It is basically the composition of two or more than two material that are intermixed
with each other. They show different chemical and physical properties that lead to a
new material having enhanced properties of its constituents.
In early days people mixed mud in straws to make a solid particle which had
improved strength so that it was used in housing. Later concrete cement took the
place of mud. It was also a composite. We are doing constant modification process
by mixing and improving their properties in such a way that new composites are
being made.
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1.4 Nanocomposites
NANOCOMPOSITES
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1.5 Polymer:
It is the large molecular mass or macromolecule which consists of connecting
repeated structural subunits derived from the corresponding monomers. They are
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If only one type of monomer is used then we call it homopolymer that used for the
creation of long chain and it is called co-polymer when two or more than two types of
polymer are used. This may have various types of structures such as linear, cross
linked and branched structures. It can have either semi-crystalline or amorphous
structure. Amorphous nature polymers are like soft material having low mechanical
and melting point. A long chain generally is present in polymer for complex
structures
POLYMER
Thermoplastic:
These polymers are generally getting hard and below glass transition temperature
when cooled they become brittle. So, this reversible transition process where
polymer is hard and brittle below temperature and soft and molded above
temperature. Due to light weight property they can get desirable shape and they can
be recycled. They have a wide use in automotive industry.
Thermoset:
These type polymers are generally undergo irreversible cycle process where you
can’t re melt the cooling from molten state as they form strong cross linking chain
between the polymers which is very hard for brittleness. They are having low ductility
and harder than thermoplasts.
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Elastomers:
These are basically rubbers or rubberlike materials in which the bonds are held by
weak intermolecular forces. They have property which put them somehow between
Thermoset and Thermoplastic. Lower concentration of cross linked branches holds
the rubber.
Isotactic means all stereocenters have same orientation. These polymers are
semi crystalline in nature.
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Nanofillers plays a major role for improving the properties of a matrix such as
electrical, thermal, chemical and optical. The uniform dispersion of nanofiller and
nonuniform dispersion effect the morphology and internal properties of the PNC. In
nanocomposite there is always a difficulty to maintain the uniform dispersion of
nanofillers as some of them are less soluble. So technically sol gel process is not
better for preparation. Physical method like melt mixing are good for the dispersion
of these polymer nanocomposites.
There are various synthesis methods for polymer nanocomposite but some important
methods are
In situ polymerization:
In this method we use polymer matrix as solute and a suitable solvent that helps to
dissolve the solute. The heating procedure continues resulting the start of gelation. A
gel like structures are formed and when we dry it we get the nanocomposite with
having low agglomeration. As these polymers are completely or partially inert,
therefore it is difficult to get them completely dissolved in the solvent.
In this method, firstly we grind the polymer and nanofiller in mortar and pestle by
mixing it then sintering the sample. This method is useful for chemically inert and low
soluble product but there is nanofiller agglomeration is present. When we increase
the nanofiller concentration we get the high agglomeration. So there is certain
drawback is present. It is a tiring process as there is a lot of mixing required.
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In this process we dissolve the powder in solution then we apply a small amount of
this solution on the centre of the substrate resulting the rotation with constant speed.
This is a useful method for making the thin films of polymer nanocomposite.
polymer type
(a) Electrical Properties:
These properties of polymer are varied with the temperature. At low temperature,
polymer shows the glass like brittle characteristic to a rubber like behaviour at
high temperature. Due to interfacial region prevents the propagation of the crack,
PNC has good fatigue resistance and high damage tolerance because
It has high chemical corrosion resistance and high thermal stability. These
materials hold the good friction property and high frequency dielectric properties.
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In various fields such as industrial and petrochemical, PNC have many applications.
Polymer nanocomposite having enhanced mechanical property are used in
automotive sector, tools, electrical equipments etc.
PNC has wide defence sector applications due to improvement in the physical
properties of material. Common examples are high performance fibre, ballistic
protection, microwave absorbers, ultraviolet irradiation resistance, corrosion
protection, supersonic jets etc.
Polymers have significant effects on the transparency of thin films with the
incorporation of nanofillers in the matrix.
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Tacticity of Polyethylene:
PE is isotactic in nature and it has all the methyl group on the same side. Due to this
PE is semi-crystalline in nature. This affects the various properties such as its
melting point and glass transition temperature.
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(source http://what-when-how.com/wp-
content/uploads/2011/07/tmp840_thumb22.jpg)
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(source https://www.doitpoms.ac.uk/tlplib/ferroelectrics/phase_changes.php)
The cubic phases of Barium Titanate changes to a tetragonal phase while cooling at
120° C. The movement of Ti atoms along with respect to O results the rise of dipole
moment of the molecule. Above 120° C the polarization spontaneously disappears
due to cubic structure. Barium Titanate has other two phases named as
orthorhombic and rhombohedral. All the phases except cubic phases contains
ferroelectric effect in Barium Titanate. It is mostly uses in thermal switches.
1.11 Motivation:
We have to give our best to modify material and to make a new composite to
develop materials which will satisfy the requirement of human being.
1.12 Objective:
Study of the morphology of PE100-x(BaTiO3)x nanocomposite by melt mixing
method.
Study of the optical characteristics of PE100-x/(BaTiO3)x polymer
nanocomposite for different compositions (where x=0, 2, 4, 6, 8, 10).
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Chapter 1
This chapter gives the introduction parts of nanofillers, nanocomposites and their
types, polymer and polymer types, polymer nanocomposites and their properties,
application, motivation and objective of the dissertation work.
Chapter 2
This chapter gives the literature review of polymer nanocomposite that are provided
and knowledge gap in the current work.
Chapter 3
This chapter explains the experimental procedure and techniques followed for
synthesis and characterization of the sample.
Chapter 4
This chapter contains the result analysis and detail discussion of prepared
nanocomposite samples from the different experimental methods.
Chapter 5
This chapter consists of summary and conclusion of dissertation work and also
future scope of this work.
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CHAPTER 2
LITERATURE REVIEW
This chapter contains the literature survey related to PE100-x(BaTiO3)x polymer
nanocomposite. Many researches have tried to improve the structural optical, thermal,
mechanical and electrical and other properties of polymer nanocomposite by doing tiresome
research in this field. The improvement in properties are discussed in the literature. Last
section of this chapter provides knowledge gap regarding polymer nanocomposite and gives
indication for improvement in it.
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He-Xin Zhang et al. (2017) used in-situ polymerisation for the successful
synthesis of PE/OMoS2 nanocomposites. The resultant nanocomposites had
a layered morphology in polymer matrix. The OMoS2 fillers were well
dispersed in the PE matrix with strong interfacial adhesion in the surface. With
the addition of OMoS2, the thermal stability and mechanical properties of PE
were significantly enhanced.
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Weijun Miao et al. (2016) PE21Cl was chosen to study the impact of
substituent on epitaxial crystallization. Kebab-like and rod-like PE21Cl thinner
crystals formed on CNT and RGO, respectively, by traditional and
supercritical CO2 assisted solution crystallization. The melting point of rod-like
crystal on RGO is 75 °C higher owing to structural transformation induced by
epitaxial crystallization.
Kangsheng Liu et al. (2016) two step solution method generally used to
reduce graphene oxide nanoplatelets (rGONs)/ (HDPE) nanocomposites. The
rheological percolation measured by linear oscillatory rheology reveals a
threshold at 4.0 wt %. Strong chain–filler interaction inducing chain orientation
was shown time resolved WAXD/SAXS on the HDPE/rGON samples
subjected to shear flow. Strong interaction between rGON
and polyethylene chains were demonstrated by combined rheological and
WAXD/SAXS results.
Giovani Pavoski et al. (2015) GO and RGO obtained from graphite were
used as support in ethylene polymerization. He obtained the layered particles
which flew easily and avoided the reactor fouling. With the use of few
graphene layers filler he found the onductivity was improved. The support of
the catalyst on RGO improved dispersion and percolation threshold.
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Meng Guo et al. (2017) saw enhanced erosion resistances in all LDPE/POSS
composites, from 6% to 46%. By POSS addition a 6% thermal conductivity
improvement was achieved. POSS largely retain or even reduce the viscosity
of LDPE. Among all the composites studied, LDPE/1 wt% octaisobutyl-POSS
composite is the best for high-voltage power cable insulation.
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Xiangrong Wang et al. (2012) Glass additive was employed to improve the
microstructures and energy storage properties of Barium Titanate ceramics
using liquid phase sintering technology. Microstructural observation indicated
that the average grain size reduced obviously with increasing glass
concentration. Also, the dielectric constant decreased and the dielectric
breakdown strength increased as glass concentration increased. The increase
in the breakdown strength with decreasing grain size was consistent with the
well-known relationship for the mechanical failure. The activation energies of
bulk grain and grain boundary as well as their differences were calculated
using measured impedance values. Good inverse dependence of the
dielectric breakdown strength on the difference between activation energies of
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bulk grain and grain boundary was obtained for the glass-added
BaTiO3 ceramics.
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CHAPTER 3
Melt mixing method are those in which nanoparticles are added to the polymer
above glass transition temperature. Generally, in polymer the shear stress is induced
to melt by viscus drag so that the nanoparticle aggregates completely broken down
by the shear stress. Therefore, the dispersion of homogenous and uniform
nanoparticle in the polymer matrix is possible. Only it has a little bit of agglomeration
problem with increase in the nanofiller concentration.
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SINTERING AT 100℃
FOR 12 HOURS
GRINDING AND
CHARACTERIZATION
OF SAMPLES
Field emission scanning electron microscopy or FESEM are generally used for
studying morphological properties of the sample. It is applied for viewing small
molecule having size in nanometre range. Regarding the surface of material two
things are studied such as morphology of the surface which is qualitative analysis
and the other one is topological surface comes under the category of quantitative
analysis.
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(source http://blog.phenom-world.com/edx-analysis-scanning-electron-micrscope-
sem)
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(source https://www.researchgate.net/figure/Schematic-diagram-of-Field-Emission-
Scanning-Electron-Microscope-FESEM_fig31_318487306)
Comparing FESEM with SEM, FESEM is an advanced version with much better
facility than the previous one. In SEM thermionic gun is used. It is basically done by
heating the filament. On the other hand, FESEM uses field emission gun which in
order to workout requires strong electric field. In Sem the scanning rate is
discontinuous where as in FESEM it is continuous and without any pause.
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side of electron of element there is a vacancy in core shell and in order to fill the
shell the electron from upper shell move forward with de-excitation of electrons. A
high energy beam of charged particles such as electrons is focused on the sample to
study about the specimen. The excited electron due to incident beam ejected from
the inner shell creating an electron hole. Then outer higher energy electron fills the
hole and energy difference between two shells released in x-ray. The elemental
composition of the specimen is measured with the difference in energy of x-rays and
of the element having atomic structure helped them to emit. For K shell vacancy if
the L shell electron helps to fill the vacancy then it will be called K𝛼. And if M shell
helps to fill up the electron in vacant K shell it will be called K𝛽. Similarly it will be L𝛼
and L𝛽 for L shell vacancy.
(source https://commons.wikimedia.org/wiki/File:EDX-scheme.svg)
3.2.3 Fourier Transform Infrared Spectroscopy (FTIR)
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are divided into three types near IR region having different vibration and rotational
energy. 12800 to 4000𝑐𝑚−1 is the near IR region, 4000 to 200𝑐𝑚−1is the mid IR
region and far IR region which ranges from 500 to 1000𝑐𝑚−1.
When we discuss the internal structure of FTIR then we know that it is based on
three basic spectrometer component such as a radiation source required for
radiating energy, an interferometer for division of radiant beams and a detector for
detection of repetitive interference signals measured by optical path difference.
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FIXED MIRROR
MOVING MIRROR
SOURCE COLLIMATOR
BEAM
SPLITTER
SAMPLE
COMPARTMENT
DETECTOR
Advantages of FTIR
It measures all frequencies simultaneously instead of scanning through individual
frequency. So, it’s sensitivity is better. Less energy required from the source and less
time probably 1-2 seconds required for a scan. The signal is improved as several
scan completed in a few seconds and averaged. A laser beam is used alongside the
IR beam to control the speed of the moving mirror and to time the collection of data
points so the resolution and accuracy are improved. The spectrometer accurately
calibrated by the light beam of precise frequency.
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The intensity of the light passing through the sample cell is also measured for that
wavelength which we name as “I”. If I<Io, then the sample has absorbed some of the
light. Computer does the simple bit of math to convert this into something named as
the absorbance of the sample which we name as “A”. The absorbance of a transition
depends on two external assumptions such as
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A∝c
A=log10 (I0/I)
A∝l
A∝ cl
A= ∈ c l
This formula is the common form of the Beer-Lambert Law, although it can also be
written in terms of intensities:
A= log10(Io/I) = ∈ l c
The optical band gap can be found in UV visible spectrum using Tauc relation and by
drawing Tauc plot.
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Tauc relation is
(𝛼ħ𝜔)𝑟 = 𝐵(ħ𝜔 − 𝐸𝑔 )
The resulting plot has a distinct linear regime which denotes the onset of absorption.
Thus, extrapolating this linear region to the abscissa yields the energy of the optical
band gap of the material. (Tauc, J. et al. 1968)
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CHAPTER 4
RESULTS AND DISCUSSIONS
In this chapter we can discuss the result of the experiment that carried out. We can
extensively discuss about the morphological and optical properties.
Fig 4.1 (a) are the image of pure PE which has a molten morphology. In Fig 4.1 (b),
2% BaTiO3 is incorporated in polyethylene matrix and it is uniformly dispersed in PE
matrix. In Fig 4.1 (c) it shows also dispersion means sintering has been done
properly. In fFg 4.1 (c) 4% BaTiO3 is incorporated in PE matrix. In Fig 4.1 (d) 6%
BaTiO3 is incorporated. With the increase in the concentration of of BaTiO3, the
dispersion is also increased. The trend continues in fig 4.1 (e) and 4.1 (f). By
FESEM analysis we see there is a different level of dispersions of BaTiO3 nanofiller
is obtained. Comparing the loading of BaTiO3 in lower concentration to higher
concentration we get there is increase in the dispersion in each image. All the
nanocomposites have morphologically molten structure due to the melt mixing
method of synthesis.
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Figures 4.1 FESEM image of (a) pure PE, (b) 2% BaTiO3 in PE, (c) 4% BaTiO3 in
PE, (d) 6% BaTiO3 in PE, (e) 8% BaTiO3 in PE, (f) 10% BaTiO3 in PE
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Here the above one is the image of pure BaTiO3 Nanopaticle. While doing FESEM
we find the Barium Titatnate of homogenous, spherical and cubic in nature.
The EDX analysis confirms the presence of all elements and components in
stoichiometric ratio. There is no impurity present in the nanocomposite. In the figure
4.3 (a) the EDX peak has its main spectrum in carbon and oxygen as carbon is the
main element in the nanocomposite. In other diagram there is some gold peaks as in
order to make the insulating polymer conducting, gold coating is used. In the doping
of Barium Titanate smaller concentration of titanium and oxygen are also seen.
When we take the EDX analysis of pure BaTiO3 nanoparticles we get the presence
of barium, titanium and oxygen in stoichiometric ratio. There is also a little bit peak
due to gold coating is found. The EDX analysis shows there is a little bit of
inhomogeneity present in the polymer matrix.
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Figures 4.3 EDX plots of of PE100-x(BaTiO3)x nanocomposites (a) 0%, (b) 2%, (c)
4%, (d) 6%, (e) 8%, (f) 10%
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With increase in the number of BaTiO3 the band gap is showing unusual behaviour,
sometime it is increasing then decreasing, then again increasing and then
decreasing. Using the absorbance datas we use Tauc expression to find out optical
band gap of PE.
(𝛼ħ𝜔)𝑟 = 𝐵(ħ𝜔 − 𝐸𝑔 )
where
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In the above figure we take the Tauc plot and get the band of 5.68 eV in 10% BaTiO3
concentration. Similarily for pure PE and for different concetration of doped BaTiO3
we are getting different types of band gap. For pure PE band gap is 5.69 eV, for 2%
BaTiO3 concentration it is 5.89 eV, for 4% BaTiO3 concentration it is 5.82 eV, for 6%
BaTiO3 concentration it is 5.86 eV, for 8% BaTiO3 concentration it is 5.86 eV. From
the above data we come into conclusion that when we increase the concentration of
BaTiO3 the band gap is increasing first and then decreasing. But the decreasing
value is not much due to the agglomeration in higher concentration. We found there
is inhomogeneity in some samples due to not sintering of the sample properly.
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CHAPTER 5
CONCLUSION AND SUMMARY
5.1 CONCLUSIONS
In this research work I have successfully synthesized polyethylene and barium
titanate where PE was a polymer matrix and barium titanate was a reinforcement
phase. I have synthesized 6 samples with different concentration of reinforcement
phases from 0% to 10%. I have used melt mixing method for synthesis of the
sample. I have also used various characterization technique for the analysis of the
sample.
EDX analysis almost confirms the presence of all essential element in polymer
nanocomposite having specific atomic and molecular weight. There is no impurity
found though a small amount of gold coated for conducting the insulating polymer. In
the pure BaTiO3 sample there is a little bit of in homogenous peak found due to gold
coating.
FTIR spectroscopy confirms the presence of functional group in the polymer and
nanoparticles. With increase in the doping concentration of nanoparticles peaks get
more intense. When there is no chemical reaction between the two materials then
there is almost no change in shifting of absorption peaks. In some samples there
was an unusual peak due to inhomogeneity of the sample.
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Main problem we face regarding this polymer nanocomposite is that the dispersion
of nanofiller. It generally depends upon the method we are synthesizing the
nanoparticles. Compared to other methods for synthesizing nanoparticles melt
mixing method is a good method. If the dispersion is done properly and also the
sintering process then the particles shows much better thermal, mechanical, optical
and electrical properties.
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