PHASE AND MICROSTRUCTURE ANALYSIS OF ZINC OXIDE-

BASED NANOFIBERS

SUPERVISED BY: PROF: YASEEN IQBAL

SUBMITTED BY: IQRA JAMIL &

ASHFAQ AHMAD
MSC PHYSICS

DEPARTMENT OF PHYSICS
UNIVERSITY OF PESHAWAR
SESSION 2019-21
ACKNOWLEDGEMENT

In the name of Allah, the Most Beneficent and the Most Merciful. All praises to Almighty
Allah, the creator of the universe. We bear witness that Holly Prophet Muhammad (PBUH)
is the last messenger, whose life is a perfect model for the whole of mankind till the Day
of Judgment. Allah blessed us with knowledge related to the earth. We are enabled by Allah
to complete our work. Without the blessings of Allah, we would not be able to complete
our work and be at such a place.
We are especially indebted to our honourable supervisor Prof. Yaseen Iqbal for giving us
the initiative in this project and for the guidance he has provided us. He reviewed our work
and project. Without his assistance, this dissertation would never have been the same.
We especially acknowledge the prayers, endless love, efforts, and support of our whole
family. Without them, we would be unable to reach this stage. We pay our thanks to the
whole faculty of my department, especially the respected teachers whose valuable
knowledge, assistance, cooperation, and guidance enabled us to take initiative, develop and
furnish our academic careers. We are extremely thankful to all our teachers and friends
who have helped us a lot during our academic careers.

Iqra Jamil &

Ashfaq Ahmad

I
ABSTRACT
Zinc oxide nanofibers are prepared by electrospinning technique using polyvinyl alcohol
and zinc acetate as precursors. The fibres were then calcined at 500 degrees Celsius for two
hours. The calcined and uncalcined nanofibers were characterized by using scanning
electron microscopy (SEM), X-RAY diffraction (XRD), Ultraviolet-visible spectroscopy
and Fourier transform infrared ray (FTI-R). SEM images confirmed the formation of
nanofibers of diameters of 124 nm. The diameter of fibres reduced firstly and then
increased with the rising calcinate temperature. The XRD peaks at angle 2theta 31.73°,
34.37°, 36.21°,47.48°, 56.53°,62.77°,66.30° and 67.86° confirm the formation of zinc
oxide in crystal form.

II
Table of Contents
ACKNOWLEDGEMENT I

ABSTRACT II

CHAPTER 1 1

INTRODUCTION 1

OBJECTIVE AND MOTIVATION 1

1.1 NANOFIBERS 1

1.1.1 THE ROLE OF NANOFIBERS 2

1.1.2 THE NEED FOR NANOFIBERS 3

1.1.3 BACKGROUND OF NANOFIBERS 3

1.1.4 STRUCTURE AND MORPHOLOGY OF POLYMERIC NANOFIBERS 4

1.1.5 PROPERTIES OF NANOFIBERS 5

1.1.6 APPLICATIONS OF NANOFIBERS 6

1.1.7 ADVANTAGES OF ELECTROSPUN NANOFIBERS 7

1.1.8 CHALLENGES IN NANOFIBERS 9

CHAPTER 2 10

LITERATURE REVIEW 10

CHAPTER 3 14

FABRICATION AND CHARACTERIZATION TECHNIQUE 14

3.1 OVERVIEW OF THE ELECTROSPINNING METHOD 14

3.1.1 HISTORY OF ELECTROSPINNING 15

3.1.2 ELECTROSPINNING THEORY AND PROCESS 16

3.1.3 ELECTROSPINNING APPARATUS SETUP 17

3.1.4 ELECTROSPINNING MECHANISM 17

3.1.5 ELECTROSPINNING PROCESS PARAMETERS 18

III
 3.2 SCANNING ELECTRON MICROSCOPE 19

3.2.1 PRINCIPLE OF SEM 21

3.2.2 APPLICATIONS OF SEM 22

3.3 X-RAY DIFFRACTION 22

3.3.1 WORKING MECHANISM 23

3.3.2 XRD BENEFITS AND APPLICATIONS 24

3.4 FT-IR 24

3.4.1 FT-IR WORKING MECHANISM 25

3.4.2 FT-IR SAMPLING TECHNIQUES 26

CHAPTER 4 28

MATERIAL AND SETUP 28

4. 1 MATERIALSion PROCESSING 28

4.2 MATERIAL BACKGROUND 29

4.2.1 ZINC ACETATE DIHYDRATE 30

4.2.2 ZINC OXIDE 30

4.2.3 POLYVINYL ALCOHOL 31

4.3 EXPERIMENT 31

4.3.1 SAMPLE PREPARATION FOR FIBERS 32

CHAPTER 5 34

RESULTS AND DISCUSSION 34

5.1 SEM ANALYSIS OF PVA/ZINC ACETATE COMPOSITE FIBERS 34

5.2 XRD ANALYSIS 35

5.3 FT-IR ANALYSIS 37

5.4 ULTRAVOILET VISIBLE GRAPH 38

CHAPTER 6 40

IV
CONCLUSION 40

REFERENCES 41

Figure 3. 1 Schematic of the electrospinning setup .......................................................... 19

Figure 3. 2 Basic components of electrospinning ............................................................. 19
Figure 3. 3 Taylor cone formation .................................................................................... 19
Figure 3. 4 Scanning Electron Microscope ....................................................................... 22
Figure 3. 5 X-ray machine Figure 3. 6 X-ray diffraction process 24
Figure 3. 7 FT-IR machine Figure 3. 8 FT-IR graph sample
........................................................................................................................................... 27

Figure 5. 1 SEM image of uncalcined nanofibers............................................................. 34

Figure 5. 2 SEM images of PVA/Zinc acetate after calcination at 500 degrees Celsius .. 35
Figure 5. 3 XRD graph of PVA/Zinc acetate after calcination at 500 degrees Celsius for 2
hours, angles are marked................................................................................................... 36
Figure 5. 4 XRD graph of PVA/Zinc acetate after calcination at 500 degrees Celsius for 2
hours, here reflecting planes are shown. ........................................................................... 37
Figure 5. 5 FT-IR graph of PVA/Zinc acetate before calcination .................................... 38
Figure 5. 6 FT-IR graph of zinc oxide nanofibers after calcination at 500 degrees Celsius
for 2 hours ......................................................................................................................... 38
Figure 5. 7 Absorbance vs. Wavelength graph for Zinc Oxide nanofibers. ..................... 39
Figure 5. 8 Tauc plot for semiconductor Zinc oxide nanofibers....................................... 39

Table 4. 1 Concentration of composite ............................................................................. 32

Table 4. 2 Typical range of operating parameters used for electrospinning experiments
with PVA/Zinc Acetate ultrafine fibre .............................................................................. 33

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VI
 CHAPTER 1

INTRODUCTION

OBJECTIVE AND MOTIVATION

This research deals with the fabrication and characterization of zinc oxide nanofibers. The
precursor polymeric solution for zinc oxide nano-fibres was prepared using zinc acetate
and PVA (polyvinyl alcohol). The surface morphology of prepared nanofibers would be
characterized by Scanning Electron Microscopy (SEM). The overall objective of this work
is to develop a suitable processing methodology to produce ZnO nano-fibres with properly
controlled interconnectivity by using the electrospinning technique.
Nanotechnology has shown astounding prospects and progress in recent years and it is
viewed as a high-end tool for numerous technological advancements. The objective of this
thesis is to explore the possibility of using nanotechnology to create high-performance
nanomaterials. The process for producing polymeric nanofibers and the effect of process
parameters on its structure and morphology has been analysed.
Research work reported in this thesis has exploited electrospinning nanotechnology to
develop high-performance nanofiber webs that have advanced applications. The
motivation for this thesis has been the ongoing development in the field of nanotechnology
and the interesting properties of nanostructures. Nanotechnology offers the advantage of
increased sensitivity, selectivity, and response time.
The potential of nanofiber materials has motivated this present research work. Results
obtained from this current research work will hopefully lead to further understanding of
the electrospinning of nanofibers (Mirjalali & Zohoori, 2016).

1.1 NANOFIBERS
Research and development of nanofiber products are very active over the world. Many
types of polymers were processed into nanofibers of 50 to 1000 nanometres in diameter.

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1.1.1 THE ROLE OF NANOFIBERS
Several amazing characteristics arise when polymer fibre materials shrink in diameter from
micrometres to sub-microns or nanometres. Among their important properties, two that
stand out are a very large ratio of surface area to volume, and superior mechanical
performance (stiffness and tensile strength) compared to any other known fibre-material
form. These outstanding properties make polymer nanofibers optimal candidates (Huang,
Zhang, Kotaki, & Ramakrishna, 2003).
Fibbers with a diameter of between 100nm and 500 nm are generally classified as
nanofibers. These fibres can be made from a wide variety of materials ranging from metals
to ceramics to polymers. What makes nanofibers of great interest is their extremely small
size. With higher surface area to volume ratios and smaller spaces between individual
fibres than larger fibres, nanofibers offer an opportunity for use in a wide variety of
applications. Increased awareness of the current and the potential applications of
nanofibers have in recent years accelerated the research and development of these
structures (Xue, Wu, Xia, & Xia, 2019).
Up to date, polymer composites reinforced with electrospun nanofibers have been
developed mainly for providing some outstanding physical (e.g., optical and electrical) and
chemical properties while keeping their appropriate mechanical performance and less work
has been done on the development of electrospun polymer nanofiber reinforced
composites.
First of all, not a sufficient quantity of uniaxial and continuous nanofibers has been
obtained and could be used as reinforcements. The non-woven or randomly arranged
nanofiber mats generally cannot result in a significant improvement in the mechanical
properties of the composites with their reinforcement. Another reason may be that
polymers yielding these fibres are generally considered less suitable for structural
enhancement. Although carbon nanofibers are principally achievable from post-processing
of electrospun precursor polymer nanofibers such as polyacrylonitrile (PAN) nanofibers,
these fibres seem to have not been obtained in a large quantity of continuous single yarns
yet. Thus, extensive work both from the standpoint of nanofiber composite science
(fabrication, characterization, modelling, and simulation) and from an industrial base
(applications) viewpoint is necessary for the future.

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1.1.2 THE NEED FOR NANOFIBERS
Electrospinning has been recognized as an efficient technique for the fabrication of
polymer nanofibers. Various polymers have been successful elec into ultra-fine fibres in
recent years mostly in solvent solution and some in melt form. Nanofibers are an exciting
new class of material used for several value-added applications such as medical, filtration,
barrier, wipes, personal care, composite, garments, insulation, and energy storage.
Special properties of nanofibers like an extremely high surface-to-weight ratio compared
to conventional non-woven. Low density, large surface area to mass, high pore volume,
and tight pore size make the nanofiber suitable for a wide range of applications (Costa, et
al., 2013).

1.1.3 BACKGROUND OF NANOFIBERS

In recent years, the term nanotechnology has spread across the globe worldwide. Millions
of dollars in research grants and investments are being devoted to making proof less than
100 nanometres in size. Unlike many other aspects of the traditional textile industry in the
United States which is said to be on death's doors, nanotechnologies generate quite a bit of
interest.
The nonwoven industry generally considers nanofibers as having a diameter of less than
one micron, although the National Science Foundation (NSF) defines nanofibers as having
at least one dimension of 100 nanometres (nm) or less. The name derives from the
nanometre, a scientific measurement unit representing a billionth of a meter, or three to
four atoms wide (Zhang, Lin, Wang, & Wei, 2012).
When the diameters of polymer fibre materials are shrunk from micrometres (e.g.,10 —
100 pm. to sub-microns or nanometres (e.g.,10 x 10 -3 - 100 x10 -3 pt), A nanofiber is an
elongated and threadlike structure with a diameter in the nanometre range. At this scale,
several amazing characteristics such as a very large surface area to volume ratio (this ratio
for a nanofiber can be as large as 10 3 times that of a microfiber), flexibility in surface
functionalities, and superior mechanical performance (e.g., stiffness and tensile strength)
compared with any other known form of the material. These outstanding properties make
the polymer nanofibers to be optimal candidates for many important applications like
filtration, protective clothing, and biomedical applications. A large number of synthetic

3
and fabrication methods have already been demonstrated for generating nanostructures in
the form of fibres.
Many processing techniques such as drawing, template synthesis, phase separation, self-
assembly, electrospinning, etc. have been used to prepare polymer nanofibers in recent
years.
Materials ranging from metals to ceramics to polymers. What makes nanofibers of great
interest is their extremely small size. With higher surface area to volume ratios and smaller
spaces between individual fibres than larger fibres, nanofibers offer an opportunity for use
in a wide variety of applications. Increased awareness of the current and the potential
applications of nanofibers have in recent years accelerated the research and development
of these structures.
The process takes a relatively long period to transfer the solid polymer into the nano-porous
foam. Self-assembly is a process in which individual, pre-existing components organize
themselves into desired patterns and functions. However, similarly to phase separation self-
assembly is time-consuming in processing continuous polymer nanofibers. Thus, the
electrospinning process seems to be the only method that can be further developed for the
mass production of one-by-one continuous nanofibers from various polymers (Wang, et
al., 2016).

1.1.4 STRUCTURE AND MORPHOLOGY OF POLYMERIC NANOFIBERS

Nanofibers have attracted the attention of researchers due to their pronounced micro and
nanostructural characteristics that enable the development of sophisticated materials that
have advanced applications. More importantly, high surface area, small pore sizes, and the
possibility of producing three-dimensional structures have increased the interest in
nanofibers. As theoretical studies on electrospinning, the process has been conducted by
various groups for a while to understand the electrospinning process, there have been some
simultaneous efforts to characterize the structure and morphology of nanofibers as a
function of process parameters and material characteristics.
The production of nanofibers by the electrospinning process is influenced both by the
electrostatic forces and- the viscoelastic behaviour of the polymer. Process parameters like
solution feed rate, applied voltage, nozzle-collector distance, spinning environment, and

4
material properties like solution concentration, viscosity, surface tension, conductivity, and
solvent vapour pressure influence the structure and properties of electrospun nanofibers
(Mirjalali & Zohoori, 2016).

1.1.5 PROPERTIES OF NANOFIBERS

The properties associated with nanofibers can be traced back to both process parameters
and morphological characteristics. For example, electrospun fibres have small pores that
are a result of the evaporation of the solvent used during the electrospinning process and
these pores affect mechanical properties of the fibres such as tensile strength and Young's
modulus. Other studies have found that the physical properties of nanofibers tend to be
somewhat inferior to that of their film and resin counterparts of a similar thickness. This is
believed to be a result of lower crystallinity due to rapid evaporation of the solvent followed
by rapid cooling, which occurs in the final stages of the electrospinning process (Queen,
2006).

1.1.5.1THERMAL PROPERTIES
There are a few published reports on the thermal properties of nanostructured materials.
Thermal analysis has been carried out on several electrospun polymeric materials to
understand the relationship between nanostructure and thermal properties attributed to the
decrease in the glass transition temperature to the large surface-to-volume ratio of
nanofibers with air as the plasticizer. The high evaporation rate followed by rapid
solidification at the final stages of electrospinning is expected to be the reason for the low
crystallinity.
The glass transition temperature and the peak crystallization temperature of the electrospun
polyethene terephthalate (PET) and polyethene naphthalate (PEN) decreased significantly,
while the heat of crystalline melting increased. The decrease in glass transition and the
increase in the heat of melting was attributed to the increase in the segmental mobility. The
melting temperature of the PEN electrospun fibres remained almost constant without any
significant variations compared to that of regular fibre form. Polyethylene oxide nanofibers
have shown a lower melting temperature and heat of fusion than the Polyethylene oxide
powder, which is attributed to the poor crystallinity of the electrospun fibres.

5
Polyethylene oxide nanofibers retained the same crystal structure as Polyethylene oxide
powders while there is a clear indication of reduced crystalline order in nanofibers.
Thermal degradation of PET and PEN before and after electrospinning was analysed by
Kim and Lee using the TGA thermograms and they found that on electrospinning the
intrinsic viscosities of both PET and PEN reduced significantly. The thermal degradation
and hence the decrease in intrinsic viscosities (i.e., a decrease of molecular weight) were
postulated to be the reasons for the decrease in glass transition temperature and peak
crystallization temperature caused by reduced entanglements (Mirjalali & Zohoori, 2016).

1.1.5.2 MECHANICAL PROPERTIES

Electrospun fibres have nanostructured surface morphologies with tiny pores that influence
mechanical properties like tensile strength, Young's modulus, etc. scientists have found
that there is no significant change in Young's modulus of electrospun Pellethane
thermoplastic elastomers. When compared with cast films, electrospun elastomers have
shown a 40% reduction in the peak tensile strength and a 60% reduction in elongation at
maximum applied stress.
Nanofiber reinforced polymer composites have shown highly enhanced mechanical
properties than the unfilled or carbon/glass fibre-filled composites. Young's modulus of a
nanofiber composite is tenfold greater than the pure Styrene-Butadiene rubber. As is
evident, there is less information available on the mechanical properties of nanofibers and
nanofiber composites. Research on the mechanical properties of nanofibers and their
composites from a variety of polymers is essential for a greater understanding of the
contributions of nanofiber to the mechanical and performance-related characteristics of
nanofiber composites (Mirjalali & Zohoori, 2016).

1.1.6 APPLICATIONS OF NANOFIBERS

Nanomaterials have been attracting the attention of global materials research these days
primarily due to their enhanced properties required for application in specific areas like
catalysis, filtration, NEMS, nanocomposites, nanofibrous structures, tissue scaffolds, drug
delivery systems, protective textiles, storage cells for hydrogen fuel cells, etc.

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1.1.6.1 ELECTRICAL AND OPTICAL APPLICATION
Conductive nanofibers are expected to be used in the fabrication of tiny electronic devices
or machines such as Schottky junctions, sensors, and actuators. Due to the well-known fact
that the rate of electrochemical reactions is proportional to the surface area of the electrode,
conductive nanofibrous membranes are also quite suitable for use as porous electrodes in
developing high-performance batteries. Conductive (in terms of electrical, ionic, and
photoelectric) membranes also have the potential for applications including electrostatic
dissipation, corrosion protection, electromagnetic interference shielding, photovoltaic
devices, etc.
Waters et al reported using electrospun nanofibers in the development of a liquid crystal
device of optical shutter which is switchable under an electric field between a state in which
it is substantially transparent to incident light and a state in which it is substantially opaque.
The main part of this liquid crystal device consisted of a layer of nanofibers permeated
with liquid crystal material, having a thickness of only a few tens of micrometres. The layer
was located between two electrodes, through which an electric field could be applied across
the layer to vary the transmissivity of the liquid crystal nanofiber composite. It is the fibre
size used that determines the sensitivities of the refractive index differences between the
liquid crystal material and the fibres and consequently governs the transmissivity of the
device. Nanoscale polymer fibres are necessary for this kind of device (Almetwally, El-
Sakhawy, Elshakankery, & Kasem, 2017).

1.1.7 ADVANTAGES OF ELECTROSPUN NANOFIBERS

The advantages of electrospun fibres are very appealing to a broad array of potential
applications in many industry segments. The composites industry for one is especially
interested in nanofibers technology because it now becomes possible to create products
that are much smaller and lighter in weight, yet capable of performing at the same or
enhanced mechanical standards. If the fibres can be collected individually and aligned to
specific orientations, it is possible to increase the maximum volume fraction of fibres in a
matrix thus increasing the strength of the material. The increased surface area/weight will

7
also allow for better bonding with the matrix to help prevent failure by the pullout of the
fibres.
In addition to the composites industry, the filtration industry has already begun utilizing
nanofibers and in some cases has generated commercially available products. Nanofibrous
mats can be made with varying fibre diameters based on several input parameters. With
varying fibre diameters, the pore size of the mat can be controlled to a fairly high degree.
As a result, nanofibrous mats can be designed to block out molecules of specific sizes. In
addition to mechanical filtration as described above, nanofibrous mats can be treated so
that when molecules of a specific design pass through, a chemical reaction takes place
which neutralizes any potential hazards.
Similarly, nanofibrous mats are being explored as biomedical grafts and wound dressings.
It has been found that cells can adhere and proliferate into the mats with a great deal of
success. Also, because of the extremely small size of the nanofibers, the potential exists
for layering of different polymers with specific functionalities. Electrospinning techniques
can be applied to nearly every polymer of sufficient molecular weight, including those
which are FDA approved; therefore, no issues with biocompatibility exist.
One of the greatest attributes of electrospinning and nanofibrous technology is that it is
very much still in its infancy. Numerous ideas and concepts have been proposed or written
about, but in many cases, the theoretical expectations have yet to be realized. It has been
shown that nearly every polymer imaginable can be electrospun either from solution or
melt so there are no limitations in that regard. Today, the fibres are collected in the form
of a mat of staple aligned fibres. Future developments and processing technologies must
find a way to orient a continuous fibre for the technology to continue to advance in the
right direction.
It has been shown to some degree that electrostatic attraction and repulsion can be used to
control the path of the jet to some degree. With enhanced methods of doing so, it may be
capable of directly producing woven or braided fabrics from the electrospinning station.
While the process itself is waiting for the mechanical/processing mechanisms to catch up
that are capable of manoeuvring single fibres into specific configurations, much work still
needs to be done to optimize the conditions for making a specific fibre diameter with a

8
specific polymer. It is only after we can truly control the process, that we can use it to the
best of our ability and capabilities (Teo & Ramakrishna, 2006).

1.1.8 CHALLENGES IN NANOFIBERS

The process of making nanofibers is quite expensive compared to conventional fibres due
to the low production rate and high cost of technology. In addition, the vapours emitting
from the electrospinning solution while forming the web need to be recovered or disposed
of in an environmentally friendly manner. This involves additional equipment and cost.
The fineness of fibre and evaporated vapour also raises much concern over possible health
hazards due to the inhalation of fibres. Thus, the challenges faced can be summarized as:
• Economics
• Health hazards
• Solvent vapour
• Packaging shipping handling

Because of its exceptional qualities, there is an ongoing effort to strike a balance between
the advantages and the cost (Zhang, Lin, Wang, & Wei, 2012).

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 CHAPTER 2

LITERATURE REVIEW

A lot of work has been done on the formation of zinc oxide nanofibers. In the research that
was carried out in 2003, the morphology and optical properties of zinc oxide fibres with
diameters in the nanometre to micrometre range are reported. The PVA/zinc acetate
organic/inorganic hybrid nanofibers were successfully prepared by electrospinning using
polyvinyl alcohol (PVA) and zinc acetate. Pure zinc oxide fibres were obtained by high-
temperature calcination of the hybrid fibres in the air. The nanofibers were characterized
by scanning electron microscopy (SEM), atomic force microscopy (AFM), x-ray
diffractometry (XRD) and Raman spectroscopy. The photoluminescence spectra under
excitation at 325 nm showed an ultraviolet emission at 3.13 eV and a green emission at
2.21 eV. These nanofibers could be used as light-emitting devices in nanoscale
optoelectronic applications (Viswanathamurthi, Kim, Bhattarai, & Lee, 2003).

In 2004 another research was Carried out on the fabrication of ZnO based nanofibers for
electrical and optical use. Nano structural zinc oxide fibres were fabricated by a simple
vapour transport method of heating the mixture of zinc oxide, gallium oxide,
and carbon powders in the air. The zinc oxide nanofibers showed cauliflower-like,
disordered, vertically and horizontally aligned morphologies in different temperature
regions. The aligned nanofibers were composed of hexagonal zinc oxide with good
crystallinity. Gallium was doped into zinc oxide with a concentration of 0.73 at. %. The
growth process and the characteristics can be interpreted by a vapour-liquid-solid
mechanism. The field emission of the vertically aligned zinc oxide fibre array showed a
low field emission threshold, high current density, rapid surge, and high field enhancement
factor. The threshold electric field is about 2.4 V/μm at a current
density of 0.1 μA/cm−2. The field enhancement factor was 2991. The emission current
density and the electric field followed the Fowler–Nordheim relationship (Xu, et al., 2004).

10
In another research, the ZnO nanofibers were fabricated using the electrospinning
technique in 2006. Ultra-thin fibres of zinc oxide (ZnO) were prepared by sol-gel
processing and the electrospinning technique using poly (vinyl acetate) and zinc acetate as
precursors. The fibres were characterized by thermogravimetric analysis, scanning electron
microscopy, Fourier-transfer infrared, and X-ray diffraction, respectively. The results
showed that the diameter of the precursor fibres increased with increasing zinc acetate
content, and the size of the inorganic ZnO nanofibers decreased obviously as the calcining
time increased (Wu & Pan, 2006).
In 2017 Zinc oxide nanofibers were fabricated to use in renewable energy applications.
Nanometre (nm) scale 1D zinc oxide (ZnO) nanofibers were fabricated through sol-gel
processing and electrospinning of Polyvinyl alcohol (PVA) and zinc acetate precursors.
The structure and morphologies of the zinc acetate/PVA precursor and ZnO nanofibers
were studied by Fourier transform infrared (FTIR), X-ray diffraction (XRD), and
thermogravimetric analysis (TGA) and field emission scanning electron microscopy (FE-
SEM). Bead free smooth nanofibers with increased average diameters (278 nm (5 wt.%)
and 423 nm (15 wt.%)) were obtained as the content of zinc acetate precursor was
increased. The calcination temperature of 480 °C was determined from TGA. FTIR, XRD
and TGA studies carried out after calcination, confirmed the formation of ZnO nanofibers
by the appearance of a band at 472 cm−1, characteristic ZnO pattern (i.e. peaks at ∼31.820,
34.331, 36.496, 47.569 and 57.168 2θ degree) and no weight loss after 480 °C,
respectively. The burning of the polymer has also been confirmed by a significant decrease
in average diameter (124 nm (5 wt.%) and 197 nm (15 wt.%)) of the ZnO nanofibers.
Electrospinning is a simple and cost-effective technique for the synthesis of ID ZnO
nanofibers mat for potential applications in renewable services (Imran, Haider, Ahmad,
Mahmood, & Al-Masry, 2017).

Most recent work has been done for the detection of Aflatoxin B1 using Zinc oxide
nanofibers. The precise and rapid detection of hazardous molecules, microorganisms,
pollutants, and toxins currently remains a global challenge. Aflatoxin B1 (AFB1) is a toxic
and dangerous product of fungi that are considered cancerogenic, mutagenic, and
immunosuppressive for humans and animals. Therefore, the screening of AFB1 in food

11
and beverages plays an important role in preventing foodborne illnesses. In this study,
AFB1 molecules were detected in a microfluidic device with integrated
polyacrylonitrile/zinc oxide (PAN/ZnO) nanofibers fabricated via a combination of the
electrospinning, and atomic layer deposition (ALD) techniques. The structural and optical
analyses of PAN/ZnO nanofibers were performed and samples with the most suitable
properties were utilized for AFB1 detection. To obtain the biorecognition layer towards
AFB1, PAN/ZnO samples were modified by (3-Aminopropyl) triethoxysilane (APTES),
glutaraldehyde (GA), bovine serum albumin (BSA) and monoclonal antibodies (Anti-
AFB1). Subsequently, a photoluminescence (PL)-based immunosensor was integrated into
a microfluidic cell and tested for AFB1 detection. The mechanism of PL changes caused
by AFB1 & Anti-AFB1 complex formation was analysed and developed. The proposed
approach enables the detection of AFB1 with the lowest concentration (LOD) of about
39 pg/ml, while the sensitivity range was evaluated as 0.1–20 ng/ml. The obtained values
of LOD and sensitivity, as well as the simplicity of the detection method, make this
approach a prospect for further application (Myndrul, Coy, Bechelany, & Iatsunskyi,
2021).

Most recent work in ZnO nanofibers has helped enhanced electromagnetic interference
shielding properties of phenolic resin. The incessant technological advancement has led to
excessive usage of electronics and telecommunication devices. This, however, has created
a critical electromagnetic (EM) pollution concern. EM pollution affects the functioning of
highly sensitive electronic devices and is hazardous to human health. While several
metallic or polymeric materials have been employed to combat this concern, however, most
of them suffer from many intrinsic limitations. Herein, we developed a novel lightweight
carbon foam (CF) decorated with zinc oxide nanofibers (ZONF) for high-performance
electromagnetic interference (EMI) shielding. First, the CF was synthesized from the
phenolic resin using the polyurethane (PU) foam impregnation method followed by
carbonization, and then as prepared CF was decorated by ZONF using the electrospinning
method. The EMI shielding effectiveness (SE) and relative complex permittivity of
decorated foams were examined through bay and vector network anal in ttheXOysterbd
(8.2–12.4 GHz) at the thickness of 2.0 mm. It was found that the open porous structure and

12
ZONF can synergistically enhance the EMI shielding properties. The impedance matching
and interfacial polarization provided by the porous structure and ZONF lead to improve
the EM wave absorption performance in CFs. Due to the decoration of ZONF, the resultant
CF exhibited excellent absorption-dominant with an EMI SE of 58.6 dB and a specific EMI
SE of 1046 dB cm2 g−1 at only 0.28 g/cm3 density. Thus, the lightweight ZONF decorated
CF is a promising material for aerospace and next-generation smart devices (Sharma, et
al., 2022).

13
 CHAPTER 3

FABRICATION AND CHARACTERIZATION TECHNIQUE

Electrospinning is the process of using electrostatic forces to form a fine filament of the
polymer solution.

3.1 OVERVIEW OF THE ELECTROSPINNING METHOD

Engineers have successfully created polymer fibres using mechanical methods for several
decades using mechanical processes. Conventional mechanical fibre spinning techniques
cannot produce fibres with diameters smaller than about 2 pm robustly. Although
conventional methods of producing polymer fibres are capable of producing fibres with
diameters in the micrometre range, many applications require the nm range (Wang, et al.,
2008).
Production of synthetic filaments using electrostatic forces has been known for more than
one hundred years. The process of spinning fibres with the help of electrostatic forces is
known as electrospinning. It has been shown recently that the electrospinning process is
capable of producing fibres in the submicron range. In fibre science-related literature,
fibres with diameters below 100 nm are generally classified as nanofibers (Mirjalali &
Zohoori, 2016).
Recently a process called electrospinning has been developed. This process has produced
fibres as small as 5 nm in diameter and is appropriately called nanofibers (Wang, et al.,
2008). The electrospinning process uses a high voltage electric field to produce electrically
charged jets from a polymer solution or melts, which on drying utilizing evaporation of the
solvent produces nanofibers. The highly charged fibres are fields directed toward the
oppositely charged collector, which can be a flat surface or a rotating drum to collect the
fibres (Mirjalali & Zohoori, 2016).
Electrospinning is a technique for producing polymer fibres in the range of 10 pm to 10
nm by accelerating a charged polymer solution using a high electric field. These fibres due
to their lightweight and large surface area to volume ratio have potential applications in
several fields such as "smart clothing" for the military, filters, sensors, nanocomposites,
nanoelectronic devices, wound dressing, etc. In normal conventional spinning techniques,

14
the fibre is subjected to a group of tensile, gravitational, aerodynamic, rheological and
inertial forces (Sundaray, Subramanian, Natarajan, & Krishnamurthy, 2006) .
In electrospinning, the spinning of fibres is achieved primarily by the tensile forces created
in the axial direction of the flow of the polymer by the induced charges in the presence of
an electric field (Wang, et al., 2008).

3.1.1 HISTORY OF ELECTROSPINNING

Electrospinning traces its roots back to electrostatic spray painting, which has been in
operation for almost 100 years. In 1934, a process for the production of polymer filaments
using electrostatic force was patented by Formhals. Formhals encountered many problems
early in his work, but by 1940 he had not only overcome those initial problems, but he had
also developed methods of producing composite fibres using multiple polymers and for
producing fibres that were aligned parallel to one another. Although the fibres produced by
Formals were much larger than the nanofibers, his work set the stage for the production of
these structures.
Taylor did a study of the polymer droplet at the end of the needle in an electrospinning
setup in 1969. This study led to a better understanding of the process by which the polymer
solution streams from the needle. In 1987, the experimental conditions and factors that
cause highly conductive fluids exposed to increasing voltages to produce unstable streams
were studied by Hayati. These conditions cause the fluid stream to whip around in different
directions as it leaves the needle. The work of Doshi and Reneker explored how changing
the concentration of the polymer solution and the voltage applied to the solution affected
the formation of nanofibers.

Numerous other studies have been done to examine the effect of changing both the polymer
solution and the experimental setup. Based on these studies it is clear that characteristics
such as fibre diameter, fibre morphology, and the amount of beading are dependent upon
a large number of variables. These variables include solution concentration, viscosity,
surface tension and conductivity, and process variables, such as voltage, needle diameter,
flow rate, and needle-to-collector distance (Xue, Wu, Xia, & Xia, 2019).

15
3.1.2 ELECTROSPINNING THEORY AND PROCESS
Electrospinning is a unique approach using electrostatic forces to produce fine fibres.
Electrostatic precipitators and pesticide sprayers are some of the well-known applications
that work similarly to the electrospinning technique. Fibber production using electrostatic
forces has invoked glare and attention due to its potential to form fine fibres. Electrospun
fibres have a small pore size and high surface area. There is also evidence of sizable static
charges in electrospun fibres that could be effectively handled to produce three-
dimensional structures.
Electrospinning is a process by which a polymer solution or melt can be spun into smaller
diameter fibres using a high potential electric field. This generic description is appropriate
as it covers a wide range of fibres with submicron diameters that are normally produced by
electrospinning. Based on earlier research results, it is evident that the average diameter of
electrospun fibres ranges from 100 nm - to 500 nm. In textile and fibre science-related
scientific literature, fibres with diameters in the range of 100 nm - 500 nm are generally
referred to as nanofibers.
The advantages of the electrospinning process are its technical simplicity and its easy
adaptability. The apparatus used for electrospinning is simple in construction which
consists of a high voltage electric source with positive or negative polarity, a syringe pump
with capillaries or tubes to carry the solution from the syringe or pipette to the spinnerets,
and a conducting collector like aluminium. The collector can be made of any shape
according to the requirements like a flat plate, rotating drum, etc. The schematic of the
electrospinning process is shown in Figure 3.1.
Polymer solution or the melt that has to be spun is forced through a syringe pump to form
a pendant drop of the polymer at the tip of the capillary. A high voltage potential is applied
to the polymer solution inside the syringe through an immersed electrode thereby inducing
free charges into the polymer solution. These charged ions move in response to the applied
electric field towards the electrode of opposite polarity thereby transferring tensile forces
to the polymer liquid. At the tip of the needle, the pendant hemispherical polymer drop
takes a cone-like projection in the presence of an electric field. And, when the applied
potential reaches a critical value required to overcome the surface tension of the liquid, a
jet of liquid is ejected from the cone tip.

16
Most charge carriers in organic solvents and polymers have lower mobilities and hence the
charge is expected to move through the liquid for larger distances only if given enough
time. After the initiation from the cone, the jet undergoes a chaotic motion in the field
directed towards the oppositely charged collector, which collects the charged fibres. As the
jet travels through the vacuum, the solvent spins straight and it is left behind a dry fibre on
the collecting device. For low viscosity solutions, the jet breaks up into droplets while for
high viscosity solutions it travels to the collector as fibre jets (Mirjalali & Zohoori, 2016).

3.1.3 ELECTROSPINNING APPARATUS SETUP

The electrospinning apparatus must contain a needle or spinneret, a high voltage power
supply, and a grounded collector. Figure 3.2 demonstrates the basic components needed to
perform electrospinning as mentioned above. A syringe is filled with a polymer solution
which is fed through a needle (or occasionally a spinneret) into an electric field usually
through the use of a syringe pump or gravity. A syringe pump allows the solution to be
introduced to the spinning system at a precisely controlled rate.

The polymer solution travels from the syringe into a metallic needle, which is connected
to a high voltage power supply that is typically capable of producing between 1 to 30 kV.
To create an electric field the system must contain, along with the charged needle, a
grounded plate. This conductive plate completes a circuit and allows a strong electric field
to be created between the needle and the plate. This grounded plate also serves as the
collector for the completed nanofiber web that is fabricated during the electrospinning
process (Queen, 2006).

3.1.4 ELECTROSPINNING MECHANISM

Fibres are produced during electrospinning due to static electric forces that manipulate a
polymer solution as it is carried through an electric field. The process begins as an electric
field is generated by a high voltage power supply, between a conducting capillary (needle
or spinneret) that holds a polymer solution and a grounded collector plate. The polymer
solution is held in a droplet shape by surface tension and as the electric field moves from
the high voltage supply to the needle and then to the solution, a charge is induced on the
surface of the droplet.

17
An opposite charge (repulsion force) is also formed at this time that pulls the droplet
towards the electric field. As the electric field increases, the charge on the droplet also
increases and causes the spherical droplet to deform into a conical shape. This is known as
the Taylor cone shown in Figure 3.3, when the force from the electric field influences the
repulsion force until it overcomes the surface tension, the charged solution is pulled into
the electric field towards the ground plate.
As the solution, now a fluid filament is pulled through the electric field, and internal and
external charges cause the liquid jet to be whipped around within the field as it accelerates
towards the grounded collector. This action simultaneously causes the solvent in the
solution to evaporate and the polymer chains within the solution to stretch and slide past
one another. This whipping motion allows the fibres found on the grounded collector to
have diameters small enough to classify them as nanofibers (Queen, 2006).

3.1.5 ELECTROSPINNING PROCESS PARAMETERS

While the electrospinning setup and process itself may be relatively simple the variables
involved in producing a nano-sized diameter, fibre mesh with relative uniformity are
numerous. Both solution and machine parameters must be considered.
Solution parameters include polymer type, polymer concentration, type of solvent, solvent
concentration, viscosity, the molecular weight of the polymer, conductivity, and surface
tension. Machine or process parameters include electric field strength, flow rate, distance
from the capillary to the collector, shape, and movement of the collector, room temperature,
and humidity.
Solution viscosity is a particularly important parameter and is heavily influenced by
polymer concentration. To produce fibres in any spinning mechanism a minimum amount
of polymer chains must be present to allow for chain entanglement and fibre production.
Increasing polymer concentration, which increases the number of polymer chains present
in the solution, also increases viscosity which can become too high to allow flow through
a needle or spinneret and prevents the formation of the Taylor cone and subsequent fibres
(Queen, 2006).

18
 Figure 3. 1 Schematic of the electrospinning setup

Figure 3. 2 Basic components of electrospinning

Figure 3. 3 Taylor cone formation

3.2 SCANNING ELECTRON MICROSCOPE

The first Scanning Electron Microscope (SEM) debuted in 1942 and the first commercial
instruments appeared around 1965. Its late development was due to the electronics involved
in "scanning" the beam of electrons across the sample. It is a microscope that uses electrons
rather than light to form an image. There are many advantages to using SEM instead of a
light microscope.

19
The SEM has a large depth of field, which allows a large amount of the sample to be in
focus at one time. The SEM also produces images of high resolution, which means that
closely spaced features can be examined at high magnification. Preparation of the samples
is relatively easy since most $EMs require the sample to be conductive. The combination
of higher magnification, larger depth of focus, greater resolution, and ease of sample
observation makes the SEM one of the most heavily used instruments in research areas
today.
Scanning electron microscopes (SEM) are patterned after Reflecting Light Microscopes
and yield similar information:
Topography
The surface features of an object or "how it looks", its texture; • detectable features limited
to a few manometers.
Morphology
The shape, size, and arrangement of the particles making up the object that is lying on the
surface of the sample or have been exposed by grinding or chemical etching; detectable
features limited to a few manometers.
Composition
The elements and compounds, the sample is composed of and their relative ratios, in areas
—I micrometre in diameter.
Crystallographic Information
The arrangement of atoms in the specimen and their degree of order; is only useful on
single-crystal particles>20 micrometres,
1. The "Virtual source" at the top represents the electron gun, producing a stream of
monochromatic electrons.
2. The stream is condensed by the first condenser lens (usually controlled by the
"coarse probe current knob"). This lens is used to both form the beam and limit the amount
of current in the beam. It works in conjunction with the Condenser aperture to eliminate
the high-angle electrons from the beam.
3. The beam is then constricted by the condenser aperture (usually not user selectable),
eliminating some high-angle electrons.

20
4. The second condenser lens forms the electrons into a thin, tight, coherent beam and
is usually controlled by the "fine probe current knob".
5. A user-selectable objective aperture further eliminates high-angle electrons from
the beam.
6. A set of coils then "scan" or "sweep" the beam in a grid fashion (like a television),
dwelling on points for a period of 9f time determined by the scan speed (usually in the
microsecond range).
7. The final lens, the objective, focuses the scanning beam onto the part of the
specimen desired.
8. When the beam strikes the sample (and dwells for a few microseconds) interactions
occur inside the sample and are detected with various instruments.

9. Before the beam moves to its next dwell point these instruments count the number
of interactions and display it on a CRT whose intensity is determined by this number (the
more relations the brighter the pixel).
10. This process is repeated until the grid scan is finished and then repeated, the entire
pattern can be scanned 30 times per second.

3.2.1 PRINCIPLE OF SEM

An electron magnification microscope utilized an electron beam (e-beam) to produce a
magnified image of the sample. There are three principal types of electron microscopes;
scanning, transmission, and emission. In the scanning and transmission electron
microscope, an electron beam incident on the sample produces an image, whereas in the
field-emission microscope the specimen itself is the source of electrons. A good discussion
of the history of electron microscopy is given by Coslett. Scanning Electron Microscope
(SEM) is similar to light microscopy, with the exception that electrons are used instead of
photons. This has two main advantages: much larger magnifications are possible since
electron wavelengths are much smaller than photon wavelengths and the depth of field is
much larger.

21
3.2.2 APPLICATIONS OF SEM
The most common use of SEMs for semiconductor applications includes materials
evaluation, failure analysis, and quality control screening. Materials evaluations are
obtained grain size, surface roughness, porosity, particle size distributions, material
homogeneity, and intermetallic distribution and diffusion. Failure analysis describes
contamination location, mechanical damage assessment, electrostatic discharge effects,
and micro-crack location. Quality Control Screening is investigated "good" to "bad"
sample comparison, film and coating thickness determination, dimension verification, gate
width measurement, and mil standard Screening (Liu, Shi, Zhou, & Tang, 2011).
The SEM is routinely used to generate high-resolution images of shapes of objects (SEI)
and to show spatial variations in chemical compositions (usually EDS, also BSE and CL
[add images here later]). This instrument is also widely used to identify phrases based on
qualitative chemical analysis and/or crystalline structure [add images here later]. Precise
measurement of very small features and objects down to 50 nm in size is also accomplished
using the SEM. Backscattered electron images can be used for rapid discrimination of
phases in multiphase samples. SEMs equipped with diffracted backscattered electron
detectors can be used to examine micro fabric and crystallographic orientation in many
materials.

Figure 3. 4 Scanning Electron Microscope

3.3 X-RAY DIFFRACTION

22
X-ray diffraction analysis (XRD) is a technique used in materials science to determine the
crystallographic structure of a material. XRD works by irradiating a material with incident
X-rays and then measuring the intensities and scattering angles of the X-rays that leave the
material.
The primary use of XRD analysis is the identification of materials based on their diffraction
pattern. As well as phase identification, XRD also yields information on how the actual
structure deviates from the ideal one, owing to internal stresses and defects (wikipedia,
n.d.).

3.3.1 WORKING MECHANISM

Crystals are regular arrays of atoms, whilst X-rays can be considered waves of
electromagnetic radiation. Crystal atoms scatter incident X-rays, primarily through
interaction with the atoms’ electrons. This phenomenon is known as elastic scattering; the
electron is known as the scatterer. A regular array of scatterers produces a regular array of
spherical waves. In the majority of directions, these waves cancel each other out through
destructive interference, however, they add constructively in a few specific directions, as
determined by Bragg’s law:

2dsinθ = nλ

Where d is the spacing between diffracting planes, θ {\display style \theta} is the incident
angle, n is an integer, and λ is the beam wavelength. The specific directions appear as spots
on the diffraction pattern called reflections. Consequently, X-ray diffraction patterns result
from electromagnetic waves impinging on a regular array of scatterers.

X-rays are used to produce the diffraction pattern because their wavelength, λ, is often the
same order of magnitude as the spacing, d, between the crystal planes (1-100 angstroms)
(wikipedia, n.d.).

23
3.3.2 XRD BENEFITS AND APPLICATIONS

XRD is a non-destructive technique used to:

Identify crystalline phases and orientation
Determine structural properties:

- Lattice parameters
- Strain
- Grain size
- Epitaxy
- Phase composition
- Preferred orientation
Measure the thickness of thin films and multi-layers
Determine atomic arrangement.

Figure 3. 5 X-ray machine Figure 3. 6 X-ray diffraction process

3.4 FT-IR

Fourier Transform Infrared Spectroscopy (FTIR) Analysis measures the infrared region of
the electromagnetic radiation spectrum, which has a longer wavelength and a lower
frequency than visible light. This spectrum is measurable in a sample when submitted to
infrared radiation (IR). The basic theory at work is that the bonds between different
elements absorb light at different frequencies.

24
With FTIR testing, the light is measured using an infrared spectrometer which produces
the output of an infrared spectrum. The IR spectrum is a graph of infrared light absorbance
by the substance on the vertical axis and the frequency (wavelength) on the horizontal axis
(encyclopedia, n.d.).

3.4.1 FT-IR WORKING MECHANISM

FTIR analysis measures the range of wavelengths in the infrared region that is absorbed by
a material. This is accomplished through the application of infrared radiation (IR) to
samples of material. The sample’s ability to absorb infrared light’s energy at various
wavelengths is measured to determine the material’s molecular composition and structure.

Unknown materials are identified by searching the spectrum against a database of reference
spectra. Materials can be quantified using the FTIR materials characterization technique as
long as a standard curve of known concentrations of the component of interest can be
created.
FTIR Analysis can be used to identify unknown materials, additives within polymers,
surface contamination on a material, and more. The results of the tests can pinpoint a
sample’s molecular composition and structure.
A simple device called an interferometer is used to identify samples by producing an
optical signal with all the IR frequencies encoded into it. The signal can be measured
quickly.
Then, the signal is decoded by applying a mathematical technique known as Fourier
transformation. This computer-generated process then produces a mapping of the spectral
information. The resulting graph is the spectrum which is then searched against reference
libraries for identification.
With the microscope attachment, samples as small as 20 microns can be analysed. This
allows quick and cost-effective identification of unknown particles, residues, films or
fibres. FTIR testing can also measure levels of oxidation in some polymers or degrees of
cure in other polymers as well as quantify contaminants or additives in materials
(encyclopedia, n.d.).

25
3.4.2 FT-IR SAMPLING TECHNIQUES

Several FTIR analysis sampling techniques can be used to understand a material’s structure
and identify the material, each with its proficiency:
Attenuated Total Reflectance – ATR spectroscopy only requires the sample to come into
contact with the ATR crystal.
Specular Reflectance – SR typically occurs with glossy samples, such as glass and crystal.
Reflection-Absorption – RA works with thin samples such as residues and paints
Transmission – TR passes IR (radiation) through gas, liquid or solid samples and measures
how well the sample absorbs that infrared radiation.
Photoacoustic – PAS can be difficult, but not impossible. Infrared absorptions are
converted to heat inside the sample, creating the photoacoustic signal.
What about UV Vis?
UV (ultraviolet) is similar to FTIR analysis in that they both use light. However, ultraviolet
light is usually monochromatic, while FTIR uses multiple colour frequencies.

Testing Process
Step 1: Place sample in FTIR spectrometer. The spectrometer directs beams of IR at the
sample and measures how much of the beam and at which frequencies the sample absorbs
the infrared light. The sample needs to be thin enough for the infrared light to transmit
through, or a thin slice of the material must be removed.
Reflectance techniques can be used on some samples and no damage is done to the sample.
Samples conducive to reflectance are residues, stains or films on a fairly flat reflective
surface or somewhat pliable materials that are thin enough to fit under the microscope using
the attenuated total reflectance attachment to the microscope.

Step 2: The reference database houses thousands of spectra, so samples can be identified.
The molecular identities can be determined through this process.
FTIR Sampling
Samples as small as 10 microns can be evaluated using FTIR analysis. The tiny sample
size allows for cost-effective identification of particles, residues, films or fibres. FTIR

26
analysis can also measure levels of oxidation or degrees of cure in some polymers as well
as measure the level of contaminants or additives.

Figure 3. 7 FT-IR machine Figure 3. 8 FT-IR graph sample

27
 CHAPTER 4

MATERIAL AND SETUP

4. 1 MATERIALS PROCESSING

Zinc acetate and polyvinyl alcohol were chosen as the polymer. This polymer was best
suited for this project. In the electrospinning setup as depicted in Figure 4.1, this setup has
been modified through the progression of the experiment to eliminate problems that
occurred during the experiments. The electrospinning process takes place inside a chamber
that has very limited exposure to elements exterior to the chamber. This chamber helps
control the environment in which the electrospinning is taking place, namely the
unpredictable air currents in an uncontrolled environment that can dramatically alter
nanofiber production.

28
There are three components to fulfil the process: a high voltage supplier, a syringe, and a
metal collecting screen. In the electrospinning process, a high voltage is used to create an
electrically charged jet of polymer solution or melt out of the syringe needle. Before
reaching the collecting screen, the solution jet evaporates or solidifies, and is collected as
an interconnected web of small fibres. The electric field is subjected to the end of the
syringe needle that contains the solution fluid held by its surface tension. This induces a
charge on the surface of the liquid. Mutual charge repulsion and the contraction of the
surface charges to the counter electrode cause a force directly opposite to the surface
tension.
As the intensity of the electric field is increased, the hemispherical surface of the fluid at
the tip of the syringe needle elongates to form a conical shape known as the Taylor cone.
When a critical value is attained with which the repulsive electrostatic force overcomes the
surface tension and the charged jet of the fluid is ejected from the tip of the Taylor cone.
The discharged polymer solution jet undergoes an instability and elongation process, which
allows the jet to become very long and thin.
Meanwhile, the solvent evaporates, leaving behind charged polymer fibre. Some polymers
may emit unpleasant or even harmful smells, so the processes should be conducted within
chambers with a ventilation system. Furthermore, a DC voltage in the range of several to
several tens of kV is necessary to generate the electrospinning. One must be careful to
avoid touching any of the charged jets while manipulating. Polymers, melting at high
temperatures, can also be made into nanofibers through electrospinning. Instead of a
solution, the polymer melt is introduced into the syringe. However, different in the case of
polymer solution, the electrospinning process for a polymer melt has to be performed in a
vacuum condition. Namely, the syringe, the travelling of the charged melt fluid jet, and the
metal collecting screen must be encapsulated within a vacuum (Wang, et al., 2016).

4.2 MATERIAL BACKGROUND

29
4.2.1 ZINC ACETATE DIHYDRATE

Zinc acetate is the chemical compound with the formula Zn (CH3C00)2 but is more
commonly referred to as the dihydrate Zn (CH3C00)2.2H20. Both the hydrate and the
anhydrous forms are colourless solids that are commonly used in chemical synthesis and
as dietary supplements. The acetate group is capable of binding to metal ions in a variety
of ways through its two oxygen atoms and several connectivities are observed for the
various hydrates of zinc acetate. Anhydrous zinc acetate adopts a polymeric structure
consisting of zinc coordinated to four oxygen atoms in a tetrahedral environment, each
tetrahedron being connected to neighbours by the acetate groups.
Zinc acetate is used as a dietary supplement and in lozenges used to treat the common
cold. Zinc acetate alone is thought to be more effective at treating the common cold than
zinc gluconate. Zinc acetate can also be used to treat zinc deficiencies. As an oral daily
supplement, it is used to inhibit the body's absorption of copper as part of the treatment for
Wilson's disease. Zinc acetate is also sold as an astringent in the form of an ointment, a
topical lotion; or combined with an antibiotic for the topical treatment of acne. Industrial
applications include wood preserving, manufacturing other zinc salts, and polymers, and
manufacturing ethylene acetate, as a dye mordant, and analytical reagent (Brewer, Zinc
acetate for the treatment of Wilson's disease, 2001).

4.2.2 ZINC OXIDE

ZnO is widely used as a functional material with a wide bandgap of 3.37ev, large exciton
binding energy, and excellent chemical and thermal stability (Srikant & Clarke, 1998). As
a wide bandgap material, zinc oxide has received an increasing amount of attention due to
its possible applications in ultraviolet (UV) lasers, and light-emitting devices (Wu & Pan,
2006). ZnO is one of the hardest materials in II-VI compound semiconductors due to the
higher melting point (1975°C) and larger cohesive energy. The constituent elements of zinc
oxide are abundant and low cost. Also, the material is non-toxic, which is an important
consideration for the environment.
Among the II-VI compound semiconductors, ZnO has found use in both
electrophotography as a photosensitive material and paints and varnishes. Zinc oxide is
mainly used in sensors, solar cells, and other electronic applications (Wu & Pan, 2006).

30
4.2.3 POLYVINYL ALCOHOL

Polyvinyl alcohol has excellent film-forming, emulsifying, and adhesive properties. It is

also resistant to oil, grease, and solvent. It is odourless and nontoxic. It has high tensile
strength and flexibility. However, these properties are dependent on humidity, in other
words, with higher humidity more water is absorbed. The water, which acts as a plasticizer,
will then reduce its tensile strength, but increase its elongation and tear strength. PVA is
fully degradable and is a quick dissolver. PVA has a melting point of 230°C and 180-190°C
for the fully hydrolysed and partially hydrolysed grades. It decomposes rapidly above
200°C as it can undergo pyrolysis at high temperatures (Gaaz, et al., 2015).

4.3 EXPERIMENT

The locally-made electrospinning apparatus contains a needle or spinneret, a high voltage

power supply, and a grounded collector. The horizontal experimental setup was chosen for
the electrospinning process. To obtain the capability of producing a high voltage in the
range of (10kV-30kV, 60 IOW) resistors are used in series connection. It is known for
using a high voltage probe that produces a maximum voltage of 27.32kV but the operating
voltage is 25.19kV. A syringe holder and a collector are kept inside the chamber shape, 9
cm apart from each other. The DC voltage generator of the positive terminal is connected
with the needle of the syringe and the square shape of the Al collector which is covered
with Al foil is connected by the negative terminal of the Power Supply as system ground.
ZnO fibres were formed by electrospinning the precursor PVA/Zinc acetate solution. In
this study, zinc acetate dihydrate (Zn (CH3COO) 2.2H20), distilled water, and PVA
(Polyvinyl alcohol) were used as raw materials for the preparation of PVA/Zinc acetate
composite fibre. Firstly, Zinc acetate powder was weighed by digital balance. This powder
is dissolved in water and a Zinc acetate solution was obtained after magnetic stirring for an
hour. Polyvinyl alcohol was added to it and it was magnetically stirred vigorously for about
3 hours at 80 degrees Celsius. Then, a viscous gel solution of PVA/Zinc acetate was
obtained.

31
 Zinc acetate (g) PVA (g) Water
(ml)

3 4.5 30

Table 4. 1 Concentration of composite

4.3.1 SAMPLE PREPARATION FOR FIBERS

Before setting the vacuum glass-ambient, the experimental setup was prepared. PVA/Zinc
acetate precursor solution of about 5 ccs was put into the syringe. The projectile of
precursor solution and target aluminium foil was apart 9cm. When the power supply was
turned on the electrostatic force of attraction overcome the surface tension of the viscous
solution inside the syringe. And the flow of solution from the needle of the syringe starts
and the fibre gets embedded in the aluminium foil. The resultant Al-foil was examined with
a microscope. Then after drying the fibres, we removed them from the foil and calcined
them at 500 degrees Celsius for two hours. The surface morphology of each PVA/Zinc
oxide-coated Al-foils before and after calcination was examined by using the Scanning
Electron Microscope shown in Figure 3.4.

Syringe Capacity 5 cc

Electrode Spacing 9 cm

calcination Temperature 500.degree Celsius

32
 calcination Time 2h

Table 4. 2 Typical range of operating parameters used for electrospinning experiments

with PVA/Zinc Acetate ultrafine fibre

33
 CHAPTER 5

RESULTS AND DISCUSSION

5.1 SEM ANALYSIS OF PVA/ZINC ACETATE COMPOSITE FIBERS

The PVA/Zinc acetate composite fibre was this formed on Al-foil and SEM was employed
to characterize these fibres. The set of SEM images for PVA/Zinc acetate composite fibre
was recorded in Figure 5.1. The figure confirms the formation of nanofibers with a
diameter of sizes 116nm, 148nm, 107 nm, 123nm, and 129 nm. The average diameter of
these fibres is around 124 nm. The size of the diameter is not strictly constant but rather
varies slightly. The orientation of nanofibers is different. The surface of the nanofibers
appears smooth.
Figure 5.2 shows the SEM image of zinc oxide nanofibers after calcination at 500 degrees
Celsius. The image confirms the removal of the polymers from the samples, there appears
some kind of beat which might be the result of some kind of human negligence during
dealing with the samples or it could be due to the original material’s impureness, as they
were bought from the local market, not from some standard international companies.

Figure 5. 1 SEM image of uncalcined nanofibers

34
 Figure 5. 2 SEM images of PVA/Zinc acetate after calcination at 500 degrees Celsius

5.2 XRD ANALYSIS

Figure 5.1 shows the XRD patterns of ZnO-PVA composite nanofibers after calcination at
500°C for 2 hours obvious diffraction peaks come from the substrate used for XRD
measurement. After calcination at 500°C for 2 h, five diffraction peaks at 31.73°, 34.37°,
36.21°,47.48°, 56.53°,62.77°,66.30° and 67.86° appear, corresponding to (100), (002),
(101), (102), (110), (103), (200) and (112) of the wurtzite crystal structure, respectively.
All of the five diffraction peaks are consistent with the reported data for ZnO of a wurtzite
hexagonal phase with parameters a=3.249 Å, c=5.206 Å. The ZnO nanofibers calcined at
500°C show better-defined diffraction peaks evolve. It shows only a strong and broad peak
coming from ZnO (101) planes with a plane spacing of 2.47 Å. It agrees well with the
JCPDS card, No. 89-1397 for pure ZnO, again confirming the formation of a pure ZnO
phase after calcination at that temperature. No characteristic peaks for other impurities,
except for the substrate, were found. This means that the phase of the fibres obtained after
calcination at 500°C for 2 is rather pure. These observations imply that the calcination
condition plays an important role in removing the PVA component from the composite
fibres and improving the crystallinity of ZnO nanofibers.

35
Figure 5. 3 XRD graph of PVA/Zinc acetate after calcination at 500 degrees Celsius for 2
hours, angles are marked.

36
 (101)
500.0

(100)
400.0

(002)

(103)
500.0

400.0

Intensity
300.0

200.0

100.0

0.0
Intensity

10.0 20.0 30.0 40.0 50.0 60.0 70.0 2Theta

300.0

(112)
(200)
(110)
200.0

100.0

0.0
10.0 20.0 30.0 40.0 50.0 60.0 70.0 2Theta

Figure 5. 4 XRD graph of PVA/Zinc acetate after calcination at 500 degrees Celsius for 2
hours, here reflecting planes are shown.

5.3 FT-IR ANALYSIS

FT-IR analysis of the sample is given below in figure 5.6. The absorption peak at 1469 cm-
1
could be due to CH2, which is a clear indication of the presence of PVA in the sample.
The absorption peak at 1000cm-1 to 1100cm-1 can be assigned as C-O-C stretching. The
absorption peak at 618 cm-1can is assigned to the presence of ZnO.
In the high-frequency region figure 5.5, the absorption peaks at about 3440 cm-1can are
assigned to the bending vibrations of adsorbed molecular water and stretching vibrations
of OH groups. The peaks that appeared at about 2340 cm-1 correspond to the CO2 that was
adsorbed on the surface of the samples. C–H groups’ stretching vibration peaks are at about
2850–2900 cm-1. The absorption peaks in the range of 1630–1716 cm-1 exhibit the
vibration modes of the COOH (C = O and C = C) functional group. In the low frequency
or fingerprint region, the peaks at about 484 and 910 cm-1 are related to the Zn–O bonds

37
 S1

100

98 2990
CO2 1166
96

Transmittance (%)
1730

94
3344
2916 C-H
92 O-H 1569 C=O
C=C
90 1423
835
1095
88

86 610
Zn-O
84
4000 3500 3000 2500 2000 1500 1000 500

wavenumber (cm-1)

Figure 5. 5 FT-IR graph of PVA/Zinc acetate before calcination

Figure 5. 6 FT-IR graph of zinc oxide nanofibers after calcination at 500 degrees Celsius
for 2 hours

5.4 ULTRAVOILET VISIBLE GRAPH

Optical absorption and transmission spectra of composite nanofibers are calcined at

500 °C. The UV absorption edge of the ZnO nanofibers was recorded in the wavelength
range from 250 nm to 1400 nm. The spectra results expose that the absorption edge of ZnO
nanofibers varied from 3.40 eV to 3.35 eV. With this result, the annealing at 500 °C has its

38
maximum bandwidth. These results clearly show that bandgap energy is closely associated
with annealing temperatures

Figure 5. 7 Absorbance vs. Wavelength graph for Zinc Oxide nanofibers.

140

120
(ahn)2(eVcm-1)2

100

80
Direct Bandgap
60
Energy Bandgap Eg=3.37eV
40

20

1 2 3 4 5 6 7
Energy (eV)

Figure 5. 8 Tauc plot for semiconductor Zinc oxide nanofibers.

39
 CHAPTER 6

CONCLUSION

The nanofibers have been prepared by the following sequential steps;

(1) Preparation of a solution with a suitable inorganic precursor i.e., zinc acetate and
polyvinyl alcohol.
(2) Electrospinning of the solution to obtain PVA/zinc acetate nanofibers.
(3) Calcination of the as-prepared PVA/zinc acetate nanofibers to yield pure zinc oxide
nanofibers.
The electrospinning process took place in a chamber that had very limited exposure to
elements exterior to the chamber. This chamber helped control the environment in which
the electrospinning was taking place, namely the unpredictable air converts in an
uncontrolled environment that could dramatically alter fibre production. Our apparatus had
three compact components: a high voltage supplier, a 5ml syringe filled precursor solution,

40
and a grounded Aluminium foil. In this process, a high voltage was needed to create an
electrically charged jet of the polymer solution.
(4) Using simple and inexpensive electrospinning technology, ultra-thin fibres of
PVA/zinc acetate could be easily prepared. After calcination of the PVA/zinc acetate
nanofibers, ZnO nanofibers were fabricated. ZnO nanofibers possessed excellent surface
morphologies and diameters in the range of 124–197 nm., the average fibre diameter
(AFD) of Zinc Oxide fibres was 126 nm.

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