Isaac Dissertation 2018

ELECTROSPINNING APPROACH FOR THE IMPROVEMENT OF MECHANICAL
AND DIELECTRIC PROPERTIES OF ANISOTROPIC NANOFIBER MAT
BY USING A NOVEL FIBER ALIGNMENT TECHNIQUE
by
BLESSON ISAAC
DISSERTATION
Submitted in partial fulfillment of the requirements

for the degree of Doctor of Philosophy at
The University of Texas at Arlington
December, 2018
Arlington, Texas
Supervising Committee:
Robert M. Taylor
Ashfaq Adnan
Kenneth Reifsnider
Rassel Raihan
Sunand Santhanagopalan
ABSTRACT
ELECTROSPINNING APPROACH FOR THE IMPROVEMENT OF MECHANICAL
AND DIELECTRIC PROPERTIES OF ANISOTROPIC NANOFIBER MAT
BY USING A NOVEL FIBER ALIGNMENT TECHNIQUE
Blesson Isaac, Ph.D.
The University of Texas at Arlington, 2018
Supervising Professor: Robert M. Taylor
Many advanced applications, including aerospace, can benefit from materials with
superior mechanical and dielectric properties. For these applications, most fiber alignment
electrospinning research has focused on either mechanical property improvement or dielectric
property improvement, but not both simultaneously. Through an improved apparatus design and
system parameter optimization, this work develops an electrospinning apparatus that produces an
increased electrostatic force and more tightly controlled discharged particle path to enable a
more uniform distribution and higher degree of alignment in deposited electrospun material,
which results in simultaneous improvement of both mechanical and dielectric properties.
The current state-of-the-art in aligned electrospinning techniques are limited. Parallel
collectors have aligned fibers but there is a possibility of extraction challenge for applications
ii
because of larger volume fraction of gaps. Rotating mandrel collectors have fibers better
molecular orientation in the fiber direction because of elongation strain. But the fibers are
oriented randomly and the parameter optimization can deliver only limited alignment
capabilities.
Electrospinning has been successfully used to develop aligned micro- and nano-fiber
mats for lightweight reinforcement of composite materials and structures. A horizontal
electrospinning apparatus has been designed and fabricated for improved micro- and nano-fiber
alignment that provides the possibility of developing better reinforcement and dielectric
materials in the form of aligned fiber mats. The design of experiments results show that the
improved system has better combined mechanical and dielectric properties because of better
degree of aligned fibers than that of the original system.
iii
ACKNOWLEDGEMENTS
I would like to thank my supervising committee for guidance and supports throughout the
research work. I thank my supervising professor, Dr. Robert M. Taylor for his timely responses
on the research update and his support for completing this dissertation. I thank Dr. Ashfaq
Adnan, my co-advisor, for his guidance on writing journal papers and using Multiscale
Mechanics and Physics Laboratory, UTA. I thank Dr. Kenneth Reifsnider, for his guidance for
completing the research work at Institute of Predictive Performance and Methodologies (IPPM),
UTARI and encouragements for publishing papers. I thank Dr. Rassel Raihan for his support on
conducting experiments and using the IPPM laboratory facilities. I thank Dr. Sunand
Santhanagopalan for his guidance on analyzing some of the research outputs. I thank Mr. Ron
Laposa, facility manager, UTARI, Mr. Kermit Beird, machine shop supervisor, UTA, and Mr.
Dave Manivanh, equipment technician, UTARI. Also, I would like to thank colleagues including
Mr. Vamsee Vadlamudi, Mr. Muthu Ram Prabhu Elenchezhian, Ms. Rajini Chahal, and Mr.
Khandakar Abu Hasan Mahmud.
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DEDICATION
I dedicate this dissertation to Almighty God for his wisdom to complete the research work. I
dedicate this work to my wife, Bincy Paul, for her support throughout the research work. Also, I
dedicate this work to my parents, brothers’ families, parent-in-laws’ family, relatives, and
friends, especially Christian Campus Center (TRI-C) family at UTA, for their support.
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TABLE OF CONTENTS
ABSTRACT…………………………………………………………………………... ii
ACKNOWLEDGEMENTS…………………………………………………………... iv
DEDICATION………………………………………………………………………… v
LIST OF FIGURES…………………………………………………………………… vii
LIST OF TABLES……………………………………………………………………. xi
CHAPTER ONE: INTRODUCTION.………………………………………………... 1
CHAPTER TWO: BACKGROUND………………………………………………….. 5
References…………………………………………………………….. 31
CHAPTER THREE: METHODOLOGY.…………………………………………….. 49
References……………………………………………………………….. 60
CHAPTER FOUR: VARIABILITY IN TESTING……. RESPONSES…………….. 63
References……………………………………………………………….. 77
CHAPTER FIVE: ANISOTROPIC CHARACTERIZATIONS….SYSTEM……… 80
References……………………………………………………………….. 103
CHAPTER SIX: CONCLUSIONS AND FUTURE WORKS………………………. 106
APPENDIX
1. COMSOL SIMULATION FOR ELECTROSPINNING………………… 108
2. MATLAB CODE FOR ORIGINAL SYSTEM-TENSILE………………. 109
vi
LIST OF FIGURES
Figure Page
1. Schematics of electrospinning apparatus of vertical set up (left) and

horizontal set up (right)…………………………………………………………. 2
2. Electrospinning set up by A. Formhals [5]…………………………………………... 3
3. Applications of electrospun nanofibers………………………………………............ 6
4. Working principle of electrospinning……………………………………………….. 8
5. a. Rotating Drum Collector ………………………………………………………… 12

b. Rotating Disk Collector [33]…………………………………………………....... 12
6. a. Parallel conductor stripes method (Reprinted with permission from [40].

Copyright 2003 American Chemical Society)…………………………………. 13
b. Uniaxially aligned nanofibers [41]………………………………………………. 13
c. Wire Drum Collector (Reprinted with permission from [47].
Copyright 2004 American Chemical Society)…………………..……………… 15
d. Wheel Rotor Collector [48]………………………………………………………. 15
7. a. Tensile strength/modulus vs fiber diameter [33]………………………………..… 16

b. Crystallinity vs fiber diameter [33]…………………………………………….… 17
8. Typical stress-strain curve of CNF (left) and the average fiber diameter (right) [58]... 18
9. Stress-strain graph of as-spun PAN nanofibers (left) and strength of annealed

nanofibers (right) (Reprinted with permission from [59]. Copyright 2004
American Chemical Society)…………………………………………………… 19
10. Strength and modulus of individual carbon nanofiber obtained

from PAN nanofiber mat [34]………………………………………………….. 19
11. Stress-strain relationship of individual PAN nanofibers [35]……………………… 20
12. Stress-strain curve of carbon nanofiber mats [60]…………………………………. 20
13. Predicted tensile strength of individual nanofiber vs tensile strength

of nanofiber mat [60]…………………………………………………………… 21
14. Tensile strength as a function of porosity [60]…………………………………….. 22
15. Dependence of density and porosity of PAN nanofiber membranes

at frequency of 1 MHz [67] ……………………………………………………... 24
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16. Dielectric constant of PAN at 8 w % in the radio frequency range [67]……………. 24
17. Dielectric constant of PAN as a function of

graphene nano flakes concentrations [68] ………………………………………. 25
18. Permittivity (ε΄) (left) and EMI-SE (right) of carbon fibers

with different proportions of ZrO2 [74] ………………………………………….. 26
19. Schematic of electrospinning technique……………………………………………… 51
20. Enclosure, Syringe pump, and High voltage power supply…………………………. 52
21. Mandrel and D.C.Motor ………………………………………………………….…. 53
22. Enclosure in the 3D model [78].………………………………………………….…. 55
23. The final electrospinning set up [78]…………………………………………….….. 55
24. Fiber mat is being formed on mandrel (left) and the fiber mat (right) [78]……….… 56
25. NanoSEM 230, SEM of fibermats using 18G (middle), and

22G (right) needles [78]…………………………………………………………. 56
26. a. Sample 1, 2, and 3 at 20μm magnification………………………………..……… 57

b. Tensile strength of best three samples [78]……………………………………… 57
c. Dielectric constant of best three samples………………………………………… 58
27. SEM images at 5μm and respective angle measurements of

samples 1, 2, and 3 [78] …………………………………………………………. 59
28. Stress-strain curve of nanofiber mat [7]……………………………………………. 64
29. PAN/DMF is stirred in heating stir plate (left) and

the final yellowish solution (right)………………………………………………. 65
30. Electrospinning original system [17]…………………………………………….….. 65
31. Electrospun mat is being fabricated at the mandrel……………………………..…... 65
32. Schematic of frame and specimen (left) and the tensile test is being run (right)……. 66
33. Schemmatic of square specimen (left) and

Faraday cage (right) for dielectric test …………………………………………… 66
34. PAN specimen (left) and optical microscope image in micro inch scale (right)……. 68
35. Variability in stress-strain curves when using strain rate for nanofiber mat……….... 68
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36. Variability in force-stroke curves when using strain rate for nanofiber mat………. 68
37. a. Force-stroke plot of a nanofiber mat…………………………………………….. 69

b. Normalized force-stroke plot of a nanofiber mat………………………….…….. 69
38. Specific strength for 5v speed and 10w% of two mats………………………….….. 70
39. Specific strengths for 3v speed and 10w% of two mats……………………….…… 71
40. a. Main effects for tensile tests…………………………………………….……….. 71

b. Standard deviation for tensile tests……………………………………………… 71
41. Force rate behavior of mat at 1N/min and 5N/min………………………………… 72
42. Dielectric constant with high variability…………………………………………… 73
43. a. Dielectric constant of 15cm-4v-10w% mats…………………….……….……... 73

b. Normalized dielectric constant of specimens from
two mats of same combination………………………………………..……...... 74
44. Dielectric constant of 3v-10w% mats……………………………………………… 74
45. a. Main Effects for dielectric tests…………………………………………………. 75

b. Standard deviation for dielectric tests………………………………………….... 75
46. Below 0.025g has shear failure (left) and above 0.025g
resembles brittle failure (right)………………………………………………….. 75
47. a. Fracture mode at 5N/min force rate……………………………………………… 76

b. Fracture modes of specimens below and above 0.025g …………………….…… 76
48. Stirrer and heater (left) and yellowish solution (right)……………………………… 82
49. Schemmatics of improved system…………………………………………….…….. 83
50. Flow chart of improved system………………………………………………..……. 84
51. Pictorial representation of improved system……………………………………..…. 84
52. Aligned fibers formed in the improved system (shadow is alligator clip) …………... 85
53. SEM images and angular measurements of mats from

original and improved system……………………………………………..……… 85
54. Improved system shows consistent mass along the mat……………………………… 86
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55. Test configuration and schematic representation of
dielectric constant measurement ………………………………………………... 87
56. Test configuration and schematic of tensile test specimen………………………… 89
57. Main effects, standard deviation, and interactions for

dielectric data of original system…………………………………………….….. 90

dielectric data of improved system……………………………………………… 91

tensile data of original system…………………………………………………… 92

tensile data of improved system…………………………………………………. 93
61. Tensile strengths of improved system (left) and

original system (right) nanofiber mats…………………………………………… 94
62. SEM images shows better alignment for mats at 5v speed (left) than that at
4v speed (right)…………….. ………………………………………………… 94
63. The fiber direction side of mat is in coincidence with

the vertical axis of SEM device………………………………………………….. 95
64. Intensity vs 2ϴ plot of XRD analysis of PAN at 8w% for

original and improved system…………………………………………………… 96
65. Fitted model of specific tensile strength from original system…………………….. 98
66. Goodness of fit for original system from tensile response……………………..…. 98
67. Fitted model of specific tensile strength from improved system………………..… 99
68. Goodness of fit for improved system from tensile response…………..…………... 99
69. Fitted model of normalized dielectric constant from original system…..…………. 100
70. Goodness of fit for original system from dielectric response……………..………. 100
71. Fitted model of normalized dielectric constant of improved system………....…… 101
72. Goodness of fit for improved system from dielectric response………………..….. 101
73. Dielectric versus tensile for original and improved system……………………….. 102
x
LIST OF TABLES
Table Page
1. Mechanical properties of as-spun/pure nanofibers…………………………………. 18
2. Comparison of CNT and CNF [7]…………………………………………………… 25
3. Dielectric properties of different nanofibers…………………………………………. 27
4. Tensile and dielectric properties of three samples [78]……………………………… 58
5. Full factorial test matrix for DOE……………………………………………………. 67
6. Test matrix for original and improved system………………………………….......... 87
7. Two factors and three levels for each factor…………………………………………. 87
8. Angle measurements using image J for 4v and 5v at 9w% …………………………. 95
9. a. Increment in improved tensile…………………………………………………….. 102
b. Percentage increment in tensile……………………………………………………. 102
10. a. Increment in improved dielectric…………………………………………………. 102
b. Percentage increment in dielectric………………………………………………… 102
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CHAPTER 1
INTRODUCTION
This research work discusses the development of an electrospinning system capable of
producing high quality alignment characteristic of rotating mandrel by controlling the path of
electric field and producing the controlled deposition and uniform distribution of fibers.
Electrospinning is a process of producing micro- and nano-fibers using polymer solution in an
enclosed apparatus with a syringe pump, collector and high voltage power supply. This
technique results in a simpler and more economical design configuration than other techniques.
The design and set up of an electrospinning apparatus to produce the micro- and nanofibers is
carried out. The set up consists of a high voltage power supply, positive and negative electrodes,
syringe pump and enclosure. Many advanced applications can benefit from electrospun materials
with superior mechanical and dielectric properties. For these applications, it is paramount to
understand the effects of electrospun fiber alignment on mechanical and dielectric properties.
Anisotropic nanofiber mats are achievable through aligned fibers in mats produced through
electrospinning. The mechanical and dielectric property can be tailored for applications through
aligned nanofiber mats.
Electrospinning is a process of producing micro- and nano-fibers using polymer solution with
a syringe pump, syringe, needle, collector, and high voltage power supply. The typical set up of
an electrospinning apparatus is either horizontal electrospinning or vertical electrospinning [1].
Figure 1 shows the schematic set up of both types. The idea of electrospinning can be traced
back to 1902, when John. F Cooley received the patent for his apparatus for electrically
dispersing fluids [2]. Later in the same year, William James Morton invented a method of
1
dispersing fluids by the process of separating from composite fluids the volatile components and
breaking up the fixed component [3].
Figure 1. Schematics of electrospinning apparatus of vertical set up (left) and horizontal set up (right)
Anton Formhals received a patent in the year 1934 for his invention of producing polymer
threads using electrostatic force. He claimed the patent with his paper titled “Process and
apparatus for preparing artificial threads [4].” He used solutions of cellulose esters, specifically
cellulose acetate, for the spinning solution. In U.S. Patent No. 2,160,962 (1939), he described
collecting artificial fibers as substantially parallel to each other on a moving collecting device
[5]. There he introduced the term “electrical spinning” of fibers. He revealed that he had
experienced difficulties in solidifying the formed fibers. In addition, the as-processed fibers were
so sticky that, not only would they stick to the collecting device, but also they would stick to
each other. He observed that it was difficult to control the paths of high-speed liquid streams and
the corresponding fibers out of it. As shown in Figure. 2, he tried to use a fiber direction guide
(55 in Figure 2), which consists of shields (57 in Figure 2) to direct the fibers along fixed,
predetermined paths towards the collecting electrodes. He claimed that his invention made it
possible to obtain smooth, continuous, compact, and coherent fiber bands composed of
heterogeneous filaments arranged substantially parallel to each other.
2
Salas (2017) showed that electrostatic forces play a key role on the electrospinning of
polymer solutions. As such, the Coulomb’s force is considered as the driving factor for better
design.
𝑞𝑞1 𝑞𝑞2
𝐹𝐹 = 𝑘𝑘 ----------------------------------- (1)
𝑟𝑟 2
In equation (1), F is the Coulomb’s force, 𝑘𝑘 is the constant of proportionality, 𝑞𝑞1 , 𝑞𝑞2 are
charges, and r is the distance between the charges. In principle, the smaller the distance, the
greater the electrostatic force on a charged particle.
Figure 2. Electrospinning set up by A. Formhals [5]
According to Luo, Stoyanov, Stride, Pelan, and Edirisinghe (2012), there are various
spinning techniques available for producing micro and nanofibers [6]. Zhang, Kang, Tarascon,
and Kim (2016) reported that other production methods include vapor growth, arc discharge,
laser ablation, and chemical vapor deposition [7]. These processes are very expensive because of
low product yield and high equipment cost. However, electrospinning processes can produce
fibers with diameters ranging from 10nm to 10µm from a polymer solution under the application
3
of an electrostatic force [8]. These fibers have high surface area to volume ratio, high porosity,
and tunable porosity [1]. Solution electrospinning compared to melt electrospinning requires a
solvent. The melt electrospinning method uses a molten polymer, but the absence of solvent
excludes the effect of solvent properties on the fiber formation. In emulsion electrospinning, two
immiscible fluids are used [9]. Magnetic electrospinning and near-field electrospinning are good
examples of interdisciplinary technological convergence between magnetism and electric
potential methods. Dip-pen nanolithography with traditional electrospinning can also be used,
but the alignment of fibers is not satisfactory [6].
4
CHAPTER 2
BACKGROUND
This section examines the current state-of-the-art in fabrication of aligned fibers via
electrospinning techniques and the effects of these techniques on the mechanical and dielectric
properties of electrospun fibers. Aligned and heat treated electrospun mats, when added to other
composites, have better specific strength and specific stiffness properties. These aligned nano
fiber composites have better mechanical and dielectrical properties for many structural and
multi-functional applications, including advanced aerospace applications. For these applications,
most fiber alignment electrospinning research has focused on either mechanical property
improvement or dielectric property improvement alone, but not both simultaneously. Relative to
many other nanofiber formation techniques, the electrospinning technique exhibits superior
nanofiber formation when considering cost and manufacturing complexity for many situations.
This nanofiber formation often leads to superior mechanical properties as well as superior
combinations of mechanical-dielectric properties. Even though the dielectric property of pure
nanofiber mat may not be of general interest, the analysis of the combined effect of mechanical
and dielectric properties is relevant to the present analysis of alignment. An exploratory study by
the author demonstrates the relationship between mechanical and dielectric properties for
specimens obtained from a rotating mandrel horizontal set up.
2.1 ELECTROSPINNING APPLICATIONS
The typical applications of electrospun fibers include filtration [10-11], energy, structures,
biomedical, textiles, and others as shown in Figure 3.
5
Figure 3. Applications of electrospun nanofibers
Other applications include optical and chemical sensors, textiles, reinforcement of
composites, health care and defense, and security. Electrospun fibers are projected to play an
important role in the development of air filtration, energy storage devices, super-capacitors, and
rechargeable batteries [12-14]. The applications of nanofiber mats in the reinforcement of
nanocomposites are discussed by Huang, Zhang, Kotaki, and Ramakrishna (2003), who executed
mechanical characterization of nanofibrous membranes of various polymers and examined their
potential applications [15]. Nanofibers can have better mechanical properties than micro fibers
and therefore superior structural properties can be anticipated. Bergshoef and Vancso (1999)
showed that smooth nylon-4, 6 electrospun fibers with diameters in the range of 30-200 nm can
be produced from formic acid solutions. These fibers demonstrated reinforcement of transparent
composites with an epoxy matrix [16]. Highly porous nanofibers with pore interconnectivity and
relatively uniform pore distributions improve membrane performance in the application of
desalination (water filtration) [17]. The large surface area of the constituent fibers provides high
functionalization capability and mechanical bonding to limit delamination between laminae [18].
6
Biomedical applications include tissue engineering scaffolds, wound dressing, drug delivery
[19], and creation of artificial blood vessels. The non-woven nanofibrous mats produced by
electrospinning techniques mimic the extracellular matrix components.
Some important issues and challenges in the 21st century are addressed using electrospun
fibers in the domains of tissue regeneration, energy conversion and storage, and water treatment.
Large surface areas, high porosity, and the unique mat structure of electrospun nanofibers have
provided improvements over the last decade in the fields of tissue regeneration (skin, nerve,
heart, and bone), energy conversion and storage (solar cells, fuel cells, and batteries), and water
treatment (adsorption, photocatalysis, and filtration) [14]. Potential applications and promising
advantages are overviewed by Bhardwaj and Kundu (2010), who highlighted more than 200
polymers that are electrospun for various applications. Teo and Ramakrishna (2006) has given a
detailed review on electrospinning design and nanofiber assemblies [20].
2.2 PARAMETERS AND PARAMETER OPTIMIZATION
The working principle for electrospinning is shown below in the Figure 4. A sufficiently high
voltage is applied at the location of the liquid droplets formed at the tip of the needle. The local
body of the liquid becomes charged. Electrostatic repulsion counteracts the surface tension. So
the droplet is stretched, and at a critical point a stream of liquid erupts from the surface. The
point of eruption is called a Taylor Cone. Sir Geoffrey Taylor developed the equation which
shows the relationship between the critical voltage and the surface tension as shown in equation
(2) [21].
4𝐻𝐻 2 2𝐿𝐿 3
𝑉𝑉𝑐𝑐2 = (𝑙𝑙𝑙𝑙 − )(0.117ᴨ𝛾𝛾𝛾𝛾)----------------------- (2)
𝐿𝐿2 𝑅𝑅 2
7
where 𝑉𝑉𝑐𝑐 is the critical voltage, H is distance between the needle tip and the collector, L is the
length of the needle with radius R, and 𝛾𝛾 is the surface tension of the liquid (units: 𝑉𝑉𝑐𝑐 in kilovolts,
H, L, R in cm, and 𝛾𝛾 in dyne per cm).
Figure 4. Working principle of Electrospinning
Important parameters that affect the quality of electrospun fibers formed from polymer
solutions can be categorized as solution-specific parameters, process-specific parameters, and
environmental-specific parameters [22]. The solution-specific parameters include (i) viscosity
and (ii) polymer concentration. It is observed that low viscosity is typically responsible for bead
generation and significant increase in fiber diameter. Additionally, polymer concentration
directly controls fiber diameter. In general, an increase in fiber diameter can be achieved by
increasing the polymer concentration. Applied voltage and distance between the tip and
controller are the two parameters that are regarded as process-specific. In general, fiber diameter
can be reduced by increasing applied voltage and vice-versa. The distance between the tip and
the controller mainly controls fiber solidification because a minimum distance is required to
allow the fibers sufficient time to dry before reaching the collector. Distances that are too close
or too far can cause beads to form. Humidity and temperature are treated as environment-specific
8
parameters. According to De Vrieze et al. (2009), the evaporation rate increases with increase in
temperature [23]. Also, the viscosity of solution generally decreases with an increase in
temperature. As the humidity increases, the average fiber diameter increases.
Parameter optimization has been studied by Gu, Ren, and Vancso (2005) using a Design of
Experiments approach [24]. A detailed mathematical modeling and review has been conducted
by Rafiei, Maghsoodloo, Noroozi, Mottaghitalab, and Haghi (2013) [25]. The review included
the Leaky dielectric model and Whipping model for electrospinning processes. Ismail, Maksoud,
Ghaddar, Ghali, and Tehrani-Bagha (2016) developed a model for stable region and unstable
region in the jet propulsion stream for predicting the fiber diameter [26]. Rafiei et al. (2014)
modeled and simulated viscoelastic elements for jet propulsion to predict and improve control of
nanofiber diameter [27]. Pandya, Akash, and Runkana (2015) modeled straight jet dynamics of
electrospun nanofibers using a momentum equation, charge conservation equations, and
viscosity models [28]. Modeling electrospinning of nanofibers for short range and long range
electrostatic interactions has been conducted by Kowalewski, Barral, and Kowalczyk (2009)
[29]. The whipping instability in the unstable region of the electrospinning jet propagation has
been studied in three solutions by Kowalewski, Blonski, and Barral (2005) [30]. Ghaly (2015)
modeled the electrospinning jet with an inkjet printer techniques using computer-aided
fluid/multi-physics/multi-phase flow simulations in COMSOL [31]. Only a few papers have
provided details on parameter optimization using design of experiments. Gu et al. (2005) used
two factors and four and three respective levels for finding average fiber diameter. Senthil and
Anandhan (2005) examined three variables and seven, four, and three respective factor levels for
finding the average fiber diameter [32].
9
Here, a detailed review of molecular orientation and system configuration to align nanofibers
will be discussed. The current state-of-the-art mechanical and dielectric properties of not only
electrospun fibers but also that of nanofibers from other techniques must be known and the
influence of porosity and density on mechanical and dielectric properties will be discussed. The
applications of aligned fibers will be discussed based on these facts. The authors will discuss the
mechanical and dielectric properties of the polyacrylo nitrile (PAN) nanofiber mat in the end.
They suggest alignment improves our ability to tailor for specific applications.
2.3 MOLECULAR ORIENTATION AND SYSTEM CONFIGURATION TO ALIGN
FIBERS
Two key factors affecting mechanical and dielectric properties are molecular orientation due
to elongation of fibers on the periphery of the rotating mandrel and system configuration
improvement for better alignment. Other properties, such as thermal and electrical, also often
improve in the direction of improved alignment.
2.3.1 MOLECULAR ORIENTATION
High orientation of polymer molecular chains along the fiber axis and aligned electrospun
fibers have important consequences in the field of carbon fiber-reinforced nano composites. The
electrospun fibers are generally stronger than traditional fibers because of their higher orientation
of macromolecular polymer chains along the fiber axis. The polymer jet under the influence of
an electrostatic field experiences a high degree of molecular orientation due to high elongation
strains and shear forces. Also, Baji, Mai, Wong, Abtahi, and Chen (2010) studied the effects of
electrospun polymers on oriented morphology and tensile properties. The lower the diameter of
the fibers, the higher the modulus and strength of the fibers. They observed that finer fibers have
enhanced properties because of gradual ordering of molecular chains and increase in crystallinity
10
[33]. Also, Beese, Papkov, Dzenis, and Espinosa (2013) concluded that electrospun PAN fibers
have better mechanical properties at lower diameters [34]. Arshad, Naraghi, and Chasiotis (2011)
observed that the strength of the carbonized nanofibers at 800˚C increased by 100% when the
diameter was reduced from 800nm to 200nm [35]. Baji et al. (2010) noticed that the modulus and
tensile properties of polycaprolactone (PCL) fibers increased significantly when the fiber
diameter was reduced to below 500nm. The molecular orientation improves gradually as the
fiber diameter is reduced [33]. According to Fennessey and Farris (2004), twisted yarns of higher
degree of molecular orientation resulted in better mechanical properties [36]. The degree of
orientation can be quantified by the X-ray diffraction analysis of the samples. For composite
applications, a decrease in diameter of fiber at the nanoscale level can improve mechanical
properties as the specific reinforcement area per unit mass increases. Uyar, I. Cianga, L. Cianga,
Besenbacher, and Yagci (2009) observed self-aligned bundled fibers of polyphenylene-g-
polystyrene/poly (a-caprolactone) (PP-g-PS/PCL) when blended with polystyrene (PS) or
polymethyl methacrylate (PMMA). This is because of the unique molecular architecture of PP-g-
PS/PCL and its interaction with PS or PMMA [37]. Lin (2005) used selected area electron
diffraction (SAED) to show that the degree of molecular orientation in individual polylactic acid
(PLLA) nanofibers increased as the nanofiber diameter decreased [38].
2.3.2 SYSTEM CONFIGUARTION TO ALIGN FIBERS
In addition to molecular orientation, physical alignment of electrospun fibers contributes to
the production of high strength/high toughness fiber reinforced composites [7]. Among the many
ways to produce aligned fibers using an electrospinning technique, drum collection and rotating
disk collectors are the two most popular designs, as shown in Figure 5 (a)-(b).
11
Figure 5a. Rotating Drum Collector
In the drum collector method, the drum collector rotates at high speed and the deposited fiber
diameter can be controlled based on the rotational speed of the drum. The linear speed at the
surface of the rotational drum should match the evaporation rate of the solvent so that fibers are
deposited and taken up on the surface of the drum. At a rotational speed less than the fiber take-
up speed, randomly oriented fibers are obtained on the drum. At higher speed the fiber take-up
velocity breaks the fiber, and continuous fibers are not collected. Therefore, the optimal speed of
the rotating drum that matches the evaporation rate is required for maximum alignment.
Figure 5b. Rotating Disk Collector [33]
In the rotating disk collector, higher alignment is possible but the production rate is lower
because fibers are effectively deposited at only a small area at the disk edge. Theron, Zussman,
12
and Yarin (2001) reported that polyethylene-based polymer nanofibers can be aligned and wound
on a disk wheel-like bobbin using an electrostatic field–assisted technique [39].
Other collection methods that are suitable for fiber alignment are parallel conductor, wire
drum collector, and wheel rotor collector as shown in Figure 6(a)–(d).
In the parallel conductor method, the length of aligned fibers is restricted by the distance
between conductive stripes as shown in Figure 6a.
Figure 6a. Parallel conductor stripes method (Reprinted with permission from [40]. Copyright 2003
American Chemical Society)
Uniaxially aligned PAN nanofibers were electrospun using a collector consisting of two
conductive strips separated by a gap as shown in Figure 6b.
Figure 6b. Uniaxially aligned nanofibers [41]
13
According to Jalili, Morshed, and Ravandi (2006), the best alignment received using
conductive stripes gap method was up to a width of 3cm [41]. The best alignment was formed
between 10 w% to 15 w% solutions. Here, a bundle collector is moved across the gap to another
side. Uniaxially aligned fibers formed had an aspect ratio (l/d) of higher than 5000. Also, Fryer,
Scharnagl, and Helms (2018) studied the effect of alignment on fiber modulus using electrostatic
gap method. Aligned polyethylene oxide (PEO) fibers have higher modulus than the non-aligned
fibers of similar diameter [42]. Cai et al. (2017) provided an insight in to fabricating ultra-long
polyvinylidene fluoride (PVDF) fibers. Here, parallel conducting U-shaped collectors are used to
fabricate fibers [43]. According to Lei, Z. Xu, Cai, L. Xu, and Sun (2018), more than a meter
long aligned PVDF nanofibers were fabricated using gap electrospinning, where the needle is
connected to positive power supply and the parallel plates are connected to the negative power
supply [98]. These fibers have applications in reinforcing composites. Yang, Lu, Zhao, and Jiang
(2007) demonstrated a method that generates parallel fibers using magnetic-particle-doped
polymers in a magnetic field. The magnetic field guides the magnetized electrospun polyvinyl
alcohol (PVA) fibers to align in a parallel fashion [44]. Park and Yang (2011) built uniaxial
aligned PCL fibers by introducing an inclined gap into dual collectors that consisted of two
conductive stripes [45]. Dabirian, Sarkeshik, and Kianiha (2009) used a hollow metallic cylinder
with needle placed at the center of the cylinder. Fibers produced by this method are claimed to be
well aligned and spread over large area [46].
Next, in the wire drum collector method, shown in Figure 6c, fibers are deposited without the
need for high speed rotation. However, thick films are not possible with this method.
14
Figure 6c. Wire Drum Collector (Reprinted with permission from [47]. Copyright 2004 American Chemical
Society)
Finally, a wheel rotor collector, as shown in Figure 6d, provides elongation strain and
therefore more strength to the fibers. But the many electrodes on the rotating wheel complicate
apparatus design.
Figure 6d. Wheel Rotor Collector [48]
The limitations of other methods imply that drum collection is more likely to be scalable to
commercial capacities than other electrospinning methods for fiber alignment.
Grasl, Arras, Stoiber, Bergmeister, and Schima (2013) developed a technique using two
parallel rotatable auxiliary electrodes applied with time-varying square wave potential, which led
to aligned fiber-deposition of PEO [49]. Lei et al. (2017) used a collecting system consisting of
hollow cylinder and grating-like electrodes for aligning PVDF fibers using whipping instability
[50]. Khamforoush and Mahjob (2011) used a modified rotating jet method for aligning fibers.
The degree of alignment enhanced by more than two times [51]. Despite the simplicity of the
electrospinning methodologies, industrial applications are relatively rare due to low fiber
15
throughput for existing fiber collection methods. This throughput limitation could be addressed
with larger drum sizes and other innovations.
2.4 MECHANICAL PROPERTIES OF NANOFIBERS
Among many nanofibers discussed for mechanical properties, PAN nanofibers are widely
reported because of their excellent tensile strength and modulus. In this section, mechanical
properties of different electrospun nanofibers including PCL, polyvinyl pyrrolidone (PVP), PEO,
and PAN will be reported. Also, PAN nanofibers (in general) and carbon nanofillers will be
discussed.
Baji et al. (2010) proved that as the PCL fiber diameter reduces, the tensile strength and
modulus increase. Figure 7a shows the tensile strength and modulus versus fiber diameter
Figure 7a. Tensile strength/modulus vs fiber diameter [33]
For fiber diameters greater than 2 µm, both tensile modulus and tensile strength appear not to
change with diameter. The degree of crystallinity increases gradually as the PCL fiber diameter
is reduced as shown in Figure 7b [33].
16
Figure 7b. Crystallinity vs fiber diameter [33]
Also, for polymers in general, an increase in the degree of crystallinity increases the density,
stiffness, strength, and toughness [52].
Huang et al. (2016) showed that with the addition of conductive filler materials, the diameter
of fibers reduced due to increasing composition of PVP/ cellulose nanocrystal (CNC) /silver
particles [53]. The addition of CNC increased the tensile strength. According to Kancheva,
Toncheva, Manolova, and Rashkov (2015), the mechanical strength of various combinations of
polylactic acid (PLA) and PCL mats was reported to be enhanced after thermal treatment at
60˚C. The melting of PCL enabled the sealing of the fibers thus enhancing the mechanical
properties of mats [54]. Wang, Jin, Kaplan, and Rutledge (2004) reported an increase in modulus
of silk/PEO fibers from as-spun to methanol-treated and to water extracted fibers [55]. The
mechanical properties of single fibers were characterized by AFM nanoindentation. Tan, Goh,
Sow, and Lim (2005) studied tensile property by an approach using atomic force microscope tip
to stretch a single electrospun PEO nanofiber. The elastic modulus of PEO nanofiber is found to
be 45MPa [56]. Lin et al. (2012) demonstrated characterization of mechanical properties of ultra-
thin electrospun polymer fibers. Electrospun techophilic, tecoflex, nylon 6, PVP, and PEOX
17
fibers were captured directly on the testing device, stretched at controlled rates, and deflected
with forces created by different velocities of streams of air [57].
The mechanical properties of different nanofibers are shown in Table 1.
Nanofibers: Tensile Tensile

as-spun/pure Strength Modulus Characteristics
5.4 GPa 287 GPa Hot drawn and carbonized at 1100˚C, 400nm in diameter [58]
PAN CNF 7.3 Gpa 262 GPa Carbonized at 800˚C, 108nm in diameter [34]
PCL 66 MPa 340 MPa 400nm in diameter [33,100]
PVP 2.3MPa [53] - 300nm in diameter [53]
7 MPa [57] 500 MPa [57] 800nm in diameter [57]
PEO - 0.75 GPa [55] 200nm in diameter [55]
45 MPa [56] 22 MPa [56] 700nm in diameter [56]
Nylon 6 900 MPa 304 MPa 800nm in diameter [57]
Table 1. Mechanical properties of as-spun/pure nanofibers
2.4.1 PAN NANOFIBERS
Chawla, Cai, and Naraghi (2017) observed that carbon nanofibers (CNF) obtained from hot-
drawn samples demonstrated strength as high as 5.4 GPa and modulus 287 GPa as shown in
Figure 8.
Figure 8. Typical stress-strain curve of CNF (left) and the average fiber diameter (right) [58]
Here, 400nm PAN nanofibers reached a maximum strength (5.4 GPa) after hot-drawn and
carbonized at 1100˚C [58].
18
Papkov et al. (2013) studied simultaneous improvement in strength, modulus, and toughness in
ultrafine as-spun PAN nanofibers as shown in Figure 9 [59]. A reduction of as-spun PAN
nanofiber diameter from 2.8μm to 100nm resulted in higher modulus, strength, and toughness.
Figure 9. Stress-strain graph of as-spun PAN nanofibers (left) and strength of annealed nanofibers (right)
(Reprinted with permission from [59]. Copyright 2004 American Chemical Society)
The 100nm annealed PAN fibers showed a modulus of 48GPa and strength of 1.75GPa. This
study recorded dramatic increase in strength and modulus for nanofibers finer than 200-250nm.
Beese et al. (2013) compared the result with Arshad et al. (2011) and showed the dependence
of fiber diameter on strength and modulus as shown in Figure 10. As the fiber diameter
decreases, the tensile strength and modulus increase.
Figure 10. Strength and modulus of individual carbon nanofiber obtained from PAN nanofiber mat [34]
Beese et al. (2013) observed that individual PAN nanofibers with 108nm in diameter, heat
treated at 800˚C, showed a maximum modulus of 262 GPa and strength of 7.3 GPa.
19
Arshad et al. (2011) showed that individual PAN nanofibers with 9 w% and other given
parameters had the stress-strain relationship shown in Figure 11.
Figure 11. Stress-strain relationship of individual PAN nanofibers [35]
The plot shows a linear relationship until 125 MPa and thereafter a strain hardening region
where crystallinity occurs. The maximum ultimate strength was found with 1 KV/cm and 430nm
in diameter.
Wan, Wang, Gao, and Ko (2015) reported that tensile strength of carbon nanofiber mats can
be approximately estimated as the sum of individual nanofibers as shown in Figure 12 [60].
Figure 12. Stress-strain curve of carbon nanofiber mats [60]
The nanofiber mat reached their maximum strength where the curves dropped sharply, which
means the majority of nanofibers break simultaneously.
20
Wan et al. (2015) showed that a quantitative relationship exists between the tensile strength
of a nanofiber mat and that of individual nanofibers as in Figure 13.
Figure 13. Predicted tensile strength of individual nanofiber vs tensile strength of nanofiber mat [60]
The tensile strength of nanofiber mat is described by Equation 3 below.
(1−𝑃𝑃)(𝜃𝜃+𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠)2
𝜎𝜎 = 𝜎𝜎𝑓𝑓 --------------------------(3)
2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋
where 𝜎𝜎𝑓𝑓 is the fiber strength and θ is the diagonal angle of fibers to the longitudinal axis of
loading. The value of θ can be obtained from L=D cosθ and W=D sinθ, where L,W, and D are
the length, width, and diagonal respectively of rectangular tensile testing specimen. According to
Wan et al. (2015), tensile strength is also a function of the porosity of a nanofiber mat as shown
in Figure 14.
Fiber volume is determined using Equation 4 below.
𝑉𝑉𝑓𝑓 = 𝑉𝑉𝑚𝑚 (1 − 𝑃𝑃) ----------------------------------- (4)
where 𝑉𝑉𝑚𝑚 is the volume of mat and 𝑃𝑃 is the porosity.
21
Figure 14. Tensile strength as a function of porosity [60]
2.4.2 CARBON NANOFILLERS
Edie (1998) reported that PAN-based carbon fibers have higher tensile strengths and
reasonable tensile moduli compared to pitch-based carbon fibers [61]. PAN fibers are widely
used for carbon fiber production. Zhang et al. (2016) reported that carbon nano fibers (CNF) are
used in reinforcement of nanocomposites [7]. A carbon nanotube (CNT) is one of the allotropes
of carbon. According to Naebe, Lin, and Wang (2010), electrospinning of CNT/polymer has
been shown to induce alignment of nanotubes with in the matrix. Electropsun CNT/polymer
nanofibers showed significant improvement in fiber strength, modulus, and conductivity [62].
One dimensional CNF and CNT have high aspect ratios (typically over a few hundred) that
enable them to form a conductive network. CNF and CNT possess excellent mechanical
properties. According to Zhang et al. (2016), CNF, compared to CNT, exhibits good dispersion
and low fabrication cost. CNT has excellent electrical conductivities, a large surface area to
volume ratio, and structural stability [7]. As noticed by Chung (2016), CNT and CNF are
difficult to disperse and bond relatively weakly in a matrix. The large area of interface associated
with small diameter CNT and CNF aggravate the issue [63]. Two types of MWNT are possible;
22
one is long MWNT and the other is short MWNT. Short MWNTs are 0.5-2µm in length and the
diameter could be 30-50nm [64]. PAN is soluble in polar solvents like dimethylformamide
(DMF), dimethylsulfone (DMS), dimethylsulfoxide (DMSO), and dimethylacetamide (DMAc)
[8]. Among organic solvents DMF and DMSO are known to be good solvents of PAN [65].
Alarifi, Alharbi, Khan, Rahman, and Asmatulu (2009) reported the mechanical property of a
PAN-derived carbon nanofiber composite and the effect of molecular orientation along the fiber
direction [66]. The study placed electrospun carbonized PAN nanofibers on a stacking sequence
of 0, 45, -45, and 45 to create a laminate of ten plies. The tensile testing of PAN-derived carbon
nanofiber composites revealed that they possess a high elastic modulus due to stabilization at
high temperature (280˚C) for 1 hour in an oxygen atmosphere. Thermogravimetric analysis
(TGA), dynamic mechanical analysis (DMA), thermomechanical analysis (TMA) and
differential scanning calorimetry (DSC) analyses confirmed that the nanofibers were crystalline
and had good mechanical and thermal properties. Thinner nanofibers have larger surface area to
volume ratios. Therefore, thinner fibers have better mechanical integrity between the matrix and
the surface of the reinforcing agent for effective load transfer in composites
2.4.3 DIELECTRIC PROPERTIES OF NANOFIBERS
According to classical theory, the dielectric constant (k) is defined as the ratio of the
permittivity (E) of a substance to the permittivity of free space (E0). Values of k are always
greater than or equal to 1. For most polymers, k values are in the range of 2 to 10. According to
Li et al. (2010), the dielectric property depends on porosity and density as shown in Figure 15
[67]. The figure shows the dependence of density and porosity of PAN nanofiber membranes at
the frequency of 1 MHz. The dielectric constant gradually increases with density ranging from
23
0.164 g/cm3 to 0.182g/cm3. Also, the dielectric decreases with increasing porosity from 84.4%
to 86.1%. The apparent porosity can be found by Equation 5.

𝜌𝜌𝑀𝑀
P (%) = (1- )*100---------------------------------- (5)
𝜌𝜌𝑃𝑃
where P is the porosity, 𝜌𝜌𝑀𝑀 is the membrane density and 𝜌𝜌𝑃𝑃 is the polymer density.
Figure 15. Dependence of density and porosity of PAN nanofiber membranes at frequency of 1 MHz [67]
Figure 16 shows the dielectric constant of PAN at 8 w% in the radio frequency range.
Figure 16. Dielectric constant of PAN at 8 w % in the radio frequency range [67]
Khan, Asmatulu, Rodriguez, and Ceylan (2014) reported the dielectric constant of PAN and
PMMA as a function of graphene nano flakes as in Figure 17.
24
Figure 17. Dielectric constant of PAN as a function of graphene nano flakes concentrations [68]
The physical properties including dielectric constant were significantly increased with
graphene concentrations [68].
Among many conventional carbon fillers, CNTs have been preferred for high dielectric
constant. Bhattacharya (2016) gave a detailed review of processing of CNTs as potential
nanofillers to form nanocomposites [69]. CNFs have been widely used in electrochemical energy
storage devices as reviewed by Zhang et al. (2016) [7]. Electrospun polymer/CNF or CNT fibers
has been used in energy storage devices. The comparison between the CNF and CNT are shown
in Table 2.
Thermal
Allotropes of Specific gravity Electric conductivity
carbon (𝒈𝒈𝒈𝒈𝒈𝒈−𝟑𝟑 ) conductivity (𝑺𝑺𝑺𝑺𝑺𝑺−𝟏𝟏 ) (𝑾𝑾𝒎𝒎−𝟏𝟏 𝑲𝑲−𝟏𝟏 )
CNF 1.5-2.0 10−7 -103 5-1600
CNT 0.8-1.8 102 − 106 2000-6000
Table 2. Comparison of CNT and CNF [7]
Wang et al. (2011) studied that an increase in dielectric constant was achieved in a
combination of high aspect ratio barium titanate (BaTiO3) and graphene platelets in a silicon
rubber matrix compared to their spherical counterparts. Higher volume fractions of ferroelectric
particles lead to increased dielectric constant but also to a lower mechanical properties.
Composites with high aspect ratio fillers at lower loading exhibit higher dielectric constant [70].
25
Wei et al. (2014) reported the dielectric characterization of annealed electrospun BaTiO3 fibers.
Crystallized BaTiO3 nanofibers showed better dielectric permittivity [71]. Issa, Al-Maadeed,
Luyt, Ponnamma, and Hassan (2017) reported an increase in permittivity by the addition of silver
nanoparticles (AgNP) in PVDF. This is due to the interfacial polarization associated with
entrapment of free charges generated at the interfaces between the AgNPs and PVDF [72].
Electrospun PVDF fibers has higher β-crystalline content which enhances the piezoelectric
property and its energy-harvesting application. Jabbarnia, Khan, Ghazinezami, and Asmatulu
(2016) reported various electrospun PVDF/PVP mats fabricated with different percentages of
carbon black nanoparticles for the applications such as supercapacitor separators and other
energy storage devices. The dielectric constant values were increased with the carbon black
loading [73]. According to Im, Kim, Bae, and Lee (2011), the increase in dielectric property of
permittivity increases the electromagnetic interference shielding effectiveness (EMI-SE) as
shown in Figure 18. The permittivity of carbon fibers with different proportions of ZrO2 is
shown at left side and the EMI-SE of the same proportions at the right side. This relationship is
more evident below 2000 MHz [74].
Figure 18. Permittivity (ε΄) (left) and EMI-SE (right) of carbon fibers with different proportions of ZrO2 [74]
26
Lee, Jang, and Choa (2016) studied the effect of Fe and Co mixed with PVP. The analysis of
FE-SEM images of electrospun products obtained using solutions with and without citric acids
were carried out. The composite showed excellent electromagnetic (EM) wave absorption
properties where the power loss of the FeCo nanofibers increased to 20 GHz [75]. EM waves
with frequencies in the microwave range of from 12 to 18GHz are widely used in wireless
communication networks, radar systems, military aircraft, and satellite communication devices.
Anita and Natarajan (2015) studied the potential of ZnO nanopowders with PVA matrix for the
use of UV shielding [76]. The in-situ sol-gel method (ISM) and direct deposition method (DDM)
have been discussed to analyze the effect of UV shielding. The ISM-PVA/ZnO composite
showed better UV absorption in optical transmission measurements due to the uniform
dispersion of the ZnO in the fibrous matrix. S. M. Kim, S. H. Kim, Choi, and Lee (2016)
analyzed the EMI SE of MWNT-PU in the DMF with THF solvents and coated with conductive
poly (3, 4-ethylenedioxythiophene) (PEDOT) [77]. The EMI SE from a network analyzer shows
25dB at the frequency range of 50 MHz-10GHz.
The dielectric properties of different nanofibers are shown below in Table 3.
Pure Dielectric Property

PAN ̴ 3.5 Physical properties can increase with graphene [68]
PMMA ̴ 3.5 Physical properties can increase with graphene [68]
PVDF ̴ 11 Physical properties can increase with addition of AgNP[72]
PVP - EMI increases with addition of FeCo (ε΄ ̴ EMI) [75]
PVA - Uniform distribution of ZnO increases EMI (ε΄ ̴ EMI) [76]
PU - EMI increases with PEDOT (ε΄ ̴ EMI) [77]
Table 3. Dielectric properties of different nanofibers
2.5 APPLICATIONS OF ALIGNED FIBERS
Isaac, Taylor, Adnan, and Raihan (2017) observed improvements in the mechanical strength
and dielectric constant with increase in degree of alignment of fibers [78]. Aligned fibers are
27
greatly beneficial when they are used in applications including field effect transistors, gas and
optical sensors, fiber reinforced composite materials, and tissue engineering [79-80]. Bashur
(2009) discussed the application of aligned fibers in the field of tissue engineering [81]. Also,
Lawrence and Liu (2006) and Katti, Robinson, Ko, and Laurencin (2004) stated that there are
other applications found in the variety of areas if the fibers are in aligned form [82-83]. This
section discusses mechanical and dielectric applications of electrospun aligned fibers.
2.5.1 MECHANICAL APPLICATIONS OF ALIGNED FIBERS
Hou et al. (2005) showed that well-aligned, multi-walled carbon nanotubes (MWCT) can
improve the mechanical properties of a PAN-based nanofiber mat [84]. Kannan, Eichhorn, and
Young (2007) demonstrated that electrospun polymer/CNT leads to nanocomposite fibers with
embedded CNTs orienting parallel to the nanofiber axis [85]. Also, alignment of CNTs in the
fiber direction can improve thermal conductivity [86]. Dhakate et al. (2016) reported that semi-
aligned electro spun carbon nanofiber composites show excellent bending strength and
interlaminar shear strength [87].
Aligned micro scale fibers (7µm diameter) have application in composite reinforcement.
There is increased need to manufacture complex composites for light weight applications.
Carbon/epoxy composites have greater application in aircraft, sports cars, and space crafts
because of better strength to weight ratio than that of metals like aluminum alloys. They are
thermally stable because of the lower coefficients of thermal expansion properties of carbon
fibers. Yu, Potter, and Wisnom (2014) showed that short carbon fiber composites can be used in
places where complex shapes and ductile properties are required [88]. Short carbon fibers, with
an aspect ratio of 400, resulted in composites with a tensile modulus of 119 GPa and strength of
1.211 GPa.
28
Compton and Lewis (2014) reported that cellular composites with controlled alignment of
multi-scale and high aspect ratio fibers can result in reinforcement of hierarchical structures [89].
They demonstrated the first 3D printed cellular composites composed of oriented fiber-filled
epoxy with exceptional mechanical properties. Malek, Raney, Lewis, and Gibson (2017)
developed a new carbon fiber reinforced epoxy for 3D printing which resulted in printing
materials with longitudinal Young’s modulus up to 57 GPa [90].
2.5.2 DIELECTRIC APPLICATIONS OF ALIGNED FIBERS
Ning et al. (2014) showed that aligned MWCNT/PVA has high dielectric constant, low
dielectric loss, high breakdown strength, and high energy density. These properties contribute in
applications such as artificial muscles, energy storage, flexible electronics, and sensors [91].
Aligned MWCNT/PVA composite films were prepared using electrospinning in-situ film-
forming technique. Also, Liu, Lai, Sun, and Chen (2012) confirmed the tailoring of dielectric
property by controlling the alignment of CNTs [92]. Ma et al. (2012) reported that aligned PVDF
had better molecular orientation than its random fiber counterparts. This is because of the smaller
diameter of the aligned fibers. These nanofibers have applications in the field of sensors and
actuators [93]. Agarwal, Greimer, and Wendorff (2009) reported that aligned fibers have
applications in nanofluidics, superhydrophobic patterning, nanoelectronics, and nanophotonic
circuits [94]. Edmondson, Cooper, Jana, Wood, and Zhang (2012) demonstrated the significance
of fiber alignment in improving the piezoelectric property using centrifugal electrospinning.
PVDF and PEO have piezo-, pyro-, and ferro-electric properties and these aligned fibers can
provide for applications in actuators, transistors, textiles, and composites [95]. P. Kumar, A.
Kumar, Cho, Das, and Sudarsan (2017) showed that aligned graphene films improved EMI
shielding. Electromagnetic (EM) waves cause interference or device malfunction and also can
29
cause harm to human bodies [96]. Song et al. (2013) observed that aligned carbon-based fillers
enhanced EMI shielding. The alignment produced anisotropic characteristics that achieve
enhancement in absorption and reflection performance [97].
2.6 FUTURE WORK
While a few studies have methodically experimented with system parameter optimization for
limited sets of parameters, none have studied the nonlinear effects of two or more factors with
three levels per factor for obtaining the mechanical and dielectric responses. Consequently,
parameter interactions and nonlinearities have not been studied in depth in order to optimize
alignment for mechanical and dielectric properties. Very few studies have been conducted on the
nanofiber orientation variations along the fiber direction using a rotating mandrel and its effect
on mechanical and dielectric properties. Variability of data in both dielectric and tensile tests
need to be quantitatively addressed and therefore a modified improved system should be
developed. The improved system will lead to consistencies in the behavior of nanofiber
specimens and acceptable standard deviations in variability that indicate meaningful parameter
levels and trends. Future work will focus on system improvements and methodical
experimentation (Design of Experiments) to optimize system parameters for improved
mechanical and dielectric responses, and application of PAN nanofiber mat materials in
advanced mechanical and energy applications. Future research work will determine the nature of
the trade-off between mechanical strength and dielectric properties—whether it is linear or non-
linear, synergistic or detrimental.
2.7 CONCLUSIONS
This work has provided a detailed review and analysis of methods for alignment of
electrospun fibers and their resulting mechanical and dielectric properties. A key consideration is
30
the molecular orientation of fibers along the fiber direction as it is important for improvement in
mechanical properties. Also, design configuration options for electrospinning apparatuses have
been surveyed in order to analyze the ability of each to improve fiber alignment. Given the
mechanical and dielectric performance improvement possible with increasing fiber alignment,
the need to improve electrospinning apparatus capabilities for fiber alignment is paramount and
worthy of further study and experimentation.
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Mesenchymal Progenitor Cells. Tissue Engineering Part A, 15(9), 2435–2445.
[142] Taylor, G. (1964). Disintegration of Water Drops in an Electric Field. Proceedings of the
Royal Society A: Mathematical, Physical and Engineering Sciences, 280(1382), 383–397.
[143] Isaac,B., Taylor, R., Reifsnider, K., Raihan, R., Adnan, A., & Santhanagopalan, S. (2018).
Review of effects of electrospun fiber alignment on mechanical and dielectric properties.
Manuscript submitted for publication.
48
CHAPTER 3
METHODOLOGY
Electrospinning has been successfully used to develop aligned micro- and nano-fiber mats for
lightweight reinforcement of composite materials and structures. Electrospinning systems can be
oriented either vertically, utilizing gravity-assisted electric field material deposition, or
horizontally, utilizing electric field with little effect on gravity. A horizontal apparatus has been
designed and fabricated for improved micro- and nano-fiber alignment that provides the
possibility of developing better reinforcement materials in the form of aligned fiber mats. These
nano fiber mats are stiffer, stronger and have better mechanical, electrical and thermal properties
for structural and multi-functional applications. The micro- and nano-fiber mats produced with
the set up were scanned under Scanning Electron Microscope (SEM). These images show
successful deposition of micro- and nano-fibers with alignment comparable with current
electrospinning systems. System enhancement is in work to enhance alignment of deposited
fibers through additional electromagnetic controls.
This section discusses the design and set up of an apparatus to produce the micro- and nano-
fibers using an Electrospinning Technique. Electrospinning is a process of producing micro- and
nano-fibers using polymer solution in an enclosed apparatus with a syringe pump, collector and
high voltage power supply. This technique results in a simpler and more economical design
configuration than other techniques. The nanofibers produced through this technique can be used
in many applications including reinforcement of composites, tissue engineering, water filtration,
air filtration, and electromagnetic interference (EMI) shielding. The electrospinning design used
here is a horizontal set up and the apparatus yields consistent and uniform nanofibers compared
49
to a vertical set up. The set up consists of a high voltage power supply, positive and negative
electrodes, syringe pump and enclosure.
For structural applications, composites having higher mechanical specific strength (strength
per density) and specific stiffness (stiffness per density) are preferred. Anisotropic polymer
matrix composites (PMC) are found to have better specific strength and specific stiffness in the
fiber directions compared to that of the isotropic metal or alloy structures. Nanofiber mats are
applied to the composites to improve mechanical strength. Anisotropic nanofiber mats are
achievable through aligned fibers in mats produced through electrospinning. The EMI shielding
effectiveness (EMI-SE) can be achieved through aligned fibers as well. The EMI shielding helps
the structures to prevent unnecessary and harmful radiations.
3.1 APPARATUS
This section discusses the operating principle, design, and fabrication of the horizontal drum
collector electrospinning apparatus used in this work.
3.1.1 OPERATING PRINCIPLE
In electrospinning apparatuses, there are two types of standard configurations, namely a)
vertical electrospinning and b) horizontal electrospinning [7]. In a vertical configuration, gravity
promotes bead formation, which leads to lower quality deposited material morphology. For this
reason drum collection methods do not allow for vertical configurations and therefore this work
uses a horizontal configuration. Figure 19 depicts a schematic of the horizontal set up. Despite
the simplicity of the electrospinning in this setup, industrial applications are relatively rare due to
low fiber throughput for currently available fibers [8]. This throughput limitation could be
addressed with larger drum sizes.
50
Figure 19. Schematic of Electrospinning Technique
To operate, electrospinning apparatus requires a sufficiently high voltage applied to the
liquid droplets formed at the tip of the syringe needle. The body of the liquid gets charged and
electrostatic repulsion counteracts the surface tension. Consequently, the droplet is stretched and
at a critical point the stream of liquid erupts from the surface. The point of eruption is called the
Taylor Cone.
3.1.2 DESIGN
The horizontal drum collector electrospinning apparatus used in this work consists of four
main parts
a) Enclosure
b) Syringe pump
c) High voltage power supply
d) Mandrel
The design has been created for the enclosure and mandrel in 3D CAD software. The syringe
pump and high voltage power supply have been purchased and integrated into the designed
components. Various parts are shown in Figure 20 below.
51
Figure 20. Enclosure, Syringe pump, and High voltage power supply
a) ENCLOSURE
The enclosure, shown in Figure 20, consists of high definition polyethylene (HDPE) sheets
forming four sides and the back. The front sliding door is made out of polycarbonate sheet.
White polyethylene brackets are used to assemble the enclosure together. Nylon screws and nuts
are used to fix the brackets in position. Impact resistant polycarbonate sheet is used for the
mandrel holder. ABS sheets hold the mandrel holder in place while the mandrel rotates at high
speed. Impact resistant polycarbonate channels are used to hold the ABS sheets, and allow the
adjustment of mandrel position relative to the syringe tip.
b) SYRINGE PUMP
The programmable syringe pump, shown in Figure 20 above, is capable of holding two
syringes up to 60ml each. Blunt needle tips are used.in each syringe. The inside diameter of the
syringe is 11.99 mm. Dimensions of needle used here is 22g and 18g luer lock needles. The input
voltage to the pump is 120v. The syringes along with needles are held at the v-slot provided at
the pump.
c) HIGH VOLTAGE POWER SUPPLY
The high voltage power supply, shown in Figure 20 above, is capable of 11kv-18kv output
voltage. The input voltage to the power supply is 24v.
52
d) MANDREL
The mandrel, shown in Figure 21 below, is made of aluminum and is press fit to the extruded
structural aluminum brackets through needle bearings. The mandrel along with the brackets are
attached to the mandrel holder using set screws. The mandrel is connected to the 9v DC motor
which is capable of rotating at no load speed of 7000 rpm.
Figure 21. Mandrel and D.C.Motor
OPERATING PROCEDURE:
The following steps are used to operate the electrospinning system.
1. The mandrel is wound with an aluminum foil before the setup is run.
2. The syringe pump is turned on with the polymer solution in the 5 ml syringe. The syringe
pump is set to operate at 5ml/hr. A droplet of polymer solution forms at the tip of the
needle.
3. The high voltage power supply is turned on.
4. The polymer film is formed on the rotating collector or mandrel.
5. After the required amount of solution is made to pass through the syringe, the syringe
pump is turned off first and then the high voltage power supply.
6. The walls of the enclosure and the needle are touched with ground stick.
7. The polymer film formed on the aluminum foil is left for some time for curing. After the
curing process, the aluminum foil is detached with a scalpel very carefully. Then the film
53
is kept under as Scanning Electron Microscope (SEM) for verifying the fiber distribution
and its diameter measurement.
3.2 MATERIAL CHARACTERIZATION
This section discusses material composition, material builds, morphological tests, tensile and
dielectric results
3.2.1 MATERIAL COMPOSITION
Polymer solution: Polymer solution is prepared with 15% weight/volume of the PCL in
TriFluoroEthanol (TFE) solvent. This means that 15 g of PCL is used to prepare 100 ml of
solution. PCL is used as nanofibrous scaffolds in tissue engineering. The fiber morphology and
properties of electrospun fibers are affected by the following process parameters and solution
parameters.
PROCESS PARAMETERS:
a. Voltage: Higher voltage leads to stronger repulsion of polymer jet. The decrease in diameter
would make the control of distribution of fibers more difficult.
b. Flow rate: A stabilized Taylor Cone is required for smooth operation of electrospinning. A
uniform flow rate is adjusted using syringe pump.
c. Collector-needle distance: Collector-needle distance is kept at 10cm, 15cm, and 20cm. The
longer the distance, the smaller the fiber diameter.
SOLUTION PARAMETERS:
a. Concentration: The concentration of solution in weight per volume percentage (w/v %)
affects the deposited fiber diameter.
b. Volume: The volume in milliliters used in the syringe determines the morphology and
properties of nanofiber mat.
54
c. Viscosity: Viscosity is measured in poise. Viscosity measures the ease with which the
solution can be pumped through the syringe.
d. Surface tension: the greater the surface tension, the higher the voltage required for creating
Taylor Cone.
The effects of alignment on mechanical and dielectric properties were studied using a set up
designed and drawn in 3D modeling software as shown in Figure 22 below.
Figure 22. Enclosure in the 3D model
The electrode, mandrel holding sheet, ABS sheet for adjusting the distance between needle
tip and mandrel, and the sliding front door are shown above. The final electrospinning system is
shown in Figure 23.
Figure 23. The final electrospinning set up
55
The whole apparatus is placed under a fume hood for safety purposes so that any toxic
solvent escapes through the fume hood. Using this setup, electrospun fiber mats were fabricated,
fiber morphology analyzed, tensile and dielectric properties characterized.
3.2.2 MATERIAL BUILDS
The electrospinning device was run for ten minutes in order to form sufficient fibers on the
aluminum foil wrapped on the mandrel. Figure 24 below shows the fiber mat is being formed on
the mandrel (left) and the fabricated fiber mat unfolded from the mandrel (right).
Figure 24. Fiber mat is being formed on mandrel (left) and the fiber mat (right)
3.2.3 FIBER MORPHOLOGICAL ANALYSIS
The electrospun fiber mat formed was examined under a NanoSEM 230 SEM microscope as
in order to measure fiber diameter. As shown in the Figure 25, the fiber diameter decreases as the
needle size decreases from 18G to 22G. The feed rate was 0.3ml/hr. The 18G needle produced
fibers with 1 µm, whereas the 22G needle produced fibers in the range of 300nm to 900nm.
Figure 25. NanoSEM 230, fibermats using 18G (middle), and 22G (right) needles
56
3.2.4 TENSILE AND DIELECTRIC TEST RESULTS OF ELECTROSPUN MATS
More than thirteen experimental runs were carried out to determine suitable process
parameter settings for the best degree of fiber alignment using PAN precursor with DMF at 8w%
using a 22G needle. The SEM images, tensile, and dielectric test results for the best identified
process parameters are given below in Figure 26(a)-(c) respectively.
Figure 26a. SEM of samples 1, 2, and 3 at 20μm magnification
The SEM image of sample 1 shows loosely packed nanofibers. Samples 2 and 3 have more
closely packed fibers and sample 3 has the highest densely packed fibers. These images are
viewed at 20 μm magnification. The tensile and dielectric results are shown below.
Figure 26b. Tensile strength of best three samples
Samples 2 and 3 show higher tensile strength, and sample 1 is the least. Sample 2 shows a
tensile strength of 4.47Mpa.
57
Figure 26c. Dielectric constant of best three samples
As shown above, sample 3 shows the highest dielectric constant. The dielectric constant for
sample 3 is 2.56Hz at 0.1Hz.
The best parameters are chosen by comparing the three given samples for their SEM images,
tensile strengths, and dielectric properties as shown in Table 4.
Table 4. Tensile and dielectric properties of three samples
The SEM images at 5μm magnification for three samples viewed under NanoSEM 230 and the
mean values of degree of alignment of three samples are shown below in Figure 27.
58
Figure 27. SEM images at 5μm and respective angle measurements of samples 1, 2, and 3
The mean value of fiber orientation with respect to vertical axis for sample 3 is 26.2 degrees
and standard deviation is 24.59 whereas the mean value of fiber orientations for sample 1 and 2
are 50.27 and 51.23 degree respectively.
Sample 3 gives consistent and uniform fibers. The best parameters at 8w% correspond to
sample 3. The sample 3 has uniform fiber distribution with the lowest range in diameters. Also,
the fibers are formed without beads. The tensile strength and dielectric constant of sample 3 is
found to be 4.43MPa and 2.56 respectively.
3.3 CONCLUSIONS
With this exploratory study, system improvement has been carried out for an electrospinning
nanofiber deposition system. The nanofibers produced from the best determined system
59
parameters have good alignment with the intended direction. Furthermore, tensile tests show that
material strength in the loading direction improves with the degree of fiber alignment as
expected so the system can effectively be used for mechanical property tailoring. Also, the
nanofibers deposited with the best system parameters have improved dielectric properties that
can be used for EMI shielding from harmful radiation. The current work, while limited in scope,
has shown that the electrospinning nanofiber deposition system developed can produce fiber
mats that can be tailored to improve both mechanical and EMI response for simultaneous
structural reinforcement and EMI shielding applications.
3.4 FUTURE WORK
Future work will focus on methodical experimentation to optimize system parameters for best
mechanical and EMI response, process simulation, and application of fiber mat materials.
First, the system parameter optimization will be performed using Design of Experiments.
Design improvement at the electrode side and electromagnetic deflection will be targeted for
controlled deposition and uniform distribution of fibers. Second, simulations will be carried out
before the hardware design changes are performed. Finally, the aligned fiber mats will be applied
on structures like aircraft wings for mechanical and shielding property improvement.
REFERENCES
[1] Zhang, B., Kang, F., Tarascon, J. M., & Kim, J. K. (2016). Recent advances in electrospun
carbon nanofibers and their application in electrochemical energy storage. Progress in
Materials Science, 76, 319–380.
[2] Wong, S. C., Baji, A., & Leng, S. (2008). Effect of fiber diameter on tensile properties of
electrospun poly(ε-caprolactone). Polymer, 49(21), 4713–4722.
60
[3] Groover, M. P. (2012). Fundamentals of modern manufacturing: Materials, processes, and
systems (5th ed.). Hoboken, NJ: John Wiley & Sons.
[4] Beese, A. M., Papkov, D., Li, S., Dzenis, Y., & Espinosa, H. D. (2013). In situ transmission
electron microscope tensile testing reveals structure-property relationships in carbon
nanofibers. Carbon, 60, 246–253.
[6] Baji, A., Mai, Y. W., Wong, S. C., Abtahi, M., & Chen, P. (2010). Electrospinning of
polymer nanofibers: Effects on oriented morphology, structures and tensile properties.
Composites Science and Technology, 70(5), 703–718.
[7] Rodoplu, D., & Mutlu, M. (2012). Effects of electrospinning setup and process parameters on
nanofiber morphology intended for the modification of quartz crystal microbalance
surfaces. Journal of Engineered Fibers and Fabrics, 7(2), 118–123.
[8] Yarin, A. L., & Zussman, E. (2004). Upward needleless electrospinning of multiple
nanofibers. Polymer, 45(9), 2977–2980.
55(10), 2570–2577.
[10] Im, J. S., Kim, J. G., Bae, T. S., & Lee, Y. S. (2011). Effect of heat treatment on zro2-
embedded electrospun carbon fibers used for efficient electromagnetic interference
shielding. Journal of Physics and Chemistry of Solids, 72(10), 1175–1179.
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[12] Zafar, M., Najeeb, S., Khurshid, Z., Vazirzadeh, M., Zohaib, S., Najeeb, B., & Sefat, F.
(2016). Potential of electrospun nanofibers for biomedical and dental applications.
Materials, 9(2), 15–17.
[13] Bhardwaj, N., & Kundu, S. C. (2010). Electrospinning: A fascinating fiber fabrication
technique. Biotechnology Advances, 28(3), 325–347.
[14] Anita, S., & Natarajan, T. S. (2015). Electrospun Fibrous Nanocomposite Membrane for UV
Shielding Applications. Journal of Nanoscience and Nanotechnology, 15, 9705–9710.
[15] Kim, S. M., Kim, S. H., Choi, M. S., & Lee, J. Y. (2016). Electrospun Carbon Nanotube-
Reinforced Nanofiber. Journal of Nanoscience and Nanotechnology, 16, 2908–2911.
[16] Kowalewski, T. A., Blonski, S., & Barral, S. (2005). Experiments and modelling of
electrospinning process. Bulletin of the Polish Academy of Sciences: Technical Sciences,
53(4), 385–394.
[17] Cooley, J. F. (1900). U.S. Patent No. 692631. Washington, DC: U.S. Patent and Trademark
Office.
[18] Morton, W. J. (1902). U.S. Patent No. 705691. Washington, DC: U.S. Patent and
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[19] Bashur, C. A. (2009). Effect of Electrospun Mesh Diameter, Mesh Alignment, and
Mechanical Stretch on Bone Marrow Stromal Cells for Ligament Tissue Engineering.
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fibrous media for gas filtration. Chemical Engineering and Technology, 29(8), 957–967.
62
CHAPTER 4
VARIABILITY IN TESTING ELECTROSPUN PAN NANOFIBER MAT FOR DIELECTRIC AND
TENSILE RESPONSES
Electrospinning technology has been found to have applications in various fields including
medical, structural reinforcement, filtration, storage, energy, and others. Electrospinning has
been successfully used to develop aligned micro- and nano-fiber mats for lightweight
reinforcement of composite materials and structures. A horizontal apparatus has been designed
and fabricated for improved micro- and nano-fiber alignment that provides the possibility of
developing better reinforcement materials in the form of aligned fiber mats. These nano fiber
mats are stiffer, stronger, and have better mechanical, electrical and thermal properties for
structural and multi-functional applications. Understanding the behavior of nanofibers at its nano
scale is important for realizing benefits in these fields. In this research, the dielectric properties,
tensile strength, toughness properties, specimen geometries, measurement challenges, and
characterizing failure modes at the failure regions have been demonstrated.
This section discusses the characterization of tensile and dielectric properties to project the
variability issues for specimens from as spun nanofiber mat. This work also paves the ways for
improved system parameter optimization and apparatus design that produces an increased
electrostatic force and more tightly controlled discharged particle path to enable a more uniform
distribution and higher degree of alignment in deposited electrospun material. This results in
simultaneous improvement of both mechanical and dielectric properties. The design of
experiment approach leads to parameter optimization for the mechanical and dielectric properties
for the electrospun mats. For this approach, tightly controlled tensile test and dielectric test
63
results are required. In measuring the tensile strength of nanofiber mat specimens, the stress-
strain curves provide high variability. This shows that measuring thickness is not accurate for
stress-strain relationship. It is important to accurately measure the tensile behavior of mat to
verify the alignment of fibers. Also, there should be repeatability between the mats.
According to L.Y. Wan et.al, stress-strain curve for electrospun nanofiber mat has high
variability as shown below in Figure 28. Thickness and porosity can be rarely accurately
measured because of variability and mass is used instead of them [7]. It is also a known fact that
1 kv/cm results in optimal alignment as well as narrow fiber distribution [8].
Figure 28. Stress-strain curve of nanofiber mat [7]
4.1 METHOD
In this section, materials and specimen fabrication, test configuration, and test matrix for
DOE study are discussed. System configuration has been discussed in Isaac, B.et.al. (2017) [17].
4.1.1 MATERIALS
PAN powder is mixed with DMF in a conical glass ware having a stopper. 8, 9 and 10 w% of
solute and solvent are stirred and heated at 300rpm and 80 °C for 4 hours until a homogeneous
yellow colored solution is formed as shown in Figure 29. PAN and DMF are bought from Sigma
Aldridge with product number 181315 and D158550 respectively. The molecular weight of PAN
64
is 150,000 Da. DOE for current set up includes concentrations of 8w%, 9w%, 10w%. 15kv
voltage is applied throughout the experiments.
Figure 29. PAN/DMF is stirred in heating stir plate (left) and the final yellowish solution (right)
4.1.2 SPECIMEN FABRICATION
The original electrospinning is shown below in Figure 30.
Figure 30. Electrospinning original system [17]
Figure 31 below shows the electrospun mat is being fabricated at the rotating mandrel.
Figure 31. Electrospun mat is being fabricated at the mandrel
The specimens are cut from the mat for tensile and dielectric tests.
65
4.1.3 TEST CONFIGURATION
Tensile tests are conducted as per the ASTM D882-02 standard as shown in Figure 32.
Figure 32. Schematic of frame and specimen (left) and the tensile test is being run (right)
The thin specimen is placed between two rectangular frames of card board sheet. The
specimens for tensile tests are cut in to sizes of 80mm x 10mm.
As shown in Figure 33, Faraday cage has two electrodes of size 0.5x 0.5 inch which are
connected to Broadband Dielectric Spectrometer for dielectric measurements. The specimens are
cut a little more than the electrode size to avoid any electrode to electrode contact and placed in
between the electrodes.
Figure 33. Schemmatic of square specimen (left) and Faraday cage (right) for dielectric test
4.1.4 TEST MATRIX FOR DESIGN OF EXPERIMENTS
In this section, the full test matrix for the current system configuration is discussed.
66
FULL FACTORIAL TEST MATRIX
The full factorial test matrix with two factors and three levels are shown below in Table 5.
Speed A Concentration B
+ 5V 3100 rpm + 10w%
- 3V 1700 rpm - 8w%
0 4V 2400 rpm 0 9w%
Serial Speed Concentration Mechanical Dielectric

number A B
1 + + 6 6
2 0 + 6 6
3 - + 6 6
4 + 0 6 6
5 0 0 6 6
6 - 0 6 6
7 + - 6 6
8 0 - 6 6
9 - - 6 6
Total 54 54
Table 5. Full factorial test matrix for DOE
There are 54 specimens for each mechanical and dielectric tests. Three specimens from each
mat of same combinations. Two mats are fabricated for each combination.
4.2 RESULTS
In the results, geometric challenges, the tensile, toughness, dielectric responses, and failure modes
are discussed.
4.2.1 SPECIMEN GEOMETRY AND MEASUREMENT CHALLENGES
Figure 34 shows the optical microscopic image of nanofiber mat with thickness variation. The
specimen on left is according to the dimension mentioned in Figure 32. While conducting tensile and
dielectric tests, the thickness is required for stress-strain analysis and dielectric constant measurement.
Therefore, thickness should be avoided and mass should be used to avoid variability. From the figure it
is obvious that measurement of thickness brings challenges.
67
Figure 34. PAN specimen (left) and optical microscope image in micro inch scale (right)
4.2.2 TENSILE RESPONSE
Figure 35 shows the stress-strain plot using stroke control at 5mm/min strain rate. Figure 36 shows
force-stroke plot to avoid thickness measurement.
Figure 35. Variability in stress-strain curves when using strain rate for nanofiber mat
Figure 36. Variability in force-stroke curves when using strain rate for nanofiber mat
68
The following steps are done to reduce the variability issues. The force-stroke plot is used to avoid
the measurement of thickness. The force-stroke plots of the 20cm needle tip to mandrel, 3v rotating
speed, 9w% concentration nanofiber mat with an applied voltage of 15kv have been shown in Figure 37
(a)-(b). Strain rate is avoided and replaced with force rate. The force rate is 1N/min. Most importantly
mass is used instead of thickness for measuring strength. The specimens are cut with consistent width
measurement at the substrate (aluminum foil) side of electrospun mat. Finally, the force is normalized
with respect to mass for specific strength.
Figure 37a. Force-stroke plot of a nanofiber mat
Figure 37b. Normalized force-stroke plot of a nanofiber mat
69
Though the figure above shows consistent specific strength measurements for four specimens, the
fact is that the needle to collector distance of 20cm reduces the electrostatic repulsion between the
fibers when compared to 15 cm. But the 15kv-15cm (1kv/cm) is necessary for the current set up of
electrospinning system as it produces better alignment. Figure 38 shows the specific strength versus
stroke plot for 5 specimens from the first mat and 3 specimens from the second mat of 5v speed and
10w % concentration. There are difference in consistencies between mats. The solid line represents the
first mat and the dashed lines represent the second mat.
Figure 38. Specific strength for 5v speed and 10w% of two mats
The specific strengths of specimens in a mat, unlike that of the Figure 36, follow a pattern. But the
variation of specific strengths between the mats could be because of the environmental factors such as
humidity change or temperature variation. Figure 39 shows specific strengths for two mats of 3v speed
and 10w% combination which has more variability between the specific strengths. The variation in
strengths within mat is because of higher electrostatic repulsion between the bigger fibers resulting in
random fiber mat.
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Figure 39. Specific strengths for 3v speed and 10w% of two mats
Note that 3v speed results in bigger fibers than 5v speed. For Figure 39, there were 6 and 4
specimens possible for mats 1 and 2 respectively.
The main effects and standard deviation of dielectric tests are shown in Figures 40 (a)-(b)
respectively. The total difference for the factor A is 8018 and it is 71.41 % of the maximum value.
Figure 40a. Main effects for tensile tests
Figure 40b. Standard deviation for tensile tests
71
The coefficient of variation for A0 is 36.52% and that of A+ is 50.32%. Variability in the data is too
great to draw conclusion on the main effects.
4.2.3 TOUGHNESS PROPERTIES
As shown in Figure 41, the 15cm-5v-8w% specimens with two force rates are plotted with force
versus stroke.
Figure 41. Force rate behavior of mat at 1N/min and 5N/min
The specimens are built at 15cm needle tip to collector distance, 5v corresponding speed of the
mandrel and 8w% concentration of PAN solution. The force control method is used so that thickness
measurement is avoided for mass consideration. It is worth noting that the black colored plot is at
1N/min and the fibers have enough time to catch up with load increment rate so that the weakest fiber
breaks first, and then the next weaker fiber and so on. But in the case of 5N/min, the behavior of each
fiber is not recorded accurately because of higher force increment rate.
4.2.4 DIELECTRIC CONSTANT RESPONSE
The dielectric test is conducted at Broadband Dielectric Spectrometer. The dielectric data were
plotted against 1 kHz for measurement. Tests are conducted on each 0.5x0.5 inch specimen for 9
readings. Therefore, there are total of 27 measurements for 6 specimens (samples).
72
Before solving the variability issues, the variability is found to be more than 600% as shown in
Figure 42. The needle to collector distance was 20cm, 4v speed is applied, and 10w% concentration
mat is used. The dielectric constant is taken at 1 kHz.
Figure 42. Dielectric constant with high variability
The data show that there are variability issues with dielectric measurements also. After solving the
variability issues, the coefficient of variation is found to be lower as shown in Figure 43(a)-(b). Though
taking sufficient number of thickness measurements (five or more) for each specimen with size a little
more than 0.5 x 0.5 inch tightened the data, the fact is that by reducing the distance from 20cm to 15cm
reduced the variability.
Figure 43a. Dielectric constant of 15cm-4v-10w% mats
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The distance to collector distance was 15cm to keep the 1kv/cm criteria. The reason of this
reduction in variability is that the porosity is more consistent as in Figure 43a, because it gives better
aligned fibers at 1kv/cm.
Figure 43b. Normalized dielectric constant of specimens from two mats of same combination
The dielectric constants from two mats of 4v speed and 10w% concentration has lower coefficient
of variation when compared to Figure 42.
Figure 44 shows dielectric constants of 15cm-3v-10w% mats. The fibers are bigger at 3v and
therefore higher repulsion between the fibers resulting in higher variability than 4v.
Figure 44. Dielectric constant of 3v-10w% mats
74
The main effects and standard deviation of dielectric tests are shown in Figures 45(a)-(b)
respectively. The total difference of main effects for the factor A is 3.76 and it is 88.4 % of the
maximum value. The coefficient of variation for A- is 27.17% and that of A0 is 28.3%.
Figure 45a. Main effects for dielectric tests
Figure 45b. Standard deviation for dielectric tests
Variability in the data is too great to draw conclusion on the main effects.
4.2.5 FAILURE MODES
The fracture mode below 0.025g resembles a shear failure (left) and that of above 0.025g shows
brittle failure (right) as shown in Figure 46.
Figure 46. Below 0.025g has shear failure (left) and above 0.025g resembles brittle failure (right)
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There are two failure modes in a mat fabricated with parameters 10cm needle tip to collector, 3v
speed and 9w% concentration. One is shearing failure and the other is a brittle fracture. As shown in
Figure 47(a)-(b) below, the fracture mode above 0.025g resembles brittle fracture.
Figure 47a. Fracture mode at 5N/min force rate
Figure 47b. Fracture modes of specimens below and above 0.025g
4.3 CONCLUSIONS AND FUTURE WORK
The DOE needs tight data for good results. It is important to reduce the variability issues in
characteristic tests with as spun nanofiber mat for tensile and dielectric tests. DOE study with
76
electrospinning for tensile and dielectric results are inconclusive because of high variability. In this
research work, the tensile test and dielectric test variability issues are projected. Also, the force rate
behavior of nanofiber mat and the failure modes are demonstrated in this research work. The tensile
tests require thin film and dielectric tests need thicker film. Above the mass of 0.025g of tensile test
film with 80mm x10mm size brings higher variability and the dielectric test provides good results at
that mass. The notion of thicker film is that it avoids the electrode-electrode contact while measuring
the dielectric constant as the electrospun mat has high porosity. It is important to find a trade-off
between these two tests. It is advisable to take all specimens towards the middle region (trimming 1 and
½ inch each from vertical sides) of electrospun mat of size 3 inch x 5.5 inch, where the thickness is
supposed to be almost equal. Future work will focus on system improvement for reducing the
variability of thickness along the horizontal direction of the mandrel and also controlled deposition and
uniform distribution of fibers.
REFERENCES
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CHAPTER 5
ANISOTROPIC CHARACTERIZATIONS OF ELECTROSPUN NANOFIBER MATS USING NOVEL
ALIGNMENT SYSTEM
This section studies the dielectric and mechanical characterizations of polyacrylonitrile (PAN)
aligned electrospun nanofiber mats. A two factor three levels full factorial experiment is conducted to
understand the effect of various parameters on dielectric and mechanical responses. These responses
are recorded against randomly oriented and aligned nanofiber mats. Improved properties of electrospun
mats have applications in the field of energy storage and nanocomposites reinforcement.
Dielectric and mechanical characterizations of PAN mats are vital as the aligned electrospun mats
have found to be useful in advanced energy and mechanical reinforcement applications. Therefore, it is
paramount to understand the effects of system parameters to these properties. Design of Experiments
(DOE) includes two factors and three level full factorial experiments with concentrations of PAN
solutions at 8w%, 9w%, and 10w% and speed of the rotating mandrel (collector) at 3v, 4v and 5v input
voltages. The electric field intensity is 1kv/cm. The viscosity of 10w% concentration is 28.4 Poise or
2.84 Pa-s at 20° C. Design of experiments are conducted to understand the nonlinear interactions of
parameters to these responses. The dielectric and mechanical characterizations of 8w%, 9w%, and
10w% with different speeds for original and improved system are discussed in this paper.
5.1 BACKGROUND
Taylor (1964) showed that liquid disintegrates due to instability when subjected to a uniform
electric field [1]. Coulomb’s force is thought to be the main cause for instability. Arshad, Naraghi, and
Chasiotis (2011) showed that maximum ultimate strength for PAN fibers occurred at 1kv/cm [2]. Also,
Mei, Han, Gao, Fu, and Liu (2013) reported that maintaining the electric field intensity at 1 kv/cm
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produced optimal alignment [3]. Popkov et al. (2013) showed that different concentrations from 8-
11w% polymer solutions have PAN nanofibers with extraordinary strength, modulus, and toughness
[4]. Jalili, Morshed, and Ravandi (2006) showed that the best alignment for PAN/DMF occurs for 10-
15% using parallel plates [5]. However, Khan et al. (2015) showed 6 to 12w% concentration with
increasing fiber diameter from 6w% [6]. Uniform PAN nanofibers were obtained at concentration of
8w% and 10w% under the applied voltage of 10-20 kv [7]. According to Gu, Ren, and Vancso (2005),
applied voltage had no significant influence on fiber diameter whereas concentration of solution
impacts the diameter of fibers. The average fiber diameter increased with polymer concentration
according to a quadratic relationship. Alignment maximizes modulus and strength and it makes the
composite anisotropic [8]. Among the various organic and inorganic solvents, dimethyl formamide
(DMF) offered the best properties. With solvent and polymer solute, there are three types of spinning:
wet, dry, and gel spinning. An additional technique, melt spinning, uses no solvent. For that method,
the polymer precursor can be prepared by melting polymer at elevated temperature between 250 ͦ C and
400 ͦ C in the absence of solvent. PAN based nanofibers are widely used for carbon fiber production.
PAN is soluble in polar solvents like DMF, dimethylsulfone (DMS), dimethylsulfoxide (DMSO), and
dimethylacetamide (DMAc) [11]. Among organic solvents DMF and DMSO are known to be good
solvents of PAN [12]. Optimization of PAN precursor fibers results in enhanced performance for the
use in aerospace applications [6]. Edmonsdon, D. et.al. (2012) demonstrated the capability of his
system using PVDF as a model polymer, which has the favorable piezo-, pyro-, and ferro-electric
properties, that aligned PVDF fibers can provide for applications in actuators, transistors, textiles, and
composites [10]. Electrospinning is used to increase specific area, alignment of fibers, and the β-phase
content for polymorphic materials. The β-phase increment is due to shearing force through the needle,
columbic force between the collector and the needle, and mechanical force due to elongation of fibers
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on rotating drum. Depending on the applications, material properties generated or enhanced through
electrospinning are exploited using appropriate polymer selections. In our scope of study, two
applications are important.
1. Specific area for composite reinforcement. PAN is an example for the polymer.
2. β-phase for energy generation (electrode cells). PVDF is an example for polymer. Fiber
alignment can improve piezoelectric effect of voltage generation [10].
5.2 MATERIALS
PAN powder bought from Sigma Aldridge with product number 181315 is mixed with DMF bought
from Sigma Aldridge with product number D158550. The molecular weight of PAN is 150,000 Da.
They are mixed in a conical glass ware having a stopper. 8 w% of solute and solvent are stirred and
heated at 300rpm and 80 °C for 4 hours until a homogeneous yellow colored solution is formed. For
9w% and 10w %, the stirring can change. The syringe and needle are bought from Becton and
Dickinson. The syringe is 5ml and the needle is 22G x1 1/2 (0.7mm x 40mm) in dimensions. Figure 48
shows the stirrer and PAN solution after heating and stirring.
Figure 48. Stirrer and heater (left) and yellowish solution (right)
The solution is pumped through a programmable syringe pump. The speed of the mandrel and the
input voltages are propertional. 5v, 4v and 3 v input voltages are 3100rpm, 2400rpm, and 1700rpm
respectively.
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5.3 SYSTEM IMPROVEMENT
The original system has basic components namely; high voltage power supply, syringe, needle, and
collector. They are enclosed in a closed chamber. The collector is a rotating type horizontal mandrel.
The improved system has an additional negative electric potential and the syringe and needle moves at
the controlled rate along the horizontal direction of the mandrel.The schemmatics of improved system
is shown below in Figure 49. The improved system has the capability of reducing the repulsion of
fibers while they are formed on the madrel. The deposition of fibers is controlled by linear movement
of syringe and needle. With the improved system the fibers formed are aligned and uniform. The
improved system supplies -6kv negative voltage in addition to the 15kv from high power voltage
supply to the needle. The distance from needle tip to mesh tip was 20cm. Thus, the electric field
intensity is 23/20=1.15kv/cm. Volume dispensed was 1ml.
Figure 49. Schemmatics of improved system
The flowchart for the electrospinning improved system is shown below in Figure 50. The computer
interface enables precise movement of linear stage connected to programmable syringe pump and
syringe needle using a bolted base plate. The needle moves accordingly along the horizontal direction
of the mandrel. The syringe pump is mounted with syringe and needle. The solution in the syringe is
supplied at a controlled rate.

83
Figure 50. Flow chart of improved system
The positive electrode and the grounded mandrel bring an electrostatic potential to form fibers on
the mandrel. The negative electrode and mesh provides additional potential that pulls the fibers in the
perpendicular direction of horizontal mandrel reducing the repulsion between the fibers. A pictorial
representation of improved system is shown in Figure 51.
Figure 51. Pictorial representation of improved system
Aligned fibers formed on the mesh is shown below in Figure 52. These fibers are formed on the
negative electrode to show that the improvement system works. The width of the aligned fibers is
1inch.
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Figure 52. Aligned fibers formed in the mesh of improved system (shadow is alligator clip)
The difference in alignment using the improved electrospinning system and original electrospinning
system is shown below. Both the original and improved systems are kept at 20cm needle tip to collector
distance. Therefore, both are kept at electric field intensity of 1.15kv/cm. The scanning electron
microscope (SEM) images of electrospun mats from both the system with angle measurements are
shown in Figure 53.
Figure 53. SEM images and angular measurements of mats from original and improved system
85
The angle measurement is taken through Image J software. The mean value is taken to analyze the
improvement in alignment. The SEM images show that improved system has better alignment. Mean
value of all the fibers of improved system is 19.55 degrees, whereas that of the original system is 40.03
degrees. There is 51% increment in degree of alignment for improved system. Figure 54 shows that the
variability along the mats are reduced through improved system.
Figure 54. Improved system shows consistent mass along the mat
For improved system, coefficient of variation of mass is 8.43% whereas the coefficient of variation
of original system is 4.72%.
5.4 CHARACTERIZATION FOR DIELECTRIC AND TENSILE TESTS
Various tests conducted for DOE are tensile and dielectric. DOE test matrix for original and
improved system is shown below in Table 6. The two factors used are speed (A) and concentration (B).
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Table 7 shows the three levels used for each factor. Number of samples taken for mechanical and
dielectric tests are 54 each.
Speed Concentration Mechanical Dielectric

A B
1 + + 6 6
2 0 + 6 6
3 - + 6 6
4 + 0 6 6
5 0 0 6 6
6 - 0 6 6
7 + - 6 6
8 0 - 6 6
9 - - 6 6
Total 54 54
Table 6. Test matrix for original and improved system
Speed A Concentration B
+ 5v + 10
- 3v - 8
0 4v 0 9
Table 7. Two factors and three levels for each factor
5.4.1 DIELECTRIC TEST
Dielectric test is conducted using 0.5x0.5 inch electrode in Faraday Cage using Broadband
Dielectric Spectrometer (BbDS). It uses the frequency range between 1MHz and 0.1 Hz. The
dielectric constants increases after 1 kHz. Dielectric test is conducted using ASTM D-150. The
test configuration and schematic of dielectric test are shown below in Figure 55.
Figure 55. Test configuration and schematic representation of dielectric constant measurement
87
The interfacial polarization comes in to play below the frequency of 1 kHz as the charges get
accumulated at lower frequencies between the pores and fibers [8]. Therefore, values are taken
only at 1 kHz for DOE study. The relative permittivity of nanofiber mat [17],
𝑙𝑙
𝜀𝜀𝑟𝑟 = 𝐶𝐶 ∗
𝐴𝐴 ∗ 𝜀𝜀𝑜𝑜
where 𝜀𝜀𝑟𝑟 𝑖𝑖𝑖𝑖 the relative dielectric is constant, 𝐶𝐶 is the capacitance, 𝐴𝐴 represents area of
plates, 𝑙𝑙 is the thickness of the film, and 𝜀𝜀𝑜𝑜 is the relative permittivity of the vacuum.
𝜀𝜀𝑟𝑟 is a function of porosity and density [17].

𝜌𝜌𝑀𝑀
P (%) = (1- )*100
𝜌𝜌𝑃𝑃
where P is the porosity, 𝜌𝜌𝑀𝑀 is the membrane density and 𝜌𝜌𝑃𝑃 is the polymer density.
Normalized dielectric constant in kg-1m,
𝜀𝜀𝑟𝑟 𝜀𝜀𝑟𝑟
=
𝜌𝜌∗𝐴𝐴 𝐺𝐺/𝑙𝑙
where G is the mass of the specimen in kg, 𝑙𝑙 is the thickness of the film in m, ρ is the density
of the mat in kgm-3, and A is the surface area of the mat in m2.
5.4.2 TENSILE TEST
Mechanical testing: ASTM D882-12 standard test method is followed. From practical
perspective, porosity and thickness can be hardly accurately measured. Mass is used instead of
thickness [9].
For improved system, the tensile tests are taken from specimen sizes 2inchx1/2 inch length
and width respectively. The test configuration and schematic representation of tensile specimen
are shown below in Figure 56.
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Figure 566. Test configuration and schematic of tensile test specimen
Specific strength of a nanofiber mat [11] 𝜎𝜎𝑠𝑠𝑠𝑠 ,
𝐹𝐹 𝐹𝐹
=
𝜌𝜌 ∗ 𝐴𝐴 𝐺𝐺/𝐿𝐿
where 𝜎𝜎𝑠𝑠𝑠𝑠 is the specific strength of the tensile specimen in N kg-1m, ρ is the fiber density of
fiber in kgm-3, A is the cross sectional area of the specimen in m2, G is the mass of nanofiber mat
in kg, and L is the gauge length of the specimen in m. Also,
𝜎𝜎
𝜎𝜎𝑠𝑠𝑠𝑠 =
𝜌𝜌(1 − 𝑃𝑃)
where σ is the tensile strength of nanofiber mat in Nm-2 and P is the porosity.
5.5 RESULTS AND DISCUSSIONS
The results of dielectric and mechanical tests for DOE are given below. The dielectric and
tensile test responses are discussed here.
5.5.1 DIELECTRIC–MAIN EFFECTS AND INTERACTIONS
Figure 57 shows the main effects, standard deviation, and interaction between the factors for
dielectric data from original system. For factor A, the difference in main effects is 3.76 from A-
to A0 and the coefficients of variations are 27.2% and 28.3% respectively. The difference in
main effects is 8.89 from B- to B+. This is 72.6% of the highest value. For factor B, the
coefficient of variations are 30.6% and 34.2% at B- and B+ respectively.
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Figure 57. Main effects, standard deviation, and interactions for dielectric data of original system
At the highest concentration (10w %), 5v corresponds to the highest value of normalized
dielectric constant. The interaction is more evident at 9w% and 3v contributes to the highest
value of normalized dielectric constant.
Figure 58 shows the main effects, standard deviation, and interactions between the factors for
dielectric data from improved system. For factor A, the difference in main effects is 6.23 from
A- to A+. This is 72.3 % of the highest value. For factor B, the difference in main effects is 5.93
from B- to B0. This is 73% of the highest value and the coefficient of variations are 56% and
26% at B- and B0 respectively.
90
Figure 58. Main effects, standard deviation, and interactions for dielectric data of improved system
At concentration 8w %, 3v corresponds to the highest value of normalized dielectric constant
and the next higher value corresponds to 4v.
5.5.2 TENSILE-MAIN EFFECTS AND INTERACTIONS
tensile test data from original system. For factor A, the difference in main effects is 8018 from
A+ to A0, which is 71.4% of the highest value. The coefficient of variations are 50.3% and
36.5% at A+ and A0 respectively. For factor B, there is a difference of 3772.8 from B- to B+.
This is 85% of the highest value and the coefficient of variations are 50% and 21.4% at B- and
B+ respectively.
91
Figure 59. Main effects, standard deviation, and interactions for tensile data of original system
At the lowest concentration (8w %), 5v corresponds to the highest specific strength. At 9w%,
3v and 5v correspond to the highest specific strength.
tensile test data from improved system. The specific tensile strength data from improved system
shows that there is a difference of 5510 in main effects from A+ to A-. This is 79.7% of the
highest value. For factor B, the difference in main effects is 4069.6 from B+ to B-. This is 84% of
the highest value. For factor B, the coefficient of variations are 23.5% and 24.5% at B+ and B-
respectively.
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Figure 60. Main effects, standard deviation, and interactions for tensile data of improved system
At the lowest concentration (8w %), 5v corresponds to the highest specific strength. At 9w%,
5v corresponds to the highest specific strength, 4v corresponds to higher value, and 3v
corresponds to the least.
Figure 61 shows that specific tensile strengths at 8w% of the improved system have
consistency and therefore mats produced from improved system are useful in applications. As
shown below, the 5v speed nanofiber mats have an average tensile strength higher than that of
the 4v speed nanofiber mats. The average specific strength of 5v and 8w% specimens is 24828.7
N-kg-1 m and the average specific strength of 4v and 8w% is 20629.7 N-kg-1 m. Figure 62 shows
5v and 4v speed mats for 9w% of original system. As shown in Figure 62, the fiber alignment is
better at 5v speed than at 4v speed.

93
Figure 61. Tensile strengths of improved system (left) and original system (right) nanofiber mats
Figure 62. SEM images shows better alignment for mats at 5v speed (left) than that at 4v speed (right)
94
Table 8 shows that alignment is better at higher speed. This shows that mats with
comparatively aligned fibers have better mechanical strength than that with less aligned fibers.
That is, the thinner the fibers, the better the mechanical strength.
Angle in degrees Angle in degrees

for 5v-9w% mat for 4v-9w% mat
1 31.329 1 11.94
2 91.102 2 117.03
3 31.504 3 66.95
4 29.745 4 149.47
5 52.651 5 125.79
6 6.499 6 140.71
7 32.55 7 68.96
8 17.879 8 117.00
9 16.639 9 64.26
10 148.671 10 92.05
Mean 45.86 Mean 95.42
Standard Standard
Deviation 43.08 Deviation 42.54
Table 8. Angle measurements using image J for 4v and 5v at 9w%
The mean angle for 5v is 45.86 degrees whereas for 3v speed is 95.42 degrees. The
alignment is better at higher speed. The fiber direction side of the mat is in coincidence with the
vertical axis of the SEM HR S-4800 as shown in Figure 63. Therefore, the alignment of fibers is
measured along the fiber direction.
Figure 63. The fiber direction side of mat is in coincidence with the vertical axis of SEM device
Figure 64 shows the XRD analysis of mats from original and improved system at 8w%.
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Figure 64. Intensity vs 2ϴ plot of XRD analysis of PAN at 8w% for original and improved system
Crystallinity is determined as the ratio of the peaks to the total area of the curve. Though the
peak in improved system is smaller, the percentage of crystallinity is higher in improved system.
This shows that the mats from the improved system has higher tensile strength. Also, it is
noticeable that planes are distorted in improved system so that only one plane is predominant.
This shows that the improved system distorted other planes by molecular orientation due to
alignment.
5.5.3 LINEAR REGRESSION MODELS [18]
A model that might describe an empirical model relating the tensile strength or dielectric
constant of a polymer to the speed and concentration of electrospinning rotating mandrel and
solution respectively is
96
𝑦𝑦 = 𝛽𝛽0 + 𝛽𝛽1 𝑥𝑥1 + 𝛽𝛽2 𝑥𝑥2 + 𝛽𝛽3 𝑥𝑥12 + 𝛽𝛽4 𝑥𝑥22 + 𝛽𝛽5 𝑥𝑥1 𝑥𝑥2 + ε
where y represents the tensile strength or dielectric constant, 𝑥𝑥1 represents the speed, and 𝑥𝑥2
represents the concentration. If we let 𝑥𝑥3 = 𝑥𝑥12 , 𝑥𝑥4 = 𝑥𝑥22 , and 𝑥𝑥5 = 𝑥𝑥1 𝑥𝑥2 , the above equation
becomes a multiple linear regression model. Applying method of least squares, the sum of the
squares of the errors, 𝛆𝛆𝒊𝒊 is minimized.
The least squares function is

𝑛𝑛
𝐿𝐿 = � 𝛆𝛆𝟐𝟐𝒊𝒊
𝑖𝑖=1
The function L is to be minimized with respect to regression coefficients 𝛽𝛽0 , 𝛽𝛽1 𝛽𝛽2, …..,𝛽𝛽𝑘𝑘 .
The least squares estimators must satisfy
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕
𝜕𝜕𝛽𝛽𝟢𝟢
= 0 and 𝜕𝜕𝛽𝛽 = 0 j= 1,2,3,….,k.
𝑗𝑗
The least squares normal equations above may be written in matrix notation as
y = X𝜷𝜷 +𝛆𝛆
The fitted regression model,

�
𝒚𝒚� = X 𝜷𝜷
� = (𝑿𝑿′ 𝑿𝑿)−𝟏𝟏 𝑿𝑿′ 𝒚𝒚

𝜷𝜷
� is the least squares estimators of the regression coefficients, 𝜷𝜷.

where 𝜷𝜷
And residual
�
𝒆𝒆 = 𝒚𝒚 − 𝒚𝒚
Tensile–Original system
Response surface regression equation of specific tensile strength is
𝒀𝒀𝟏𝟏 = −𝟐𝟐. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎 + 𝟏𝟏. 𝟖𝟖𝟖𝟖𝟖𝟖𝟖𝟖𝟖𝟖 + 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎 + 𝟎𝟎. 𝟒𝟒𝟒𝟒𝟒𝟒𝟒𝟒𝑨𝑨𝟐𝟐 + 𝟎𝟎. 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝑩𝑩𝟐𝟐 − 𝟎𝟎. 𝟓𝟓𝟓𝟓𝟓𝟓𝟓𝟓𝟓𝟓𝟓𝟓
where 𝒀𝒀𝟏𝟏 is the specific tensile strength of original system, A and B are speed and
concentrations. Figure 65 shows the fitted model of specific strength mats from original system.
97
4
Specific tensile strength of original system 10
4 3.4
10
4
3.2
3.5
specific tensile strength, N/(kg/m) 3
3
2.8
2.5 2.6
2 2.4
1.5 2.2
10
9.5 5 2
9 4.5
4
8.5 1.8
3.5
concentration, w% 8 3 speed, v
Figure 65. Fitted model of specific tensile strength from original system
The goodness of fit is shown below in Figure 66. The coefficient of determination is 71.91%.
Figure 66. Goodness of fit for original system from tensile response
Tensile –Improved system
Similarly for improved system as shown in Figure 67,
𝒀𝒀′𝟏𝟏 = −𝟏𝟏. 𝟒𝟒𝟒𝟒𝟒𝟒 + 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎 + 𝟎𝟎. 𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑 + 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝑨𝑨𝟐𝟐 − 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝑩𝑩𝟐𝟐 − 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎
98
4
Specific tensile strength of improved system
10
2.8
4 2.7
10
3
2.6
Specific tensile strength, N/(kg/m) 2.5
2.5
2.4
2.3
2
2.2
2.1
1.5
10 2
9.5 5
1.9
9 4.5
4
8.5 1.8
3.5
Figure 67. Fitted model of specific tensile strength from improved system
The goodness of fit is shown below in Figure 68. Coefficient of determination is 80.96%.
Figure 68. Goodness of fit for improved system from tensile response
Dielectric–Original system
Similarly for dielectric original system,
𝒀𝒀𝟐𝟐 = 𝟓𝟓. 𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑 − 𝟎𝟎. 𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑 − 𝟏𝟏. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎 + 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝑨𝑨𝟐𝟐 + 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝑩𝑩𝟐𝟐 + 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎
Figure 69 shows the fitted model of normalized dielectric constant of mats from original
system.
99
Normalized dielectric constant of original system
34
36 33
34 32
Normalized dielectric constant, 1/(kg/m) 32 31
30
30
28
29
26
28
24
10 27
9.5 5
26
9 4.5
4
8.5 25
3.5
Figure 69. Fitted model of normalized dielectric constant from original system
Figure 70. Goodness of fit for original system from dielectric response
Dielectric –Improved system
Also for dielectric improved system as shown in Figure 71,
𝒀𝒀′𝟐𝟐 = −𝟒𝟒. 𝟕𝟕𝟕𝟕𝟕𝟕 − 𝟎𝟎. 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏 + 𝟏𝟏. 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏 + 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝑨𝑨𝟐𝟐 − 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝑩𝑩𝟐𝟐 − 𝟎𝟎. 𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎𝟎
100
Normalized dielectric constant of improved system
34
32
35
30
Normalized dielectric constant, 1/(kg/m) 30
28
25
26
20
24
15
10 22
9.5 5
9 4.5
20
4
8.5
3.5
Figure 71. Fitted model of normalized dielectric constant of improved system
Figure 72. Goodness of fit for improved system from dielectric response
The Pareto Front for original and improved system is shown in Figure 73 below. It shows
that for the original system, as the tensile strength increases from 21 to 29 kN-kg-1m, the
dielectric constant decreases from 33 to 26 kg-1m. For improved system, as the tensile strength
increases from 23.2 to 24.8 kN-kg-1m, the dielectric constant decreases from 34.4 to 30.8 kg-1m.
101
Figure 73. Dielectric versus tensile for original and improved system
The results show that for improved specific tensile strength and for 5v speed, at 10w% there
is an increment from 20887.8 to 26386.6 N-kg-1m, at 9w% there is an increment of 23753.2 to
30272.4 N-kg-1m, and at 8w% there is a decrement from 39483.4 to 24828.7 N-kg-1m. Similarly,
the specific tensile results for other speeds and concentrations are given in Table 9 (a)-(b).
10w% 9w% 8w% 10w% 9w% 8w%

5v 5498.81 6519.24 -14654.71 5v 26.33% 27.45% -37.12%
4v 446.55 5643.07 2008.86 4v 1.94% 30.67% 10.79%
3v 6598.38 -4560.58 1662.29 3v 33.12% -18.80% 9.73%
Table 9a. Increment in improved tensile Table 9b. Percentage increment in tensile
The decrement at lower concentrations are due to less alignment and randomness of fibers
because of lower electrostatic potential. For normalized dielectric constant and for 5v speed, at
10w% there is a decrement from 33.9 to 19.6 kg-1m, at 9w% there is a decrement from 24.4 to
23.2 kg-1m, and at 8w% there is a decrement from 30.6 to 22.4 kg-1m. Similarly, the dielectric
constants for other speeds and concentrations are given in Table 10 (a)-(b).
10w% 9w% 8w% 10w% 9w% 8w%

5v -14.3 -1.2 -8.2 5v -42.18% -4.92% -26.80%
4v -2.5 1.8 -13.8 4v -8.04% 7.38% -45.70%
3v -5.9 7.2 -8.3 3v -18.21% 23.15% -24.78%
Table 10a. Increment in improved dielectric Table 10b. Percentage increment in dielectric
102
The decrement in dielectric constants are due to the alignment of fibers. The charges are not
getting accumulated or in other words the capacitance of the mat is reduced due to alignment.
The effect of randomness of fibers comes in to play at 9w% and the alignment effect is overtaken
by less porous specimens and results in increased dielectric constant.
5.6 CONCLUSIONS
The improved system definitely shows higher tensile strength and lower dielectric property.
Therefore, the mats produced from the improved system are useful in nanocomposite
reinforcement applications and controlled energy applications. The DOE study shows the
extensive outlook of speed and concentration and their interactions when analyzing the dielectric
and tensile outputs.
REFERENCES
[1] Taylor, G. (1964). Disintegration of Water Drops in an Electric Field. Proceedings of the
Royal Society A: Mathematical, Physical and Engineering Sciences, 280(1382), 383–397.
[4] Papkov, D., Zou, Y., Andalib, M. N., Goponenko, A., Cheng, S. Z. D., & Dzenis, Y. A.
(2013). Simultaneously strong and tough ultrafine continuous nanofibers. ACS Nano, 7(4),
3324–3331.
103
[5] Jalili, R., Morshed, M., & Ravandi, S. A. H. (2006). Fundamental parameters affecting
electrospinning of PAN nanofibers as uniaxially aligned fibers. Journal of Applied
Polymer Science, 101(6), 4350–4357.
[6] Khan, Z., Kafiah, F., Zahid Shafi, H., Nufaiei, F., Ahmed Furquan, S., & Matin, A. (2015).
Morphology, Mechanical Properties and Surface Characteristics of Electrospun
Polyacrylonitrile (PAN) Nanofiber Mats. International Journal of Advanced Engineering
and Nano Technology, 2347–6389.
[7] Gu, S. Y., Gu, S., Ren, J., & Vancso, G. J. (2005). Process Optimization and Emperical
Modelling for Electrospun Polyacrylonitrile (PAN) Nanofiber Precursor of Carbon
nanofibers. European polymer journal, 41(11), 2559-2568.
[8] Bhattacharya, M. (2016). Polymer nanocomposites-A comparison between carbon nanotubes,
graphene, and clay as nanofillers. Materials, 9(4), 1–35.
[9] Chen, J. C., & Harrison, I. R. (2002). Modification of polyacrylonitrile (PAN) carbon fiber
precursor via post-spinning plasticization and stretching in dimethyl formamide (DMF).
Carbon, 40(1), 25–45.
[10] Issa, A., Al-Maadeed, M., Luyt, A., Ponnamma, D., & Hassan, M. (2017). Physico-
Mechanical, Dielectric, and Piezoelectric Properties of PVDF Electrospun Mats
Containing Silver Nanoparticles. C, 3(4), 30.
[11] Wan, L. Y., Wang, H., Gao, W., & Ko, F. (2015). An analysis of the tensile properties of
nanofiber mats. Polymer (United Kingdom), 73, 62–67.
[12] Edmondson, D., Cooper, A., Jana, S., Wood, D., & Zhang, M. (2012). Centrifugal
electrospinning of highly aligned polymer nanofibers over a large area. Journal of
Materials Chemistry, 22(35), 18646–18652.
104
[13] Nataraj, S. K., Yang, K. S., & Aminabhavi, T. M. (2012). Polyacrylonitrile-based
nanofibers - A state-of-the-art review. Progress in Polymer Science (Oxford), 37(3), 487–
513.
55(10), 2570–2577.
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[17] Khan, W. S., Asmatulu, R., Rodriguez, V., & Ceylan, M. (2014). Enhancing thermal and
ionic conductivities of electrospun PAN and PMMA nanofibers by graphene nanoflake
additions for battery-separator applications. International Journal of Energy Research,
38(15), 2044–2051.
[18] Montgomery, D. C. (2001). Design and analysis of experiments (5th ed.). N.Y.: Wiley.
105
CHAPTER 6
CONCLUSIONS AND FUTURE WORKS
This work has provided a detailed review and analysis of methods for alignment of
electrospun fibers and their resulting mechanical and dielectric properties. A detailed review has
been done for all nanofiber polymers with mechanical and dielectric properties. Molecular
orientation concepts and design configuration options for electrospinning apparatuses have been
surveyed in order to analyze the ability of each to improve fiber alignment. An exploratory study
has been conducted for best parameter settings in the current system. Variability study has been
conducted while performing 3 levels 2 factors experimentations for original system. Geometric,
measurement challenges, and normalization effects have been analyzed. Finally, the improved
system has been developed to align fibers and provide more consistency in mechanical properties
but controlled and decreased dielectric properties. Given the improvements in mechanical and
dielectric performances possible with increasing fiber alignment of improved system, the
improved electrospinning apparatus can be tailored for specific applications with energy and
reinforcement.
The results show that the specific tensile strength has the highest percentage increment at 3v
and 10w% and then at 4v and 9w%. The percentage increments are 33.12% and 30.67%
respectively for these combinations. Similarly, for dielectric constant the highest percentage
decrement (decrement is desirable because of better alignment) is at 4v and 8w% and then at 5v
and 10w%. The percentage decrements are 45.7% and 42.18% respectively for these
combinations. Through the improved alignment, the system is capable to tailor the properties for
specific applications. For example, a higher tensile strength and lower dielectric constant should
be chosen for composite reinforcement where the application calls for only strength. For a higher
106
energy applications, a lower tensile strength and higher dielectric constant should be chosen. The
response data for these applications should be chosen from Pareto Front. Then the parameters
should be selected from the response surface regression equations.
Future works should include different materials for specific applications. For example, PVDF
is a polymer for energy application. PVP/Ag nanoparticle is a polymer/filler for medical
application. The parameters can be optimized using DOE while conducting experiments in
improved system. Viscosity of these polymers are related to the concentration. The Pareto Front
results from current research work show the feasible regions of specific tensile strength and
normalized dielectric constant with the current configuration. Therefore, knowing the
concentration of other polymers, we should be able to give insights in to the feasible regions of
other polymers. It is advisable to add input parameters, voltage and distance from needle to
mandrel to analyze the effect on dielectric and tensile responses in future works. Also, the other
parameters’ effects should be analyzed. Negative electrode mesh distance from mandrel,
curvature of the mesh, number of pointed edges in mesh, vertical height of needle tip from the
center of mandrel, and negative potential should be varied to find an overall effect of various
parameters on dielectric and tensile responses.
107
APPENDIX
COMSOL SIMULATION FOR ELECTROSPINNING
108
MATLAB CODE FOR ORIGINAL SYSTEM-TENSILE
clear all;
clc;
format long
X = [1 5 10 25 100 50;
1 4 10 16 100 40;
1 3 10 9 100 30;
1 5 9 25 81 45;
1 4 9 16 81 36;
1 3 9 9 81 27;
1 5 8 25 64 40;
1 4 8 16 64 32;
1 3 8 9 64 24];
y =
[20887.79;23050.25;19924.02;23753.16;18399.13;24257.38;39483.41;18620.84;17076
.21];
xtransx = (transpose(X))*X;
xtransy = (transpose(X))*y;
beetacap = inv(xtransx)*transpose(X)*y
clear all
clc
[X1,X2]=meshgrid(3:0.1:5,8:0.1:10);
Y1=(-
20602.9555556294)+(18403.3166666682.*X1)+(887.716666619510.*X2)+(4206.93333333
313.*X1.^2)+(1037.18333333537.*X2.^2)-(5360.84999999980.*X1.*X2);
surf(X1,X2,Y1);
colorbar();
zlabel('Specific tensile strength,
1/(kg/m)','fontsize',8,'fontweight','bold');
ylabel('concentration, w%','fontsize',8,'fontweight','bold');
xlabel('speed, v','fontsize',8,'fontweight','bold')
title('Specific tensile strength,N/(kg/m) of original
system','fontsize',8,'fontweight','bold');
109

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ELECTROSPINNING APPROACH FOR THE IMPROVEMENT OF MECHANICAL

AND DIELECTRIC PROPERTIES OF ANISOTROPIC NANOFIBER MAT

BY USING A NOVEL FIBER ALIGNMENT TECHNIQUE

Submitted in partial fulfillment of the requirements

ELECTROSPINNING APPROACH FOR THE IMPROVEMENT OF MECHANICAL

AND DIELECTRIC PROPERTIES OF ANISOTROPIC NANOFIBER MAT

BY USING A NOVEL FIBER ALIGNMENT TECHNIQUE

Blesson Isaac, Ph.D.

The University of Texas at Arlington, 2018

Supervising Professor: Robert M. Taylor

electrospinning research has focused on either mechanical property improvement or dielectric

which results in simultaneous improvement of both mechanical and dielectric properties.

The current state-of-the-art in aligned electrospinning techniques are limited. Parallel

mats for lightweight reinforcement of composite materials and structures. A horizontal

degree of aligned fibers than that of the original system.

Khandakar Abu Hasan Mahmud.

LIST OF FIGURES…………………………………………………………………… vii

CHAPTER ONE: INTRODUCTION.………………………………………………... 1

CHAPTER TWO: BACKGROUND………………………………………………….. 5

CHAPTER THREE: METHODOLOGY.…………………………………………….. 49

CHAPTER FOUR: VARIABILITY IN TESTING……. RESPONSES…………….. 63

CHAPTER FIVE: ANISOTROPIC CHARACTERIZATIONS….SYSTEM……… 80

CHAPTER SIX: CONCLUSIONS AND FUTURE WORKS………………………. 106

1. COMSOL SIMULATION FOR ELECTROSPINNING………………… 108

2. MATLAB CODE FOR ORIGINAL SYSTEM-TENSILE………………. 109

1. Schematics of electrospinning apparatus of vertical set up (left) and

2. Electrospinning set up by A. Formhals [5]…………………………………………... 3

3. Applications of electrospun nanofibers………………………………………............ 6

4. Working principle of electrospinning……………………………………………….. 8

5. a. Rotating Drum Collector ………………………………………………………… 12

6. a. Parallel conductor stripes method (Reprinted with permission from [40].

7. a. Tensile strength/modulus vs fiber diameter [33]………………………………..… 16

9. Stress-strain graph of as-spun PAN nanofibers (left) and strength of annealed

10. Strength and modulus of individual carbon nanofiber obtained

11. Stress-strain relationship of individual PAN nanofibers [35]……………………… 20

12. Stress-strain curve of carbon nanofiber mats [60]…………………………………. 20

13. Predicted tensile strength of individual nanofiber vs tensile strength

14. Tensile strength as a function of porosity [60]…………………………………….. 22

15. Dependence of density and porosity of PAN nanofiber membranes

17. Dielectric constant of PAN as a function of

18. Permittivity (ε΄) (left) and EMI-SE (right) of carbon fibers

19. Schematic of electrospinning technique……………………………………………… 51

20. Enclosure, Syringe pump, and High voltage power supply…………………………. 52

21. Mandrel and D.C.Motor ………………………………………………………….…. 53

22. Enclosure in the 3D model [78].………………………………………………….…. 55

23. The final electrospinning set up [78]…………………………………………….….. 55

25. NanoSEM 230, SEM of fibermats using 18G (middle), and

26. a. Sample 1, 2, and 3 at 20μm magnification………………………………..……… 57

27. SEM images at 5μm and respective angle measurements of

28. Stress-strain curve of nanofiber mat [7]……………………………………………. 64

29. PAN/DMF is stirred in heating stir plate (left) and

30. Electrospinning original system [17]…………………………………………….….. 65

31. Electrospun mat is being fabricated at the mandrel……………………………..…... 65

33. Schemmatic of square specimen (left) and

37. a. Force-stroke plot of a nanofiber mat…………………………………………….. 69

38. Specific strength for 5v speed and 10w% of two mats………………………….….. 70

39. Specific strengths for 3v speed and 10w% of two mats……………………….…… 71

40. a. Main effects for tensile tests…………………………………………….……….. 71

42. Dielectric constant with high variability…………………………………………… 73