Synthesis Modification Characterization and Processing of Molde

University of South Florida
Scholar Commons
Graduate Theses and Dissertations Graduate School
March 2018
Synthesis, Modification, Characterization and

Processing of Molded and Electrospun
Thermoplastic Polymer Composites and
Nanocomposites
Tamalia Julien
University of South Florida, tjulien@mail.usf.edu
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Julien, Tamalia, "Synthesis, Modification, Characterization and Processing of Molded and Electrospun Thermoplastic Polymer
Composites and Nanocomposites" (2018). Graduate Theses and Dissertations.
https://scholarcommons.usf.edu/etd/7631
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Synthesis, Modification, Characterization and Processing of Molded and Electrospun
Thermoplastic Polymer Composites and Nanocomposites
by
Tamalia Julien
A dissertation submitted in the partial fulfillment

of the requirements for the degree of
Doctor of Philosophy
Department of Chemistry
College of Arts and Sciences
University of South Florida
Major Professor: Julie P. Harmon, Ph.D.

Sylvia Thomas, Ph.D.
Jianfeng Cai, Ph.D.
Theresa Evans-Nguyen, Ph.D.
Date of Approval:
March 26th, 2018
Keywords: Polycarbonate Polyurethane, Nanoparticles, Nanosilica, Nanosilver, Carbon black,

Soft Thermoplastic Urethane
Copyright © 2018, Tamalia Julien

Dedication
This dissertation is dedicated to my father, Nicholas Anthony Lawrence Julien, who has passed
before this day could be realized but who firmly believed that I was destined for greatness since I
was a child. I love you and miss you every day Dad.
Acknowledgments
Firstly, I would like to give thanks and praise to the Lord for his unwavering love and
guidance (Psalm 27). My mom, who has been my rock, and my number one supporter, I would
like to thank you for your love and guidance and encouraging words, that has lifted me up
through the low times and kept me going. My sister Tanielle, who was always just a facetime
call away who has always filled me with laughter and energy. To Lyndon for your unwavering
support in helping to raise our son while I was completing my studies, thank you for all your
help. To my son Julien who gives me strength and motivation and to the rest of my family and
friends, I am truly thankful and appreciative of your love and support.
To my advisor Dr. Julie Harmon, I genuinely want to thank you for your support, for
being my guide and my mentor, for encouraging me to step out of my comfort zone during my
doctoral study. I would also like to thank my committee members, Dr. Jianfeng Cai, Dr. Theresa
Evans-Nguyen and Dr. Xiao (Sheryl) Li, for your time, insight and willingness to be a part of my
doctoral journey. Dr. Sylvia Thomas, I want to thank you for allowing me to be collaborate with
your lab, you always had kind words and great advice and always made me feel welcomed.
Additionally, I would like to thank the members of Dr. Harmon’s lab both past and
present for welcoming me in the lab and making the lab feel like a home away from home. Mu
Seong Kim, Parul Jain, Kenneth Kull, Alejandro Rivera, Garrett Craft, Imalka Arachchilage and
Taranjot Kaur. To my original USF girls’ posse, Tarah, Josanne-Dee and Kia, thank you ladies
for being my support group, I am so thankful to have you in my life and to have each one of you
play an integral part of my USF journey. To my friends, Santana, Anne-Claire, Taylor, Shahid,
Ryan, Bryan, and to my RFM ladies, Kyoka, Khalifa, Aleya, Rohini, Eboni, and FAMU friends,
Solange and Kalisa, you are all awesome and thank you for all the memories that we have made
together and for making my college experience more enjoyable.

Table of Contents
List of Tables ................................................................................................................................. iv
List of Figures ..................................................................................................................................v
List of Equations ..............................................................................................................................x
Abstract .......................................................................................................................................... xi
Chapter 1: Thermal and Mechanical Analysis of Sustainable Biopolymer Nanocomposites .........1
1.1 Introduction ...................................................................................................................1

1.1.2 Types of Nanocomposites .............................................................................. 3
1.2 Experimental ................................................................................................................ 5
1.2.1 Materials .........................................................................................................5
1.2.2 Purification of Polycarbonate Polyurethane ..................................................5
1.2.3 Polymer- nanoparticle composite synthesis ....................................................6
1.2.4 Preparation of molded nanocomposites ..........................................................6
1.2.5 Surface Free Energy Measurement .................................................................6
1.2.6 Fourier-Transform Infrared Spectroscopy (FTIR) ..........................................8
1.2.7 Differential Scanning Calorimetry (DSC) ......................................................9
1.2.8 Parallel Plate Rheology ...................................................................................9
1.2.9 Tensile Testing ...............................................................................................9
1.3 Results and Discussion ................................................................................................10
1.3.1 Surface Free Energy Measurement ...............................................................10
1.3.2 Fourier-Transform Infrared Spectroscopy (FTIR) ........................................15
1.3.3 Differential Scanning Calorimetry (DSC) ....................................................18
1.3.4 Parallel Plate Rheology .................................................................................22
1.3.5 Tensile Testing ..............................................................................................29
1.4 Conclusions ..................................................................................................................34
1.5 References ....................................................................................................................35
Chapter 2: Fabrication of Polycarbonate Polyurethane Nanofibers and Nanomembranes ............43
2.1 Introduction ..................................................................................................................43

2.2 Experimental ................................................................................................................46
2.2.1 Materials .......................................................................................................46
2.2.2 Electrospinning Process ................................................................................47
2.2.3 Solution Viscosity Measurements.................................................................47
i
2.2.4 Scanning Electron Microscopy (SEM) .........................................................47
2.2.5 Contact Angle Measurement.........................................................................48
2.2.6 Thermogravimetric Analysis (TGA).............................................................48
2.2.8 Wide-angle X-ray Scattering (WAXS) .........................................................49
2.2.9 Small- angle X-Ray (SAXS) .........................................................................50
2.2.10 Tensile Testing ............................................................................................50
2.3.1 Solution Viscosity Measurements ................................................................50
2.3.3 Contact Angle Measurement.........................................................................52
2.3.6 Wide-angle X-ray Scattering (WAXS) .........................................................57
2.3.7 Small- angle X-Ray (SAXS) .........................................................................59
2.3.8 Tensile Testing ..............................................................................................60
2.3.9 PCPU/ nanocomposite membranes ..............................................................62
2.3.9.1 Solution Viscosity Measurements .........................................62
2.3.9.2 Scanning Electron Microscopy (SEM) ..................................63
2.3.9.3 Thermogravimetric Analysis (TGA)......................................64
2.3.9.4 Differential Scanning Calorimetry (DSC) .............................65
2.3.9.5 Wide-angle X-ray Scattering (WAXS) ..................................67
2.3.9.6 Tensile Testing .......................................................................70
2.4 Conclusions ..................................................................................................................73
2.5 References ....................................................................................................................74
Chapter 3: Rheological and Electrical Characterization of Thermoplastic and Thermoset Polymer

Lithium electrolyte. ........................................................................................................................79
3.1 Introduction ..................................................................................................................79

3.2 Experimental ................................................................................................................82
3.2.1 Polymer Lithium Composites .......................................................................82
3.2.2 Electrospinning of Polyimide .......................................................................83
3.2.3 Polyimide /Lithium Nanomembrane Electrolyte ..........................................83
3.2.4 Dynamic Mechanical Analysis (DMA) ........................................................83
3.2.5 Four-Point Probe ...........................................................................................84
3.2.6 Solution Rheology Measurement ..................................................................85
3.2.8 Fourier-Transform Infrared Spectroscopy (FTIR) ........................................86
3.3.1 Dynamic Mechanical Analysis (DMA) ........................................................86
3.3.2 Secondary Relaxation ...................................................................................93
3.3.3 Primary Relaxation .......................................................................................94
3.3.4 Conductivity..................................................................................................99
3.3.5 Polyimide nanomembrane electrolyte.........................................................103
ii
3.3.5.1 Solution Rheology Measurement .................................................103
3.3.5.2 Scanning Electron Microscopy (SEM) ........................................104
3.3.5.3 Thermogravimetric Analysis (TGA)............................................105
3.3.5.4 Fourier-Transform Infrared Spectroscopy (FTIR) .......................106
3.3.5.5 Conductivity of Polyimide fibers .................................................107
3.4 Conclusion .................................................................................................................108
3.5 References ..................................................................................................................109
Appendix A ..................................................................................................................................114
Appendix B ..................................................................................................................................124
About the Author ............................................................................................................... End Page
iii
List of Tables
Table 1.1 Contact angle data: Contact angle measurements and surface tension for PCPU and
PCPU nanocomposites ...................................................................................................................13
Table 1.2 Activation energies of viscous flow for neat PCPU and PCPU nanocomposites ........28
Table 1.3 Tensile Data: Tensile test results for PCPU and PCPU/CB, PCPU/SiO2 & PCPU/Ag
nanocomposites. .............................................................................................................................32
Table 2.1 Glass transition temperature, melt temperature and TGA temperatures of
molded and electrospun PCPU fibers. ...........................................................................................57
Table 2.2 TGA data showing onset temperature, temperature at 99% and 50% mass for PCPU/
0.5% w/w nanoparticle fiber membranes. ....................................................................................65
Table 2.3 DSC data showing glass transition temperature (Tg) and melt temperature (Tm) for
PCPU/nanoparticle fiber membranes. ..........................................................................................66
Table 2.4 Tensile strength data on electrospun PCPU and PCPU nanocomposite fiber
membranes. ..................................................................................................................................73
Table 3.1 DMA Data: DMA Tg and tan δ for the PCPU and
PCPU/LiPF6 composites ...............................................................................................................93
Table 3.2. DMA data: Activation Energy of the β-transition for neat PCPU and PCPU lithium
composites......................................................................................................................................94
Table 3.3 Conductivity data: Conductivities for uncut and cut surfaces of PCPU and
PCPU/LiPF6 nanocomposites. .....................................................................................................103
iv
List of Figures
Figure 1.1 Schematic representation of the dispersion of nanoparticles in the

polymer matrix ................................................................................................................................1
Figure 1.2 Synthetic scheme showing the process of synthesizing PCPU ......................................2
Figure 1.3 Contact Angle data for PCPU/Ag nanocomposites using water and
cyclohexane ...................................................................................................................................12
Figure 1.4 Contact Angle data for PCPU/SiO2 nanocomposites using water and
cyclohexane....................................................................................................................................13
Figure 1.5 Contact Angle data for PCPU/carbon black nanocomposites using water and
cyclohexane....................................................................................................................................13
Figure 1.6 Water contact angle of pristine and ruptures PCPU/ Ag

nanocomposite surfaces ..............................................................................................................15
Figure 1.7 Water contact angle of pristine and ruptures PCPU/ SiO2
Figure 1.8 Water contact angle of pristine and ruptures PCPU/ CB

Figure 1.9 FTIR spectra for cut and uncut PCPU and PCPU/ 1 % w/w
nanocomposite ...............................................................................................................................17
Figure 1.10 FTIR of –NH group showing the change in transmittance from cut and uncut PCPU
nanocomposites ..............................................................................................................................18
Figure 1.11 FTIR of –C=O group showing the change in transmittance from cut and uncut PCPU
nanocomposites ..............................................................................................................................18
Figure 1.12 FTIR of –NH group showing the change in transmittance over a
24-hour period ................................................................................................................................19
Figure 1.13 DSC Data: DSC thermogram of neat PCPU and PCPU/SiO2 nanocomposites ........20
Figure 1.14 DSC thermogram of neat PCPU and PCPU/carbon black nanocomposites...............21
v
Figure1.15. DSC thermogram of neat PCPU and PCPU/ Ag nanocomposites .............................22
Figure 1.16. DSC glass transition (Tg) trends for PCPU and PCPU
nanocomposites .............................................................................................................................22
Figure 1.17 Complex viscosity (ŋ), Storage Modulus (G’) and Loss Modulus (G’’) vs angular
frequency (ω) at 100,120,150&175°C ...........................................................................................25
Figure 1.18 Complex viscosity vs shear rate for neat PCPU and PCPU/ Ag
nanocomposites at 150⁰C .............................................................................................................26
Figure 1.19 Complex viscosity vs shear rate for neat PCPU and PCPU/ SiO2
nanocomposites at 150⁰C...............................................................................................................27
Figure 1.20 Complex viscosity vs shear rate for neat PCPU and PCPU/ CB
nanocomposites at 150⁰C...............................................................................................................28
Figure 1.21 Melt Rheology Data: Arrhenius plot of melt viscosity for neat PCPU ......................28
Figure 1.22 Tensile Data: Stress vs Strain curve neat PCPU and PCPU/Ag nanocomposites ......31
Figure 1.23 Tensile Data: Stress vs Strain curve neat PCPU and
PCPU/SiO2 nanocomposites .........................................................................................................31
Figure 1.24 Tensile Data: Stress Strain Curve neat PCPU and PCPU/ carbon black
nanocomposites ..............................................................................................................................32
Figure 2.1 Electrospinning set up ..................................................................................................44
Figure 2.2. XRD showing detection of ordered structure in a. pre-stressed neat PCPU and b.
stressed undeformed bulk PCPU ...................................................................................................49
Figure 2.3. Solution Viscosities of 8%w/v, 10%w/v, 12%w/v, 14%w/v, 16%w/v & 18%w/v neat
PCPU solution concentrations .......................................................................................................51
Figure 2.4. SEM images a.-c., 14, 16, 18 % w/v fiber membranes; d.-f. Film-like membrane
composites......................................................................................................................................52
Figure 2.5. Illustration of contact angle at θ>90⁰, θ<90⁰ and θ=90⁰ .............................................53
Figure 2.6. Contact Angle Images and graph for the bulk PCPU film and 14,16 &18%w/v fiber
membranes. ....................................................................................................................................54
Figure 2.7. TGA graph showing the degradation of PCPU film and PCPU fiber membranes ......55
vi
Figure 2.8. DSC thermogram for the second heating cycle of neat PCPU, 14% w/v PCPU fiber,
16% w/v PCPU fiber & 18% w/v PCPU fiber ...............................................................................56
Figure 2.9. XRD showing detection of ordered structure for the 14% w/v and 16% w/v
solution cast film ...........................................................................................................................58
Figure 2.10. XRD showing detection of ordered structure of the 14%, 16% and 18% w/v fiber
membranes .....................................................................................................................................59
Figure 2.11. SAXS of bulk PCPU and PCPU fiber membranes ....................................................60
Figure 2.12. a. Stress-Strain behavior, b. Elastic modulus, c. Tensile strength and d. Strain at
break of bulk PCPU and PCPU fiber mats ....................................................................................61
Figure 2.13 Solution Viscosities of 0.5%w/w Ag, 0.5% w/w SiO2 & 0.5% w/w CB PCPU
nanocomposite solutions at 16% w/v concentration ......................................................................62
Figure 2.14. SEM images a.-c., 0.5%w/w Ag, 0.5% w/w SiO2 & 0.5% w/w CB PCPU w/v fiber
membranes; d.-f. Film-like membrane composites........................................................................63
Figure 2.15 TGA graph of neat polyimide (green) and 14(blue), 16% w/w (orange) PI/LiPF6
fiber membranes.............................................................................................................................64
Figure 2.16 DSC thermos gram of neat PCPU (red) vs 0.5%w/w silver (Blue) and 0.5% w/w
carbon black (green) and 0.5% w/w silica (purple) PCPU fiber....................................................66
Figure 2.17 WAXS of 0.25%w/w (blue), 0.5%w/w(green), 0.75%w/w (purple) & 1.0% w/w
(yellow)PCPU/ Ag nanocomposite fiber membranes ....................................................................68
Figure 2.18 WAXS of 0.25%w/w (brown), 0.5%w/w (yellow), 0.75%w/w (green) & 1.0% w/w
(blue) PCPU/ SiO2 nanocomposite fiber membranes ...................................................................69
Figure 2.19 WAXS of 0.25%w/w (green), 0.5%w/w (pink), 0.75%w/w (yellow) & 1.0% w/w
(blue) PCPU/ CB nanocomposite fiber membranes ......................................................................69
Figure 2.20 Stress vs strain curves for CB nanocomposite fiber membranes ...............................70
Figure 2.21 Stress vs strain curves for Ag nanocomposite fiber membranes ................................71
Figure 2.22 Stress vs strain curves for SiO2 nanocomposite fiber membranes.............................72
Figure 3.1 Polyimide GPI 15 .........................................................................................................81
Figure 3.2 Four Point probe set-up ................................................................................................84
Figure 3.3 DMA Data: Temperature sweep at multiple frequencies of neat PCPU ......................88
vii
Figure 3.4 DMA Data: Temperature sweep at multiple frequencies of 12 wt%
PCPU/LiPF6 composite .................................................................................................................89
Figure 3.5 DMA Data: Temperature sweep at multiple frequencies of 14wt%

Figure 3.6 DMA Data: Temperature sweep at multiple frequencies of 16 wt%

Figure 3.7 DMA Data: Loss modulus plot of neat PCPU and PCPU/LiPF6
composites......................................................................................................................................92
Figure 3.8 DMA Data: Tan delta (δ) plot of PCPU and PCPU/ LiPF6 composites ......................92
Figure 3.9 Plots of ln frequency vs 1000/T showing WLF behavior at Tg for a. neat PCPU, b.
12% w/w PCPU/LiPF6, c. 14%w/w PCPU/LiPF6 and
d. 16% w/w PCPU/LiPF6 ..............................................................................................................95
Figure 3.10 a. Isothermal frequency sweeps for neat PCPU and 3.10b.
the master curve ............................................................................................................................96
Figure 3.11 DMA data: WLF plot of neat PCPU .........................................................................97
Figure 3.12 DMA data: WLF plot for 12%w/w LiPF6/PCPU. .....................................................97
Figure 3.13 DMA data: WLF plot for 14%w/w LiPF6/PCPU ......................................................98
Figure 3.14 DMA data: WLF plot for 16%w/w LiPF6/PCPU ......................................................99
Figure 3.15 Conductivity data: Conductivity of PCPU/LiPF6 thin film composites ..................101
Figure 3.16 Conductivity vs time for 12wt% PCPU/LiPF6 composite for cut and
uncut surface .............................................................................................................................101
Figure 3.17 Conductivity vs time for 14wt% PCPU/LiPF6 composite for cut
and uncut surface ...................................................................................................................102
Figure 3.18 Conductivity vs time for 16wt% PCPU/LiPF6 composite for cut and
uncut surface ...........................................................................................................................102
Figure 3.19 Viscosity vs shear rate for pre-spun polyimide solutions .........................................104
Figure 3.20 A-C. SEM images of neat polyimide fibers P347, R127 & XP02691. D-F. Images of
the resultant fiber membranes collected. .....................................................................................105
viii
Figure 3.21 TGA Data: Thermogravimetric curves of 15wt% and 20wt% PI fibers
membranes ...................................................................................................................................106
Figure 3.22 FTIR spectra of neat polyimide (red) and 14%w/w (green), 16% w/w (purple)
PI/LiPF6 fiber membranes ...........................................................................................................107
Figure 3.23 Conductivity vs time graph of neat polyimide (red) and 14%w/w (green), 16% w/w
(purple) PI/LiPF6 fiber membranes .............................................................................................108
ix
List of Equations
Equation 1.1: Young’s Equation ....................................................................................................7
Equation 1.2: Dupre’s Definition of Adhesion Energy ..................................................................7
Equation 1.3: Adhesion Energy as a function of polar and dispersive

Components ..................................................................................................................................7
Equation 1.4: Fowkes Primary Equation ........................................................................................7
Equation 1.5: Condensation of Fowkes Primary Equation ............................................................8
Equation 1.6: Surface Free Energy Calculation .............................................................................8
Equation 1.7: Arrhenius Expression for Melt Viscosity ..............................................................24
Equation 3.1: Resistivity Calculation ...........................................................................................85
Equation 3.2: Arrhenius Equation ................................................................................................93
Equation 3.3: William-Landel-Ferry Equation.............................................................................94
Equation 3.4: Arrhenius Relationship to WLF .............................................................................96
x
Abstract
This dissertation focuses on the versatility and integrity of a novel, ultrasoft
polycarbonate polyurethane (PCPU) by the introduction of nanoparticles and lithium salts.
Additionally, the research takes into account the use of electrospinning as a technique to create
PCPU and polyimide (PI) fibers. These polymers are of interest as they offer a wide range of
properties and uses within the medical and industrial fields.
An industrial batch of an ultrasoft thermoplastic polyurethane (TPU) was synthesized using a
two-step process. The first was to create an end capped pre-polymer from methylene bis (4-
cyclohexylisocyanate), and a polycarbonate polyol made up of 1,6- hexanediol and 3-methyl-1,5-
pentanediol. The second step was done by reacting the pre-polymer with an excess of the
polycarbonate polyol with a chain extender, 1,4-butanediol. Biocompatibility testing such as
USP Class VI, MEM Elution Cytotoxicity and Hemolysis toxicology reported that PCPU
showed no toxicity. This novel type of polyurethane material targets growing markets of
biocompatible polymers and has been used for peristaltic pump tubing, but also can be utilized as
balloon catheters, enteral feeding tubes and medical equipment gaskets and seals. This material
is ideal for replacing materials such as soft plastisols containing diethylhexyl phthalate for use in
biomedical and industrial applications. After extensive characterization of this polymer system
another dimension was added to this research.
The addition of nanoparticles and nanofillers to polyurethane can express enhanced
mechanical, thermal and adhesion properties. The incorporation of nanoparticles such as
xi
nanosilica, nanosilver and carbon black into polyurethane materials showed improved tensile
strength, thermal performance and adhesion properties of the PCPU. Samples were characterized
using contact angle measurements, Fourier transform spectroscopy (FTIR), differential scanning
calorimetry (DSC), parallel plate rheology and tensile testing.
The second chapter entails the fabrication and characterization of PCPU nanofibers and
nanomembranes through a process known as electrospinning. The resulting PCPU
nanomembranes showed a crystalline peak from the WAXS profile which is due to electrospun
and solution strain induced crystallinity. The PCPU nanocomposite nanomembranes displayed
increased thermal stability and an increase in tensile performance at higher weight percent. The
nanomembranes were investigated using contact angle measurements, thermogravimetric
analysis (TGA), DSC, WAXS, SAXS and tensile testing.
The final chapter focuses on investigating the rheological properties of PCPU/lithium
electrolytes as well as transforming an unprocessable polyimide powder into a nanomembrane.
The PCPU/ lithium composite electrolyte showed an increase in the activation energy and
conductivity, while the PI/lithium showed increased conductivity over time. Dynamic
mechanical analysis and four-point probe was used to investigate the samples.
xii
Chapter 1:
Thermal and Mechanical Analysis of Sustainable Biopolymer Nanocomposites
1.1 Introduction
Polymer nanocomposites are created when nanoparticles are introduced to polymer
systems whether post synthetically or in-situ polymerization [1–4]. The formation of
nanocomposites by introducing nanoparticles as a reinforcing filler with the goal of enhancing
and modifying the performance and characteristics of polymers have been used for a long time in
nanotechnology [1,5-7]. Nanocomposite materials cover a wide range material from inorganic
glasses to organic polymers [8] and are important materials for many modern and future
technologies, primarily due to their wide tunability in properties and light weight [9-11].
Figure 1.1 Schematic representation of the dispersion of nanoparticles in the

polymer matrix.
Nanoparticles are extremely diverse and can be placed in many sub categories depending
on their use. They can be metallic such as Iron oxide (Fe3O4), gold (Au), Silver (Ag), carbon
derived such as single walled and multiple walled carbon nanotubes, graphene and carbon black
as well as organic nanoparticles such as dendrimers, micelles and ferritin. They can also be
1
described as zero dimensional such as spheres, one dimensional such as nano wires and nanorods,
2 dimensional such as thin films and plates and three dimensional also known as bulk
nanomaterials. Because of these attributes, nanotechnology attained acceptance by industrial
sectors due to its applications in electronic storage systems [13-14], biotechnology [15], targeted
drug delivery [16,17] and vehicles for gene therapy and drug delivery [14-18].
The polymer utilized in this study can be categorized as a thermoplastic polymer and can
be further categorized as a semi crystalline polymer which is made up of not well-defined hard
crystalline segments with a low percent crystallinity and soft amorphous region. Polycarbonate
polyurethane is an ultrasoft polymer synthesized with methylene bis (4-cyclohexylisocyanate),
1,4- butanediol as a chain extender and a polycarbonate polyol containing 1, 6-hexanediol and 3-
methyl-1, 5-pentanediol [19-21]. It displays remarkable mechanical properties together with the
proficiency to re-heal after rupture without the need for additives or implanted healing agents. A
combination of properties such as high tensile strength, ultimate elongation, toughness, abrasion,
tear resistance, low compression and tensile set, low temperature performance and resistance to
oil have allowed polyurethanes to be used in many demanding applications [22-24].
Figure 1.2 Synthetic scheme showing the process of synthesizing PCPU [20].
2
PCPU is a thermoplastic polyurethane (TPU) which is a class of polymers that possess
excellent properties including toughness, abrasion resistive, excellent hydrolytic stability,
elastomeric and durability, making it versatile for widespread uses [19-21,25–30]. Because of its
biocompatibility, non-toxicity, robustness and functionality TPUs can be used in the biomedical
industry as implantable devices (vascular grafts, pacemaker leads, blood bags, bladders and
artificial heart valves) and medical applications [31–34]. Moreover, it can also be utilized in other
industries such as electronics, automotive, sporting goods and foams [35-38].
In addition, PCPU also has properties similar to segmented polyurethanes (PUs), which
consists of hard and soft segments. It exhibits microphase separation, due to a high degree of
mixing of hard and soft segments because of hydrogen bonding between the hard segment
urethane groups and the soft segment carbonate groups [41-42]. Additionally, the mixing can be
confirmed by the small percent crystallinity with crystal lamellae d spacing of 0.45Å [20].
1.1.2 Types of Nanocomposites
Three different types of zero dimensional spherical nanoparticles are being investigated
herein; fumed nanosilica, nanosilver and carbon black. Each imparting its own unique properties
into the PCPU.
Fumed silica is produced by high-temperature hydrolysis of silicon tetrachloride in a
flame [39-40]. The use of silica with polyurethanes has been widely studied but nanosilica has not
been introduced to our novel polymer. The addition of fumed silicas to polyurethanes in solution
conveys viscosity, thixotropy and pseudoplasticity, also there is an improvement in mechanical
properties [40]. The surfaces of silica nanoparticles possess an unknown number of surface
silanol (Si-OH) groups which may participate in hydrogen bonding with amines within the
urethane unit.
3
Fumed nanosilica is known to be hydrophilic and when added to the polyurethane, the
degree of phase separation escalates because of the interaction between hydrogen-bonded silanol
groups on the nanosilica surface and soft segments of the polyurethane. This leads to an increase
in the segmental incompatibility on the polyurethane with the presence of the hydrophilic
nanosilicas. Studies have shown that these specific polymer materials have the ability to form
hydrogen bonds which result in higher phase separation due to less direct interactions between
phases. Furthermore, silanol and carbonyl group interactions are weaker than those between -NH
and ester carbonyl groups, with the addition of silica the polycarbonate chain mobility increases
and becomes more ordered relative to the neat polyurethane [43-45].
Carbon black (CB) is abundant, low cost and possesses properties such as heat stability and
electrical conductivity [46-50]. It is a versatile nanoparticle which can be incorporated in
electrochemistry and mechanical enhancements and other fields. When a conductive filler such as
carbon black is introduced into a polymer matrix a conductive polymer nanocomposite is formed
with excellent thermal and mechanical properties as well as electrical conductivity which can be
applied to sensors, conductors and anti-static materials. In this study the use of low weight percent
loading of CB nanoparticles was investigated as it is known that high amounts of CB cause poor
mechanical properties and complex loading [50-51]. Also, this particular type of carbon black
used is known to be more effective at low loadings to impart maximum enhancement of the
material’s properties.
Amongst the nanoparticles, silver (Ag) nanoparticles are of high interest as silver-based
products are continuously being sought after in the biomedical field. Silver nanoparticles allow
for enhanced thermal, mechanical and antimicrobial properties that are necessary for biomaterials
such as bandages, catheters, surgical instruments and topical ointments [52-54]. However, there
4
are adverse effects from prolonged exposure of Ag nanoparticles on human health. One way to
combat this is to entrench the silver particles into the polymer matrix. PCPU is biocompatible;
therefore, it becomes an impeccable candidate for the Ag nanoparticles which can then be used
for prosthesis as well as drug delivery devices [52, 55-56].
Herein, a series of PCPU nanosilica, nanosilver and nanoscale carbon black composites
were produced via ultrasonication. Our novel PCPU was designed to be highly flexible while
keeping its mechanical properties. This introduction of the nanoparticles will allow for increased
mobility which is expected to lead to greater thermal and mechanical performance. Also, the
literature is quite rare on rheological studies and viscoelastic behavior of PCPU nanocomposites,
therefore, the rheological properties of these PCPU nanocomposites were studied to investigate its
melt processability.
1.2 Experimental
1.2.1 Materials
Nanosilver (NTX-300ET) was purchased from Nanux Inc (Yungnam,Korea) with an
average particle size of 30-50nm. Carbon black nanoparticles (VXC72) were mass produced by
Cabot Corporation (Victoria, Australia) with a particle size of 10-30 nm. Fumed silica (nanosilica
HDK N20) was mass-produced by Wacker-Chemical Corporation (Michighan, United States).
The majority particle size in all nanosilicas used was 7 nm. All particles were used as received
without further purification. The certified ACS grade reagent tetrahydrofuran (THF) 99.9% was
purchased from Sigma-Aldrich and used without further purification.
1.2.2 Purification of polycarbonate polyurethane
100 g of PCPU chips were mixed with 1000 ml of THF in a 3L reactor for 3 hours until
the polymer was fully dissolved. Deionized water was then added to the reactor in a dropwise
5
fashion to guarantee proper crashing-out of the polymer. The water was then removed, and the
process was repeated. The purified polymer was then dried under vacuum at 60⁰C.
1.2.3 Polymer-nanoparticle composite synthesis
Polycarbonate polyurethane/nanoparticle composites were prepared by dispersing the
nanoparticles using a sonicator. 10g of the purified PCPU was dissolved in 100 ml THF (ACS
reagent, 99.9% sigma Aldrich) and then the desired amount of nanoparticles (0.1-1.0 w.t.%) were
introduced to the solution and then mixed by ultrasonication (Fisher Scientific Sonic
Dismembrator 550) at a mixing rate of 10 minutes with 3 second rest intervals for two hours to
ensure homogeneity of composites. The composites were then crashed out using deionized water
and the resulting materials were dried overnight under vacuum.
1.2.4 Preparation of molded nanocomposites
Before samples were characterized, they were compression molded using a Carver laboratory
press (model C) at 250⁰C and 3 tonnes of pressure.
1.2.5 Surface Energy Measurements
Surface energy or surface tension of solid samples gives an insight into the samples’ wettability.
This behavior is of great importance as it plays a significant role in many industrial processes
such as lubrication, painting and printing [57]. The surface energy of a solid cannot be directly
measured therefore the use of liquid on a solid surface via contact angles is employed. There are
many different theories employed in surface energy measurements such as Zisman (one
component model), Owens/Wendt (two component), Fowkes (two component) and van Oss (three
component) theories.
This study focuses on the two-component model specifically Fowkes theory.
Owens/Wendt theory and Fowkes theory are similar in that they both specify that the solid surface
6
has two components; a dispersive force and a polar (non-dispersive) force. The difference
between the two is the method with which the theories are utilized.
Fowkes theory is centered on three essential equations describing the interactions between
solid surfaces and liquids [58]. As with all theories, they begin with Young's Equation which
describes the contact angle of a liquid drop on an ideal solid surface;
𝛾𝑠𝑣 = 𝛾𝑠𝑙 + 𝛾𝑙𝑣 cos 𝜃 (1.1)
where: ɣlv = liquid-vapor interfacial tensions, ɣsv = solid-vapor interfacial tensions, ɣsl = solid-
liquid interfacial tension, and θ = the contact angle between the liquid and the solid.
Fowkes theory also considers Dupre's Definition of Adhesion Energy
𝐼𝑆𝐿 = 𝛾𝑠𝑣 + 𝛾𝑙𝑣 − 𝛾𝑠𝑙 (1.2)
where: ISL = Adhesion energy per unit area between a liquid and a solid surface.
Fowkes stipulated that the adhesive energy between a solid and a liquid can be expanded into
interactions between the dispersive components of the solid and liquid as well as the interactions
between the polar components of the two components.
2 2 2
+ √𝛾𝑙𝑣𝑝 × √𝛾𝑠𝑣
𝑑 2
𝑑 𝑝
𝐼𝑆𝐿 = 2[ √𝛾𝑙𝑣 × √𝛾𝑠𝑣 ] (1.3)
d p
where: ɣlv = dispersive component of the surface tension of the test liquid, ɣlv = polar component
d
of the surface tension of the test liquid, ɣsv = dispersive component of the surface energy of the
p
solid surface, and ɣsv = the solid surface polar component.
The combination of the three equations produces the primary equation of the Fowkes'
surface energy theory:
2 2 𝛾𝑆𝐿 (cos 𝜃+1)

+ √𝛾𝑙𝑣𝑝 × 𝛾𝑠𝑣
𝑑 𝑑 𝑝
√𝛾𝑙𝑣 × 𝛾𝑠𝑣 = (1.4)
2
7
To use the Fowkes' theory on a solid sample to determine solid surface energy, the first liquid
p d
must only have a dispersive component for example a liquid must have ɣL = 0, so that ɣL = ɣSL.
Because of this, the primary equation condenses to:
𝑑 𝛾𝑙𝑣 (cos 𝜃+1)2

𝛾𝑠𝑣 = (1.5)
4
d
and ɣsv can be calculated directly from the contact angle measured from the solid surface.
The next step is to test the solid for contact angle with another liquid which has both a dispersive
component and a polar component. The contact angle produced from the liquid on the solid and
d p
the calculated ɣsv from the previous step, ɣsv can be calculated as the only unknown in the
equation 1.4. The overall surface energy of the solid, ɣsv, is then calculated as
p d
ɣsv = ɣsv + ɣsv (1.6)
Uniform drops of deionized water and cyclohexane were displaced on the polymer
nanocomposite surface and the contact angles were measure using a KSV CAM-101 video based
optical contact angle measuring device equipped with a hamilton syringe in an environmentally
controlled chamber (KSV-1TCU). All measurements were performed in air, at room temperature.
The samples were tested and then the surface was cut away and the cut surface was retested with
the deionized water.
1.2.6 Fourier Transform Infrared Spectroscopy (FTIR)
Perkin Elmer spectrum two furnished with and Attenuated Total Reflection (ATR)
accessory was utilized for this study. A scanning range of 400-4000cm-1 set at a resolution of
4cm-1 and 16 repetitions were done on the nanocomposites. The composites were scanned, then
cut along its length and then re-scanned for 24 hours to detect any shifts of functional groups.
8
1.2.7 Differential Scanning Calorimetry (DSC)
DSC analysis was performed using TA instruments 2920 Differential Analysis
Calorimeter to obtain glass transition temperature (Tg) and melt temperature (Tm) of the polymer
and polymer nanocomposites. The heat cool heat method was utilized a starting temperature of -
70⁰C and then heated to 200⁰C at a ramp rate of 10⁰C/ minute to ensure all samples has the sample
thermal history. The sample was the cooled down to -70⁰C, using a refrigerated accessory, with
the similar ramp rate and then reheated to 200⁰C. The Tg values were taken from the second
heating run.
1.2.8 Parallel Plate Rheology
Rheological properties of the polymer nanocomposites were analyzed by TA instruments
AR 2000 equipped with parallel plates with a 25mm diameter. The plate gap was kept at 3mm
during experimentation. The measurements were done at different temperatures from 100⁰C to
190⁰C
The strain sweeps were performed from 0.01% to 100% at a constant frequency of
0.33HZ. This was done to detect the linear viscoelastic region at different temperatures.
Frequency sweeps were carried at strains within the viscoelastic region of 1% and 5%
respectively. The frequency sweeps were done from 0.05 to 100 Hz. Specimen discs were of
average of 25mm and 3mm thickness.
A temperature ramp was done at different strains of 1% and 5% at a constant frequency of 1Hz to
detect the viscoelastic behavior at high temperatures.
1.2.9 Tensile Testing
9
Tensile strength characterization was done using Shimadzu ASJ tensile tester to measure
displacement of samples. All tensile testing was done at a rate of 100mm/min at room
temperature according to ASTM D638 IV. Dog bone cut samples were of various thickness 0.8
to1mm. Five measurements for each sample were done and the average tensile strength was
recorded.
1.3 Results and Discussion
1.3.1 Surface Free Energy Measurement
The surface free energy was determined from contact angle measurements using deionized
water and cyclohexane, and is presented in Figures 1.3, 1.4 & 1.5. The total surface energy of a
polymer’s surface is equal to the sum of the dispersion component and the polar component. The
polar water creates a noticeable semicircular shape while the non-polar cyclohexane spreads
across the surface of the composite. Fowkes theory which is explained in the experimental section
was then used to calculate the dispersive component of the surfaces as well as the polar
component. Table 1.1 gives the contact angles of the PCPU nanocomposites together with the
resulting surface energies. The contact angles for the nanocomposites when the water was used
had varying trends. For the silver nanocomposites there was a decrease in the contact angle from
102⁰ for the neat PCPU to 96⁰, 85⁰, 100⁰ and 88⁰ for the 0.1%, 0.25%, 0.375% as well as the 0.5%
w/w. Then the 0.75% and 1.0% w/w increased to 107⁰. The silica nanocomposites showed a slight
decrease in contact angle to 96⁰ and the carbon black composite as seen displayed a slight
decrease in the angle from the neat PCPU. However, when the cyclohexane was used the contact
angle for the neat PCPU was 12.8⁰. The contact angle increased slightly for the Ag
nanocomposites to as high as 19⁰; it doubled for the silica composites with 24⁰ and a slight
increase to 20⁰ for the carbon black nanocomposites. There was a trend demonstrated on the
10
calculation of the dispersive component for the nanocomposites. The silver nanocomposites
trended downward with a constant decrease in the dispersive energy from 24.4 mJ/m to 24.0
mJ/m as well as the silica component from 24.4 to 23.1 mJ/m. The carbon black nanocomposites
however, trended upwards showing that the increase in the % w/w of carbon black nanoparticles
added, increased the dispersive component of the polymer matrix.
When the PCPU nanocomposite surface was cut away the use of the cyclohexane as a
testing parameter was futile. Figures 1.6, 1.7 & 1.8, show the contact angle of the pristine surface
against the ruptured surface of the nanocomposites using deionized water only. When the surface
is cut away there is a decrease in the contact angle below that of 90⁰ compared to the pristine
surface >100⁰. Moreover, the general trend downward for the silver nanoparticle composite is
noted with an increase in the Ag content resulting in increased hydrophilicity. This is evidence of
available hydrogen bonding sites, which will be explained further in the FTIR section.
11
Figure 1.3 Contact Angle data for PCPU/Ag nanocomposites using water and
cyclohexane.
12
Figure 1.4 Contact angle data for PCPU/SiO2 nanocomposites using water and
cyclohexane.
Figure 1.5 Contact angle data for PCPU/CB nanocomposites using water and
cyclohexane.
13
Table 1.1 Contact angle data: Contact angle measurements and surface tension for PCPU and
PCPU nanocomposites
SAMPLE AVG CA (H20) AVG CA ƔSV ƔSVD ƔSV

(C6H6) P
NEAT PCPU 102 ± 2 12.5 ± 1.2 25.3 24.7 0.6

0.1WT% AG 96 ± 5 18.9 ± 5.5 26.2 24.5 1.7
0.25WT%AG 85 ± 3 11.6 ± 2.7 30.0 24.5 5.5
0.375WT% AG 100 ± 4 16.9 ± 0.8 25.3 24.4 0.9
0.5WT% AG 88 ± 5 17.2 ± 2.7 28.4 24.2 4.2
0.75WT% AG 107 ± 5 17.5 ± 3.4 24.3 24.2 0.1
1.0WT% AG 107 ± 2 18.5 ± 5 24.2 24.02 0.2
0.1WT% SIO2 102 ± 3 12.6 ± 2.3 25.0 24.4 0.6
0.25WT% SIO2 100 ± 2 18.2 ± 1.8 25.5 24.4 1.1
0.375WT% SIO2 97 ± 3 17.4 ± 2.5 25.9 24.2 1.7
0.5WT% SIO2 96 ± 8 17.5 ± 2.1 26.0 24.2 1.8
0.75WT% SIO2 103 ± 1 19.6 ± 3.5 24.5 23.9 0.6
1.0WT% SIO2 96 ± 2 24.3 ± 0.7 25.1 23.1 2.0
0.1 WT % CB 94 ± 4 19.9 ± 4.8 25.6 23.2 2.4
0.25WT% CB 99 ± 5 20.0 ± 3.3 25.0 23.8 1.2
0.375WT% CB 104 ± 4 17.9 ± 3.9 24.5 24.1 0.4
0.5WT% CB 102 ± 2 20.3 ± 3.9 24.6 23.9 0.7
0.75WT% CB 92 ± 8 17.2 ± 5.5 27.1 24.2 2.9
1WT% CB 102 ± 3 18.4 ± 2.4 24.6 24.1 0.5
14
Figure 1.6 Water contact angle of pristine and ruptures PCPU/ Ag
nanocomposite surfaces.
Figure 1.7 Water contact angle of pristine and ruptures PCPU/ SiO2 nanocomposite
surfaces.
15
Figure 1.8 water contact angle of pristine and ruptures PCPU/ CB nanocomposite
surfaces.
1.3.2 Fourier-Transform Infrared Spectroscopy (FTIR)
Figure 1.9 shows the IR spectra for cut and uncut surfaces of the PCPU and its
nanocomposites. The expected absorbance for associated N-H groups is 3318-3338 cm-1 and
associated C=O 1718 cm-1 and unassociated C=O is 1740 cm-1. Yokoyama et al. 1968 [59];
Seymour et al. 1970 [60]; Boerio and Wirasate 2006 [61]; Na, Lv et al. 2009] [62] all have done
studies to demonstrate associated and unassociated hydrogen bonding using FTIR. The
characteristic peaks for nanoparticles; SiO2 (1626, 1103, 809 cm-1), CB (1630, 1114, 1118 cm-1)
and silver nanoparticles (3420 and 1638 cm-1) did not show up on any of the FTIR spectra. This
can be as a result of the low concentrations together with the nanometer size of the particles used.
Figure 1.10 and 1.11 show a magnified view of the –NH region and –C=O of the spectra.
There is a shift in the wave number of the associated -NH region from 3305 cm-1 to 3307 cm-1 on
16
the addition of the nanoparticles. This suggests interactions between the particles and the NH
groups within the polymer matrix. When the surface is cut away there is a decrease in the %
transmittance for the H-bonded region at 3305cm-1 which tells us that when the surface is cut
away hydrogen bonds become available and the H-bonded regions are reduced. This correlates
with the decrease in the contact angle when the surface is cut away. Available H-bonds allow for
lower contact angle which makes the surface hydrophilic. Figure1.12 shows what happens to
these bonds if they are left over time. After 1 hour you see the transmittance decrease and after 24
hours the scan gets closer to the original scan. This is evidence of the hydrogen bonds folding
onto themselves when left alone [21].
100
90
80 Free N-H
stretch at H-bonded
-1 N-H
70 3380cm
stretch at
-1
3305cm
%Transmittance
60
Neat PCPU uncut
50 neat PCPU cut
1wt% SiO2/PCPU
1wt% SiO2/PCPU cut
40
H- 1wt% Ag/PCPU cut
1wt% Ag/PCPU uncut
bonded
30 Free C=O 1wt% CB/PCPU uncut
C=O at 1wt% cb/pcpu cut
absorptions 1718 cm
20 -1 -1
at 1740cm
10
4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wavenumber cm-1
Figure 1.9 FTIR spectra for cut and uncut PCPU and PCPU/ 1%w/w nanocomposites.
17
100
98
%Transmittance
96
Neat PCPU uncut
Neat PCPU cut
94 1wt% nanocilica uncut
1wt% nanosilica cut
1wt% silver cut
92 1wt% silver uncut
1wt% cb uncut
1wt% cb cut
90
3500 3450 3400 3350 3300 3250 3200
Wavenumber cm-1
Figure 1.10 FTIR of –NH group showing the change in transmittance from cut and uncut PCPU
nanocomposites.
100
90
80
%Transmittance
70
60
50
40
30
1800 1700 Wavenumber cm-1 1600
Figure 1.11 FTIR of –C=O group showing the change in transmittance from cut and uncut PCPU
nanocomposites.
18
100
99
98
% Transmittance
97
.25 cb cut
96
%T0.25cb uncut
95 %T-0.25cb 24hr cut
%T-0.25 1hr
94
3500 3450 3400 3350 3300 3250 3200
Wavenumber cm-1
Figure 1.12 FTIR of –NH group showing the change in transmittance over a 24-hour period.
The glass transition, Tg and melting temperatures were recorded as seen in Figure 1.13,
1.14 and 1.15. Stevens et al demonstrated that the addition of nanoparticles would induce
plasticization of the polymer composites leading to lower Tg. The PCPU/Ag composites’ Tg
ranged from -23.5⁰C to -25.4⁰C as the % w/w of silver nanoparticles were added. The PCPU silica
composites’ Tg ranged from -24.1⁰ C to -22⁰C and the PCPU/CB composites were from -24⁰C to -
22.5⁰C.
The trends of the nanoparticles are shown in figure 1.16. The silica nanocomposites and
the carbon black nanocomposites responded similarly. There was an initial decrease in the glass
transition temperature at the lower %w/w which is due to the increase in free volume space of the
polymer chains, then at 0.5 %w/w nanoparticles, the glass transition temperature increased. This
can be due to the reduction in the motion of the polymer backbone from the additional
nanoparticles which would reduce the plasticization effect and therefore allowed a rise in the Tg.
19
Because the silica and carbon black have the ability to aggregate and agglomerate this may cause
a reduction in the free volume of the polymer backbone which leads to the increase in the glass
transition temperature. Contrastingly, nanosilver particles do not aggregate so the increase in the
amount of nanosilver added increases the ability to plasticize and which leads to a continuous
decrease in the glass transition temperature.
-22.6⁰C
-23.4⁰C
-23.8⁰C
-24.1⁰C
-23.5⁰C
-23.1⁰C
-22⁰C
Figure 1.13 DSC Data: DSC thermogram of neat PCPU and PCPU/SiO2 nanocomposites.
20
-22.5⁰C
-23.2⁰C
-23.5⁰C
-24⁰C
-22.8⁰C
-22.6⁰C
-22.6⁰C
Figure 1.14. DSC thermogram of neat PCPU and PCPU/carbon black nanocomposites.
21
-22.6⁰C
-23.5⁰C
-23.6⁰C
-23.9⁰C
-24.9⁰C
-25.3⁰C
-25.4⁰C
Figure1.15. DSC thermogram of neat PCPU and PCPU/ Ag nanocomposites.
-21.5 CB SiO2 Ag
Glass Transition temperature Tg/ ⁰C
-22
-22.5
-23
-23.5
-24
-24.5
-25
-25.5
-26
0 0.25 0.5 0.75 1
Wt% nanoparticle added
Figure 1.16. DSC glass transition (Tg) trends for PCPU and PCPU nanocomposites.
22
1.3.4 Parallel Plate Rheology
Parallel plate rheology tells about the deformation of flow for viscoelastic polymer
composites at elevated temperatures above their Tg. This is essential for the processability for the
polymers. Figure 1.17 shows the melt rheology profile of the neat PCPU at different temperatures.
The PCPU nanocomposites all showed that the viscosities of the polymer composites are
temperature dependent as well as frequency dependent and that our material is in fact viscoelastic.
This can be seen when the frequencies are lower the viscosity is proportional to the change in
frequency but as the frequencies increase the viscosity is directly proportional to the frequency.
Additionally, an increase in the temperature allowed for a decrease in the viscosity. Hence, the
polymer demonstrates pseudo plastic behavior by the decrease in viscosity with increase in
frequency and shear thinning occurs. Erdmann et al [63] also experienced lower viscosities and
modulus as the temperature is increased which is typical thermoplastic behavior. The intersection
point between the G’ and G” shifts to a higher frequency with increasing temperature because of
mobility and flexibility of the PCPU chains so that disentanglement is easier [63].
Figures 1.18-1.20 show the complex viscosities vs shear rate for the neat PCPU vs
PCPU/silver, silica and CB nanocomposites. The silver nanocomposites’ complex viscosity
decreased with increasing silver nanoparticle concentration, but this is expected as stated by
Ghosh and Maiti that at high shear rates, the viscous stresses predominate over the silver particle-
particle interactions, leading to particle alignment and, therefore, lower melt viscosity [64-66].
The silica PCPU nanocomposites showed an initial decrease in the viscosity but the 1%w/w
PCPU/silica showed a higher complex viscosity at low shear rates, but it decreased as the shear
rate increased. What is also noted is that all the composites joined at the higher shear rate at a
viscosity of 630 Pa which is not evident in the other nanocomposites. The carbon black
23
nanocomposites showed very little variation in complex viscosity compared to the neat PCPU but
as the % w/w increased the viscosity decreased.
The log of complex viscosities (n), of the nanocomposites was plot against the inverse
temperature; the result was a straight line which represents Arrhenius behavior. The Arrhenius
expression for viscosity

∆𝐸𝑎
𝑛 = 𝐴 𝑒 𝑅𝑇 (1.7)
Where n is the complex melt viscosity, A is the Arrhenius constant, ΔEa is the activation
energy of viscous flow and R is the universal gas constant. The slope of the line generated from
the plot can be used to calculate the activation energy of viscous flow. The ΔEa of viscous flow
for neat PCPU came to be 70.1kJ/mol. With the addition of the Ag nanoparticles the ΔEa
decreased but as the %w/w increased the Activation energy remained unchanged giving the aspect
that the activation energy is independent of the silver content. The silica’s activation energy was
close to that of the neat polymer which suggests homogeneity of the composite. Contrastingly the
ΔEa for the carbon black PCPU composites almost doubled at higher %w/w of carbon black
nanoparticles. This suggests that the carbon black nanocomposites are less temperature sensitive
as the nanoparticles have the packing ability, so it provides less change in free volume space as
the temperature changes as experienced by Ghosh and Plochcki [66-67].
24
Figure 1.17 Complex viscosity (ŋ), Storage Modulus (G’) and Loss Modulus (G’’) vs angular
frequency (ω) at 100,120,150&175°C.
25
Overlay
Figure 1.18 Complex viscosity vs shear rate for neat PCPU and PCPU/ Ag
nanocomposites at 150⁰C.
26
Overlay 2
Figure 1.19 Complex viscosity vs shear rate for neat PCPU and PCPU/ SiO2
27
Overlay
Figure 1.20 Complex viscosity vs shear rate for neat PCPU and PCPU/ CB
13
y = 8435.9x - 9.9026
R² = 0.9999
12
Ea 16.7kCal/mol
11
ln (ŋ)
10
8
0.0022 0.0023 0.0024 0.0025 0.0026 0.0027 0.0028
1/T (K-1)
Figure 1.21 Melt Rheology Data: Arrhenius plot of melt viscosity for neat PCPU.
.
28
Table 1.2 Activation energies of viscous flow for neat PCPU and PCPU nanocomposites.
SAMPLE EA OF VISCOUS FLOW EA OF VISCOUS

(KJ/MOL) FLOW(KCAL/MOL)
NEAT PCPU 70.1 16.7
0.1WT% AG 62.5 14.9
0.25WT%AG 62.5 14.9
0.375WT% AG 63.7 15.2
0.5WT% AG 64.4 15.4
0.75WT% AG 62.2 14.9
1.0WT% AG 62.3 14.9
0.1WT% SIO2 69.8 16.7
0.25WT% SIO2 72.6 17.3
0.375WT% SIO2 70.2 16.8
0.5WT% SIO2 69.4 16.6
0.75WT% SIO2 55.8 13.3
1.0WT% SIO2 60.9 14.6
0.1 WT % CB 69.8 16.7
0.25WT% CB 67 16
0.375WT% CB 63.8 16.4
0.5WT% CB 124.5 29.7
0.75WT% CB 110.8 26.4
1WT% CB 116.9 27.9
29
PCPU can be described as a viscoelastic material, which means they are positioned
between viscous liquids and elastic solids as mentioned above. Melt rheology gives us an idea of
the mechanical behavior of the polymer at elevated temperatures and frequencies. There are two
laws associated with the elasticity and viscosity of materials. Hooke’s Law demonstrates that for
an ideal linear elastic solid, the stress is directly proportional to the strain; and Newton’s law for
an ideal viscous liquid which states that the stress should be proportional to the rate of change of
the strain [66]. Tensile testing allows us to take into consideration the mechanical behavior at
room temperature. An ideal linear elastic solid obeys Hooke’s law, i.e. stress is proportional to
strain. An ideal viscous liquid obeys Newton’s law, i.e. stress is proportional to the rate of change
of strain.
Tensile testing was conducted to evaluate mechanical properties of the resulting composites for
the reasons discussed in the introduction. Stress-strain curves are given for the averages of 5
specimens of each sample: Neat vs Silica nanocomposites (figure 1.23), neat vs carbon black
composites (figure 1.24), neat vs silver nanocomposites (figure 1.21). The results of the tensile
test including averages and statistical data are summarized in table 2.3. The tensile curve of the
neat PCPU is similar to that of other polyurethanes [67], consisting of three distinct regions of
deformation. The first region is known as the elastic region where Young’s modulus is calculated
and the resistance to deformation of the polymer is noted. Just after the curve or yield point, there
is a plateau region associated with the plastic region where the amorphous soft segments of the
polymer deform, and the last region is known as the strain hardening region associated with strain
induced crystallinity and hard segment disassociation as demonstrated by the steep slope right
before fracture [68].
30
18
Stress vs Strain of Neat PCPU vs PCPU/Ag
16
14
12
Stress (Mpa)
10 neat pcpu
0.1wt % silver
8
0.25wt%silver
6
0.375wt silver
4 0.5 wt % silver
2 0.75 wt% silver

1.0wt% silver
0
0 300 600 900 1200
Strain %
Figure 1.22 Tensile Data: Stress vs Strain curve neat PCPU and PCPU/Ag nanocomposites.
25
Stress vs Strain Neat PCPU vs PCPU/SiO2
20
neat pcpu
0.1wt% SiO2
15
Stress Mpa
0.25wt% SiO2
0.5wt% SiO2
10
0.75wt%SiO2
0.375wt% SiO2
5 1.0wt% SiO2
0
0 300 600 900 1200
Strain %
Figure 1.23 Tensile Data: Stress vs Strain curve neat PCPU and PCPU/SiO2 nanocomposites.
31
14
Stress vs Strain Neat PCPU vs PCPU/CB
12
10
Stress Mpa
neat pcpu
6
0.1wt% cb
0.25wt% cb
4 0.375wt% cb
0.5wt% cb
2 0.75wt%cb
1.0wt%cb
0
0 300 Strain % 600 900 1200
Figure 1.24 Tensile Data: Stress Strain Curve neat PCPU and PCPU/ carbon black nanocomposites.
Table 1.3 Tensile Data: Tensile test results for PCPU and PCPU/CB, PCPU/SiO2 & PCPU/Ag
nanocomposites.
Youngs
Modulus Ultimate Tensile strength
Sample Mpa Mpa Elongation%
neat pcpu 2.3 ± 0.1 10.2 ± 0.2 1071 ± 18
0.1 wt % cb 2.9 ± 0.03 12.1 ± 0.6 777 ± 11
0.25wt% cb 2.8 ± 0.02 13.1 ± 0.2 783 ± 18
0.375wt% cb 3.3 ± 0.02 10.2 ± 0.4 720 ± 14
0.5wt% cb 3.3 ± 0.07 10.2 ± 0.8 708 ± 20
0.75wt% cb 2.9 ± 0.08 11.2 ± 0.5 737 ± 12
1wt% cb 3.2 ± 0.03 12.4 ± 0.5 708 ± 15
0.1wt% SiO2 3.1 ± 0.1 13.3 ± 0.8 864 ± 13
0.25wt% SiO2 5.4 ± 0.1 19.4 ± 0.2 661 ± 23
0.375wt% SiO2 4.4 ± 0.1 13.6 ± 0.3 873 ± 15
0.5wt% SiO2 5.3 ± 0.02 11.4 ± 0.1 847 ± 12
0.75wt% SiO2 2.2 ± 0.1 12.2 ± 0.5 922 ± 25
32
Table 1.3 continued
1.0wt% SiO2 2.1 ± 0.2 12.4 ± 0.1 656 ± 20

0.1wt% Ag 2.2 ± 0.1 12.3 ± 1.2 936.6 ± 24
0.25wt%Ag 4.8 ± 0.6 13 ± 0.4 874 ± 14
0.375wt% Ag 4.8 ± 0.2 14.9 ± 1.0 542 ± 26
0.5wt% Ag 3.0 ± 0.1 10.1 ± 0.7 602 ± 36
0.75wt% Ag 4.9 ± 0.5 15.3 ± 0.2 838 ± 11
1.0wt% Ag 3.6 ± 0.1 9.2 ± 1.2 787 ± 20
The tensile curves indicate that the addition of nanoparticles displays an increased
mechanical behavior. This is confirmed by an increase in the elastic modulus and yield strength as
well as, ultimate tensile strength but a slight reduction in the ductility as seen in the elongation %.
The increase in mechanical properties is drastic in the silica composites such as the 0.25% w/w
silica, where the Young’s modulus rose to 5.4 MPa from 2.3 MPa of the neat PCPU and the
ultimate tensile strength moved from 10.1 to 19.1 MPa. The show of superior mechanical strength
illustrates successful interfacial adhesion as well as good homogeneity and compatibility between
the silica nanoparticles and the polymer matrix. What is also demonstrated in the silica
composites is that there is an effected load amount needed. As the %w/w increased to 0.75 and
1.0% the tensile properties decreased which suggests that the interfacial adhesion is no longer
effective leading to a mechanically inferior nanocomposite. The most surprising results come
from the carbon black nanocomposites which showed less free volume space in the melt rheology
results, which should have allowed for a stronger and tougher material. The nanocomposites
showed only a small increase in tensile properties as well as ultimate tensile strength at room
temperature which could mean that higher tensile strength may be seen at higher temperatures.
On the other hand, the silver nanocomposites showed promising results as the tensile strength
doubled from 2.3 MPa to 4.8MPa and 4.9 MPa for the majority of the silver nanocomposites. The
33
tensile data showed good interfacial adhesion of the nanoparticles to the polymer matrix to create
a mechanically enhanced polymer nanocomposite.
1.4 Conclusion
This study herein proves that enhancement of the thermal and mechanical properties of
PCPU can be successfully done by the dispersion of spherical silica, silver and carbon black
nanoparticles. The spherical nature of the nanoparticles showed ease of movement of the polymer
matrix by the reduction of the glass transition temperature showing that these nanoparticles move
in association with the polymer backbone. This allows for a higher thermal performance of
PCPU. Additionally, hydrogen bonding played a key role in the properties of the PCPU
nanocomposites as evidenced by the change in the contact angle and the change in the FTIR
spectra. Characterization of the polymer nanocomposites via parallel plate rheology supports
previously stated literature that the activation energy of viscous flow is independent of the
addition of silver nanoparticles. The silica nanoparticles showed homogeneity of mixing and the
carbon black nanoparticles showed that it can increase the activation energy by its packing ability
to decrease free volume space. The rheology also showed no drastic changes in complex viscosity
on the addition of the nanoparticles. The tensile properties of the ultrasoft polymer increased on
the addition of the nanoparticles especially at the low concentrations where the Young’s modulus
was double that of the neat PCPU.
The implications of the formation and characterization of the polymer nanocomposites
suggests that polymeric materials for industrial use can be enhanced by the addition of
nanoparticles to create superior polymers with high thermal and mechanical performance.
34
1.5 References
1. I.V. Khudyakov, D. R. Zopf and N.J. Turro (2009), Designed Monomers and Polymers,
12:4, 279-290
2. S. Cheng, B. Carroll, W. Lu, F. Fan, J. Y. Carrillo, H. Martin, A.P. Holt, N.Kang, V.
Bocharova, J. W. Mays, B. G. Sumpter, M. Dadmun, and A.P. Sokolov (2017) Interfacial
Properties of Polymer Nanocomposites: Role of Chain Rigidity and Dynamic
Heterogeneity Length Scale; Macromolecules, 50, 2397−2406
3. T. J. Pinnavaia and G. W. Beall (2001), Polymer-Clay Nanocomposites. Wiley, New York,
NY.
4. M. Rosoff (2000), Nano-Surface Chemistry. Marcel Dekker, New York, NY.
5. D. R. Paul and L. M. Robeson (2008), Polymer Nanotechnology Nanocomposites,
Polymer 49, 3187-3290.
6. A. Saralegi, S. C. M Fernandes, A. Alonso-Varona, T. Palomares, E. J. Foster, C. Weder,
A. Eceiza, M.A. Corcuera (2013), Shape-memory bionanocomposites based on chitin
nanocrystals and thermoplastic polyurethane with highly crystalline soft segment,
Biomacromolecules 14, 4475-4482.
7. T. Wu, M. Frydrych, K. O’Kelly, B. Chen (2014), Poly (glycerol sebacate urethane)-
cellulose nanocomposites with wateractive shape-memory effects, Biomacromolecules,
15, 2663.
8. Moon, R. J.; Martini, A.; Nairn, J.; Simonsen, J.;Youngblood, (2011), Cellulose
nanomaterials review: structure, properties and nanocomposites , J. Chem. Soc. Rev. 40,
3941.
35
9. A. Nicharat, A. Shirole, E. J. Foster, C. Weder. (2017) Thermally activated shape
memory behavior of melt-mixed polyurethane/cellulose nanocrystal composites. J. Appl.
Polym. Sci. DOI: 10.1002/APP.45033
10. B. M. Novak, (1993) Hybrid nanocomposite materials—between inorganic glasses and
organic polymers. Adv. Mater. 5, 422
11. S. C. Tjong and Y. W. Mai (2010) Physical Properties and Applications of Polymer
Nanocomposites; Woodhead Publishing Limited: Cambridge, UK.
12. A. C. Balazs, T. Emrick and T. P. Russell (2006) Nanoparticle Polymer Composites:
Where Two Small Worlds Meet. Science, 314:5802, 1107−1110.
13. S. Cheng, S. J. Xie, J. M. Y. Carrillo, B. Carroll, H. Martin, P. F. Cao, M. D. Dadmun, B.
G. Sumpter, V. N. Novikov, K. S. Schweizer and A. P. Sokolov (2017) Big Effect of
Small Nanoparticles: A Shift in Paradigm for Polymer Nanocomposites. ACS Nano, 11:1,
752−759.
14. V.V Mody, R. Siwale, A. Singh and H.R. Mody (2010), Introduction to metallic
nanoparticles, J Pharm Bioallied Sci, 2:4: 282-289.
15. Y. S. Kang, S. Risbud, J. F. Rabolt and P. Stroeve (1996) Synthesis and characterization
of nanometer-size Fe3O4 and γ-Fe2O3 Particles. Chem Mater, 8:22, 09–11.
16. Q. A. Pankhurst, J. Connolly, S. K. Jones and J. Dobson (2003) Applications of magnetic
nanoparticles in biomedicine. J Phys D Appl Phys. 36:R167.
17. J. Dobson (2006) Gene therapy progress and prospects: magnetic nanoparticle-based gene
delivery, Gene Ther. 13:283–287.
36
18. S. Rudge, C. Peterson, C. Vessely, J. Koda, S. Stevens and L. Catterall (2001) Adsorption
and desorption of chemotherapeutic drugs from a magnetically targeted carrier (MTC) J
Elsevier 74:335–340.
19. T. Appenzeller (1991) The man who dared to think small, Science; 254:1300.
20. K.L. Kull, R.W. Bass, G. Craft, T. Julien., E. Marangon, C. Marrouat and J.P. Harmon
(2015), Synthesis and Characterization of an Ultra-soft Poly (Carbonate Urethane),
European Polymer Journal 71:510-522.
21. R.W. Bass: Ph.D. Thesis, Synthesis and Characterization of Self-Healing Poly (Carbonate
Urethane) Carbon-Nanotube Composites, University of South Florida (2011)
22. J.P. Harmon and R.W. Bass (2014), Self-Healing Polycarbonate Polyurethane Nanotube
Composites. US Patent: 8,846,801.
23. R. W. Bass, T. Julien, A. Rigolo, S. Hong, X. Li, and J. P. Harmon (2016) Thermal and
mechanical properties of single-walled and multi-walled carbon nanotube polycarbonate
polyurethane composites with a focus on self-healing International Journal of Materials
Research 107, 8, 692-702
24. E. N. Doyle (1971) The Development and Use of Polyurethane Products, McGraw-Hill
Book Company New York.
25. C. Hepburn (1992) Polyurethane Elastomers, Elsevier. London: Applied Science; 1992.
26. Z. Wirpsza and T. J. Kemp (1993), Polyurethanes: chemistry, technology, and
applications. London: E. Horwood.
27. J. Ju, Z. Shi, L. Fan, Y. Liang, W. Kang, B. Cheng (2017), Preparation of elastomeric
tree-like nanofiber membranes using thermoplastic polyurethane by one-step
electrospinning, Materials Letters 205, 190–193
37
28. N.A.M. Barakat, M.A. Kanjwal, F.A. Sheikh, H. Yong Kim (2009), Spider-net within the
N6, PVA and PU electrospun nanofiber mats using salt addition: Novel strategy in the
electrospinning process, Polymer 50 4389-4396.
29. A. Cornille, R. Auvergne, O. Figovsky, B. Boutevin, S. Caillol (2017), A Perspective
Approach to Sustainable Routes for Non-Isocyanate Polyurethanes, Eur. Polym. J. 87 535-
552.
30. S.H. Choi, D.H. Kim, A.V. Raghu, K.R. Reddy, H.I. Lee, K.S. Yoon, H.M. Jeong, B.K.
Kim (2012), Properties of graphene/waterborne polyurethane nanocomposites cast from
colloidal dispersion mixtures , J. Macromol. Sci. B 51, 197-207.
31. K.R. Reddy, A.V. Raghu, H.M. Jeong (2008), Synthesis and characterization of. novel
polyurethanes based on 4,4'-{1,4-phenylenebis[methylylidenenitrilo]}. diphenol Polym.
Bull. 60 609-616
32. M. Dasdemir, M. Topalbekiroglu, A. Demir (2013). Electrospinning of thermoplastic
polyurethane microfibers and nanofibers from polymer solution and melt J. Appl. Polym.
Sci. 127,3,1901-1908, DOI: 10.1002/APP.37503
33. C. Akduman, I.Özgüney , E. Perrin, A. Kumbasar (2016), Preparation and characterization
of naproxen-loaded electrospun thermoplastic polyurethane nanofibers as a drug delivery
system, Materials Science and Engineering C 64, 383–390
34. B.S. Gupta and J.V. Edwards (2009) Textile materials and structures for wound care
products, in: S. Rajendran (Ed.), Advanced Textiles for Wound Care, Woodhead
Publishing Limited, Cambridge pp. 48–97.
38
35. T. T. N. Huynh, K. Padois, F. Sonvico, A. Rossi, F. Zani, F. Pirot, J. Doury ad F. Falson
(2010), Characterization of a polyurethane-based controlled release system for local
delivery of chlorhexidine diacetate, Eur. J. Pharm. Biopharm. 74:2, 255–264.
36. R. J. Zdrahala and I. J. Zdrahala (1999), Biomedical applications of polyurethanes: a
review of past promises, present realities, and a vibrant future, J. Biomater. Appl. 14:1,67–
90.
37. A. Huang, X. Peng, Lih-Sheng Turng. (2018), In-situ fibrillated polytetrafluoroethylene
(PTFE) in thermoplastic polyurethane (TPU) via melt blending: Effect on rheological
behavior, mechanical properties, and microcellular foamability. Polymer 134, 263-274.
38. X.D. Wang, X. Luo (2004) A polymer network based on thermoplastic polyurethane and
ethylene–propylene–diene elastomer via melt blending: morphology, mechanical
properties, and rheology, Eur. Polym. J. 40,2391-2399.
39. H.Y. Mi, X. Jing, M.R. Salick, L.S. Turng, X.F. Peng (2014), Fabrication of
thermoplastic poly-. urethane tissue engineering scaffold by combining microcellular
injection molding. and particle leaching, J. Mater Res. 29, 911-922.
40. K. A. Ames (2004) Elastomers for shoe applications, Rubber Chem. Technol. 77 413-475.
41. R. Bode, H. Ferch, H. Fratzscher (1982), Basic Charâcteristics and Applications of
Aerosils, DEGUSSA Technical Bulletin Pigments no. 11.
42. A. Torro-Paulau, J. Fernandez-Garcia, A.C. Orgiles-Barcelo, J. Martin-Martinez (2001)
Characterization of polyurethanes containing different silicas. International. Journal of
Adhesion and Adhesives, 21, pp. 1-9, 0143-7496
39
43. P.A. Gunatillake, G. F. Meijs, S. J. McCarthy, R. Adhikari, N. Sherriff (1998), Synthesis
and characterization of a series of poly(alkylene carbonate) macrodiols and the effect of
their structure on the properties of polyurethanes. J. Appl. Polym. Sci, 69: 1621-1633.
44. Y. He, D. Xie and X. Zhang (2014) The structure, microphase-separated morphology, and
property of polyurethanes and polyureas, J Mater Sci 49:7339–7352
45. M. S. Sánchez-Adsuar, E. Papón and J. Villenave (2000). Influence of the
prepolymerization on the properties of thermoplastic polyurethane elastomers. Part I.
Prepolimerization characterization. Journal of Applied Polymer Science, 76, pp. 1596-
1601, 0021-8995.
46. R. C. R. Nunes, J. L.C. M. Fonseca, and M. R. Pereira (2000) Polymer–filler interactions
and mechanical properties of a polyurethane elastomer, Polymer Testing, 19, pp. 93-103,
0142-9418
47. R. C. R. Nunes, R. A. Pereira, J. L. C. Fonseca, and M. R. Pereira (2001) X-ray studies on
compositions of polyurethane and silica, Polymer Testing, 20, pp. 707-712, 0142-9418.
48. Y. Tien and K. Wei (2001) Hydrogen bonding and mechanical properties in segmented
montmorillonite/polyuretane nanocomposites of different hard segment ratios, Polymer,
42, pp. 3213-3221, 0032-3861
49. J. Chen, X. Cui, K. Sui, Y. Zhu and W. Jiang (2017) Balance the electrical properties and
mechanical properties of carbon black filled immiscible polymer blends with a double
percolation structure, Composites Science and Technology 140, 99-105
50. L. Sun, W.M. Huang, Z. Ding, Y. Zhao, C.C. Wang, H. Purnawali and C. Tang (2012)
Stimulus-responsive shape memory materials, Mater. Des. 33, 577-640.
40
51. W. Wang, H. Pan, B. Yu, Y. Pan, L. Song, K. Meow, Liew and Y. Hu (2015) Fabrication
of carbon black coated flexible polyurethane foam for significantly improved fire safety,
RSC Adv., 5, 55870
52. C.K. Leong and D. Chung (2004), Black Dispersions and Carbon-Silver. Combinations as
Thermal Pastes That Surpass Commercial Silver and Ceramic Pastes in. Providing High
Thermal Contact Conductance. Carbon, 42, 2323–2327.
53. F. Delor-Jestin, J. Lacoste, N. Barrois-Oudin, C. Cardinet and J. Lemaire (2000), Photo-,
thermal and natural ageing of ethylene– propylene–diene monomer (EPDM) rubber used
in automotive applications. Influence of carbon black, crosslinking and stabilizing agents,
Polym. Degrad. Stab., 67, 469–477.
54. K. Cheah, M. Forsyth and G.P. Simon (2000) Processing and morphological development
of carbon black filled conducting blends using a binary host of poly(styrene co-
acrylonitrile) and poly(styrene), J. Polym. Sci. Part B Polym. Phys. 38:23, 3106-3119.
55. H. Deka, N. Karak, R. D. Kalita and A. K. Buragohain (2010) Bio-based thermostable,
biodegradable and biocompatible hyperbranched polyurethane/Ag nanocomposites with
antimicrobial activity, Polymer Degradation and Stability 95,1509-1517
56. X. Chen and H. J. Schluesener (2008) Nanosilver: A nano product in medical application.
Toxicol Lett, 176:1-12.
57. A. Travan, C. Pelillo, I. Donati, E. Marsich, M. Benincasa, T. Scarpa, et al. (2009)
Noncytotoxic silver nanoparticle-polysaccharide nanocomposites with antimicrobial
activity, Biomacromolecules, 10:1429-35
58. H. Planck, I. Syre, M. Dauner and G. Egbers (1987) Polyurethane in biomedical
engineering II, progress in biomedical engineering. Amsterdam: Elsevier.
41
59. Y. Yuan and T. R. Lee (2013) Contact Angle and Wetting Properties, Surface Science
Techniques, Springer Series in Surface Sciences 51, 1-33.
60. KRÜSS GmbH, Borsteler Chaussee 85, 22453 Hamburg, Germany www.kruss.de 4
61. T. Tanaka, T. Yokoyama, et al. (1968) Quantitative Study on Hydrogen Bonding Between
Urethane Compound and Ethers by Infrared Spectroscopy, Journal of Polymer Science
Part a-1-Polymer Chemistry 6 (8PA1): 2137-2152.
62. R. W. Seymour, G. M. Estes, et al. (1970) Infrared Studies of Segmented Polyurethane
Elastomers. 1. Hydrogen Bonding, Macromolecules 3:5, 579-583.
63. F. J. Boerio, and S. Wirasate (2006) Measurements of the Chemical Characteristics of
Polymers and Rubbers by Vibrational Spectroscopy, John Wiley & Sons, Ltd
64. B. Na, R. Lv, et al. (2009) Enhanced hydrogen bonding and its dramatic impact on
deformation behaviors in a biomedical poly(carbonate urethane) with fluorinated chain
extender, Journal of Polymer Science Part B: Polymer Physics 47:22, 2198-2205
65. R. Erdmann, S. Kabasci, J. Kurek and S. Zepnik (2014) Study of Reactive Melt
Processing Behavior of Externally Plasticized Cellulose Acetate in Presence of Isocyanate
Materials, Materials, 7, 7752-7769.
66. K. Ghosh and S. N. Maiti (1997) Melt Rheological Properties of Silver-PowderFilled
Polypropylene Composites, Polymer—Plastics Technology and Engineering, 36:5, 703-
722
67. A. F. Plochcki, in Polymer Blends, edited by D. R. Paul and S. Newman, Academic Press,
New York, 1978, Vol. 2.
68. A. K. Bhowmick (2002) Mechanical Properties of Polymers, Materials Science and
Engineering Vol. I
42
Chapter 2
Fabrication of Polycarbonate Polyurethane Nanofibers and Nanomembranes
2.1 Introduction
In 1900 John Francis Cooley was the first to file a patent for electrospinning. But, the first
presence of electrostatic attraction of a liquid, dates back to 1600 which was observed by William
Gilbert. By 1745, Bose used the electrical potentials on the surface of droplets in order to develop
aerosols. Christian Friedrich Schӧnbein was able to produce highly nitrated cellulose in 1846 and
then in 1887 Charles Vernon Boys described the process in a paper on nano-fiber manufacture.
After the filing of the first patent occurred published work on the behavior of fluid droplets began
by John Zeleny in 1914 and since then patent and publications about electrospinning have
increased each year [1].
Electrospinning is a well-established versatile technique that produces fibers with
diameter sizes in the micro and nanometer range [3-4]. This methodology employs an
electrostatic potential to create nanofibers from viscoelastic polymer solutions or polymer melts
[5-7]. Electrospinning ensues when a polymer solution or melt emits a charged fluid jet in the
presence of an electric field. When the electric field force reaches a certain threshold, the charged
polymer overcomes the surface tension and the jet undergoes a series of vigorous stretching and
splaying until it reaches a grounded target, thereby completing the circuit [5,9]. Material
properties, such as viscosity, conductivity, molecular weight and surface tension, as well as
43
processing parameters, such as applied electric field, the distance between the tip and the collector
feeding rate, air temperature and humidity, all influence spinnability and tuning properties of the
fabricated products [10-11].
Figure 2.1. Electrospinning set up [2].
The electrospinning process has the ability to produce highly porous membranes with
structural integrity. The nanofiber scaffolds possess extremely high surface to volume ratio,
tunable porosity and malleability and can be produced in a wide variety of sizes and shapes [13].
Due to these advantages, nanofiber membranes are being used in various fields like bio-medical,
pharmaceutical, nanotechnology-based industries, optical electronics, environmental engineering
and the defense industry [2, 11]. Electrospun materials have been proven to be an excellent
candidate for tissue engineering, drug delivery, vascular grafts, protective clothing systems, and
44
wound dressing as well as filtration systems for sub atomic particles [12-24].
Over the years a wide variety of polymer fibers including polyethylene (PE), polystyrene
(PS), polylactides, polyurethanes, poly(vinylidene fluoride), and polyamides have been generated
by electrospinning for various research findings [20,25]. Gazzano et. al., used semicrystalline
polymers such as, polyacrylonitrile (PAN), Nylon 6,6 (NYL) and poly(ethylene oxide) (PEO) to
investigate the structural and morphological properties of the fibers [26]. Song et al modified a
polyurethane using polyhedral oligomeric silsesquioxane (POSS) to look at improved blood
compatibility [27]. Most recently Li et. al, researched tensile properties in
silica/polydimethysiloxane (PDMS) and polymethyl methacrylate(PMMA) fibrous mats [5].
These examples show the broad range in which such a simple technique can create different
research outcomes.
The ability to electrospin our novel polycarbonate polyurethane to fabricate nanofibers
and nanomembranes, has broadened its applications in the medical and industrial fields for sensor
fabrications, drug delivery systems and scaffolds for tissue engineering where lightweight
material with larger surface area is needed. Moreover, the addition of nanoparticles to the polymer
can aid in improved catalytic activity and selectivity by silica nanoparticles [28-30], silver
nanoparticles can decrease surface inflammation and promote zinc utilization in wound healing,
[13] and carbon black nanoparticles added to a polymer matrix can create an electroactive
polymer nanomembrane [31]. These factors are in addition to its enhanced thermal and
mechanical properties already imposed on the PCPU material.
Our previous research [31-33] on the novel PCPU has shown that our polymer is ultrasoft
with a shore A hardness of 70, has high tensile strength and shows partial self-healing, which can
be enhanced with the addition of carbon nanotubes [31,33] . Now it is imperative to investigate
45
the effect of transforming the PCPU to fiber membranes to investigate whether the thermal and
mechanical properties are affected as well as how the addition of the nanoparticles affects the
overall properties of the polymer. In these studies, the utilization of thermal and mechanical
testing were completed to compare the characteristics of electrospun polymers with the bulk
PCPU and the electrospun neat PCPU with PCPU nanocomposite fibers. This research looks at
the thermomechanical and structural properties of electrospun PCPU and PCPU nanocomposite
nanofibers. Thermal properties were examined by differential scanning calorimetry (DSC).
Structural analysis was performed by Wide Angle X-ray scattering (WAXS) and Small Angle X-
ray scattering (SAXS), at room temperatures. Mechanical characterization was done by tensile
testing and morphological studies on the fiber membranes were done using Scanning Electron
Microscopy (SEM).
2.2 Experimental
2.2.1 Materials
The certified ACS grade reagent dimethylformamide (DMF) 99.9%, chloroform, tetrahydrofuran
(THF) with 250 ppm BHT inhibitor 99.9% and Ethyl Acetate (EtOAc) was purchased from
Sigma-Aldrich and used without further purification. The Polycarbonate polyurethane was
synthesized as described earlier [32-34] and the bulk sample was produced by hot pressing in a
carver press to create a film. PCPU was dissolved in the following solvent mixtures: ChCl3:
EtOAc, 90:10, THF: EtOAC, 90:10 and Dimethyformamide-ethylacetate (DMF:EtOAc) solution
in a 90:10 ratio. Polymer concentrations varied from 8-18% w/v. For the polymer
nanocomposites, the 16%w/v solution was used as the control. 0.25%, 0.5%, 0.75% 1.0% w/w of
silver, silica and carbon black nanoparticles were then added to the solution by ultrasonication for
2 hours to produce a composite polymer solution.
46
2.2.2 Electrospinning process
For the electrospinning process, each of the solutions was filled up in a 3ml syringe. A 20-gauge
needle with a flat tip was used as a spinneret. A collection distance of 20cm was done and a fixed
voltage of 20kV was applied at a feeding rate of 50μl/min.
2.2.3. Solution Viscosity Measurement
A Fungilab alpha series rotational viscometer equipped with a TR8 spindle was used to
measure the viscosity of the polymer solutions. 10ml of each solution was placed in the
cylindrical chamber and the spindle is immersed in the solution. The rotational speed was varied,
and viscosity readings were recorded. All measurements were performed at 21⁰C.
2.2.4 Scanning Electron Microscopy (SEM).
Scanning Electron Microscopy (SEM) is typically used to study surface topology such
as, the shapes and sizes of nanoparticles, the dispersion of nanoparticles within materials as well
as phase boundaries in polymer blends [35]. Research in polymer nanocomposite fiber
membranes has utilized SEM to investigate the shape and fiber diameter of electrospun polymers.
In SEM there is an electron beam and a beam in a cathode ray tube which is simultaneously
scanned across the surface of the sample. A signal is then produced by scattered electrons
resulting in an image with a three-dimensional appearance [35].
A Hitachi S-800 SEM was used in my work which has a magnification power of
300,000 times the actual sample size. SEM gives us information about fiber diameter, bead
formation, quality of the fibers or fiber membranes. The SEM is located in the Nanomaterials and
Nanomanufacturing Research Center in the Department of Engineering at the University of South
Florida.
47
2.2.5 Contact Angle Measurement
Uniform drops of the deionized water were deposited on the bulk PCPU and PCPU
electrospun membrane surface and the contact angles were measured using KSV CAM-101
video-based optical contact angle measuring device equipped with a Hamilton syringe in an
environmentally controlled chamber (KSV-1 TCU). All measurements were performed in air, at a
temperature of 25°C. Five right angles and five left angle measurements were recorded for each
sample.
2.2.6 Thermogravimetric Analysis (TGA)
A TA instruments Q500/50 TGA equipped with a standard furnace was used to detect the
degradation temperature of the polymer and polymer composite membranes. A sample weight
between 15-20mg was placed on a tared 100 ml platinum pan. Measurements were carried out
under nitrogen atmosphere as the samples were heated to 600⁰C at a heating ramp rate of 10⁰C per
minute.
DSC analysis was performed using a TA instruments 2920 Differential Analysis
Calorimeter to obtain glass transition temperature (Tg) and melt temperature (Tm) of the polymer
and polymer membranes. The heat cool heat method was utilized a starting temperature of -70⁰C
and then heated to 200⁰C at a ramp rate of 10⁰C/ minute to ensure all samples had their thermal
history erased. The sample was then cooled down to -70⁰C, using a refrigerated accessory, with
the similar ramp rate and then reheated to 200⁰C. The Tg values were taken from second heating
run.
48
2.2.8 Wide Angle X-ray Scattering (WAXS)
WAXS powder X-ray diffraction was used to investigate the degree of crystallization of
the PCPU polymer segments. In our earlier paper [32] the degree of crystallinity was measured
for the bulk PCPU there was no visible crystal peak until the polymer was stressed for 12 hours
and a peak at 12.8⁰. X-ray diffraction patterns were collected with a Bruker D8 Focus x-ray
diffractometer. The data collection was recorded in the range of 5–80° with a step of 0.010° at
25°C. Pre-electrospun polymer film was cast from the solvent and measured. These scans were
compared to scans on electrospun mats.

19.5°
19.7°
a.
b.
12.8°
Figure 2.2. XRD showing detection of ordered structure in a. pre-stressed neat PCPU and b.
stressed undeformed bulk PCPU [32].
49
2.2.9 Small Angle X-Ray Scattering (SAXS)
SAXS data was collected on a Rigaku with a MicroMax-002+ generator, a Cu anode
tube and a 120mmDET detector and a wavelength of 1.45Å. The bulk PCPU film and the fiber
membranes were tested.
Tensile strength characterization was done using Shimadzu AGS-J tensile tester equipped
with a 50N load cell to measure displacement of samples. All tensile testing was done at a
crosshead speed of 100mm/min at room temperature according to ASTM D638. Dog bone cut
samples from compression molded and fiber membrane samples had thicknesses 0.15mm;
triplicate samples were tested, and average was reported.
2.3. Results and Discussion
Preliminary electrospinning tests were run on the polymer solutions with varying solvents.
The results here within are based on the polymer solutions using DMF: EtOAc in a 90:10 ratio.
The CHCl3:EtOAc as well as the THF:EtOAc combinations caused sputtering of the fibers during
the electrospinning process.
2.3.1 Solution Viscosity
Solution viscosity is important in electrospinning of polymer solutions in order to create
quality fibers. The solution viscosities at varying shear rates of the pre-spun polymers are shown
in figure 2. As the concentration of the polymer increased the viscosity overall increases. For the
8%w/v solution at the lowest shear rate of 9 s-1, the viscosity was 126mPa, and for the 18%w/v at
the same shear rate, the viscosity was found to be more than 5 times the viscosity at 729 mPa.
50
Overall it shows that the viscosity of the polymer solution decreased with increasing shear rate.
Even the 8% w/v solution had a small but consistent decrease from 126mPa to 122 mPa with
increasing shear rate. This demonstrates the pseudo plasticity of the PCPU in solution meaning a
change in the shear rate changes its viscosity.
800
700
600
8wt%
Viscosity (mPa)
500
10wt%
400
12wt%
300
14wt%
200 16wt%
100 18wt%
0
0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0 180.0
Sheat rate (1/s)
Figure 2.3. Solution Viscosities of 8% w/v, 10% w/v, 12% w/v, 14% w/v, 16% w/v & 18% w/v
neat PCPU solution concentrations.
2.3.2 Scanning Electron Microscopy (SEM)
When fibers were spun with concentrations varying from 8% w/v to 18%, lower
concentrations (8, 10 & 12 % w/v) exhibited beading and the materials were too frail to be tensile
tested. This is partially attributed to low viscosities (<400mPa). Samples spun from 14, 16, and
18% w/v for the DMF:EtOAc easily released from the collecting plate and were fully
characterized and discussed below.
Figure 3A-C shows SEM images of 14, 16 and 18% w/v PCPU fibers. Figure 3D-F shows
the PCPU fiber material as a film with different thickness. The 14% w/v material was lightweight
and had a thickness of 0.09mm, the 16% w/v had a thickness of 0.12 mm and 18% w/v material
51
felt tough has a thickness of 0.17mm. The SEM images show the material’s porosity and the
randomness of the fibers. An increase in the concentration of the solution resulted in less beading
and thinner fiber formation. For the 14% w/v, the SEM image showed some beading which may
arise from the presence of solvent during fiber formation resulting in large flat fibers with higher
fiber diameters in the 900-2.8µm range. When the concentration was increased to 16% w/v the
fiber diameter range was between 900nm-1µm. At 18% w/v, the fiber diameter ranged from 600-
950 nm, resulting in a tighter diameter range across fibers.
Figure 2.4. SEM images a.-c., 14, 16, 18 % w/v fiber membranes; d.-f. Film-like membrane
composites.
2.3.3 Contact Angle Measurement
A contact angle below 90° indicates the material is easily wetted by the test liquid. When
water is used as the test liquid, the indication is that the material is hydrophilic. Contact angles
greater than 90° indicate a resistance to wetting by the water and a hydrophobic surface. This is
depicted in Figure 4.
52
Figure 2.5. Illustration of contact angle at θ>90⁰, θ<90⁰ and θ=90⁰ [2].
Pictoral and numeric measurements for contact angles are shown in figure 5. An increase
in the contact angle occurred from the change of bulk PCPU film to PCPU fiber membrane. In
addition, an increase in contact angle also occurred as the concentration of the polymer solution
increased. The contact angles for 14% w/v, 16% w/v and 18% w/v are 103⁰, 105⁰ and 110⁰
respectively. The contact angle for the molded PCPU film was 102⁰. The slight increase in
contact angle with % w/v of polymer in the electrospun samples may indicate trace amounts of
solvent trapper in the fibers; However, TGA studies did not reveal significant weight changes.
The use of electrospinning to create fiber membranes has allowed for interesting results for future
investigations of PCPU tunable surface wettability of the polymer.
53
Figure 2.6. Contact Angle Images and graph for the bulk PCPU film and 14,16
&18%w/v fiber membranes.
2.3.4 TGA (Thermogravimetric Analysis)
The thermal stability and residual solvent dryness of the PCPU fibers were evaluated by
TGA measurements under nitrogen atmosphere. The thermograms of the molded and electrospun
PCPU at different % w/v are shown in Figure 5. The corresponding temperature at 5% weight loss
and the onset temperature are reported in Table 1. Moving from molded PCPU to the fiber
membranes we see a decrease in the onset temperature as well as the temperature at 95% mass.
This can be due to the porosity of the fibers and trapping of solvent.
54
The TGA graph shows that the thermal stability is reduced due to remnant DMF:EtoAc
solutions remaining on the fibers but as the concentration of polymer solution increases the
thermal stability also increases. The trend shows that the 18% w/v closely mimics the shape of the
neat PCPU mold and the 14% w/v and 16% w/v closely mirror each other. This suggests that the
removal of solvent leads to a more thermally stable polymer fiber mat.
100 2.5
18wt% neat PCPU fiber
90
16wt% neat PCPU fiber
2
80 14wt% neat PCPU fiber
70 neat pcpu
Deiv. Weight (%/⁰C)

1.5
60
Weight (%)
50 1
40
0.5
30
20
0
10
0 -0.5
0 100 200 300 400 500 600
Temperature (⁰C)
Figure 2.7. TGA graph showing the degradation of PCPU film and PCPU fiber membranes.
Differential Scanning Calorimetry gives us an insight into the movement of the polymer
backbone. Results are summarized in table 1. The Glass transition temperature tells us how the
soft amorphous segments move and the melt temperature (Tm) gives us an idea of when the hard
segments melt. The glass transition temperature for the 14, 16 & 18% w/v polyurethane fibers as
well as the molded PCPU remained at -22.9⁰C. This lets us know that the soft segment
55
interactions have not changed during the electrospinning process. Wong et al mentioned that Tg
values of fiber membranes do not show a significant difference due to intermolecular coupling of
the polymer chains. DSC indicates that there is not an appreciable amount of solvent in the fibers.
The melt temperature, Tm, for the neat PCPU was at 70.5⁰C, the 14% w/v increased to 78.9⁰C,
16% to 74.4 and 18% showed two melting temperatures at 78.4 and 145⁰C. The shift to a higher
temperature means the presence of purer or more ordered crystals within the polymer matrix. The
18% w/v PCPU fiber showed a second melting which may be due to hard segment melting. There
was also an increase in the enthalpy of melt from 1.3 in the neat PCPU to 1.6 in the PCPU fibers
which can lend itself to a higher percent crystallinity not present in the bulk polymer mold.
18 % w/v
21.9 ⁰C
16 % w/v
22.8 ⁰C
14 % w/v 76.4 ⁰C
145.6
neat 22.9 ⁰C
⁰C 74.4 ⁰C
22.9
⁰C
78.9 ⁰C
70.5
⁰C
Figure 2.8. DSC thermogram for the second heating cycle of neat PCPU, 14% w/v PCPU fiber,
16% w/v PCPU fiber & 18% w/v PCPU fiber.
56
Table 2.1: Glass transition temperature, melt temperature and TGA temperatures of
molded and electrospun PCPU fibers.
Sample name First Second Tm (⁰C) ΔHm TGA Temp at 99%

Tg Tg (J/g) onset (⁰C) mass (⁰C)
(⁰C) (⁰C)
neat PCPU -24.8 -22.9 70.5 1.3 292 297
14% w/v Neat TPU -25.9 -22.9 78.9 2.7 279.0 287
fiber
16% w/v neat TPU -25.3 -22.8 74.4 1.5 280.0 288
fiber
18% w/v Neat TPU -24.8 -21.9 76.4/145.6 1.6/0.8 284.0 293
fiber
2.3.6 Wide-angle X-ray scattering (WAXS)
The DSC runs indicate that the PCPU is not highly crystalline. Indeed, this polymer is
ultrasoft and we expect and have known it to have limited crystallinity [33]. Wide-angle X-ray
scattering was used to determine the effect of electrospinning on the crystallization of PCPU.
Figure 8 Shows the WAXS intensity profile of the PCPU films cast from solution; Figure 9 is data
on the electrospun fiber. These scans exhibit more order than that found earlier in melt processed
samples [33]. In the solvent cast films, the scans showed a small peak associated with
crystallization at around 12 ° on the 2 theta scale in the 14w/v % and the 16% w/v but it
disappears in the 18% w/v PCPU film. This suggests that the DMF:EtOAc solvents influences
crystallinity in the polymer chains and as the concentration was increased (reduce the amount of
57
solvent used) the ability to create the ordered segments is reduced. Sharper reflections were noted
in the 40-50 ° regions. The electrospun polymers intensity profile shown in Figure 9, illustrates
distinct crystal peaks for all the samples. This suggests that the solvent used as well as the
electrospinning process allows for ordering of the crystal segments. Melt processed PCPU
exhibits no peak which indicates mixing of the hard crystal lamellae and the soft amorphous
regions. This is divergent to the concept that electrospinning reduces the crystallinity of the fibers
[36]. Lee et al [37] reported that the crystalline structure in fibers can be developed in ductile
polymers. Polymers that have low Tg values such as our novel PCPU (Tg~ -22.9°C) takes a
longer time to crystallize [36]. Overall, the sharper reflections in electrospun samples indicate
crystallization occurs during the electrospinning process when the polymer fibers are elongating
and possibly after the fibers have dried and solidified.
1200
14wt% neat film

1000
16wt% neat film
800 18 wt% neat film

Counts
600
400
200
0
0 20 40 60 80
2θ scale
Figure 2.9. XRD showing detection of ordered structure for the 14% w/v and 16% w/v solution
cast film.
58
7000
14wt%
6000
16wt%
5000 18wt%
4000
Counts
3000
2000
1000
0
0 20 40 60 80
2θ scale
Figure 2.10. XRD showing detection of ordered structure of the 14%, 16% and 18% w/v fiber
membranes.
2.3.7 Small-angle X-ray (SAXS)
Small angle x-ray data was recorded to understand structural features that are larger than
unit cell dimensions. Specifically, Fig [10]. There exhibits a peak at 0.14 A indicating an inter
lamellae spacing of 45Å. This was reported in our earlier paper on melt processed polymer [33].
We expected more distinct peaks in the electrospun samples, however, amplitude of the 0.14Å
peaks decreased as the concentration of the polymer solution used in spinning increased. It
appears as though alignment during the spinning process does not result thicker more well-
developed lamellae. The 45 Å structure are less plentiful in spun samples as well.
59
0.14 Å
Figure 2.11. SAXS of bulk PCPU and PCPU fiber membranes.
Representative stress-strain curves are depicted in Fig.12. Note that samples were run in
triplicate. Tensile strength, elastic modulus and strain to break are average values. We see that the
formation of electrospun PCPU fibers caused the modulus to initially decrease from 2.5MPa for
the bulk PCPU mold to 0.6 MPa in the 14% w/v neat fiber and 1.6 MPa in the 16% w/v neat fiber
then it increased to a modulus of 3.3MPa in the 18% w/v neat PCPU fiber. This shows that an
increase in the concentration of the pre-spun polymer cast solution drastically increases the tensile
strength of the polymer membrane. The elastic modulus data exhibits the same trend. The
increase in Tm noted in spun samples points to better developed crystals which may enhance
tensile moduli and strength. WAXS data did show sharper reflections in spun samples as well.
Baji et al tells us that the formation of crystals in the polymer matrix lends itself to increase
60
tensile strength [36]. The authors proposed that the strength and elastic modulus of the fibers are
influenced by the crystal lamellar and amorphous fractions of the chains within the polymer
fibers. Additionally, they proposed that structural formation changes taking place in the fibers
during electrospinning, specifically crystallinity and molecular orientation impart physical
uniqueness to the material and play an important role in the deformation behavior of the fibers
[36]. Strain to break values in spun samples are somewhat lower that of neat PCPU. Our future
studies will focus on the effect of spinning variables on tensile properties.
4.5 3.5
b
Elastic Modulus (MPa)
4 a 14 wt NEAT FIBER 3 3
3.5 . 16 wt NEAT FIBER 4 2.5 .
Stress (Mpa)
3 2
18wt NEAT FIBER
2.5 1.5
2 NEAT PCPU mold
1
1.5 0.5
1
0
0.5
14 wt 16 wt 18wt neat
0
NEAT NEAT NEAT PCPU
0 100 200 300 400 FIBER FIBER FIBER
Strain %
4.5
c.
Tensile Strength (Mpa)
4 400 d.
3.5
3
300
2.5
2
1.5 200
1
0.5 100
0
14 wt 16 wt 18wt neat 0
NEAT NEAT NEAT PCPU 14 wt NEAT16 wt NEAT 18wt NEAT neat PCPU
FIBER FIBER FIBER FIBER FIBER FIBER
Figure 2.12. a. Stress-Strain behavior, b. Elastic modulus, c. Tensile strength and d. Strain
at break of bulk PCPU and PCPU fiber mats.
61
2.3.9 PCPU/ nanocomposite membranes
2.3.9.1 Solution Viscosity
The solution viscosity for the PCPU and PCPU nanocomposite solutions are given in
figure 2.13. The solution viscosities generally increased as the % w/w of nanoparticles were
added to the PCPU solutions. For example, the 5% w/v PCPU/silica solution increased to twice
that of neat PCPU from 5 at shear rate to 13 mPa. The solutions also displayed pseudoplastic
behavior as seen in the neat PCPU which suggests that the addition of the nanoparticles does not
change the fluid like behavior of the polymer.
16 wt % neat
700 Viscosity-0.5silver 16wt% 1500

Viscosity-0.5silica16 wt%
Viscosity-0.5cb 16 wt%
1400
650
Viscosity (mPa)
Viscosity (mPa)
1300
1200
600
1100
550 1000
0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0 180.0
Shear rate (1/s)
Figure 2.13 Solution Viscosities of 0.5%w/w Ag, 0.5% w/w SiO2 & 0.5% w/w CB PCPU
nanocomposite solutions at 16% w/v concentration.
62
2.3.9.2 SEM
The SEM images were done to evaluate the fiber diameters for the PCPU nanocomposite
fibers. The 16wt% neat PCPU fiber diameter ranged from 900nm to 1μm. The nanocomposite
fibers ranged from 469 nm- 855 nm for the carbon black nanoparticles, 277-541nm for the silver
nanoparticles and 498nm-1.0μm for the Silica nanoparticles. Overall the nanofiber diameters were
drastically reduced when the nanoparticles were introduced to the PCPU solution
Figure 2.14. SEM images a.-c., 0.5%w/w Ag, 0.5% w/w SiO2 & 0.5% w/w CB PCPU w/v
fiber membranes; d.-f. Film-like membrane composites.
63
2.3.9.3 TGA
The TGA graph for the PCPU and 0.5% w/w nanoparticle membranes are shown in figure 2.15.
The graph illustrates that the degradation curve is shifted. The onset temperatures shown in Table
2.2 reveal that the nanoparticles are acting as reinforcements to the PCPU fibers which allow for a
higher degradation temperature from 286⁰C for the neat PCPU fiber to 288⁰C for the PCPU/SiO2
fiber. Even at 99% mass the composites membranes were at a higher temperature than the neat
PCPU increasing from 173⁰C to as high as 261⁰C.
100
90
80
16wt% neat pcpu fiber
70
60 0.5 wt% SiO2 fiber

weight (%)
50 0.5wt% cb fiber
40
0.5wt% Ag fiber
30
20
10
0
0 100 200 300 400 500 600
Temperature (⁰C)
Figure 2.15 TGA graph of neat PCPU (pink) and 0.5 wt% Ag (blue), 0.5 wt% SiO2 (green)
and 0.5wt% CB /PCPU nanocomposite fiber membranes.
64
Table 2.2 TGA data showing onset temperature, temperature at 99% and 50% mass for
PCPU/ 0.5% w/w nanoparticle fiber membranes.
Sample name Temperature- Temperature at Temperature at
onset (⁰C) 99% mass (⁰C) 50% mass (⁰C)
neat PCPU 289.0 173.6 338.9

16% w/v neat PCPU fiber 286.0 237.6 329.5
0.5% w/w Ag fiber 286.5 234.5 332

0.5 % w/w CB fiber 287.0 222.9 337.1
0.5% w/w SiO2 fiber 288.0 261.8 334.6
2.3.9.4 DSC
The DSC scans for the PCPU composite nanomembranes as shown in figures 2.16. The
glass transition temperatures for the nanocomposite fibers have decreased which means that
plasticization of the polymer matrix remains even though the polymer was electrospun. The silica
nanofiber composite showed a downward trend for the Tg which was opposite to that of the silica
molded composite detailed previously. This suggests that the electrospinning process may have
broken up any possible aggregation that can occur for the silica composites. The melt temperature
of the fibers varied 63⁰C and 78 ⁰C so there was no apparent melt temperature illustrated. Here the
expected crystallization peak is again absent from the thermogram which is similar to that of the
neat PCPU fiber composite.
65
16%w/v neat PCPU fiber
0.5 %w/w Ag
0.5 % w/w CB
0.5 %w/w SiO2
-25⁰C
64.5⁰C
-25.9⁰C
-25.4⁰C 63⁰C
-22.9⁰C 70.1⁰C
70.7⁰C
Figure 2.16 DSC thermos gram of neat PCPU (red) vs 0.5%w/w silver (Blue) and 0.5%
w/w carbon black (green) and 0.5% w/w silica (purple) PCPU fiber membranes.
Table 2.3 DSC data showing glass transition temperature (Tg) and melt temperature (Tm)
for PCPU/nanoparticle fiber membranes.
Sample name Tg (⁰C) Tm(⁰C) ΔHm (J/g)
neat PCPU -22.9 83.9 2.9

16% w/v neat PCPU fiber -22.8 70.7 3.3
0.25% w/w Ag fiber -25.0 73.1 1.1

0.5% w/w Ag fiber -25.4 70.1 3.6
0.75%w/w Ag fiber -25.3 61.6 0.6
1.0% w/w Ag fiber -24.6 74.6 0.3
0.25 % w/w CB fiber -25.1 61.4 2.8
0.5 % w/w CB fiber -25.9 63.0 9.9
0.75 % w/w CB fiber -22.9 77 4.0
66
Table 2.3 continued
1.0 % w/w CB fiber -25.7 75.0 3.0

0.25% w/w SiO2 fiber -23.4 78.1 0.25
0.5% w/w SiO2 fiber -25.0 64.5 9.4
0.75 % w/w SiO2 fiber -25.1 65.3 0.3
1.0 % w/w SiO2 fiber -25.4 77.1 0.1
2.3.9.5 WAXS
The WAXS data for the PCPU nanocomposite membrane are shown in figures 2.17, 2.18
& 2.19. For the silver nanocomposites the indicative intensity peaks at 38.4⁰, 44.6⁰, and 64.6⁰
represent the presence of silver nanoparticles. Because of limiting testing standards, the 77.5⁰
peak is not shown. For the 0.25 & 0.5 %w/w, the crystalline nature of the polymer
nanomembrane still exists but as we increase the % w/w the crystallinity disappears which means
that there can be interactions of the silver nanoparticles interrupting the crystal lamellae. Another
peculiar result came from the 1% w/w silver composite. It shows an extra peak which is known as
an amorphous peak. This can be from the presence of moisture at the surface of the
nanomembrane from the transportation of the fiber for testing. The amorphous nature of the silica
nanocomposite became more prevalent at a lower weight percent. There was a small crystal peak
present at 12.6⁰ in the 0.25 % w/w nanomembrane but it was absent in the other % w/w
nanomembrane samples. The WAXS scans for the PCPU/ carbon black composite
nanomembranes showed a crystalline peak at 12.5⁰ and 12.7⁰ for the 0.25 %, 0.5% and 0.75 %
w/w. For the 1% w/w carbon black composite fiber, the amorphous nature from the transport of
the fibers gave amorphous peaks at 30.1 ⁰.
67
Figure 2.17 WAXS of 0.25%w/w (blue), 0.5%w/w (green), 0.75%w/w (purple) & 1.0%
w/w (yellow) PCPU/ Ag nanocomposite fiber membranes.
68
Figure 2.18 WAXS of 0.25%w/w (brown), 0.5%w/w (yellow), 0.75%w/w (green) &
1.0% w/w (blue) PCPU/ SiO2 nanocomposite fiber membranes.
Figure 2.19 WAXS of 0.25%w/w (green), 0.5%w/w (pink), 0.75%w/w (yellow) & 1.0%
w/w (blue) PCPU/ CB nanocomposite fiber membranes.
69
2.3.9.6 Tensile Testing
The graphs in figures 2.20-2.22 show the stress strain curves for the 16% w/w neat PCPU
and PCPU composite fibers. For the carbon black the tensile profile initially decreased compared
to the neat PCPU tensile profile, but as the % w/w increased the tensile strength profile of the
fiber increased. The modulus of the 1%w/w carbon black composite fiber had a modulus of
4.3MPa which is three times the modulus of the neat PCPU fiber 1.3MPa (Table 2.3). The silver
nanocomposite fibers tensile profile decreased compared to neat PCPU for 0.25% to 0.75%w/w
silver whereas the 1%w/w increased only slightly. The silica fiber samples also showed reduced
mechanical strength on the addition of the nanoparticles. This suggests that adding the
nanoparticles adversely affected the mechanical strength when the PCPU nanocomposite was
electrospun.
4.5
neat PCPU fiber

3.5
0.25wt% CB fiber
3 0.5wt% CB fiber
Stress (Mpa)
0.75wt% CB fiber
2.5
1.0wt% CB fiber
1.5
0.5
0
0 50 100 150 200 250
Strain %
Figure 2.20 Stress vs strain curves for CB nanocomposite fiber membranes.
70
2.5 neat PCPu fiber 0.25wt% Ag fiber
0.5wt% Ag fiber 0.75wt% Ag fiber
1.0wt% Ag fiber
2
1.5
Stress (Mpa)
0.5
0
0 50 100 150 200 250
Strain %
Figure 2.21 Stress vs strain curves for Ag nanocomposite fiber membranes.
71
0.25wt% SiO2 fiber
1.6 0.5wt% SiO2 fiber

0.75wt% SiO2 fiber
1.4 1.0wt% SiO2 fiber

neat PCPU fiber
1.2
1
Stress (Mpa)
0.8
0.6
0.4
0.2
0
0 50 100 150 200 250
Strain %
Figure 2.22 Stress vs strain curves for SiO2 nanocomposite fiber membranes.
72
Table 2.4 Tensile strength data on electrospun PCPU and PCPU nanocomposite fiber
membranes.
Elastic Modulus Ultimate Tensile Strength Strain at Break
Sample (MPa) (MPa) (%)
16 wt NEAT
FIBER 1.3 1.5 297.9
0.25 %w/w CB 0.5 0.53 191
0.5 %w/w CB 0.77 1.03 252
0.75 %w/w CB 0.99 1.4 219
1 %w/w CB 4.3 4.5 258
0.25 %w/w Ag 0.43 0.49 190
0.5 %w/w Ag 0.5 0.62 211
0.75 %w/w Ag 0.88 0.92 139
1 %w/w Ag 1.5 1.94 199
0.25 %w/w SiO2 0.32 0.5 209
0.5 %w/w SiO2 0.6 0.6 181
0.75 %w/w SiO2 1.01 1.05 175
1 %w/w SiO2 1.31 1.35 119
2.4 Conclusion
An ultrasoft polycarbonate polyurethane was electrospun to create fiber membranes. The
resulting material showed variations in its thermal, mechanical and molecular properties when the
polymer solution concentration was varied. The 18% w/v polymer membrane showed the highest
thermal stability with an onset of 284 ⁰C compared to the 14 % w/v at 279 ⁰C. One glass transition
73
temperature was found to be -22.9 °C and it did not change as we moved from the bulk polymer
to the fiber membranes. The enthalpy of melt showed a slight increase to suggest crystal
formation. WAXS data demonstrated the presence of clearer reflections in spun samples than
those obtained in solution cast films and bulk polymer. SAXS did not show any variations in the
interdomain spacing which remained at 0.45Å. Singular fiber SAXS yield a better idea of the
molecular orientation of the electrospun PCPU. The mechanical properties showed that the
electrospun PCPU high Young’s modulus of 3.3 MPa as well as an ultimate tensile strength of 4
MPa compared to the bulk PCPU. The 16% w/v sample had the highest elongation at break of
280% which showed that its fiber membrane has the ability to stretch to almost four times its
original length.
On the addition of the nanoparticles, the fiber diameter of the PCPU nanofibers decreased
well within the nm range. However, the tensile properties were greatly affected. Only the 1% w/w
carbon black composite fiber showed a dramatic increase in strength by having a young’s
modulus of about 3 times that of neat PCPU fiber membrane. Contrastingly the thermal
performance of the nanocomposite fibers was increased on the addition of the nanoparticles by an
increase in the thermal stability of the composite fibers and the decrease in the glass transition
temperature. These results give us a clearer impression of how processing conditions can be
modified to tune the properties of the fibers.
2.5 References
1. N. Tucker, J. J. Stanger, M. P. Staiger, H. Razzaq and K. Hofman (2012) The History
of the Science and Technology of Electrospinning from 1600 to 1995, Journal of
Engineered Fibers and Fabrics, SPECIAL ISSUE, 63-73.
74
2. H. Katakam, Master’s Thesis, Fabrication and Characterization of Polycarbonate
Polyurethane (PCPU) Nanofibers Impregnated with Nano fillers.
3. S. Wang, Y. Wan, B. Sun, L. Liu and W. Xu (2014), Mechanical and electrical
properties of electrospun PVDF/MWCNT ultrafine fibers using rotating collector,
Nanoscale Research Letters, 9:522
4. H. Mi, X. Jing, E. Yu, X. Wang, Q. Lid, L. Turng (2018), Manipulating the structure
and mechanical properties of thermoplastic polyurethane/polycaprolactone hybrid
small diameter vascular scaffolds fabricated via electrospinning using an assembled
rotating collector, Journal of the Mechanical Behavior of Biomedical Materials, 78,
433–441
5. J. Li, C. Nie, B. Duan, X. Zhao, H. Lu, W. Yin, Y. Li, X. He (2017), Tensile
performance of silica-based electrospun fibrous mats, Journal of Non-Crystalline
Solids 470, 184–188
6. D. Li, Y.N. Xia (2004), Electrospinning of Nanofibers: Reinventing the Wheel? Adv.
Mater 16, 1151–1170.
7. D. H. Reneker, I. Chun (1996), Nanometre diameter fibres of polymer, produced by
electrospinning, Nanotechnology 7, 216–223.
8. A. Greiner, J. H. Wendorff (2007), Electrospinning: a fascinating method for the
preparation of ultrathin fibers, Angew Chem. Int. Ed. 46, 5670–5703.
9. M. G. McKee, C. L. Elkins, T. E. Long (2004), Influence of self-complementary
hydrogen bonding on solution rheology/electrospinning relationships, Polymer 45,
8705–8715.
75
10. H. Karakaş, A. S. Saraç, T. Polat, E. G. Budak, S. Bayram, N. Dağ, and S. Jahangiri
(2013) World Academy of Science, Engineering and Technology, International,
Journal of Health and Medical Engineering Vol: 7, No:3.
11. E.J. Chong, T.T. Phan, IJ Lim, Y.Z. Zhang, B.H. Bay, S. Ramakrishna S. Acta Mater;
3:321– 30, 2007.
12. S. W. Thomas, N. A. Alcantar, Yanay Pais (2017) . US patent US20170157571 A1
13. L. R. Lakshman, K. T. Shalumon, S. V. Nair, R. Jayakumar and S. V. Nair (2010)
Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 47, 1012–
1018
14. G. E. Martin, I. D. Cockshott and F. J. Fildes (1977) US Patent 4,044,404.
15. H. Planck and P. Ehrler (1984) US Patent 4,474,630.
16. How TV (1985). US Patent 4,552,707.
17. D. Groitzsch and E. Fahrback (1986) US Patent 4,618,524.
18. W. Simm (1976) US Patent 3,994,258.
19. A. Pedicini and R. J. Farris (2003), Mechanical behavior of electrospun polyurethane,
Polymer 44, 6857–6862
20. J. Liu, D. Y. Lin, B. Wei and D. C. Martin (2017), Single Electrospun PLLA and PCL
Polymer Nanofibers: Increased Molecular Orientation with Decreased Fiber Diameter,
Polymer 118, 143-149
21. P. Gibson, H. Schreuder-Gibson and D. Rivin (2001), Transport properties of porous
membranes based on electrospun nanofibers, Colloids Surfaces A Physicochem Eng.
Asp. 187-188, 469-481.
76
22. W. J. Li, C. T. Laurencin, E. J. Caterson, R. S. Tuan amd F.K. Ko (2002), Electrospun
nanofibrous structure: A novel scaffold for tissue engineering, J. Biomed. Mater. Res.
60, 613-621.
23. J. A. Matthews, G. E. Wnek, D. G. Simpson and G. L. Bowlin (2002), Electrospinning
of Collagen Nanofibers, Biomacromolecules 3 232-238.
24. D. H. Reneker, A. L. Yarin, E. Zussman and H. Xu (2007) Electrospinning of
nanofibers from polymer solutions and melts, Adv. Appl. Mech. 41, 43-195.
25. M. Gazzano, C. Gualandi, A. Zucchelli, T. Sui, A. M. Korsunsky, C. Reinhard and M.
L. Focarete (2015), Structure-morphology correlation in electrospun fibers of
semicrystalline polymers by simultaneous synchrotron SAXS-WAXD, Polymer 63,
154-16.
26. X. Song, T. Li, B. Cheng and J. Xing (2016), POSS–PU electrospinning nanofibers
membrane with enhanced blood compatibility, RSC Adv., 6, 65756-65762.
27. M. Hartmann (2004), Hierarchical zeolites: a proven strategy to combine shape
selectivity with efficient mass transport, Angew Chem Int Ed, 43:5880-5882.
28. H. Ogihara, S. Takenaka , I. Yamanaka, E. Tanabe, A. Genseki, K. Otsuka (2006),
Synthesis of SiO2 Nanotubes and Their Application as Nanoscale Reactors, Chem.
Mater. 2006;18:996–1000.
29. L. Chen, J. Liao, S. Lin, Y. Chuang and Y. Fu (2009) Synthesis and characterization of
PVB/silica nanofibers by electrospinning process, Polymer 50, 3516–3521
30. S. Chuangchote, A. Sirivat and P. Supaphol1 (2007) Mechanical and electro-
rheological properties of electrospun poly(vinyl alcohol) nanofibre mats filled with
carbon black nanoparticles, Nanotechnology, 18, 145705
77
31. R. W. Bass: Ph.D. Thesis, Synthesis and Characterization of Self-Healing Poly
(Carbonate Urethane) Carbon-Nanotube Composites, University of South Florida
(2011),
32. J.P. Harmon, R.W. Bass, Self-Healing Polycarbonate Polyurethane Nanotube
Composites. US Patent: 8,846,801, (2014)
33. K. L. Kull, R. W. Bass, G. Craft, T. Julien., E. Marangon, C. Marrouat and J. P.
Harmon (2015), Synthesis and Characterization of an Ultra-soft Poly (Carbonate
Urethane), European Polymer Journal 71, 510-522.
34. R. W. Bass, T. C. M. Julien, A. Rigolo, S. Hong, X. Li, and J. P. Harmon (2016),
Thermal and mechanical properties of single-walled and multi-walled carbon nanotube
polycarbonate polyurethane composites with a focus on self-healing, International
Journal of Materials Research, 107:8, 692-702
35. M. P. Stevens (1999), Polymer Chemistry: An Introduction, 3rd Ed. New York:
Oxford.
36. A. Baji, Y. Mai, S. Wong, M. Abtahi, P. Chen (2010), Electrospinning of polymer
nanofibers: Effects on oriented morphology, structures and tensile properties,
Composites Science and Technology 70, 703–718
37. K. H. Lee, H. Y. Kim, Y. M. La, D. R. Lee and N. H. Sung (2002) Influence of a
mixing solvent with tetrahydrofuran and N, N-dimethylformamide on electrospun
poly(vinyl chloride) nonwoven mats. J Polym Sci Part B: Polym Phys, 40:2259–68.
78
CHAPTER 3
Rheological and Electrical Characterization of Thermoplastic and Thermoset Polymer
Lithium electrolyte.
3.1 Introduction
When it comes to electronic devices and other electronic consumer goods, lithium ion
batteries are the main system used to power them. This is because lithium ion batteries possess
high energy density, a long lifespan and is flexible [1]. However, lithium ions have the propensity
to form dendrites during charge-discharge routes which can lead to explosive hazards. Therefore,
the idea of using lithium ions within polymers as an alternative was proposed. The demand for
lithium ion batteries in numerous devices have increased, therefore, polymer electrolytes research
has gained widespread notoriety due to their technological uses in solid state electrochemical
devices, electrochromic devices, rechargeable lithium batteries, fuel cells, super capacitors,
biosensors [2-7]. Moreover, solid polymer electrolytes (SPEs) are an advantage over liquid or gel
electrolytes as the SPEs have the added mechanical property which would allow for better
maintenance. These electrolytes are important for electronic materials for our everyday use. The
earliest work on ions within a solid came from Armand et al [8] as well as Fenton et al [9] which
prompted further study metal salts in polymers.
Polymers range from highly crystalline stiff polymers to blend polymers, however highly
crystalline polymers are not well suited to become electrolytes as the highly crystalline nature
would not allow for the lithium ions to flow within the polymer matrix. Therefore, a
79
semicrystalline polymer with low crystallinity is better suited. Polyethylene oxide (PEO) is one of
the most sought after polymer used as an electrolyte but PEO tends to crystallize at ambient
temperatures which would hinder the migration and movement of the lithium resulting in a low
conductive electrolyte [3,10-12]. Therefore, polymers need to have good thermal stability; its
polymer backbone needs to be mobile at ambient temperatures and should not crystallize. Many
studies have been executed to show modifications of PEO to develop an improved high
conductive polymer electrolyte [6, 13-16]. These modifications came from linear polymers [17-
19, 27] comb-branched copolymers [20- 21], block copolymers [22-23], cross-linked network
polymers [24] and polymer blends [25-26]. Parveen et al [3] used an amorphous polyurethane to
incorporate into PEO to reduce the crystallinity of the polymer to create an electrolyte fiber.
PCPU has a characteristic two-phase morphology that shows mixing of its hard and soft
segments. PCPU above is Tg makes for a mobile backbone that allows the ions to flow within the
matrix. Polycarbonate polyurethane (PCPU) combined with lithium salt was analyzed for its
ability to be a highly conductive electrolyte that does not easily degrade. PCPU has a Shore A
hardness of 64, whereas not many polyurethanes can reach such soft grades and maintain
processability. This is due to the PCPU’s composition of a hard segment, providing stability, and
soft segment allowing the polymer to flow at high temperatures instead of degrading.
Polyimides are also good contenders for lithium applications. They are high-performance
polymers that possess excellent thermal stability, outstanding mechanical properties, and low
dielectric constants [28]. Moreover, highly aligned polyimide nanofiber membranes prepared by
electrospinning, showed excellent mechanical and thermal properties [33-34]. Electrospun PI
nanofiber membranes which have been intensively investigated resulted in high-performance and
multifunctional composite fiber membranes [32-34]. Cho et al [29], Yang et al [30] and Wu et al
80
[31] investigated and evaluated electrospun polyacrylonitrile (PAN) and poly(vinylidene fluoride)
(PVF) nanofiber based nonwovens in LIBs and exhibited outstanding battery performances, such
as large capacity, high-rate capability and long cycle life. PI has the ability to avoid short
circuiting because it is thermally stable at temperatures above 500⁰C whereas conventional
separators can only go as high as 150⁰C. PI nanofiber nanomembranes’ extraordinary thermal,
mechanical and electrochemical properties demonstrate its capability to be used as an ideal
separator for Lithium ion batteries to achieve high battery performance, such as large capacity,
high-rate capability and long cycle life [28].
Figure 3.1 Polyimide GPI 15.
An ultrasoft thermally stable molded and fibrous polymer electrolyte with lithium salts
was developed by direct addition of industrial grade Lithium phosphate (LiPF6) to novel
polycarbonate polyurethane (PCPU) via ultrasonication. LiPF6 of varying concentration from
12w/w% - 16w/w% was investigated which covers the industrial amount (14 w/w%) used in
electrolytes. The thermal and electrical properties of varying concentrations of PCPU/LIPF6
molded and fibrous electrolytes were investigated using Dynamic Mechanical Analysis (DMA)
and four point probe. DMA showed a high interaction between lithium salts and the polymer
matrix which resulted in a decrease in glass transition temperature of more than ten degrees.
Greater interaction of the PCPU and the lithium salts resulted in an increase in ionic conductivity
81
at room temperature. The resulting polymer electrolyte is highly flexible, thermally stable and has
biocompatible properties which can be useful as biosensors. Through incorporation of lithium
salts, lithium hexafluorophosphate (LiPF6), this composite could lead to an innovative, ultra-soft,
conductive polymer electrolyte film.
Additionally, the research herein looks at variations of an unprocessable polyimide
powder GPI 15, and transforms it into polyimide membranes. Very little literature shows the
ability to electrospun a polyimide. Rather the studies show the electrospinning of the PI precursor
which is a polyamine acid (PAA) and then imidization. Here this study illustrates the ability to
electrospin polyimide powders. The membranes formed are then doped in two concentrations of
lithium salt solutions to create polyimide lithium electrolytes. TGA was used to characterize the
thermal ability of the polyimide fiber and morphological studies were done using SEM. The
characterization methods done on the lithium polyimide fibers include, Fourier transform infrared
spectroscopy (FTIR), and Four Point Probe.
3.2 Experimental
3.2.1 Polymer-Lithium composite synthesis
The solvents used (DMF and THF), to create the polymer lithium composite were dried
using molecular sieves and sealed with parafilm until ready for use. Polycarbonate
polyurethane/lithium composites were prepared by dispersing the lithium salt using a sonicator.
10g of the purified PCPU was dissolved in 100 ml dried THF ( ACS reagent, 99.9% sigma
Aldrich) and then the desired amount of Lithium hexafluorophosphate salt (12-16% w/w) wase
introduced to the solution and then mixed by ultrasonication (Fisher Scientific Sonic
Dismembrator 550) at a mixing rate of 10 minutes with 3 second rest intervals for two hours to
ensure homogeneity of composites. The composite was the solution cast and the resulting
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material was dried overnight under vacuum. The material was then molded using a carver press
and characterized using the following methods.
3.2.2 Electrospinning of Polyimide
For the electrospinning process, each of the solutions was filled up in a 3ml syringe. A
20 gauge needle with a flat tip was used as a spinneret. A collection distance of 20cm was done
and a fixed voltage of 23kV was applied at a feeding rate of 50μl/min. The resulting
nanomembrane was left to dry under vacuum.
3.2.3 Polyimide/Lithium nanomembrane electrolyte
The polymer electrolytes were prepared by soaking the PI fiber membranes in 14 and 16
w/v LiPF6 solutions (DMF: THF) at room temperature for 12 hours in a glove box under nitrogen
atmosphere. The resulting electrolyte was dried under vacuum for two days to ensure complete
dryness.
3.2.4 Dynamic Mechanic Analysis (DMA)
In order to investigate the dynamic viscoelasticity of the PCPU/Lithium electrolyte
composite, dynamic mechanical tests were carried out with a TA Instruments AR-2000 was used
to explore changes in the glass transition, Tg , storage modulus, G', loss modulus, G” and tan δ.
Temperature sweep tests and isothermal frequency sweep tests were performed at a strain within
the materials linear viscoelastic region.
The temperature sweep tests were planned to explore the frequency dependent glass
transition temperature Tg of the material. They were carried out from -120⁰C to 100⁰C, using a
ramp rate of 5⁰C/min, and repeated at frequencies 0.2 to 10Hz. The isothermal frequency sweep
tests were conducted in the range from 1 to 20 Hz and repeated at various temperatures ranging
from -50 to 55⁰C, with an interval of 5⁰C. The stress responses to the strain excitations in these
83
isothermal frequency sweep measurements were recorded automatically, and G’, G’’ and tan δ
were calculated from these measurements.
3.2.5 Four-Point Probe conductivity
Four-point probe is a known instrument used to perform reliable measurements of
electronic transport properties in semiconductors and electrical materials. Conventional four-point
probes are millimeter sized devices with spring loaded electrodes of tungsten carbide [35-36]. The
typical set up is shown in figure 3.2. Two of the probes are used to source the current from the
AC/DC current source and the other two inner probes are used to measure voltage from the
electrometer. The idea of using four probes eliminates measurement errors due to the probe
resistance, the spreading resistance under each probe, and the contact resistance between each
metal probe and the semiconductor material. This technique involves bringing four equally spaced
probes into contact with the material of unknown resistance.
Figure 3.2 Four Point probe set-up.
84
The volume resistivity is calculated with this equation:
𝜋 𝑉
𝜌 = 𝑙𝑛2 × 𝐼 × 𝑡 × 𝑠 (3.1)
where: ρ = volume resistivity (Ω-cm), V = the measured voltage (volts), I = the current applied
(amperes), t = the sample thickness (cm), s = the probe spacing. Conductivity can then be
calculated by taking the reciprocal of the resistivity.
Electrical examination of the PCPU/lithium composites were carried out using four point
probes attached with Kiethley 6220/ 6514 electrometer. Thin film samples were run by applying
1.0mA and voltages were recorded from the electrometer over a 60 second period. To samples of
thickness 0.1 cm, the surface of the PCPU/LiPF6 composite was cut and samples were run over a
24 hour period. The polyimide electrolytes were run over a 5 minute period.
3.2.6 Solution Rheology Measurement
A Fungilab alpha series rotational viscometer equipped with a TR8 spindle was used to
measure the viscosity of the polyimide solutions. 10ml of each solution was placed in the
cylindrical chamber and the spindle is immersed in the solution. The rotational speed was varied,
and viscosity readings were recorded. All measurements were performed at 21⁰C.
3.2.7 Surface Enhanced Microscopy (SEM)
A Hitachi S-800 SEM was used which compromises of a magnification power of
300,000 times the actual sample size. SEM gives information about fiber diameter, bead
formation, quality of the polyimide fiber membranes produced from electrospinning.
85
3.2.8 Fourier Transform Infrared Spectroscopy (FTIR)
Perkin Elmer spectrum two furnished with and Attenuated Total Reflection (ATR)
accessory was utilized for this study. A scanning range of 400-4000cm-1 set at a resolution of
4cm-1 and 16 repetitions were done on the nanocomposites. The neat PI and PI/LiPF6 nanofiber
composites were scanned.
3.2.9 Thermogravimetric Analysis (TGA)
A TA instruments Q500/50 TGA equipped with a standard furnace was used to detect the
degradation temperature of the polymer membranes. A sample weight between 15-20mg was
placed on a tared 100 ml platinum pan. Measurements were carried out under nitrogen
atmosphere as the samples were heated to 800⁰C at a heating ramp rate of 10⁰C per minute.
3.3 Results and Discussion
3.3.1 Dynamic Mechanical Analysis (DMA)
Dynamic Mechanical Analysis can be used to quantify the viscoelastic properties of
polymers. The loss modulus, G", is a measure of the ability of a material to dispel mechanical
energy by converting it into heat. This absorption of mechanical energy is often related to the
movements of molecular segments within the polymer sample [37]. There were two types of
DMA techniques employed, temperature sweep and isothermal frequency sweep. Temperature
sweep DMA was used to determine the rheological behavior of the PCPU lithium nanocomposites
as well as identify the glass transition temperature Tg which is associated with chain slippage and
movement. Tg can be determined from the peak maximum of either the G’ or tan δ.
86
Figure 3.3, 3.4, 3.5 & 3.6 shows the temperature sweep test results for neat PCPU and
PCPU composites at varying frequencies. The storage modulus of the composites displays
changes in the rubbery plateau as well as the primary alpha shift. 12% w/w and 14 %w/w
PCPU/LiPF6 maintain a longer rubbery plateau compared to the 16 %w/w and the neat PCPU.
The 16 % w/w experiences an early melt at around 50⁰C which may be due to high lithium
loading which may have affected the melting of the sample. Figure 3.7 gives us the loss modulus
overlay for neat PCPU and PCPU lithium composites which display differences in the primary
( ) and secondary (β) relaxations of the composites at low temperatures.
Figure 3.8 shows the tan δ results from the temperature sweep. It is evident that the peak
tan δ, and therefore Tg, varies as the %w/w of the PCPU/LIPF6 changes, with higher % w/w
causing a shift of Tg to lower temperatures. This is evidence of plasticization of the amorphous
region of the PCPU matrix which would suggest that the lithium salts are interacting with the soft
segments of the polyurethane as seen by [27]. Table 3.1 shows the G” values of Tg of the different
composites. There is a shift of Tg of approximately a 10 degree difference between the neat PCPU
and the 16%w/w PCPU/LiPF6 composite.
87
Neat pcpu dma neg 120 to 150-0024o
Secondary transition
Figure 3.3 DMA Data: Temperature sweep at multiple frequencies of neat PCPU.
88
DMA-12wt% LiPF6/PCPU electrolyte
Rubbery plateau
Figure 3.4 DMA Data: Temperature sweep at multiple frequencies of 12

wt% PCPU/LiPF6 composite.
89
DMA- 14 WT% LIPF6/PCPU
Figure 3.5 DMA Data: Temperature sweep at multiple frequencies of

14wt% PCPU/LiPF6 composite.
90
DMA-16wt% LiPF6/PCPU electrolyte
Figure 3.6 DMA Data: Temperature sweep at multiple frequencies of 16

wt% PCPU/LiPF6 composite.
91
Overlay
DMA Tg
Neat PCPU
12%w/w PCPU/LiPF6/PCPU
14%w/wPCPU/LiPF6/PCPU
Figure 3.7 DMA Data: Loss modulus plot of neat PCPU and PCPU/LiPF6
composites. Overlay
Neat PCPU DMA Tg

12%w/w PCPU/LiPF6/PCPU
Figure 3.8 DMA Data: tan delta plot of neat PCPU and PCPU/LiPF6
composites.
92
Table 3.1 DMA Data: DMA Tg and tan δ for the PCPU and PCPU/LiPF6 composites.
Sample DMA Tg G” (⁰C) Tan δ height Tan δ width (Δ⁰C)
Neat PCPU -19.4 0.381 55.9
12%w/w LiPF6/PCPU -23.6 0.429 44.8
14%w/w LiPF6/PCPU -28.8 0.447 44.9
16%w/w LiPF6/PCPU --29.7 0.456 50.7
3.3.2 Secondary-relaxation
The secondary relaxation or β-relaxation of neat PCPU and PCPU lithium composites, as
measured by the loss modulus G” Figure 3.7, occurs between temperature range -120 to -80 ºC. It
follows Arrhenius behavior which is characteristic of secondary relaxations in polymers.
Therefore, the activation energy can be obtained using the Arrhenius type relationship between
the experimental frequency and the temperature range in Kelvin.

∆𝐸𝑎
ln 𝑓 = ln 𝑓𝑜 − 3.2
𝑅𝑇
The resulting linear relationship gives us a slope that is used to find the activation energies
(Table 3.2). This activation energy is the amount of energy needed for the pendant methyl group
to rotate. The neat PCPU was found to have an activation energy of 34.4kJ/mol which almost
doubled to 63.7 kJ/mol for 12%w/w PCPU/LiPF6, 64.0 kJ/mol for the 14%w/w PCPU/LiPF6 and
93
65.3 kJ/mol in the 16%w/w PCPU/LiPF6 composite. This demonstrates that the lithium salts
within the backbone creates a higher need for energy in order for the side groups to rotate.
Table 3.2. DMA data: Activation Energy of the β-transition for neat PCPU and
PCPU lithium composites.
Sample Ea (kCal/mol) Ea (kJ/mol)
Neat PCPU 8.2 34.4
12%w/w PCPU/LiPF6 15.2 63.7
14%w/w PCPU/LiPF6 15.3 64.0
16%w/w PCPU/LiPF6 15.6 65.3
3.3.3 Primary-relaxation
For PCPU and its lithium composites, the alpha transition involves micro Brownian
motion in the main chain and conformational changes in the phenyl groups [38-39, 41]. The α
relaxation is apparent in tan δ vs temperature plots. The maxima in tan δ for Tg occur from -14.9
to -5.05 °C for neat PCPU,-10.8 to -9.1°C for 12% w/w PCPU/LiPF6, -4.1 to -20.3 °C for 14%
w/w PCPU/LiPF6 and from -20.7 to -20.1 °C for 16% w/w PCPU/LiPF6 (Figure 3.7A-D). The
plots of log frequency vs inverse temperature unveiled a curved behavior predicted by the
William-Landel-Ferry (WLF) equation (3.3) [40-42].
−𝐶1 (𝑇−𝑇0 )
log 𝑎 𝑇 = 3.3
𝐶2 +(𝑇−𝑇0 )
Where the aT is the shift factor that corresponds to frequency, and C1 and C2 are WLF constants.
These constants can be determined using the second DMA technique which is the isothermal
frequency sweeps.
94
1.4 0
1.3 a. b.
-0.2
Log Fmax (Hz)

Log Fmax (Hz)
1.2 -0.4
1.1
-0.6
1
-0.8
0.9
-1
0.8
-1.2
0.7
3.795 3.8 3.805 3.81 3.815
3.55 3.6 3.65 3.7 3.75
1000/T K-1
1000/T K-1
1.2 0
1 c. d.
0.8
-0.2
0.6 Log Fmax (HZ)
LogFmax (Hz)
-0.4
0.4
0.2 -0.6
0
-0.8
-0.2
-0.4 -1
-0.6
-1.2
-0.8
3.95 3.955 3.96 3.965
3.7 3.8 3.9 4
1000/T K-1
1000/T K-1
Figure 3.9 Plots of ln frequency vs 1000/T showing WLF behavior at Tg for a. neat PCPU,
b. 12% w/w PCPU/LiPF6, c. 14%w/w PCPU/LiPF6 and d. 16% w/w PCPU/LiPF6.
Figure 3.10a, shows the isothermal frequency sweep results for G’ for temperatures
between -50 to 55 °C. The graph demonstrates that at higher temperatures above the Tg from 0⁰C
to 55⁰C, there is a frequency dependence occurring which means that there is less time for
relaxation to occur but at lower temperatures a change in frequency does not change the storage
modulus. Figure 3.10b shows the master curve fit after the TTS is imposed. From this the WLF
graph is plotted (Figures 3.11-3.14), and the values of C1 and C2 were found to be 33.1, 217.7K,
for neat PCPU. The WLF equation describes the effect of temperature on the shift factor for many
95
polymers near their Tg. By putting the C1 and C2 values into equation 3.3 we would get the
following Arrhenius relationship;
𝐶
∆𝐸𝑎 = (−2.303) (𝐶1 ) 𝑅𝑇 2 (3.4)
2
Where, Ea is the activation energy, predicted by the temperature sweep experiments at the glass
transition region. The Activation energy from the WLF showed a much higher Ea because there is
a greater amount of energy needed for the polymer chains to begin moving in association with
each other.
neat pcpu freq sweep-0089o
Figure 3.10a. Isothermal frequency sweeps for neat PCPU and 3.10b. the master curve.
96
neat pcpu freq sweep-0089o
c1: 33.1850
c2: 217.029 K
Tref: -19.8247 °C
R2: 0.998615
Activation Energy: 183.482 kJ/mol

Tref: -19.8247 °C
R2: 0.999582
Figure 3.11 DMA data: WLF plot of neat PCPU.
Figure 3.12 DMA data: WLF plot for 12% w/w LiPF6/PCPU.
97
14wt Lipf6 freq sweep-0082o
c1: 41.7312
c2: 234.175 K
Tref: -30.1216 °C
R2: 0.999571

Tref: -30.1216 °C
R2: 0.999987
Figure 3.13 DMA data: WLF plot for 14%w/w LiPF6/PCPU.
98
16wt Lipf6 freq sweep -0087o
c1: 41.4971
c2: 211.755 K
Tref: -35.5678 °C
R2: 0.998433

Tref: -35.5678 °C
R2: 0.999874
Figure 3.14 DMA data: WLF plot for 16% w/w LiPF6/PCPU.
3.3.4 Conductivity
Resistivity and conductivity are fundamental properties for semiconductors and are critical
parameters in materials research [43]. The four-point probe measurements on the PCPU/lithium
composite electrolyte were done and the conductivity was measured. Figure 3.15 shows the
conductivity for the 12%,14% and 16% w/w PCPU/LiPF6 vs time. The neat sample had a too low
conductivity to display on the chart but it was recorded in table 3.3 as 2.4 e-10 S/cm. The graph
shows that the conductivity of the lithium composites increases as the % w/w of the lithium was
increased. In addition, the conductivity levels out overtime. This indicates that as the current is
initially passed through the polymer material there is a surge of lithium activity which then levels
off after a minute to give us the final constant voltage reading.
99
The conductivity was also taken of a circular mold with a thickness of 0.1cm which
allowed us to cut away the surface to see if there is any change in the conductive reading over
time Figures 3.16-3.18 displays the conductivity measurement over a period of 24 hours from the
pristine surface to the surface being cut away and what was the conductivity after 24 hrs. What
was observed is that when the surface is cut away the conductivity of the lithium composites
increased. This is due to the hydrogen bonding that is known to be exposed when the surface of
PCPU is cut away and this allowed for the availability of the lithium to become more accessible
which lead to the surge in the conductivity from 4.0 e-3 to 1.5e-2 S/cm in the 12%w/w, 2.0e-3 to
1.7 e-2 in the 14 % w/w and 5.0e-3 to 2.8 e-2 in the 16 %w/w. After 1 hour the conductivity
reduces drastically for the 12 and 14 %w/w down to 1.5 e-3 and 2.9 e-3 S/cm but there was a
small reduction to 2.3e-2 for the 16 w.t.%. Hence, it appears that the high lithium loading in the
16% w/w allows for the slowing of the H-bonds within the polymer matrix which permitted the
conductivity of the mold to remain high. After the 24 hour period the lithium composites
conductivity was closer to its starting conductive material.
100
5.050E-03
4.550E-03
4.050E-03
3.550E-03
Conductivity (S-cm)
3.050E-03
2.550E-03 16wt% LiPF6

14wt%LiPF6
2.050E-03
12wt% LiPF6
1.550E-03
1.050E-03
5.500E-04
5.000E-05
0 10 20 30 40 50 60
Time (sec)
Figure 3.15 Conductivity data: Conductivity of PCPU/LiPF6 thin film composites.
1.800E-02
12 wt % LiPF6/ PCPU
1.600E-02
1.400E-02
Conductivity (Scm)
1.200E-02 12 wt LiPF6 cut
1.000E-02
1 hr after surface cut
8.000E-03
6.000E-03 24 hr after surface cut
4.000E-03
12 wt% LiPF6 pcpu uncut
2.000E-03 surface
0.000E+00
0 10 20 30 40 50 60 70
time (s)
Figure 3.16 Conductivity vs time for 12 wt% PCPU/LiPF6 composite for cut and uncut
surface.
101
1.600E-02
14 wt % LiPF6/PCPU
1.400E-02
1.200E-02
Conductivity (Scm)
1.000E-02 Series1
8.000E-03 1 hr after cut
24 hr after cut
6.000E-03
14wt Lipf6 uncut surface
4.000E-03
2.000E-03
0.000E+00
0 10 20 30 40 50 60 70
time (sec)
Figure 3.17 Conductivity vs time for 14% w/w PCPU/LiPF6 composite for cut and uncut
surface.
3.000E-02
16 wt % LiPF6/PCPU mold
2.500E-02 LiPF6 surface cut
1 hr after cut
Conductivty (Scm)
2.000E-02
24 hr after cut
1.500E-02 uncut lipf6/pcpu surface
1.000E-02
5.000E-03
0.000E+00
0 10 20 30 40 50 60
time (min)
Figure 3.18 Conductivity vs time for 16wt% PCPU/LiPF6 composite for cut and uncut
surface.
102
Table 3.3 Conductivity data: Conductivities for uncut and cut surfaces of PCPU and
PCPU/LiPF6 nanocomposites.
Conductivity σ (S/cm)
Sample
Uncut Cut After 1 hr After 24 hr
neat PCPU 2.4 E-10 2.3 E-10 2.30E-10 2.30E-10
12wt% PCPU/LiPF6 9.1 E-4 2.60E-03 1.5 E-3 9.90E-04
14wt% PCPU/LiPF6 1.4 E-3 4.40E-03 2.9 E-3 1.40E-03
16wt% PCPU/ LiPF6 1.70E-03 3.2 E-3 3.2 E-3 2.0 E-3
3.3.5 Polyimide nanomembrane electrolyte
3.3.5.1 Solution Rheology
Figure 3.19 shows the solution viscosity as a function of shear rate for the 20% w/v
polyimides before electrospinning. Viscosity vs shear rate graphs tells us the different the
behavior of fluids. For a dilitant fluid there would be shear thickening with increasing shear stress
meaning that the viscosity would be increasing. For a pseudo plastic fluid there would be gradual
decrese in viscosity with changing stress through shear thinning and for a newtonian fluid , the
viscosity would be independent of the changing shear rate. The polyimide solutions demonstrates
psudoplastic behavior as the shear rates goes from 9s-1 to 170s-1 the viscosity of the polymer
solutions decrease from 97mPa (XP02691) to 12 mPa (P347). Another aspect realised by the
graph identifies an increase in Mw allows for a higher viscosity of the solutions from 25 mPa
(R127), whose Mw is ~68,000, to 37 mPa ( P347) whose Mw is ~78,000 and to 80 mPa (
XP02691) whose Mw ia 79,500. The polyimide solutions are low in viscosities which was also
evident by Liu et al [45] but they also exhibited pseudo plastic fluid behavior which suggest that
the orientation of the polymer chains influences the behavior of the fluid.
103
120
100
80
Viscosity (mPa)
60 R127
XP02691
40 P347
20
0
0.0 50.0 100.0 150.0 200.0
Shear rate (1/s)
Figure 3.19 Viscosity vs shear rate for pre-spun polyimide solutions.
3.3.5.2 Scanning Electron Microscopy (SEM)
The polyimide nanofibers were successfully electrospun and the SEM images are shown
in figure 3.20. The P347 PI showed fibers with diameters ranging from 155 to 650 nm and it was
easily plied from the foil collector. The R127 had fiber sizes of 341 nm but the membrane itself
could not be taken off of the foil to be used in the doping step. The XP0291 contained fiber
diameter sizes ranging from 297 to 800 nm but the pore sizes were too large for testing for battery
separator purposes. Hence polyimide P347 was used as the material to be characterized as well as
to be doped in lithium salt solution to form an electrolyte.
104
Figure 3.20 A-C. SEM images of neat polyimide fibers P347, R127 & XP02691. D-F.
Images of the resultant fiber membranes collected.
3.3.5.3 Thermogravimetric Analysis (TGA)
Figure 3.21 shows the thermal gravimetric curves for PI P347 at different 15 and 20wt%.
The initial weight lost is likely due to packing of the fibers in the weight pan. The weight losses in
the 100–200 ⁰C range are likely due to solvent effects, as the boiling point of DMF occurs at
153⁰C which happened to Liu et al [44]. The onset temperature of decomposition for the 15wt%
and 20wt% PI fiber ensued at 436⁰C and 475 ⁰C respectively. Additionally, the PI fibers held 40%
and 50% of their weight at the highest temperature run of 800⁰C. This demonstrates the thermal
stability of the polymer at high temperatures under nitrogen atmosphere.
105
474.5⁰C
436.6⁰C
Figure 3.21 TGA Data: Thermogravimetric curves of 15wt% and 20wt% PI fibers
membranes.
3.3.5.4 Fourier-transform Infrared Spectroscopy (FTIR)
The FTIR spectra for the polyimide fiber and fiber membrane electrolytes are shown in
figure 3.22. The spectra show the typical layout for polyimides, the absence of the N-O and –OH
peak [28]. The spectra appear very similar for the three composites but there are peaks found in
the PI/Li composite membranes. They are, 1658 cm-1 which is indicative of lithium interaction
between the C-N bonds of the PI, 1455 cm-1, 1355 cm-1, 1298, 1138 cm-1, 511 cm-1 in the
fingerprint region all may be attributed to lithium salts added that is not in the neat polyimide
fiber.
106
100
1658 cm-1
%Transmitance
90 1455 1
cm-1 2
9
8
c
80 %T-Neat PI m
%T 14wt% LiPF6/PI fiber 1355 -cm-1
1
%T-16wt%LiPF6/PI fiber
70
4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wavenumber cm-1
Figure 3.22 FTIR spectra of neat polyimide (red) and 14%w/w (green), 16% w/w (purple)
PI/LiPF6 fiber membranes.
3.3.5.5 Conductivity of Polyimide fibers
The conductivity, σ, at room temperature of the PI/LiPF6 nanomembranes, over a five-
minute period, is shown in figure 3.23. It took five minutes of testing for the samples to level to a
constant voltage. The conductivity of the polyimide fibers increased tremendously with increasing
lithium hexafluorophosphate. The room temperature conductivity of the PI/LiPF6 fiber

-3
membranes with 14%w/w LiPF6 was 9.3 x 10 S/cm after the five-minute period. Moreover,
when the LiPF6 salt increased to a concentration of 16% w/w the conductivity improved to 1.3 x
10-2 S/cm. This is indicative that the addition of the lithium salts creates a conductive polyimide
fiber composite.
107
1.600E-02
Conductivity of neat PI fiber vs PI/LiPF6 fiber
1.400E-02
1.200E-02
Conductivty (Scm)
1.000E-02
8.000E-03
14wt% LiPF6/PI fiber
6.000E-03
Neat PI
4.000E-03 16wt%LiPF6/PI fiber
2.000E-03
0.000E+00
0 100 200 300 400
time (s)
Figure 3.23 Conductivity vs time graph of neat polyimide (red) and 14%w/w (green),
16% w/w (purple) PI/LiPF6 fiber membranes.
3.4 Conclusion
Lithium hexafluorophosphate salts were successfully incorporated in to an ultrasoft PCPU
as well as a polyimide nanofiber membrane. Thermal and rheological analysis of the
PCPU/lithium composite electrolyte showed Arrhenius behavior in the beta transition and WLF
behavior around the Tg. The Activation energies in the beta transition from PCPU/LiPF6
composites dramatically increased compared to the neat PCPU. The possibility exists that the
structure and arrangement of the lithium salt may have attributed to the high activation energies.
The polyimide nanofiber was successfully transformed from an unusable polyimide
powder to a nanomembrane for use a lithium battery separator. The nanofiber did not possess the
ability to be thermally characterized via DSC as there were no Tg present. However, TGA shows
108
that the polyimide membrane is thermally stable in fiber form and conductivity measurements
show that the addition of the lithium salts created a highly conductive membrane.
3.5 References
1. C. Y. Li, Crystal Engineering for High Performance Solid Polymer Electrolytes , 61st
Annual Report on Research 2016.
2. J. Kim, Y. Lee, I. Lee,T. Kim, M. Ryou, J. Wook Choi (2014), Large area multi-stacked
lithium-ion batteries for flexible and rollable applications, J. Mater. Chem. A, 2, 10862
3. J. Shahitha Parveen, S.S.M. Abdul Majeed (2013), Poly (ethylene oxide)/Polyurethane
based gel polymer electrolytes for lithium batteries, International Journal of Scientific &
Engineering Research, Volume 4, Issue 12.
4. A. I. Gopalan, P. Santhosh, K. M. Manesh, J. Hee Nho, S. Ho Kim, C. Hwang, K. Lee
(2008), Development of Electrospun PVdF – PAN membrane – based Polymer
electrolytes for Lithium batteries, Journal of Membrane Science, 325, pp. 683-690.
5. J. Choi, Y. Kang, H. Shim, D. W. Kim, E. Cha, D. Kim (2010), Cycling performance of a
Lithium – ion polymer cell assembled by in- situ chemical cross – linking with
Fluorinated phosphorous-based cross – linking agent, Journal of Power Sources, 195, pp.
6177-6181.
6. S. Wang, K. Min (2010), Solid polymer electrolytes of blends of polyurethane and
polyether modified polysiloxane and their ionic conductivity, Polymer 51 2621-2628.
7. F.M. Gray (1997) ,Polymer electrolytes. UK: The Royal Society of Chemistry.
8. M. Armand (1986), Polymer Electrolytes. Annu. Rev. Mater. Res. 16, 245–261.
9. D.E. Fenton, J.M. Parker, P.V. Wright (1973), Complexes of alkali metal ions with
poly(ethylene oxide). Polymer 14, 589.
109
10. H. Cheradame, J. F. LeNest (1980), Experimental Demonstration of the importance of the
glass transition temperature of the ionic conductivity of macromolecular networks,
Makromol. Chem. Rapid Comm., 1, p595-598
11. J. R. Mac Callum, C. A. Vincent (1987), Polymer Electrolyte Reviews 1; Elsevier
London, p 103.
12. P. P. Prosini, S. Prosini (2002), A lithium battery electrolyte based on gelled polyethylene,
Solid state ionics, 146, pp 65 – 72.
13. T. Wen, M. Wu , C. Yang (1999), Spectroscopic Investigations of
Poly(oxypropylene)glycol-Based Waterborne Polyurethane Doped with Lithium
Perchlorate, Macromolecules, 32, 2712-2720.
14. J. D. van Heumen and J. R. Stevens (1995), The Role of Lithium Salts in the Conductivity
and Phase Morphology of a Thermoplastic Polyurethane Macromolecules,28, 4268-4277.
15. F. M. Gray (1991), Solid Polymer Electrolytes-Fundamentals and Technological
Applications; VCH: Weinheim, Germany, Chapter 6.
16. Z. Zhong, Q. Cao, B. Jing, X. Wang, X. Li, H. Deng (2012), Electrospun PVdF- PVC
nanofibrous polymer electrolytes for polymer lithium – ion batteries, Materials Science
and Engineering B 177, pp 86-91.
17. M. Watanabe, M. Rikukawa, K. Sanui, K. Ogata, H. Kato, T. Kobayashi, Z. Ohtaki
(1984), Ionic-Conductivity of Polymer Complexes Formed by Poly(Ethylene Succinate)
and Lithium Perchlorate,Macromolecules,17:2902-2908.
18. C. S. Harris, D. F. Shriver, M. A. Ratner, (1986), Complex formation of polyethylenimine
with sodium triflate and conductivity behavior of the complexes Macromolecules, 19,
987– 989 DOI: 10.1021/ma00158a009.
110
19. S. Clancy, D. F. Shriver, and L. A. Ochrymowycz (1986), Preparation and
characterization of polymeric solid electrolytes from poly(alkylene sulfides) and silver
salts, Macromolecules 19:606-611.
20. D. J. Bannister, G. R. Davies, I. M. Ward, and J. F. McIntyre (1984), Ionic conductivities
of poly(methoxypolyethyleneglycol monomethacrylate), Polymer 25:1600-1602.
21. J. M. G. Cowie and R. Ferguson (1985), Glass and Subglass Transitions in a Series of
Poly(itaconate ester)s with Methyl-Terminated Poly(ethylene oxide) Side Chains, J.
Polym. Sci .Polym. Phys. Ed.;23: 2181-2191.
22. F. Alloin, J.-Y. Sanchez, M. Armand (1993), Triblock copolymers and networks
incorporating oligo (oxyethylene) chains, Solid State Ionics, 60:3-9.
23. Alloin F, Sanchez JY, Armand M. Electrochem Acta 1992;37:1729.
24. H. W. Meyer (1998), Polymer Electrolytes for Lithium-Ion Batteries, Adv Mater, 10:439.
25. B. K. Choi, Y. W. Kim and H. K. Shin (2000), Ionic conduction in PEO–PAN blend
polymer electrolytes, Electrochim Acta, 45:1371.
26. T. Wen, and W. Chen (2000) ,Blending thermoplastic polyurethanes and poly(ethylene
oxide) for composite electrolytes via a mixture design approach, J Appl Polym Sci,
77:680.
27. L. Porcarelli, C. Gerbaldi, F. Bella and J. R. Nair (2016) Super Soft All-Ethylene Oxide
Polymer Electrolyte for Safe All-Solid Lithium Batteries, Scientific Reports, 6:19892.
28. Y. E. Miao, G. N. Zhu, H. Hou, Y. Y. Xia and T. Liu (2013) Electrospun polyimide
nanofiber-based nonwoven separators for lithium-ion batteries, Journal of Power Sources,
226, 82-86.
111
29. T. H. Cho, M. Tanaka, H. Onishi, Y. Kondo, T. Nakamura, H. Yamazaki, S. Tanase and
T. Sakai (2008), Battery performances and thermal stability of polyacrylonitrile nano-
fiber-based nonwoven separators for Li-ion battery, J. Power Sources, 181, 155-160.
30. C. Yang, Z. Jia, Z. Guan and L. Wang (2009) Polyvinylidene fluoride membrane by novel
electrospinning system for separator of Li-ion batteries, J. Power Sources, 189, 716-720.
31. N. Wu, Q. Cao, X. Wang, S. Li, X. Li and H. Deng (2011), In situ ceramic fillers of
electrospun thermoplastic polyurethane/poly(vinylidene fluoride) based gel polymer
electrolytes for Li-ion batteries, J.Power Sources, 196, 9751-9756.
32. L. S. Carnell, E. J. Siochi, N. M. Holloway, R. M. Stephens, C. Rhim, L. E. Niklason and
R. L. Clark (2008), Aligned Mats from Electrospun Single Fibers, Macromolecules, 41,
5345-5349.
33. D. Chen, T. X. Liu, X. P. Zhou, W. W. Tjiu and H. Q. Hou (2009), Electrospinning
fabrication of high strength and toughness polyimide nanofiber membranes containing
multiwalled carbon nanotubes, J. Phys. Chem. B 113, 9741-9748.
34. D. Chen, R. Y. Wang,W. W.Tjiu and T. X. Liu (2011), High performance polyimide
composite films prepared by homogeneity reinforcement of electrospun nanofibers,
Compos. Sci. Technol.71, 1556-1562.
35. Keithley Instruments, Inc. (2004), Low Level Measurements Handbook, 6th ed.,
Cleveland, Ohio.
36. K. Mohomed (2006), Ph.D. Dissertation, Thermal analyses of hydrophilic polymers used
in nanocomposites and biocompatible coatings, University of South Florida.
37. G. J. Pratt and M. J. A. Smith (1986), Dielectric response of commercial polycarbonate,
Br. Polym. J., 18:2, 105-11.
112
38. H. W. Spiess (1983), Molecular dynamics of solid polymers as revealed by deuteron
NMR. Colloid Polym. Sci., 261:3, 193-209.
39. M. L. Williams, R. F. Landel, and J. D. Ferry (1955) The temperature dependence of
relaxation mechanisms in amorphous polymers and other glass-forming liquids, J. Am.
Chem. Soc., 77, 3701-3707.
40. P. Jain (2013), Ph.D. Dissertation, Characterizing Interactions between Chromophores in
Synthetic and Natural Macromolecular Films via MALDI-TOF, IBF and Dielectric
Analyzer. University of South Florida.
41. U. Gedde (1999) Polymer Physics. London: Chapman and Hall.
42. M. Shahrousvand, M. S. Hoseinian, M. Ghollasi, A. Karbalaeimahdi, A. Salimi, F. A.
Tabar (2017), Flexible magnetic polyurethane/Fe2O3 nanoparticles as organic-inorganic
nanocomposites for biomedical applications: Properties and cell behavior, Materials
Science and Engineering C, 74, 556–567.
43. CAPRES Vancouver (2002) Micro Four-Point Probe Application note, CAPRES A/S.
44. J. Liu, J. Huang, E. K. Wujcik, B. Qiu, D. Rutman, X. Zhang, E. Salazard, S. Wei, Z. Guo
(2015), Hydrophobic Electrospun Polyimide Nanofibers for Self-cleaning Materials,
Macromol. Mater. Eng. 300, 358–368.
113
APPENDIX A: CHAPTER 1
Complex Viscosity of PCPU/ Nano Ag at Different Temperatures
ŋ Pa.s
ŋ Pa.s
Ẏ (1/s)
Ẏ (1/s)
ŋ Pa.s
ŋ Pa.s
Ẏ (1/s)
Ẏ (1/s)
ŋ Pa.s
ŋ Pa.s
Ẏ (1/s) 114 Ẏ (1/s)

ŋ Pa.s
ŋ Pa.s
Ẏ (1/s) Ẏ (1/s)
ŋ Pa.s
ŋ Pa.s
Ẏ (1/s)
Ẏ (1/s)
ŋ Pa.s
ŋ Pa.s
Ẏ (1/s) Ẏ (1/s)
115
ŋ Pa.s
ŋ Pa.s
Ẏ (1/s) Ẏ (1/s)
ŋ Pa.s
ŋ Pa.s
Ẏ (1/s)
Ẏ (1/s)
ŋ Pa.s
ŋ Pa.s
Ẏ (1/s) Ẏ (1/s)
116
12
y = 7527.6x - 8.045
11 R² = 0.9996
Ea=14.9 kCal/mol
ln n (Pas)
10
9
8
7
0.0021 0.0023 0.0025 0.0027
1/T (K-1)
Melt Rheology Data: Arrhenius plot of melt viscosity for PCPU/0.1wt%Ag.
13
y = 7518.3x - 8.1573
12 R² = 0.9981
11 Ea =14.9 kCal/mol
ln ŋ (Pa-s)
10
9
8
7
6
0.0021 0.0023 0.0025 0.0027
1/T (K-1)
14
y = 7665.6x - 8.1405
13 R² = 0.9946
12 Ea= 15.2 kCal/mol
ln (ŋ)
11
10
9
8
0.0023 0.0025 0.0027
1/T (K-1)
117
13
y = 7746.5x - 8.4454
12 R² = 0.9974
11 Ea= 15.4kCal/mol
ln (ŋ)
10
8
0.0023 0.0025 0.0027
1/T (K-1)

13 y = 7486x - 8.2354
R² = 1
12
Ea=14.9 kCal/mol
11
ln (ŋ)
10
8
0.0023 0.0025 0.0027
1/T (K-1)

12
y = 7489.7x - 8.409
11.5
R² = 0.9998
11
10.5 Ea 14.9 kCal/mol
ln (ŋ)
10
9.5
9
8.5
8
0.0023 0.0024 0.0025 0.0026 0.0027
1/T (K-1)
118
13
12 y = 8398.3x - 9.8813
R² = 0.9993
11
Ea= 16.7
10
ln ŋ
9
8
7
6
0.0022 0.0023 0.0024 0.0025 0.0026 0.0027 0.0028
1/T (K-1)
Melt Rheology Data: Arrhenius plot of melt viscosity for PCPU/0.1wt%SiO2.
13
y = 8735.4x - 10.789
12 R² = 0.9964
Ea= 17.3 kCal/mol
11
ln (ŋ)
10
9
8
0.0022 0.0024 0.0026 0.0028
1/T (K-1)

12
y = 8442.9x - 10.468
R² = 0.9995
11
Ea = 16.8
ln (ŋ)
10
8
0.0022 0.0024 0.0026
1/T (K-1)
119
12
y = 8351.7x - 10.303
R² = 1
11
Ea= 16.6
10
ln (ŋ)
8
0.0022 0.0024 0.0026
1/T (K-1)

12
y = 6716.5x - 6.4602
R² = 0.9899
11
Ea= 13.3
ln (ŋ)
10
8
0.0022 0.0024 0.0026 0.0028
1/T (K-1)

13
y = 7327.7x - 7.376
12 R² = 0.9987
11 Ea=14.6 kCal/mol
ln (ŋ)
10
8
0.0022 0.0023 0.0024 0.0025 0.0026 0.0027 0.0028
1/T (K-1)
120
14
y = 8390.8x - 10.308
12 R² = 0.999
10 Ea=16.7 kCal/mol
8
ln (η)
0
0.002 0.0022 0.0024 0.0026 0.0028
1/T (K-1)
Melt Rheology Data: Arrhenius plot of melt viscosity for PCPU/0.1wt%cb.
13
y = 8056.2x - 9.0602
12 R² = 0.9976
Ea= 16.0 kCal /mol

11
ln (η)
10
8
0.002 0.0022 0.0024 0.0026 0.0028
1/T (K-1)
121
11.5
y = 7677.3x - 8.253
11 R² = 0.996
10.5 Ea= 16.4 kCal/mol

10
ln (ŋ)
9.5
9
8.5
8
0.00220.002250.00230.002350.00240.002450.00250.002550.0026
1/T (K-1)
13
12.5 y = 14977x - 25.725
12 R² = 0.9949
11.5 Ea= 29.7

11 kCal/mol
ln (ŋ)
10.5
10
9.5
9
8.5
8
0.00235 0.0024 0.00245 0.0025 0.00255 0.0026
1/T (K-1)
122
12.5 y = 13325x - 21.832
12 R² = 0.9922
11.5 Ea= 26.4 kCal/mol
11
10.5
ln (ŋ)
10
9.5
9
8.5
8
0.00235 0.0024 0.00245 0.0025 0.00255 0.0026
1/T (K-1)
12.5
12
y = 14060x - 23.578
11.5 R² = 1
11
27.9 kCal/mol
10.5
ln (ŋ)
10
9.5
9
8.5
8
0.00235 0.0024 0.00245 0.0025 0.00255 0.0026
1/T (K-1)
123
APPENDIX B: Chapter 2
5
38.4
4
3
Intensity
44.6
2 64.6 77.5
0
20 30 40
2θ (⁰)50 60 70 80 90
Figure B1. WAXS on nanosilver powder.
1.5 21.9
Intensity
0.5
0
10 15 20 2θ (⁰) 25 30 35 40
Figure B2. WAXS on nanosilica powder.
124
7
6 24.5
5
Intensity
3
43.5
2
0
20 30 40 50 2θ (⁰) 60 70 80 90
Figure B3. WAXS on carbon black nanoparticle powder.
125
ABOUT THE AUTHOR
Tamalia Julien received a B.S. Degree in Chemistry from Florida A&M University in
2011. She entered the Ph.D. Chemistry program at the University of South Florida in Fall 2011
and officially joined Dr. Julie Harmon’s polymer materials research lab in Spring 2012.
While in the Ph.D. program at the University of South Florida, Tamalia was awarded the
Fred L & Helen M Tharp Endowed Scholarship Award (2015, 2017), the NOBCChe Advancing
Science Travel Grant (2015, 2017) and placed first at the 15th Annual Raymond Castle
Conference Poster Presentation.
Tamalia has co-authored three publications in various peer-reviewed scientific journals
and has participated in nine conference presentations at several regional chemical meetings.

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University of South Florida

Synthesis, Modification, Characterization and

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Scholar Commons Citation

Thermoplastic Polymer Composites and Nanocomposites

A dissertation submitted in the partial fulfillment

Major Professor: Julie P. Harmon, Ph.D.

Keywords: Polycarbonate Polyurethane, Nanoparticles, Nanosilica, Nanosilver, Carbon black,

Copyright © 2018, Tamalia Julien

friends, I am truly thankful and appreciative of your love and support.

together and for making my college experience more enjoyable.

List of Tables ................................................................................................................................. iv

List of Figures ..................................................................................................................................v

List of Equations ..............................................................................................................................x

Chapter 1: Thermal and Mechanical Analysis of Sustainable Biopolymer Nanocomposites .........1

1.1 Introduction ...................................................................................................................1

Chapter 2: Fabrication of Polycarbonate Polyurethane Nanofibers and Nanomembranes ............43

2.1 Introduction ..................................................................................................................43

Chapter 3: Rheological and Electrical Characterization of Thermoplastic and Thermoset Polymer

3.1 Introduction ..................................................................................................................79

Figure 1.1 Schematic representation of the dispersion of nanoparticles in the

Figure 1.6 Water contact angle of pristine and ruptures PCPU/ Ag

Figure 1.8 Water contact angle of pristine and ruptures PCPU/ CB

Figure 2.1 Electrospinning set up ..................................................................................................44

Figure 3.1 Polyimide GPI 15 .........................................................................................................81

Figure 3.2 Four Point probe set-up ................................................................................................84

Figure 3.5 DMA Data: Temperature sweep at multiple frequencies of 14wt%

Figure 3.6 DMA Data: Temperature sweep at multiple frequencies of 16 wt%

Figure 3.11 DMA data: WLF plot of neat PCPU .........................................................................97

Equation 1.1: Young’s Equation ....................................................................................................7

Equation 1.2: Dupre’s Definition of Adhesion Energy ..................................................................7

Equation 1.3: Adhesion Energy as a function of polar and dispersive

Equation 1.4: Fowkes Primary Equation ........................................................................................7

Equation 1.5: Condensation of Fowkes Primary Equation ............................................................8

Equation 1.6: Surface Free Energy Calculation .............................................................................8

Equation 1.7: Arrhenius Expression for Melt Viscosity ..............................................................24

Equation 3.1: Resistivity Calculation ...........................................................................................85

Equation 3.2: Arrhenius Equation ................................................................................................93

Equation 3.3: William-Landel-Ferry Equation.............................................................................94

Equation 3.4: Arrhenius Relationship to WLF .............................................................................96

This dissertation focuses on the versatility and integrity of a novel, ultrasoft

polycarbonate polyurethane (PCPU) by the introduction of nanoparticles and lithium salts.

properties and uses within the medical and industrial fields.

An industrial batch of an ultrasoft thermoplastic polyurethane (TPU) was synthesized using a

cyclohexylisocyanate), and a polycarbonate polyol made up of 1,6- hexanediol and 3-methyl-1,5-

polycarbonate polyol with a chain extender, 1,4-butanediol. Biocompatibility testing such as

another dimension was added to this research.

The addition of nanoparticles and nanofillers to polyurethane can express enhanced

mechanical, thermal and adhesion properties. The incorporation of nanoparticles such as

calorimetry (DSC), parallel plate rheology and tensile testing.

nanomembranes through a process known as electrospinning. The resulting PCPU

nanomembranes were investigated using contact angle measurements, thermogravimetric

analysis (TGA), DSC, WAXS, SAXS and tensile testing.

The final chapter focuses on investigating the rheological properties of PCPU/lithium

electrolytes as well as transforming an unprocessable polyimide powder into a nanomembrane.

Polymer nanocomposites are created when nanoparticles are introduced to polymer

systems whether post synthetically or in-situ polymerization [1–4]. The formation of

nanocomposites by introducing nanoparticles as a reinforcing filler with the goal of enhancing

Figure 1.1 Schematic representation of the dispersion of nanoparticles in the

nanomaterials. Because of these attributes, nanotechnology attained acceptance by industrial

polyurethane is an ultrasoft polymer synthesized with methylene bis (4-cyclohexylisocyanate),

oil have allowed polyurethanes to be used in many demanding applications [22-24].

excellent properties including toughness, abrasion resistive, excellent hydrolytic stability,

industries such as electronics, automotive, sporting goods and foams [35-38].