Mines

STRUCTURE-PROPERTY RELATIONSHIPS IN GRAPHENE/POLYMER
NANOCOMPOSITES
by
Muhammad Z. Iqbal
© Copyright by Muhammad Z. Iqbal, 2016
All rights reserved

A thesis submitted to the Faculty and Board of Trustees of the Colorado School of Mines
in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Chemical
Engineering).
Golden, Colorado
Date: ________________
Signed: ________________________________________
Muhammad Z. Iqbal
Signed: ________________________________________
Dr. Andrew Herring
Thesis Advisor
Signed: ________________________________________
Dr. Matthew W. Liberatore
Thesis Co-advisor
Golden, Colorado
Date: _________________
Signed: ________________________________________
Dr. David Marr
Professor and Head
Department of Chemical and Biological Engineering
ii
ABSTRACT
Graphene’s unique combination of excellent electrical, thermal, and mechanical
properties can provide multi-functional reinforcement for polymer nanocomposites. However,
poor dispersion of graphene in non-polar polyolefins limits its applications as a universal filler.
Thus, the overall goal of this thesis was to improve graphene's dispersion in graphene/polyolefin
nanocomposites and develop processing-structure-property relationships.
A new polymer matrix was synthesized by blending polyethylene (PE) with oxidized
polyethylene (OPE). Inclusion of OPE in PE produced miscible blends, but the miscibility
decreased with increasing OPE loading. Meanwhile, the Young's modulus of blends increased
with increasing OPE concentration, attributed to decreased long period order in PE and increased
crystallinity. In addition, the miscibility of OPE in PE substantially reduced the viscosity of
blends.
Using thermally reduced graphene (TRG) produced by simultaneous thermal exfoliation
and reduction of graphite oxide, electrically conductive nanocomposites were manufactured by
incorporating TRG in PE/OPE blends via solution blending. The rheological and electrical
percolations decreased substantially to 0.3 and 0.13 vol% of TRG in PE/OPE/TRG
nanocomposites compared to 1.0 and 0.3 vol% in PE/TRG nanocomposites. Improved dispersion
of TRG in blends was attributed to increased TRG/polymer interactions, leading to high aspect
ratio of the dispersed TRG. A universal Brownian dispersion mechanism for graphene was
concluded similar to that of carbon nanotubes, following the Doi-Edwards theory. Furthermore,
the improved dispersion of TRG correlated with the formation of surface fractals in
iii
PE/OPE/TRG nanocomposites, whereas the poor dispersion of TRG in PE led to the formation
of only mass fractals.
Moreover, graphene and carbon black (CB) were combined as a synergic filler for
manufacturing electrically conductive PE nanocomposites. Smaller fractals were observed at
lower CB concentration whereas increasing CB concentration produced large CB agglomerates
on the graphene surface. A remarkably high conductivity of ~1 S/cm was achieved at 15 wt%
using graphene/CB ratio of 1:1, which decreased with increasing CB relative to graphene.
Therefore, using graphene/CB 1:1 hybrid filler could reduce the cost of conductive
nanocomposites by 50%.
iv
TABLE OF CONTENTS
ABSTRACT ................................................................................................................................ iii
LIST OF FIGURES ....................................................................................................................... ix
LIST OF TABLES .........................................................................................................................xv
ACKNOWLEDGEMENT ........................................................................................................... xvi
CHAPTER-1 INTRODUCTION TO POLYMER NANOCOMPOSITES ...................................1
1.1. Polymer Nanocomposites ....................................................................................... 1
1.2. Conductive Nanocomposites .................................................................................. 3
1.3. Graphene ................................................................................................................. 6
1.3.1. Graphene/Polymer Nanocomposites ......................................................... 10
1.3.2. Dispersion of Graphene in Polymers: Issues and Answers ...................... 12
1.4. Nanocomposites Characterization ........................................................................ 17
1.4.1. Melt Rheology .......................................................................................... 17
1.4.2. Small Angle X-Ray Scattering (SAXS) .................................................... 20
1.5. Thesis Overview ................................................................................................... 22
CHAPTER-2 GRAPHENE: SYNTHESIS AND CHARACTERIZATION ...............................25
2.1. Thermally Reduced Graphene (TRG) ................................................................... 25
2.1.1. Introduction ............................................................................................... 25
2.1.2. Experimental Details ................................................................................. 27
2.1.3. Results and Discussion ............................................................................. 29
2.1.4. Summary ................................................................................................... 33
2.2. Graphene Nanoplatelets (GnP) ............................................................................. 34
Acknowledgements ........................................................................................................... 35
v
CHAPTER-3 EFFECT OF SOLVENT ON THE UNCATALYZED SYNTHESIS OF
AMINOSILANE-FUNCTIONALIZED GRAPHENE .........................................36
3.1 Introduction ........................................................................................................... 36
3.2 Experimental Details ............................................................................................. 38
3.2.1 Materials ................................................................................................... 38
3.2.2 Preparation of TRG ................................................................................... 39
3.2.3 Silylation Reaction .................................................................................... 39
3.2.4 Characterization ........................................................................................ 40
3.3 Results and Discussion ......................................................................................... 41
3.3.1 Chemical Analysis .................................................................................... 41
3.3.2 Morphological Analysis ............................................................................ 50
3.3.3 Thermal Stability and Conductivity .......................................................... 54
Conclusion ........................................................................................................................ 56
CHAPTER-4 SYNTHESIS AND CHARACTERIZATION OF

POLYETHYLENE/OXIDIZED POLYETHYLENE (PE/OPE) BLENDS
AND ROLE OF OPE AS A VISCOSITY CONTROL .........................................58
4.1 Introduction ........................................................................................................... 58
4.2 Experimental ......................................................................................................... 60
4.2.1 Materials ................................................................................................... 60
4.2.2 Preparation of Blends ................................................................................ 61
4.3 Results and Discussion ......................................................................................... 63
4.3.1 Miscibility, Phase Behavior and Thermal properties ................................ 63
4.3.2 Melt Rheological Analysis ........................................................................ 74
4.3.3 Mechanical Properties ............................................................................... 79
vi
4.3.4 SEM Morphology ..................................................................................... 80
Conclusion ........................................................................................................................ 82
CHAPTER-5 PROCESSABLE CONDUCTIVE GRAPHENE/POLYETHYLENE

NANOCOMPOSITES: EFFECTS OF GRAPHENE DISPERSION AND
POLYETHYLENE BLENDING WITH OXIDIZED POLYETHYLENE ON
RHEOLOGY AND MICROSTRUCTURE ..........................................................85
5.1 Introduction ........................................................................................................... 85
5.2 Experimental Details ............................................................................................. 88
5.2.1 Materials ................................................................................................... 88
5.2.2 Synthesis of TRG ...................................................................................... 89
5.2.3 Preparation of Composites ........................................................................ 89
5.3 Result and Discussion ........................................................................................... 92
5.3.1 Characterization of TRG and CB .............................................................. 92
5.3.2 Melt Rheological Analysis ........................................................................ 93
5.3.3 SAXS-Based Microstructure .................................................................. 104
5.3.4 Thermal Properties .................................................................................. 109
5.3.5 Mechanical Properties ............................................................................. 110
5.3.6 Electrical Properties ................................................................................ 113
5.3.7 Morphology............................................................................................. 116
Conclusions ..................................................................................................................... 119
Acknowledgements ......................................................................................................... 119
CHAPTER-6 CONDUCTIVE POLYETHYLENE/GRAPHENE/CARBON BLACK

HYBRID NANOCOMPOSITES .........................................................................121
6.1 Introduction ......................................................................................................... 121
6.2 Experimental Details ........................................................................................... 124
vii
6.2.1 Materials ................................................................................................. 124
6.2.2 Nanocomposites Synthesis...................................................................... 125
6.2.3 Characterization ...................................................................................... 125
6.3 Results and Discussion ....................................................................................... 127
6.3.1 Characterization of GnP and CB............................................................. 127
6.3.2 Microstructure and Melt Rheology ......................................................... 129
6.3.3 Electrical Conductivity ........................................................................... 136
Conclusions ..................................................................................................................... 138
Acknowledgement .......................................................................................................... 139
CHAPTER-7 CONCLUSIONS AND FUTURE RECOMMENDATIONS ..............................140
7.1 Summary and Conclusions ................................................................................. 140
7.2 Future Research Directions ................................................................................. 143
REFERENCE ..............................................................................................................................149
APPENDIX-A.......................................................................... SILANE MODIFIED GRAPHENE 172
APPENDIX-B PE/OPE MISCIBLE BLENDS ............................................................................178
APPENDIX-C PE/OPE/TRG AND PE/OPE/CB COMPOSITES ...............................................186
viii
LIST OF FIGURES
Figure 1.1 Intercalated, flocculated and exfoliated polymer/layered silicates (clay)

nanocomposites ........................................................................................................4
Figure 1.2 Representation of graphene as the building block for graphite, CNTs and
fullerenes (adapted with permission from ref.28. Copyright (2010) American
Chemical Society) ....................................................................................................7
Figure 1.3 a) 0.5 g (~0.5 mL) of GO expands to 75 mL of thermally reduced graphene

(TRG) upon rapid heating at 1050°C, b) XRD patterns of pure graphite, GO
and TRG (Reprinted with permission from ref.31. Copyright (2012)
Springer) ..................................................................................................................9
Figure 1.4 Left) TEM of TRG sheets produced from very dilute solution of TRG in
DMF and drying on amorphous lacy carbon coated Cu-grid (Reproduced
from ref.36 with permission from the Centre National de la Recherche
Scientifique (CNRS) and The Royal Society of Chemistry), right) TEM of
TRG in PMMA fractured surface revealing subsurface morphology of TRG
(Reproduced with permission from ref. 38. Copy right (2008) Nature
Publishing Group). Insert in left side shows SAED of TRG showing nicely
separated and exfoliated graphene sheets on TEM support36. ...............................10
Figure 1.5 a) Proposed reactions during isocyanate treatment of graphene oxide where
organic isocyanates reacts with the hydroxyl (left oval) and carboxylic (right
oval) groups of graphene oxide sheets to form carbamate and amide
functionalities, respectively (reproduced from ref.55, copyright (2006) with
permission from Elsevier). .....................................................................................16
Figure 1.6 Rheological parameters acting as a link between molecular structure and
final properties of a polymer (reproduced from ref.61, copyright (2001) with
permission from Elsevier). .....................................................................................18
Figure 1.7 Typical viscosity curve for polyolefins defining the range of viscosities used
in various polymer processing machines (reproduced from ref.61, copyright
(2001) with permission from Elsevier). .................................................................19
Figure 1.8 Simplified working diagram of scattering instrument ...........................................21
Figure 2.1 0.5 g of GO expands to 75 ml of TRG upon rapid heating at 1050 °C (a),
XRD patterns of pure graphite, GO and TRG (b). (reproduced from ref.88,
copyright (2012) Springer) ....................................................................................30
Figure 2.2 Raman spectra of graphite and TRG. (reproduced from ref.88, copyright
(2012) Springer) .....................................................................................................31
ix
Figure 2.3 TRG with bulk density of 17 mg/cm3 and C/O = 13: SEM (a), and HRTEM
(b). (Image reproduced from ref.88) .......................................................................32
Figure 2.4 Pore size distribution of TRG sample with bulk density of 3 g/L. Inset
shows the BET adsorption-desorption isotherm curve (reproduced from
ref.88, copyright (2012) Springer). .........................................................................33
Figure 2.5 FTIR (a) and XPS high resolution C1s spectrum (b) of TRG sample. the inset
in a) provides a structural model for TRG (reproduced from ref.37 with
permission from the Centre National de la Recherche Scientifique (CNRS)
and The Royal Society of Chemistry). ...................................................................34
Figure 2.6 TEM image of graphene nanoplatelets (GnP) .......................................................35
Figure 3.1 FTIR spectra of the pure and f-TRGp and f-TRGs ................................................42
Figure 3.2 High resolution XPS spectra of pure and f-TRG samples .....................................45
Figure 3.3 EELS Carbon K-edge a), and Oxygen K-edge b) ..................................................47
Figure 3.4 Nitrogen K-edge a) and Silicon L2-3-edge b) .......................................................48
Figure 3.5 Raman spectra of TRG samples a) D and G band and b) βG (Gˈ) band ................50
Figure 3.6 TEM images of pure TRG. (a) Graphene particle composed of overlapping
graphene sheers (inset: SAED pattern from the center of the graphene
particle), (b) HRTEM image of two overlapping graphene sheets ........................51
Figure 3.7 TEM images of functionalized graphene: (a) f-TRGp, (b) f-TRGs .......................52
Figure 3.8 TEM bright field image (a) and corresponding EFTEM maps of silicon (b)
for f-TRGp; TEM bright field image (c) and corresponding EFTEM maps of
silicon (d) for f-TRGs. ...........................................................................................53
Figure 3.9 Thermograms of TRG, f-TRGp, and f-TRGs. Samples were heated from 50-
500° C at 10° /min under nitrogen .........................................................................56
Figure 4.1 FTIR spectra of OPE (a) and PE/OPE blends at various compositions .................65
Figure 4.2 Melting temperature and melt enthalpy of the blends ...........................................67
Figure 4.3 Hoffman-Weeks plot of PE/OPE blends (a) and Tm° versus OPE
concentration (b). ...................................................................................................67
Figure 4.4 Composition dependence of the Flory-Huggins interaction parameter, χ .............69
Figure 4.5 Thermal stability of PE/OPE blends ......................................................................71
x
Figure 4.6 log-log I vs q (a) and Kratky plots of PE/OPE blends (b) at 60°C and 0%
relative humidity with Y-offset, and long period order for blends (c)...................73
Figure 4.7 WAXS patterns of PE/OPE blends with Y-offset..................................................74
Figure 4.8 Start-up transient rheology of neat PE and PE/τPE blendsμ Evolution of Gˊ
with time (a), and reduced Gˊ versus time. Data reported at T = 1θ0°C, = 1
%, ω = 1rad/s..........................................................................................................76
Figure 4.9 Complex viscosity profiles of PE/OPE blends at 160°C. The black solid
lines are the Cross model fit (left panel) and zero shear viscosity as a
function of OPE wt.% at two different temperatures (right panel) ........................78
Figure 4.10 εaster curves for Gˊ (a), G˝ (b) over the reduced frequency. Insets in (a)
and (b) show slopes in the terminal regions (at low frequencies) averaged
over all the temperatures (circles 180°C, upper triangles 160°C, lower
triangles 140°C, and squares 130°C). ....................................................................79
Figure 4.11 Mechanical properties of PE/OPE blends: (a) Stress-Strain behavior, (b)
Young’s modulus, (c) yield and break stress, and (d) yield and break strains.
Arrows in stress-strain data indicate the break points. The inset in (a) shows
stress-strain data on a linear scale. .........................................................................81
Figure 4.12 SEM micro-images of PE/OPE Blends..................................................................82
Figure 5.1 TEM image of TRG (a), and CB (b). .....................................................................93
Figure 5.2 Processing control by PE/OPE blends ...................................................................94
Figure 5.3 Representative shear modulus and complex viscosity vs. frequency curves
for PE/TRG (a, d), PE/OPE 80/20/TRG (b, e) and 60/40/TRG (c, f),
respectively. Solid lines represent the polymer matrix in each box and
numbers next to each curve correspond to weight % of TRG ...............................98
Figure 5.4 Percolation analysis of TRG filled PE, PE/OPE 80/20 and 60/40 blends.
Solid lines are linear fit to experimental data. The point of intersection of
two lines indicates the percolation threshold, Φp. Inset shows power law fit
to percolation law for PE, 80/20 and 60/40 blends-filled with TRG, and the
numbers next to each line are the power law exponents. Color schemes are
same in both panels. ...............................................................................................99
Figure 5.5 Scaling behavior of critical strain (a), and G′ (b) above percolation threshold ...102
Figure 5.6 Universal behavior for TRG-filled matrices ........................................................105
Figure 5.7 I(q)~q log-log plots of PE/TRG (a), and 60/40/TRG nanocomposites (b).
Note: The lines in all panels are stacked in the same order with Y-offset for
clarity. ..................................................................................................................107
xi
Figure 5.8 I(q) ~ q log-log SAXS data for PE/OPE 60/40 Blends-CB composites. Note:
The lines in all panels are stacked in the same order with Y-offset for clarity. ...108
Figure 5.9 Kratky analysis of TRG-filled nanocomposites (a), and CB-filled

composites (b). Color schemes in (a) show percolation of each matrix. .............110
Figure 5.10 Thermograms for PE, PE+TRG 5 wt%, PE/OPE 60/40, and 60/40+TRG 5
wt%. Inset shows derivative of TGA versus the temperature ..............................111
Figure 5.11 Comparison of the Young's moduli of TRG and CB filled composites ..............112
Figure 5.12 Mechanical properties of TRG-filled nanocomposites. Solid lines are fit to
Halpin-Tsai model, and dashed lines represent Mori-Tanaka
micromechanical model. Inset shows estimated aspect ratio (Af) of TRG for
nanocomposites from the best fit. ........................................................................114
Figure 5.13 Comparison of electrical conductivities of TRG-filled and CB-filled

composites............................................................................................................115
Figure 5.14 Electrical conductivity of TRG-filled nanocomposites. Solid lines are to

guide the eye only. Inset shows the power law fit, the numbers indicate the
power law exponents............................................................................................117
Figure 5.15 SEM images of PE/TRG (a, b), 80/20/TRG (c, d), 60/40/TRG (e, f) at 5 wt%
loading. The arrows indicate TRG sheets located in these composites ...............118
Figure 6.1 TEM morphology of GnP (a) and CB (b). Inset in (b) shows high resolution
image of CB particles...........................................................................................128
Figure 6.2 XRD patterns of graphite, GnP, and CB ..............................................................129
Figure 6.3 Rheological properties of PE/GnP nanocomposites (a), and PE/CB

composites (b). .....................................................................................................130
Figure 6.4 Effects of total filler concentration, and GnP/CB ratio on rheological
properties of PE/GnP/CB nanocomposites. .........................................................132
Figure 6.5 Comparison of viscosity of composites ...............................................................133
Figure 6.6 TEM micro-images of GnP/CB suspensions with different GnP/CB ratios: a)
1:1, b) 1:5, and c) 1:10. ........................................................................................134
Figure 6.7 SAXS I~q log-log plot for PE/hybrid filler nanocomposites at a filler
loading of a) 5 wt%, and b) 15 wt% ....................................................................135
Figure 6.8 Comparison of electrical conductivities of GnP and GnP/CB hybrid

nanocomposites ....................................................................................................137
Figure 6.9 Electrical conductivity of nanocomposites. .........................................................138

xii
Figure 7.1 Comparison of electrical conductivity of nanocomposite ...................................144
Figure 7.2 Schematics for future research plan in nanocomposites research ........................146
Figure A.1 XRD spectra of graphite, graphite oxide (GO) and TRG (a), and TEM of
pure TRG (b) ........................................................................................................174
Figure A.2 Overall XPS survey for the pure and f-TRG .......................................................175
Figure A.3 N1s and S2p high resolution XPS scans for TRGp and TRGs ...............................176
Figure B.1 Arrhenius Plot of the viscosity of OPE (at shear rate = 10 1/s). Viscosity
data was obtained from performing steady state flow test on OPE after
melting on the Peltier plate ..................................................................................178
Figure B.2 Crystallization temperature and heat of crystallization of PE/OPE blends

with different OPE wt%. ......................................................................................178
Figure B.3 Thermograms of PE/OPE blends show the melting profiles of the blends.
The inset shows the melting profile of neat OPE ................................................179
Figure B.4 Melting profile of pure PE. This area has been used for calculation of melt
enthalpy and % crystallinity.................................................................................179
Figure B.5 Complete FTIR spectrum of OPE ........................................................................180
Figure B.6 Derivative of weight loss of PE/OPE Blends ......................................................180
Figure B.7 WAXD patterns of neat PE, OPE and PE/OPE blends at 25°C with Y-offset ....181
Figure B.8 Cross model fitting to different blend compositions at various temperatures .....182
Figure B.9 Han plots for the blends .......................................................................................183
Figure B.10 Shift factor for time-temperature master curves for PE/OPE blends ...................183
Figure B.11 Time-temperature master curves for all blend compositions against the
tested temperatures...............................................................................................184
Figure B.12 Time-temperature master curves for all blend compositions against the
tested temperatures...............................................................................................185
Figure C.1 XRD of graphite, graphite oxide and TRG ..........................................................186
Figure C.2 FTIR of TRG (a, b), and OPE+TRG (c). .............................................................187
Figure C.3 DLS of TRG and CB............................................................................................188
Figure C.4 TEM of Carbon Black (CB) .................................................................................188
xiii
Figure C.5 Rheological properties of PE/OPE Blends: (a) shear and loss moduli vs
frequency, and (b) complex viscosity profiles as a function of blend
composition at 160°C. (100/0 circles; 80/20 upper triangles; 60/40 lower
triangles). Pre-factors in (a) were used to shift G′~ƒ curves vertically for
clarity. ..................................................................................................................190
Figure C.6 Rheological data of CB-filled composites ...........................................................191
Figure C.7 Representative strain sweep on PE/TRG nanocomposites at 160°C. Arrows

point out the limit of linearity used for scaling argument ....................................191
Figure C.8 Power law decaying exponent for TRG-filled nanocomposites, and CB-
filled composite, obtained from SAXS I ~ q log-log plot ....................................192
Figure C.9 SAXS patterns for CB-filled composites .............................................................192
Figure C.10 Representative Kratky plot for SAXS data ..........................................................193
Figure C.11 Thermal stability of TRG-filled, and CB-filled composites ................................193
Figure C.12 Strain at break and breakage stress of PE/TRG (a), 80/20/TRG, and
60/40/TRG (c) nanocomposites ...........................................................................194
Figure C.13 Strain at break and breakage stress of PE/CB (a), 80/20/CB (b), and
60/40/CB (c) composites......................................................................................195
Figure C.14 Young's modulus of CB-filled composites, normalized by matrix moduli.

Straight lines are linear fit to experimental data with intercept 1. .......................196
Figure C.15 Electrical conductivity of CB-filled composites. Inset shows the power law
fit to the experimental data ..................................................................................196
xiv
LIST OF TABLES
Table 1.1 Electrical percolation thresholds for selected graphene/polymer composites

and their electrical conductivities (adapted from ref.39 copyright (2011) with
permission from Elsevier) ......................................................................................14
Table 3.1 Atomic composition of pure and f-TRG as obtained from XPS ............................43
Table 3.2 High resolution fitting of C1s and O1s groups appearing in the XPS spectra of
TRG, f-TRGp, and f-TRGs .....................................................................................46
Table 5.1 Electrical and rheological percolation threshold and power law exponents
for TRG-based nanocomposites ...........................................................................117
Table A.1 High resolution fitting of functional groups in N1s and Si2p XPS scans ..............177
Table A.2 Averaged EDS results ..........................................................................................177
Table B.1 Thermal stability of blends with different compositions .....................................181
Table B.2 Cross model fitting parameters for PE/OPE Blends ............................................182
xv
ACKNOWLEDGEMENT
Though it's my name appearing on the cover of this dissertation, a great many people
have contributed to its production. I owe my gratitude to all those people who have made this
journey possible, and because of whom I will cherish my graduate experience forever.
I thank the Petroleum Institute, Abu Dhabi for funding this whole work through
Cooperative Research Partnership with Colorado School of Mines. I thank U.S. Army Research
Office through DURIP Grant No. W911NF-11-1-0306 for financial support in part of this work.
I thank U.S. DOE under the contract No. DE-AC02-06CH11357 for supporting the use of
Advanced Photon Source (APS) at Argonne National Laboratory. I thank Soenke Seifert at
Argonne National Laboratory for being so generous with his time, knowledge, and good coffee
while performing x-ray scattering experiments at APS. Jim Horan was very kind and helpful in
ensuring perfect working of conductivity instruments at Fuel Cell Center, CSM. I thank John
Dorgan for letting me use his laboratory throughout this thesis work. I could not have completed
this thesis without using his facilities. I thank Mark Grass and Mike Stadick for helping me with
many instruments and facilities. I also thank Deanna Jacobs for being so proactive, and making
my life at CSM easy by always finding a feasible solution to any issue with my documents with a
big smile on her face.
I thank Ala Bazyleva for teaching me how to use a rheometer on my first day in the
laboratory. I thank Tara Pandey and Andrew Motz for helping with x-ray scattering
measurements at APS. I especially thank Benjamin Caire for helping me with mechanical
characterization of polymer thin films. I always found him helping everyone in the laboratory
without any wrinkles on his forehead. I thank Sanket Kelkar, a great friend who made my stay at
xvi
CSM very amusing through this discussions and (very) long road trips. He was a great deal of
inspiration as a very hardworking person who always aimed at learning new things. I cannot
thank Ali Chaudhary in words for his endless discussions and new ideas, which led me to do lots
of work in this thesis. I thank undergraduate student, Travis Arnold who worked with me for
three semesters. I also thank Frederick Prehen Jr. (Fritz), graduate student in chemistry for his
ideas and knowledge of macromolecular chemistry. I always called him "Professor Fritz" for his
understanding and patience in teaching me learn chemistry of macromolecules. I thank Patrizia
Smith for letting me use her work space time to time.
I am indebted to Matthew Liberatore for his excellent guidance, and the personal
understanding he displayed during my stay at CSM. I really admire his patience in guiding me to
furnish my new ideas into purposeful documents. I wish him all the best for his new tenure at
University of Toledo. I am also indebted to Ahmed Abdala for taking me as research assistant at
Petroleum Institute, Abu Dhabi in 2009, introducing me to graphene's applications, and further
leading me to CSM for Ph.D. with Matt. Ahmed has been a great deal of inspiration for his in
depth knowledge and ideas. I could always find him either in person or through Skype for
anything anytime. I also wish him the best for transitioning to Qatar.
I thank Andrew Herring for taking me as his graduate student after Matt's leaving to
Toledo, and letting me use his laboratory facilities. I thank Stephen Boyes for helping me
understanding organic and physical chemistry. During the last six months of this thesis, I have
probably spent more time in his chemistry laboratory than in my department. I also thank Vikas
Mittal at Petroleum Institute for Skype discussions, and assisting with some experiments in his
laboratory.
xvii
I thank my family for finding time to call me every day even with a 12 hours time
difference between USA and Pakistan. Though, my parents did not live long enough to see this
day, I cannot forget their contribution to what I am today and how I reached here.
Last but not least, I am thankful to have earned my Ph.D. from CSM, and I thank all other
graduate students and faculty who helped me throughout my stay. It has not been the easiest four
years away from my family and friends, and I certainly could not have done this without my
CSM family.
xviii
CHAPTER-1
INTRODUCTION TO POLYMER NANOCOMPOSITES
This dissertation continues work on applications of thermally reduced graphene (TRG),
in collaboration with the Petroleum Institute, Abu Dhabi, to understand the interplay of
chemistry, processing, and morphology of TRG on mechanical, electrical, and processing
properties of TRG/polymer nanocomposites. The overall objective of this thesis was to better
understand reasons for poor dispersion of graphene in polyolefins, specifically polyethylene, and
further develop methods to increase graphene's dispersion, leading to improved nanocomposites.
This thesis focused on polyethylene to produce electrically conductive, mechanically robust, and
processable nanocomposites at lower graphene loadings.
1.1. Polymer Nanocomposites
Over the years, overall perspective of materials has been changed by polymers, and
nowadays we deal with various types of polymers in our daily life on regular basis. Polymers
have excellent properties: light weight, toughness, good elongation, easy processing and low
cost1, 2, 3
. However, in comparison with metals and ceramics, polymers show low stiffness,
strength, flammability, and high gas permeability as weaknesses. Despite of their low properties,
high strength and electrical conductivity in polymers are needed in some applications. Mixing
polymers with inorganic fillers imparts strength and electrical properties to the polymers.
Reinforcement with nanometer size fillers can overcome many of the weaknesses in polymers (if
fillers are well dispersed within polymers). Additionally, property enhancements (mechanical
and thermal stability) can be achieved at significantly lower weight fraction of the nanofillers
(filler loadings) than conventional micron sized fillers, resulting in light-weight nanocomposites.
1
Nanocomposites are defined as having at least one dimension of the dispersed particles
in nanometer range. The nanoparticles are classified based on their dimensions. Examples
include: 1) isodimensional nanoparticles have all dimensions on the order of nanometers, e.g.,
fullerenes, 2) elongated nanoparticles such as carbon nanotubes (CNT), carbon nanofibers (CNF)
or nano-whiskers with two dimensions on the nanometer scale and the third is larger, 3) two
dimensional nanoparticles, such as layered silicate crystals or clays and graphene, in the form of
sheets of one to a few nanometers thick and hundreds to thousands of nanometers in extent4.
Polymer/layered silicates (clay) nanocomposites attracted great interest, both in industry
and in academia, because of improved properties (mechanical and thermal stability, and gas
permeability) when compared with virgin polymers or conventional (micro- or macro-)
composites. Three most commonly used clays in manufacturing clay/polymer nanocomposites
include montmorillonite (MMT), hectorite, and saponite. The layer thickness is normally 1 nm,
and the lateral dimensions may vary from 30 nm to several microns, depending on particular type
of layered silicate. Stacking of layers leads to a regular van der Waals gap between the layers
called interlayer spacing or gallery. For manufacturing nanocomposites, layer stacking is broken
down using a solvent or inter-gallery diffusion of polymer chains in a solvent at relatively high
shear rates.
Toyota5 was the first to report the nylon-6/MMT nanocomposites for practical
applications (used in automotive parts) where a very small amount of clay substantially
improved mechanical and thermal properties of nylon-6. In the past three decades, many
researchers studied use of clay in manufacturing mechanically strong, thermally stable and flame
retardant polymer nanocomposites. Polymer/clay nanocomposites are categorized in three broad
classes based on the dispersion of layered silicates in polymers: 1) intercalated, 2) flocculated,
2
and 3) exfoliated nanocomposites (Figure 1.1). Depending on the exfoliation extent of clay and
type of clay/polymer interactions, relative increase in mechanical and thermal properties of the
nanocomposites can be achieved with increased dispersion of clay. Fu and Qutubuddin6 reported
increased mechanical stability and degradation temperature of polystyrene (PS) using ~6 wt%
MMT. Cao et al.7 showed complete exfoliation of clay in polyurethane (PU)/MMT
nanocomposites resulting 6 °C increase in glass transition temperature (Tg), and ~800%
improvement in mechanical properties.
Furthermore, compatibilizers can be used to develop interactions between clay and
polymer chains, leading to enhanced dispersion of clay. Durmus et al.8 compared maleic
anhydride-graft-polyethylene (MA-g-PE) and oxidized PE (OPE) as compatibilizers in
polyethylene (PE)/clay nanocomposites. The rheological percolation threshold for OPE-based
nanocomposites was 0.016 wt% compared with 0.01 wt% for MA-g-PE-based nanocomposites.
In another report, Durmus et al.9 showed a 50% reduction in oxygen permeability of OPE-
compatibilized PE/clay nanocomposites. The use of compatibilizers in polymer nanocomposites
has been optimized to a compatibilizer/clay ratio of 3 by Hotta et al.10 using different ratios of
the alkyl-modified clay and MA-g-PE to create PE/clay interactions whereas similar ratio was
later confirmed by Durmus and co-workers8, 9.
1.2. Conductive Nanocomposites
Conductive polymer composites are another important class of nanocomposites where
conductive fillers such as conductive carbon black (CB), CNF, CNT or graphene are dispersed in
insulating polymers. Conductive nanocomposites find use in many practical applications such as
3
electromagnetic interference shielding (EMI) effectiveness, anti-static packaging materials,
printed electronic circuits, and conductive fibers etc.
Polymer Filler
Flocculated or Intercalated Exfoliated or

micro-composites composites nanocomposites
Figure 1.1 Intercalated, flocculated and exfoliated polymer/layered silicates (clay)

nanocomposites
CNTs have attracted huge amount of interest since 199111 due to the unique combination
of mechanical, electrical and thermal properties12. Since CNT/polymer nanocomposites were
first reported by Ajayan et al.13, a lot of studies evolved on the synthesis, structure, properties,
and application of these conductive materials14. CNTs and CNF are produced by catalytic
chemical vapor deposition of a hydrocarbon (such as natural gas) on a metal surface (iron, nickel
etc.). CNFs composites are used, particularly, for EMI shielding effectiveness15. However,
compared to CNTs, CNFs have received less research attention as nanofillers because CNTs
have better mechanical properties, smaller diameter, and lower density than CNFs15, 16.
4
CNT/polymer nanocomposites are generally prepared by mixing CNTs and polymers in
solutions or dispersing CNTs in polymer melts. If polymers are not either soluble or melt-able,
the related monomers might be firstly incorporated with CNTs, followed by in situ
polymerization to produce the nanocomposites16. CNTs can be single-wall (SWCNT), double-
wall (DWCNT) or multiple-wall (MWCNT) depending on the existence of one or more
concentric cylinders present. Adhikari et al.17 studied the effects of processing conditions on
thermal stability of MWCNT/high density polyethylene (HDPE) nanocomposites. Combination
of solution mixing followed by melt extrusion of the composites improved degradation
temperature of HDPE, which was attributed to the better dispersion of MWCNTs.
Since CNTs usually agglomerate due to van der Waals forces, they are extremely difficult
to disperse and align in a polymer matrix. Thus, a significant challenge in manufacturing high
performance CNT/polymer composites is to introduce individual CNTs in a polymer matrix to
achieve better dispersion, alignment, and strong interfacial interactions, which also improve load
transfer across CNT/polymer interface. The most common method to create better dispersion of
CNTs in a polymer matrix is to use oxidized CNTs (also called purified CNTs). The purified
CNTs were reported to create good interactions in polar polymer matrices such as epoxy18, poly
(methyl methacrylate) (PMMA)19, poly (ethylene terephthalate) (PET)20 and poly (vinyl alcohol)
(PVA)21. However, in nonpolar polymers such as polyolefins, CNTs do not create strong
interface due to the inert polyolefin structure. For example, Valentino et al.22 showed ~10 orders
of magnitude increase in electrical conductivity in MWCNT/low density PE (LDPE)
nanocomposites with 8 wt% MWCNT loading. Xiao et al.23 used 10 wt% MWCNTs to improve
the Young’s modulus of PE by ~λ0%.
5
The surfactants may also help increasing the dispersion of CNTs24 but the lack of strong
CNT/polymer interface leads to high CNT loadings for the load transfer applications. For this
purpose, surface modification of CNTs has been one of the most plausible route for their better
dispersion in polymer matrices. Shanmugharaj et al.25 used amino-f-MWCNTs in manufacturing
CNT/rubber composites to improve the mechanical properties. Yang et al.26 used polypropylene-
grafted-CNT (PP-g-CNT) in PP matrix, and showed ~300% improvement in toughness at 1.5
wt% CNT loading. Thus, the surface modification of CNTs can be useful for creating strong
CNT-polymer interface, and increase dispersion.
1.3. Graphene
Graphene, a two-dimensional sp2-hybridized carbon sheet, is currently a widely studied
material. This single-atom-thick sheet of C-atoms arrayed in a honey comb pattern is the world’s
thinnest, and stiffest material which is also an excellent conductor of heat and electricity27.
Graphene is considered more promising than other nanostructured C-fillers such as 1-
dimensional CNTs, and 0-dimensional fullerenes in various applications (Figure 1.2). Due to its
high electrical conductivity (θ000 S/cm), Young’s modulus (~1TPa), and thermal conductivity
(5000 W/(m.K)) along with very high surface area (theoretically 2600 m2/g)28, graphene has
been vastly used in areas such as conductive polymer nanocomposites, field effect transistors,
transparent conductive films, gas sensors, clean energy devices and diodes, etc.29. Due to high
surface area and low bulk density (~3 mg/cm3), extremely low amounts of graphene are required
to achieve the percolation thresholds for various applications.
Since the first experimental evidence of existence of stable, free-standing graphene sheets
and their electronic applications in 200430, research was concentrated on the development of new
6
synthetic routes enabling an effective production of well-defined, and separated graphene sheets.
Recently, Kim et al28 classified graphene production methods into two major classes: bottom-up
and top-down methods. The starting material for graphene is generally the graphite, which is
composed of 2-dimensional sp2-carbon sheets (graphene sheets) stacked together, and held by
the van der Waals forces of attraction. Splitting graphite into graphene sheets can be performed
by taking graphite particles or oxidizing graphite into graphite oxide (GO) followed by splitting
GO by different methods. Nevertheless, the final physical and chemical properties of graphene
sheets depend on the main source and splitting methods.
Figure 1.2 Representation of graphene as the building block for graphite, CNTs and fullerenes
(adapted with permission from ref.28. Copyright (2010) American Chemical Society)
The size of the graphene sheets and the type of attached functional groups become
important for dispersion of graphene in polymer matrices. Therefore, a brief overview of the
7
experimental methods used for analyzing the quality of the produced graphene is provided
below.
Number of layers and size: The bulk density of graphene is a direct measure of
exfoliation of graphite or GO (Figure 1.3a). Low bulk density represents better exfoliation. The
extent of graphite exfoliation is also studied by X-ray diffraction (XRD). e.g., graphite shows a
sharp reflection at β =βθ.γ° (CuKα radiation, X-ray wavelength=1.54Å) which shifts to 14.1°-
14.9° in GO31. The XRD pattern disappears as GO exfoliates and separates into graphene single
sheets (Figure 1.3b). An indirect method to study exfoliation is surface area measurement where
theoretically, the surface area is inversely proportional to the thickness of disk-like particles. The
exfoliation must lead to a sharp increase in the surface area of graphene sheets compared with
graphite and GO. Two most common methods for surface area measurements are N 2- and
methylene blue-adsorptions. However, as reported by Schniepp et al.32, the N2-adsorption based
surface area may be influenced by the compressibility of graphene sheets. On the other hand,
methylene blue method can be highly influenced by the surface topology and chemistry of the
graphene sheets33.
Atomic force microscopy (AFM) studies the surface topology, defects, and bending
properties of graphene. Step-height scans give a complete picture of number of layers and the
lateral size of graphene sheets33. However, complications such as folded or wrinkled sheets,
adsorbed solvent or moisture, largely influence AFM measurement. Size and quality of graphene
sheets can also be determined via transmission electron microscope (TEM). In addition to the
size determination by TEM imaging, selected area electron diffraction patterns (SAED) can
clearly differentiate between single and bilayer graphene (Figure 1.4).
8
Figure 1.3 a) 0.5 g (~0.5 mL) of GO expands to 75 mL of thermally reduced graphene (TRG)
upon rapid heating at 1050°C, b) XRD patterns of pure graphite, GO and TRG (Reprinted with
permission from ref.31. Copyright (2012) Springer)
Another important tool for determining the size and morphology of platelets (graphene
sheets) is solution rheology. A reasonably precise aspect ratio of graphene can be determined via
dilute solution rheology. Recently, Tesfai et al.34 used dilute solution rheology to determine size
of aqueous graphene oxide dispersions. Moreover, the static light scattering of dilute GO
solution is also reported to give fractal dimensions of GO which, however, depends strongly on
the solvent polarity35.
Chemistry of graphene: Since, methods for mass scale production of graphene start from
GO28, the produced graphene contains small amounts of residual oxygen functionalities.
Standard combustion elemental analysis can describe overall degree of oxidation in GO, and the
level of retained oxy-groups after reduction/exfoliation. X-ray photoelectron spectroscopy (XPS)
is one of the powerful tools to identify and quantify different types of functional groups present
on graphene surface. Chemical shifts in XPS C1s and O1s spectra, e.g., confirm the existence of
C-O, C=O, O-C=O on GO, graphene, and its derivatives36. Raman spectroscopy quantifies the
9
transformation of sp3(GO) to sp2 (graphene) upon reduction of GO, and stacking in graphite
samples. The transformation from sp3 to sp2 restores the electrical conductivity; thus, indicating
that electrical conductivity is also a qualitative measure of conversion of GO to graphene31, 36. In
addition, Fourier transformed infrared spectroscopy (FTIR) can be used to identify, qualitatively,
the types of functional groups on GO and graphene36, 37.
Figure 1.4 Left) TEM of TRG sheets produced from very dilute solution of TRG in DMF and
drying on amorphous lacy carbon coated Cu-grid (Reproduced from ref.36 with permission from
the Centre National de la Recherche Scientifique (CNRS) and The Royal Society of Chemistry),
right) TEM of TRG in PMMA fractured surface revealing subsurface morphology of TRG
(Reproduced with permission from ref. 38. Copy right (2008) Nature Publishing Group). Insert in
left side shows SAED of TRG showing nicely separated and exfoliated graphene sheets on TEM
support36.
1.3.1. Graphene/Polymer Nanocomposites
Graphene/polymer conductive nanocomposites have been reported with a number of
polymers28, 39. Much of the graphene/polymer nanocomposites research parallels CNT/polymer
systems. However, compared with CNTs, graphene produced from GO contains small amounts
of hydroxyl, epoxy, and carboxylic groups on its surface37. Simultaneous thermal exfoliation and
10
reduction of GO produces thermally reduced graphene (TRG) containing pendent oxy-
functionalities31 or chemically converted graphene (CCG) produced by sonicating, and reducing
GO by chemical reducing agents that leaves other functional groups on CCG surface40. The
existence of functionalities on graphene surface facilitates dispersion of graphene in some polar
polymer matrices such as PMMA, PVA, etc.28.
Similar to CNT/polymer systems, nanocomposites of graphene can be manufactured by
solvent and melt blending, and in situ polymerization. The electrical and mechanical properties
of the composites depend on the manufacturing method.
GO, very polar in character, can exfoliate in water or protic solvents via sonication
leading to graphene oxide and therefore, the nanocomposites of graphene oxide with water-
soluble polymers (such as poly (ethylene oxide) (PEO), PVA, and PU) can be fabricated easily28.
Amine or isocyanate modification helps dispersing GO in aprotic solvents and polymers such as
polystyrene (PS), PMMA and PU. Reducing GO in the presence of a polymer has also been
performed by Stankovich et al.41 where GO/sulfonated-PS were mixed in a solvent followed by
GO reduction by hydrazine hydrate. One drawback of this method is that depending on polymer
type and reducing conditions, the polymer can also degrade.
The most economically attractive and scalable method for dispersing nanoparticles into
polymers is melt blending. However, due to the thermal instability of the modified graphene,
only a limited number of polymer composites with TRG are reported via melt blending. Owing
to very low bulk density of TRG (~3 mg/cm3), feeding TRG into melt compounding machine has
been a challenge. Torkelson and co-workers42 bypassed graphene exfoliation steps, and
exfoliated graphene in PP matrix directly via high stresses generated in solid-state shear
11
pulverization process, but XRD and TEM showed presence of small stacked graphite in the
composites. Recently, Kim et al.43 compressed TRG before melt blending with PE to tackle with
TRG’s handling issue due to low bulk density. The XRD confirmed single layer structure of
TRG after compression.
In-situ intercalative polymerization of monomers on graphene has been successfully
reported for PVA, PMMA, PU, and epoxy44, 45, 46. For PMMA/graphene composites, electrical
percolation threshold has been reported between 0.31-3.5 wt% depending on the type of
graphene used. The percolation threshold for PS/graphene composites has been reported to be
between 1-8 wt%. The in situ polymerization method gives the best mechanical and thermal
properties in nanocomposites because of the covalent bonding between graphene and polymeric
chains. However, increasing and large viscosities of the reaction mixture, make bulk-phase in
situ polymerization extremely difficult47, which also increases the system’s power requirements.
In addition, the surfactants are also required to increase graphene dispersion in high viscosity in
situ polymerization systems.
A good way to understand the dispersion of graphene in polymer matrix can be via
measuring electrical conductivity of the composites. Table 1.1 shows the electrical conductivity
thresholds for various graphene/polymer nanocomposites reported. In addition, the methods such
as TEM and melt rheology also give insights into the dispersion and percolation thresholds,
respectively.
1.3.2. Dispersion of Graphene in Polymers: Issues and Answers
Although graphene/polymer nanocomposites outperform other conductive
nanocomposites28, the required graphene loadings to reach conductive percolation for nonpolar
12
polymers, e.g., polyolefins, is significantly higher than that required for polar polymers (Table
1.1). For example, the percolation in PU/graphene composite is achieved at 0.005 vol% loading48
whereas that for PE/graphene composite is attained at about 1-8% graphene loadings39, 49. The
difference in percolation level is attributed to the poor dispersion of graphene into the nonpolar
polyolefin matrix compared to that in polar matrix. Poor dispersion does not only increase the
percolation limits but also reduces the enhancement in the mechanical properties and thermal
stability. The poor dispersion of graphene is associated with the absence of sufficient
graphene/polymer interactions. In order to address this challenge, chemical functionalization of
graphene is considered a viable solution. The attached functional groups on graphene surface can
increase dispersion of graphene, and develop interactions with polyolefins which can lower the
electrical and mechanical percolation limits.
The excellent mechanical, electrical and thermal properties of graphene are far limited by
their low solubility in aqueous and organic solvents. CCG containing smooth sheets, forms
bundles, and restacks into agglomerates when kept for some time, serving as a big disadvantage
for nanocomposite applications where dispersion is the main aim. On the other hand, TRG with
oxy-functionalities on their surface, are not dispersable in water. In order to overcome these
limitations, researchers attached different functional groups on graphene surface50 and/or have
also functionalized polymers for better dispersion and property enhancement43. In general,
because of the large volumes of polymers (90-99 %) needed in nanocomposites, functionalizing
polymers can be costly compared to functionalizing the nanofillers (0.1-9%). Since, extremely
small amounts of nanofillers, such as graphene, are required to change nanocomposites
properties, functionalizing fillers can be economical.
13
Table 1.1 Electrical percolation thresholds for selected graphene/polymer composites and their
electrical conductivities (adapted from ref.39 copyright (2011) with permission from Elsevier)
Percolation Electrical
Matrix polymer Filler type
threshold conductivity
(filler wt%) (mS/cm)
Epoxy Functionalized exfoliated graphite 1 ~50
Nylon-6 Graphite oxide 0.5 8.4
Polycarbonate Thermally exfoliated graphite oxide 0.3 500
PE Reduced graphite oxide 1-8 1300
PET Thermally exfoliated graphite oxide 1 20
PMMA Graphite nanoplatelets 0.7 1000
PP Graphite nanoplatelets 10 5
PS Functionalized reduced GO 0.2-2 150
PVA Reduced GO 0.5 100
Poly (vinyl chloride) Graphite nanoplatelets 1.4 60
Poly (vinylidene fluoride) Thermally exfoliated graphite oxide 2 0.3
PU Thermally exfoliated graphite oxide 0.6 N/A
Chemical functionalization could potentially pave ways towards the commercial
applications of graphene/polymer nanocomposites. Attaching organic molecules on graphene
surface via synthetic chemistry methods allows synthesizing p- and n-doped graphene based on
the selection of electron donating- or withdrawing-complexes bonded to graphene's sp2-carbon
network. By applying appropriate functional organic derivatives on graphene surface, graphene
can be easily processed via solvent-assisted techniques such as spin-coating, layer-by-layer
assembly, and solvent casting on glass or metal surface51.
In principle, graphene functionalization methods find their origin from CNTs due to
structural similarities between the two. The functionalization methods are classified into two
broad classes: covalent and non-covalent. In covalent functionalization, organic molecules are
covalently bonded on graphene surface whereas molecules attach to graphene via van der Waals
interactions in non-covalent methods.
14
Non-covalent or supramolecular functionalization methods primarily involve
hydrophobic, van der Waal, and electrostatic interactions between graphene and organic
molecules, and require physical adsorption on graphene surface. Non-covalent functionalization
can be achieved by polymer wrapping, adsorption of surfactant or smaller molecules, or
interactions with porphyrins or biomolecules, such as DNA and peptides. Graphene is originally
a π-system, and noncovalent intermolecular interactions involving π-systems are pivotal to the
stabilization of proteins, enzyme-drug complexes, DNA-protein complexes and organic
supramolecules, and functional nanomaterials50.
In covalent functionalization, organic molecules or polymers are grafted on graphene
surface which prevent graphene sheets from re-aggregation due to π-π-stacking. Kuilla et al.52
categorized covalent functionalization into four classes: Nucleophilic, and electrophilic
substitution reactions, condensation, and addition reactions. In nucleophililc substitution
reactions, epoxide groups on graphene surface are utilized. The amine functionality (-NH2) of
organic molecules bearing a lone pair electrons attacks the epoxy oxygen. These reactions are
easy, can occur at low temperature and in aqueous media. Essentially, all aliphatic and aromatic
amines, amino acids, amine-terminated biomolecules, and silane compounds can be used to
prepare amine-functionalized graphene.
In electrophilic substitution reactions, hydrogen atoms from graphene are replaced by an
electrophile. Spontaneous grafting of aryl diazonium salts to graphene surface is an example of
this type of reactions53. One key issue is the use of surfactants such as sodium dodecyl benzenyl
sulfonate to disperse graphene before the reaction. The functionalized graphene is highly
dispersible in DMF and other organic solvents. The electrical conductivity of sulfonated-
15
graphene has been reported by Samulski and coworkers54 to be ~1250 S/m which is much higher
than that from other functionalization techniques.
Figure 1.5 a) Proposed reactions during isocyanate treatment of graphene oxide where organic
isocyanates reacts with the hydroxyl (left oval) and carboxylic (right oval) groups of graphene
oxide sheets to form carbamate and amide functionalities, respectively (reproduced from ref.55,
copyright (2006) with permission from Elsevier).
In condensation reactions, two molecules (or functional groups) combine to form one
single molecule with the loss of entropy. The condensation reaction of graphene has been
reported with isocyanate, di-isocyante, and amine compounds through the formation of amides
and carbamate ester linkages. The isocyanate functionalized graphene was pioneered by
Stankovich et al.55 who used similar reactions with graphene oxide and GO. The resulting
functionalized graphene was highly dispersible in DMF solvent, and used for producing PU
nanocomposites48. Figure 1.5 shows the proposed schematics by Stankovich et al. for these types
of reactions.
In additional reactions, two or more molecules combine together to form a larger
molecule. Graphene has been functionalized with 1,3-dipolar cycloaddition of azomethine ylid,
and maleic anhydride (MA) where the reaction with MA proceeded with free radicals and the
16
resultant functionalized graphene was stable in THF for more than two months56, 57. Also, silane
(aminopropyl triethoxy silane, APTS) modified graphene was reported for producing different
types of polymer nanocomposites36, 58, 59, 60.
1.4. Nanocomposites Characterization
The dispersion of graphene or any nanofiller in a polymer can characterized by several
techniques. However, melt rheology and small angle x-ray scattering (SAXS) are among the
most important techniques used in this context. In the subsequent subsections, brief discussion
on the importance of rheological characterization of nanocomposites, and SAXS is presented.
1.4.1. Melt Rheology
Polymeric materials are viscoelastic (VE) by nature and therefore, exhibit distinct flow
behavior. Rheological characterization is used to analyze the melt flow properties of polymer and
nanocomposites. The knowledge and design of the flow behavior is essential in all forms of
production and processing of polymers to manufacture either small or larger parts. Therefore,
rheology has attained a key position in polymer research, being an important link between chain
structures, processing behavior and final properties of polymeric materials (Figure 1.6)61, 62.
In rheology, linear VE properties (direct relationship between stress and strain or the
range up to where viscosity or shear modulus (Gʹ) is independent of applied shear rate) are
usually used to determine the processing properties of materials. εaterial’s viscosity ( ) is the
most important parameter in defining the processing machinery used for manufacturing the
polymer products (Figure 1.7).
17
Figure 1.6 Rheological parameters acting as a link between molecular structure and final
properties of a polymer (reproduced from ref.61, copyright (2001) with permission from
Elsevier).
In a rheometer, the linear VE measurements are usually conducted at small amplitude
oscillatory strains (SAOS) where a small strain is imposed on the material in dynamic frequency
sweep experiments. The linear VE region is first determined using sinusoidal strain sweep
experiment, and a low strain is selected within the linear VE range to conduct further
experimentations.
Various groups around the world have contributed towards the standardization of the
linear VE response in polymers and nanocomposites. εacosko’s group8, 9

used critical strain
( c%) (strain at which Gʹ is equal to λ0% of its plateau value) for analysis of polymer
nanocomposites analogous to gels and colloids. For a percolating aggregated network, c% is
expected to be small, typically smaller than 10%63.
18
Figure 1.7 Typical viscosity curve for polyolefins defining the range of viscosities used in
various polymer processing machines (reproduced from ref.61, copyright (2001) with permission
from Elsevier).
In addition, being more sensitive to the structural changes in polymers, significant
increase in Gʹ at low angular frequency (ω) in SAτS experiments is another indication of
development of interfacial interactions in nanocomposites. With increasing filler loading, the
appearance of Gʹ independent of ω shows solid-like (or pseudo-solid) behavior in molten
nanocomposites which indicates strong filler/polymer interactions. The magnitude increment in
Gʹ at low ω region (Gʹp) can be used to quantify the filler dispersion64, 65 as follows:
G ' p ~ (   per )v
Here, ʋ is a power law exponent, ϕ is the volume fraction of filler, and ϕper is the
percolating volume fraction of the filler. With lower value of ϕper, dispersion of filler in a
polymer matrix is considered better. However, the accuracy of the application of the above
percolation law depends on the lowest frequency (terminal range) used to calculate the terminal
19
 0
G 'p . Typically, the polymers start degrading while acquiring data at lowest possible
frequencies. Furthermore, when the filler particle aggregate structure is sufficiently built up,
measurements of the linear VE properties can further lead to assessing the microstructure of the
dispersions. Detailed discussion on determining microstructure of graphene/polymer
nanocomposites is provided in other chapters.
1.4.2. Small Angle X-Ray Scattering (SAXS)
Electromagnetic radiation used to obtain information about materials with dimensions on
the same order as wavelength of the radiation. e.g., continuous and milky white glass of milk
appears as an emulsion of particles in ultraviolet black light because black radiation wavelength
is similar to the dimensions of the butterfat that is emulsified in milk. In electromagnetic
radiations, x-ray scattering is considered one of the most powerful characterization tools
available for both homogeneous and heterogeneous materials.
Understanding the structure of new materials on the mesoscopic scale (2-50 nm), such as
clusters, aggregates, and nanosized materials, requires suitable experimental techniques.
Scattering from x-rays is caused by the differences in electron density of the materials. Since the
larger the diffraction angle the smaller the length scale probed, wide angle x-ray scattering
(WAXS) is used to determine the crystal structure on atomic length scale, whereas the small
angle x-ray scattering (SAXS) is used to explore the microstructure on the nanometer scale.
Since studying ideal lamellae in polymers66 in 1960s, SAXS has become one of the most
widely used techniques to study morphology of solid polymers. SAXS provides indispensable
information about structural changes in polymers on supra-molecular level with dimensions in
20
the range of 10Å to a few thousands Å67. A pictorial description of SAXS working process, and
example of a scattering curve, the intensity versus the scattering vector (q) is shown in Figure
1.8. The scattering vector is calculated from the diffracting angle as q = 4π/ sin( /β). From the
absolute value of scattering intensity, the magnitude of the fluctuations of electron density can be
revealed. The shape of the curve, and the position of intensity peak or shoulder yield quantities
related to the spatial arrangement of the density fluctuations. Therefore, SAXS can supply useful
information about phase transitions if these processes are accompanied by changes in magnitude
of the fluctuation or by changes in the geometry of the scattering instrument.
sample detector
Monochromatic Beam 2ϴ q
~ 0.1-0.2nm
log (Intensity)
log (q), 1/nm or 1/Å

Figure 1.8 Simplified working diagram of scattering instrument
SAXS measurements in this thesis were obtained using a synchrotron source at Advanced
Photon Source, Argonne National Laboratory, Chicago, IL. With synchrotron x-rays, high power
density and small beam divergence of the incident x-ray beam permit design of time resolved
SAXS/WAXS experiments, and the use of very small specimens68. Since, synchrotron has high
flux, the scattering from air can be neglected, and environmentally controlled experiments can be
21
performed adequately. Details on environmentally controlled chamber used in this thesis are
described in experimental sections of specific experiments provided in proceeding chapters.
Rieker et al.69 used SAXS to study morphology of CB/PE composites prepared by
different methods. Mass fractals formed by CB in PE, and interpenetration of these fractals was
investigated, and the interpenetration of mass fractals above 20 wt% CB loading was observed
by the decreasing initial slope of log I(q) ~ log q curves. This was the first report on the effects
of polymer matrix, processing conditions, and methods on the morphology of composites.
Cattani et al.70 reviewed theories of x-ray scattering from various molecules, clusters, and
nanocomposite films. Recently, Archer's group71 used the time resolved SAXS experiments to
explain the unusual phase behavior of entangled polymers reinforced by silica nanoparticles. The
particles smaller than the radius of gyration of polymers lead to the non-Einstein flow behavior
in polymer composites72. The dynamics of polymers were slowed down due to the enthalpic and
entropic affect induced by nanoparticle size and particle-polymer interactions71.
1.5. Thesis Overview
This thesis examines the strategies to reduce percolation limits in nonpolar polymer
matrices. For this purpose, PE was selected as the main nonpolar matrix. PE is one of the most
commonly used commodity polymers, having the largest production worldwide and wide range
of practical applications.
While others have published on graphene/PE nanocomposites based on either the
functionalization of graphene or that of PE matrix, better and more economical methods to
homogenously disperse graphene in PE should be sought. I believe blending PE with OPE can
impart polar character to PE with improved processing properties, which can in return serve as a
22
better matrix for graphene dispersion. Thus, the hypothesis for this thesis is that blending non-
polar polyolefins with polar polymers will improve dispersion, processability, and conductivity
in graphene-based nanocomposites at lower graphene loadings than neat polyolefin
nanocomposites. In addition, hybrid filler synergic effects have been reported for polar polymers.
No reports have been published on using hybrid fillers for nonpolar polyolefins. I believe that the
dispersion of graphene in PE can also be enhanced by incorporating CB as a second synergic
filler to produce electrically conductive nanocomposites.
The thesis is organized in seven chapters. First, since this thesis focused on
graphene/polymer nanocomposites, details on the synthesis of TRG are discussed in chapter 2.
TRG was produced via simultaneous thermal exfoliation and reduction of GO, and characterized
by spectroscopic and surface analysis techniques. Detailed characterization procedures and
results are discussed therein.
Chapter 3 is focused on the synthesis of silane-modified TRG, where the reaction route
was altered to understand the mechanism of silane attachment onto TRG surface. Silane
modification was performed with and without the presence of an organic solvent. The
functionalized graphene were characterized by several chemical, spectroscopic, and surface
techniques. A reaction mechanism for the reaction of silane on graphene is discussed.
In chapter 4, miscible blend of PE with OPE were synthesized by solvent blending. The
role of OPE in controlling the processing properties of PE was investigated. The PE/OPE blends
were characterized by thermal, rheological, and mechanical techniques. Miscibility of OPE in PE
examined by thermal methods, and influence of OPE on the morphology of PE are discussed.
23
Chapter 5 focuses on quantification of graphene dispersion in PE and PE/OPE blends.
The nanocomposites were prepared by solvent blending. The state of graphene dispersion was
analyzed by melt viscoelasticity and SAXS, whereas the effects of increased graphene's
dispersion on electrical conductivity and mechanical properties were reported. In addition,
graphene-based nanocomposites were compared with CB-based micro-composites to illuminate
the differences between nano- and micro-composites.
Chapter 6 aims at using commercial grade graphene and CB, both together to enhance
graphene dispersion in PE. The synergic effects of graphene and CB were examined by melt
viscoelasticity and electrical conductivity measurements. Effects of increasing concentration of
hybrid fillers with different graphene/CB ratios were used to determine the most effective
graphene/CB ratio. The dispersion of hybrid fillers is also analyzed by SAXS, and electron
microscopy.
Finally, chapter 7 summarizes all key results from this thesis, and provides future
research directions. Potential applications of the developed PE/OPE blends-graphene
nanocomposites, and the use of polymer grafted-graphene in manufacturing polymer
nanocomposites are proposed at the end.
24
CHAPTER-2
GRAPHENE: SYNTHESIS AND CHARACTERIZATION
This chapter focuses on synthesizing graphene by thermal exfoliation and reduction of
GO. The graphene was synthesized at the Petroleum Institute, Abu Dhabi. The purpose of this
chapter is to give a general idea to the reader about the type of graphene used in this thesis and
their synthesis.
2.1. Thermally Reduced Graphene (TRG)
In this thesis, we have used thermally reduced graphene (TRG) as one of the main
nanofiller for polymer reinforcement. Following section provides fundamental information
regarding TRG synthesis and characterization.
2.1.1. Introduction
Selection of the synthesis route for graphene depends on the choice of potential
applications. Graphene can be synthesized from natural graphite or GO. The starting material,
and method to split that material into atomically thick graphene sheets, largely influence the final
physical and chemical properties of graphene. Recently, Kim et al.28 classified the methods for
production of graphene into two broad categories: bottom-up, and top-down methods.
In bottom-up approach, graphene is produced by methods such as chemical vapor
deposition (CVD)73, arc discharge74, epitaxial growth on SiC75, 76

, chemical conversion77,
reduction of CO78, unzipping CNTs79, and self-assembly of surfactants80. Large size and defect
free graphene is often produced from CVD and epitaxial growth on small scales. Due to small
production volumes, these methods are considered suitable for producing graphene for
25
fundamental studies and electronic applications. The nature, average size, and thickness of
graphene produced from bottom-up methods is summarized elsewhere28.
Top-down methods produce graphene or modified graphene by separation or splitting of
graphite or GO derivatives. Significant economic advantages are offered over the bottom-up
approach since starting material is graphite or its derivative. That’s why, top-down methods are
considered more suitable for mass production of graphene sheets, useful for polymer
nanocomposite applications where large quantities of fillers are usually required. Starting from
graphite, the top-down approach includes micromechanical exfoliation30, direct sonication81, 82,
electrochemical sonication83, and superacid dissolution of graphite84. On the other hand,
producing modified graphene from GO includes Li-alkylation of graphite flouride85, chemical
reduction of GO86, chemical reduction of organically modified GO86, 87

, and simultaneous
thermal exfoliation and reduction of GO28, 36, 37, 38, 88.
The simultaneous thermal exfoliation and reduction of GO36, 37, 88 results in the splitting
of a fraction of the oxygen-containing groups as CO, CO2, and small quantity of steam.
Thermally reduced graphene (TRG), a reduced form of graphene oxide, is composed of a single
or few-layer oxygen-functionalized graphene sheets containing a far less amount of oxygen-
containing groups compared to GO, and corresponding to C/O/H atomic ratio of 10/1/1. The
presence of the residual oxygen-containing groups on TRG surface can anchor various molecules
by imparting it a polar character.
In following discussion, production and characterization of TRG is reported which has
been published in several collaborative publications. Also, in some parts of this thesis, a
26
commercial graphene sample was used. A brief discussion on characterization of the commercial
graphene sample called "Graphene Nanoplatelets (GnP)" is also provided at the end.
2.1.2. Experimental Details
This section contains description of materials used, and methods of preparation of
graphene used in this study.
2.1.2.1.Materials
Natural flake graphite (-10 mesh, 99.9%, Alfa Aesar), sulfuric acid (95-97%, J.T.
Bakers), hydrochloric Acid (37%, Reidel- deHaen), hydrogen peroxide (30% solution, BDH),
potassium chlorate (Sigma Aldrich), and sodium hydroxide (Reidel-deHaen) are used as
received.
2.1.2.2.TRG Synthesis
TRG was produced following the thermal exfoliation method89. In this method, graphite
is oxidized using Staudenmaier method90 as follows: graphite (5 g) was placed in ice-cooled
flask containing a mixture of H2SO4 (90 ml) and HNO3 (45 ml). Potassium chlorate (55 g) was
added slowly to the cold reaction mixture. The reaction was stopped after 96 h by pouring the
reaction mixture into water (4 L). HCl solution (5%) was used to wash the produced graphite
oxide (GO) until no sulfite ions were detected. The mixture was then washed with water till no
chloride ions were detected. GO was dried in a vacuum over night. The dried GO was exfoliated
by rapid heating at 1000 °C in a tube furnace (Model 21100, Barnstead Thermolyne) under flow
of nitrogen for 30 s to 2 minutes.
27
2.1.2.3.Characterization of TRG
XRD (X’Pert PRτ εPD diffractometer, PAσalytical) was used to test the oxidation of
graphite, and complete exfoliation of GO into TRG. A rapid scan was conducted between 5-35o
with 0.02o/sec step size at 40 KV voltage with an intensity of β0 A using CuKα radiation of
wavelength 1.54 Å. TEM images were obtained using FEI Tecnai G20 TEM with point to point
resolution of 0.11 nm, coupled with Energy Dispersive X-Ray spectroscopy. The samples were
prepared by dispersing approximately ≈0.η mg of TRG in βη mδ of dimethyl formamide by
sonication for 10 minutes in a sonicating bath at room temperature. Two drops of the suspension
were deposited on a 400 mesh copper grid covered with thin amorphous film (lacey carbon).
SEM images were obtained using Philips FEI Quanta 200 SEM operated at high-vacuum mode.
A LabRAM HR (Horiba Scientific) was used to obtain Raman spectra. Typically, a 50x objective
was used with 633 nm excitation line. Bulk density of graphene samples was measured by
AutoTap Tap density meter (Quantachrom Instruments, Model: D-AT-3). Each sample was
tapped 2000 times before taking the measurement. Density values were recorded as average of at
least three readings. Specific surface area, pore volume and pore size distribution were
determined using Quantachrom Autosorb-1 (Quantachrom Instruments). Prior to measurement,
the sample was degassed for 16 hours at 200o C. TRG Carbon/Oxygen (C/O) ratio was
determined from CHN elemental analysis carried out by Midwest MicroLab, LLC (Indiana, US)
using a combustion analyzer at 990 °C under ultrapure oxygen; oxygen content was carried out
by Unterzaucher method at 1050 °C. Fourier transformed Infrared (FTIR) spectrum of dried
TRG with KBr pellets (spectroscopic grade, Merck) with ~0.2% TRG was obtained using
Thermo Nicolet FTIR at a resolution of 4 cm-1 and 32 scans. X-ray Photoelectron Spectroscopy
(XPS) measurement was conducted using a SSX-100 system (Surface Science Laboratories, Inc.)
28
equipped with a monochromated Al Kα X-ray source, a hemispherical sector analyzer (HAS),
and a resistive anode detector.
2.1.3. Results and Discussion
Rapid heating of GO leads to simultaneous reduction and exfoliation of GO sheets. By
controlling the exfoliation condition, the bulk density, surface area, and the C/O contents of TRG
can be varied as discussed in detail elsewhere89, 91. First direct evidence of exfoliation of GO was
the substantial volume expansion of 100-300 times due to rapid heating (Figure 2.1a).
Specifically, one gram of GO with bulk volume of about 2 cm3 yielded approximately 0.7 g TRG
with a bulk volume of about 150-180 cm3 depending on the density of the produced TRG.
The X-ray diffraction (XRD) patterns provide supporting evidence for the complete
exfoliation of GO to TRG (Figure 2.1b). A strong diffraction peak (002) was observed at 2 =
26.5° for graphite that corresponds to a d-spacing of 3.37Å. The (002) peak is an intrinsic peak
showing the stacked graphene layers in pure graphite. The oxidation of graphite led to polar
oxygen functionalities on the surface of GO. The presence of these functionalities and due to the
adsorbed water intercalation, the (002) peak shifted to 2 = 11.4° indicating interlayer expansion
to a d-spacing of 7.8Å. In contrast to the diffraction patterns in graphite and GO indicating the
ordered layered structure, TRG diffraction pattern shows no noticeable diffraction peaks
confirming the complete exfoliation of GO, and production of no stacked structure.
Raman spectroscopy probes structural and electronic features of graphitic materials.
Raman spectrum provides useful information about the defects (D band), in-plane vibrations of
sp2 carbon atoms (G band), and the stacking order (βD or Gʹ band) of graphene layers92. The
complete exfoliation of graphite into TRG was studied by Raman spectroscopy (Figure 2.2). The
29
shape of the Gʹ (or βD) peak is used to distinguish between single-layer graphene, bilayer
graphene, and the bulk graphite. Bilayer sheets or sheets with less than five layers show a
broader and symmetrical Gʹ peak, while bulk graphite exhibits a distorted peak92. The Raman
spectrum of TRG showed a broader and symmetrical Gʹ peak in the βη00-2800 cm-1 range,
indicating graphene sheets with less than five layers were obtained after thermal exfoliation and
reduction.
a) b)
TRG
GO
2
5 10 15 20 25 30
Figure 2.1 0.5 g of GO expands to 75 ml of TRG upon rapid heating at 1050 °C (a), XRD
patterns of pure graphite, GO and TRG (b). (reproduced from ref.88, copyright (2012) Springer)
The second prominent feature of the Raman spectra is the size, shape, and intensity of D
and G bands. The intensity of G band is known to increase linearly with graphene layer
thickness93. The graphite exhibited a strong and intense G band showing bulk stacked sheets as
compared to that of TRG indicating a few layered graphene. The D-band that appears as a result
of induced defects, bears an inverse relation between its intensity and number of graphene layers.
Intensity of D-band decreases with increasing graphene thickness, and it is almost invisible for
defect-less bulk graphite94. The defects are more easily introduced into the thinner graphene
92
sheets, and the intensity of these defects is governed by the method of producing graphene .
30
The differences of the spectra of graphite and TRG clearly indicates that we have successfully
produced graphene instead of multilayer graphite nano-crystallites in this work.
700
300
G
600 250
G'
200
500
Raman Intensity
150
400 100
50
300 2500 2600 2700 2800
200 D
Graphite
100 TRG
0
1100 1200 1300 1400 1500 1600 1700 1800
Frequency, cm-1
Figure 2.2 Raman spectra of graphite and TRG. (reproduced from ref.88, copyright (2012)
Springer)
The surface morphology of TRG was investigated by scanning electron microscopy
(SEM), and high resolution transmission electron microscopy (HRTEM). Though, crevice like
structure was prominent in low density TRG (Figure 2.3a), and the samples with higher densities
appear to have fluffy agglomerated structures as produced (see ref.88 for details), the HRTEM of
TRG after dispersing in DMF showed graphene layers with paper-like morphology (Figure 2.3b).
The transparent graphene sheets were clearly visible confirming that GO was successfully
exfoliated. However, the elastic corrugations, and the scrolled or folded edges often result in
95
different brightness on the surface of graphene , which was also observed in TEM image as
dark lines.
31
a) b)
10 μm
Figure 2.3 TRG with bulk density of 17 mg/cm3 and C/O = 13: SEM (a), and HRTEM (b).
(Image reproduced from ref.88)
TRG was also characterized by N2 adsorption for BET (Brunauer-Emmett-Teller) surface
area, pore volume and pore size distribution. The BET measurement indicated that the
sorption/desorption behavior of TRG followed a standard type II-b BET isotherm (inset of
Figure 2.4). The cumulative pore volume was determined using BJH cumulative desorption total
pore volume method. The TRG sample with the highest C/O ratio (17/1) and the lowest bulk
density (3 mg/mL), exhibited a surface area and pore volume of 1260 m2/g and 3.7 cm3/g,
respectively. Both the surface area and the cumulative pore volume decreased with the decrease
of C/O ratio, and increasing bulk density of graphene (see ref.88 for details).
The chemical structure of TRG was studied by FTIR and XPS to determine the type of
the oxygen groups on TRG surface. The FTIR transmission spectrum between 600 and 2000 cm -
1
(Figure 2.5a) indicated the presence of carboxylic groups (~1720 cm-1), hydroxyl groups
(~1420 cm-1, 1200-1220 cm-1) and epoxy groups (~1060 cm-1). The graphitic C=C give rise to
multiple stretching vibrations in the 1550-1680 cm-1 range where the stretching at 1600 cm-1
32
represents very small amounts of unexfoliated graphite with small amount of the adsorbed
waters96.
0.5 8
Volume Adsorbed [cc/g]

Adsorption
6 Desorption
0.4
Pore Area [cc/g-Å]
4
0.3
2
0.2
0
0.0 0.2 0.4 0.6 0.8 1.0
0.1 Relative Pressure [P/Po]
0.0
0 10 20 30 40 50 60 70
Pore Size [Å]
Figure 2.4 Pore size distribution of TRG sample with bulk density of 3 g/L. Inset shows the BET
adsorption-desorption isotherm curve (reproduced from ref.88, copyright (2012) Springer).
The high resolution C1s XPS deconvoluted spectrum is shown in Figure 2.5b. The peak at
284.57 corresponded to graphitic sp2 C=C atoms. The C-O peak observed at 285.86 eV was
attributed to the presence of epoxy and hydroxyl groups. The peak at 287.26 eV corresponded to
the carboxylic acid groups (O-C=τ). The π-π interactions between graphene layers were
reflected by the peak at 290.54 eV36, 37. These results are consistent with the findings of a recent
on identifying the structure of reduced graphene using XPS and NMR97.
2.1.4. Summary
Successful synthesis of thermally reduced graphene (TRG) is observed by simultaneous
thermal exfoliation and reduction of graphite oxide (GO). TRG contains some residual oxy-
functional groups on its surface observed by XPS and FTIR, and planar defects seen in Raman
33
spectroscopy. XRD showed the evidence of complete exfoliation, whereas Raman spectroscopy
indicated that TRG particles were composed of 4-5 atomically thick graphene sheets. The
magnitude of oxy-functional groups on graphene surface can be altered by varying the
exfoliation time and temperature, which also gives control over the surface area and bulk density
of the produced graphene.
a) 5000
284.57 b)
sp2 -C
Transmission, % (a.u.)
4000
3000
Counts
285.86
2000 C-O
287.26 290.54
C=O π*-π*
1000
5 sp2-C 2 1
0
281 283 285 287 289 291 293 295
2000 1800 1600 1400 1200 1000 800 600
Binding Energy, eV
Wavenumber (cm-1)
Figure 2.5 FTIR (a) and XPS high resolution C1s spectrum (b) of TRG sample. the inset in a)
provides a structural model for TRG (reproduced from ref.37 with permission from the Centre
National de la Recherche Scientifique (CNRS) and The Royal Society of Chemistry).
2.2. Graphene Nanoplatelets (GnP)
In parts of this thesis, a commercial graphene sample called "Graphene nanoplatelets
(GnP)" was also procured from Graphene Supermarket, and used in manufacturing polymer
nanocomposites. Therefore, a brief discussion on the characterization of GnP is presented in this
section. More details on characterization and use of GnP will also be provided in the proceeding
chapters.
TEM image of GnP was obtained by sonicating a very dilute solution of GnP in acetone,
and depositing one drop of suspension on the Cu grid with holy carbon. Similar to TRG, GnP
34
showed paper-like morphology (Figure 2.6). However, TRG sheets were smaller in lateral
dimensions whereas GnP sheets are extended over a few microns. Also, importantly, no surface
wrinkles were observed in GnP sheets which indicates the absence of any oxy-functionality on
GnP.
Figure 2.6 TEM image of graphene nanoplatelets (GnP)
Acknowledgements
The date presented in this chapter has been the part of several collaborative publications,
and many people have contributed to its production. Authors would like to thank Jamie Whelan
and Sabna Khadar from Petroleum Institute for helping with BET and SEM analysis, and Issam
Ismail from University of Minnesota for XPS experiments.
35
CHAPTER-3
EFFECT OF SOLVENT ON THE UNCATALYZED SYNTHESIS OF AMINOSILANE-
FUNCTIONALIZED GRAPHENE
This chapter is modified from a paper published in
RSC Advances1
Muhammad Z. Iqbal2, Marios S. Katsiotis3, Saeed M. Alhassan4, Matthew W.
Liberatore5, Ahmed A. Abdala6
3.1 Introduction
Since its discovery in 2004, graphene has attracted the attention of researchers owing to
its extraordinary electronic, thermal and mechanical properties30, 98, 99, 100, 101
. Due to this
combination of extraordinary properties in addition to the very high surface area, graphene is
widely used as a nano-filler in manufacturing of polymer nanocomposites with improved
mechanical, thermal and electrical properties28, 38, 102, 103, 104

. Nevertheless, homogenous
dispersion of graphene and strong interfacial interactions between graphene and the polymer
matrix is required to obtain enhanced properties. The chemical functionalization of graphene
alters the Van der Waals interactions among the nanofiller aggregates, making them easier to
disperse in a polymer matrix and can also enhance the interface between graphene and the
polymer matrix. On the other hand, the extremely high surface area of graphene makes it an ideal
1
Reprinted with permission from the Centre National de le Recherche Scientifique (CNRS) and The Royal Society
of Chemistry, (2014), 4, 6830-6839
2
Primary author and researcher at Colorado School of Mines, Golden, CO, U.S.A.
3
Co-author and postdoc at The Petroleum Institute, Abu Dhabi, U.A.E.
4
Co-author and assistant professor at The Petroleum Institute, Abu Dhabi, U.A.E.
5
Author for correspondence and associate professor at The Petroleum Institute, Abu Dhabi, U.A.E.
6
Author and advisor at Colorado School of Mines, Golden, CO, U.S.A.
36
candidate as an adsorbent for H2 storage105, removal of pollutants from water37, oil31, and
gases106. In order to enhance the compatibility of graphene with polymer matrices and increasing
its adsorption affinity functionalization of graphene may be required.
The use of residual oxygen pendent groups on thermally or chemically reduced graphene
for further attachment of the organic moieties is an attractive route exploited for covalent
functionalization of graphene50. Silane coupling agents are historically applied to surface
modification of nanofillers25, 58, 59, 60, 107. Graphene produced from reduction of graphite oxide
contains sufficient amounts of hydroxyl, epoxy and carboxyl groups on their basal planes and
edges97. These groups can be dehydrated with silane coupling agents under appropriate
conditions. Also, the functional groups of silane coupling agents can be chemically attached to
the polymer. Amongst, 3-aminopropyltriethoxysilane (APTS) has been widely reported as a
reactive coupling functionalization for CNTs25, 108 and graphene58, 59, 109. Specifically, Wang et al.
reported attachment of APTS on graphene surface and used the functionalized graphene in
graphene-epoxy nanocomposites59. The grafting of APTS was proposed to follow dehydration of
carboxylic and hydroxyl groups. In another report by Yang et al., APTS reaction with chemically
converted graphene resulted in 4% Si grafting on atomic basis58. However, the proposed
mechanism of APTS grafting was through the epoxide groups on the graphene surface. In
addition, both reports employed DCC catalyst to accelerate reaction kinetics and enhance the
grafting yield. A 3.4 atomic% Si yield has also been reported for graphene by Ganguili et al. 109.
Gasper et al. reported detailed reaction mechanism for grafting various types of silanes on
CNT108. Therefore, these studies outline the importance of silane functionalized graphene in
various applications. For the mass production of APTS-f-graphene, a method that does not utilize
a catalyst is needed. Catalyst can increase the production cost by many fold. Hence, a catalyst-
37
free method in functionalizing graphene by silane based coupling agents is highly desirable. In
addition, in order to use the APTS-f-graphene in different applications, a better understanding of
APTS chemistry is needed. This study focuses on the above mentioned question using various
characterization techniques.
In the present work, we present a simple catalyst-free method for APTS attachment on
TRG with a higher grafting yield of silane attachment. Thermally reduced graphene (TRG) is
produced via simultaneous thermal exfoliation and reduction of graphite oxide (GO). The effect
of solvent on the localization of functionalization on graphene surface is also discussed. Two
simple routes for reacting APTS with TRG are presented; 1) using an organic solvent, and 2)
using pure silane without any solvent. A mechanism involving APTS attachment onto graphene
is also proposed based on various characterization tools to reflect the effect of organic solvent on
functionalization chemistry. The resulting functionalized graphene was thoroughly characterized
using physicochemical methods to understand the nature of functionalization reaction. The
success of the simple reaction routes is expected to promote mass production of APTS-
functionalized graphene.
3.2 Experimental Details
Following sections describes details on materials used in this study, and the procedures
adapted to synthesis TRG and functionalized TRG.
3.2.1 Materials
Natural flake graphite (-10 mesh, 99.9%, Alfa Aesar), Sulfuric Acid (95-97%, J.T.
Bakers), Hydrochloric Acid (37%, Reidel- deHaen), Hydrogen Peroxide (30% solution, BDH),
38
Potassium Permanganate, Sodium Nitrate (Fisher Scientific), 3-aminopropyl triethoxysilane
(98%, Merck) and toluene (99.5%, Panreac) were used as received.
3.2.2 Preparation of TRG
TRG was produced via the thermal exfoliation of graphite oxide (GO)110. In this method,
graphite is oxidized using Staudenmaier method90 as follows: graphite (5 g) was placed in ice-
cooled flask containing a mixture of H2SO4 (90 ml) and HNO3 (45 ml) then potassium chlorate
(55 g) was slowly added to the pre-cooled (0-5° C) reaction mixture under stirring. After the
reaction proceeds for 96 h, it is stopped by pouring the reaction mixture into water (4 L). GO is
filter and washed with HCl solution (5%) until no sulfite ions are detected. Finally, the resulting
deep brown colored mixture was repeatedly washed with copious amount of water until no
chloride ions was detected. The wet GO was dried under vacuum overnight. TRG is made by
rapid heating of dry GO powder at 1050° C in a tube furnace (Model 21100, Barnstead
Thermolyne) under flow of nitrogen for 30 s.
3.2.3 Silylation Reaction
Two simple routes are proposed to reflect the effect of solvent on APTS attachment
chemistry as follows:
Method 1: 50 mg of TRG was dispersed in 30 mL of pure APTS in a 50 mL reaction
flask. The mixture was refluxed at 100° C for 3 hours under stirring then cooled to room
temperature and the functionalized TRG (f-TRG) is recovered by vacuum filtration.
Method 2: same as Method 1 except the 30 mL of pure APTS is replaced by 50 mL of 30
vol% APTS in toluene. TRG functionalized using the solution is denoted (f-TRGS).
39
To remove any physically adsorbed APTS from the surface of TRG, f-TRG was
dispersed in toluene under stirring for 15-20 minutes followed by tip-sonication for additional 5
minutes and filtering under vacuum. To ensure the complete removal of any unreacted APTS,
this washing procedure was repeated twice. The samples were then dried in at 120° C for 2 h.
3.2.4 Characterization
Transmission Electron Microscopy (TEM) analyses were performed using FEI Tecnai
G20 with 0.11 nm point resolution and operated at 200 kV. Electron Energy Loss Spectroscopy
(EELS) was performed using post column energy filtered camera (Gatan GIF 963). Energy
filtered TEM (EFTEM) mapping was applied to map the location of the elements on the surface
of f-TRG samples by measuring core, post-edge and pre-edge losses of the respective elements
using the “three-window method” technique111. X-ray Photoelectron Spectroscopy (XPS)
measurements were performed using SSX-100 system (Surface Science Laboratories, Inc.)
equipped with a monochromated Al Kα X-ray source, a hemispherical sector analyzer (HAS)
and a resistive anode detector. For the high-resolution spectra, the lowest binding energy C1s
was set at 285.0 eV and used as the reference for all of the other elements. Fourier Transformed
Infrared (FTIR) spectra of TRG, f-TRGp, and f-TRGs in the range of 400-4000 cm-1 were
collected using Thermo Nicole FTIR at a resolution of 4 cm-1 and 32 scans. The spectra of the
dried samples were obtained in KBr pellets (Merck, spectroscopic grade) containing 0.2 wt% of
TRG. A LabRAM HR (Horiba Scientific) was used to obtain Raman spectra. Typically, a 50x
objective was used with 633-nm excitation line. Thermo-gravimetric analysis was carried out by
STA coupled with a mass spectrometer (STA-QMS, 409 PC Netzsch). The temperature range
was from 35 °C to 450 °C at a ramp rate of 10 °C in an inert atmosphere of nitrogen (30
mL/min). The electrical conductivity was measured by a custom-made conductivity cell at the
40
National Renewable Energy Laboratory (Golden, CO). The samples were bath-sonicated in 10
mL of water/isopropanol solution (3/1) followed by 2 minutes of tip-sonication. The dispersed
samples were dried on copper stubs for the conductivity measurements. The resistivity was
measured using a multimeter (Waveteck 28XT, Accuracy: ±1% + 0.1 Ohm). Further details on
experimental procedures are provided in Appendix-A.
3.3 Results and Discussion
The simultaneous thermal exfoliation and reduction of GO to TRG was successfully
confirmed by XRD and TEM (see Appendix-A).
The APTS-functionalized TRG was systematically characterized to investigate the effect
of solvent on chemical, thermal, electrical and morphological properties of APTS-f-graphene.
The chemical nature of the f-TRG is studied by FTIR, XPS, Raman, and electron energy loss
(EEL) spectroscopy. A mechanism of APTS grafting on TRG has been proposed. TEM micro-
images and elemental mapping were used to study the morphology of f-TRG. The electrical
conductivity and thermal stability of f-TRG are also reported.
3.3.1 Chemical Analysis
FTIR spectroscopy (Figure 3.1) confirms the successful attachment of APTS on TRG by
the appearance of additional functional group stretches associated with APTS. The intensity of
peak D (1189 cm-1), which corresponds to –COOH groups has been reduced. This suggests that
the carboxylic groups are the active moieties for APTS attachment. Peak H (1544 cm-1), which
corresponds to C=C stretching aromatic carbons in non-graphitic domains, remains the same for
f-TRGP but shifts to a higher frequency (~1558 cm-1) for f-TRGs. This shift to a higher
41
frequency for TRGs suggests the possibility of APTS reacting with C-hexagons of the TRG
sheets in addition to the reaction with TRG’s functional groups (Also confirmed by XPS
analysis). The carbonyl group >C=O at ~1740 cm-1 (peak J) also remains the same for pure and
f-TRG. The appearance of new peaks in f-TRGP and f-TRGS is attributed to –Si-O stretching
[peak A (–Si-OH at 914 cm-1), peak B (Si-O-Si at 1015 cm-1) and peak C (–Si-O-R at 1110 cm-
1)], indicating the covalent functionalization of graphene. Clearly, the solvent has influenced
broadening of Si bonding peaks. Also, the NH- amine vibration, which is expected around 3300-
3400 cm-1 in f-TRG (peak M), is not prominent, likely due to overlapping with the characteristic
bands of adsorbed water in the same region58. Peak F (1380 cm-1) corresponds to in-plane –OH
deformation and peak G (1485 cm-1) is assigned to phenyl groups. The –NH bending vibration
mode112 (peak I at 1629 cm-1) also confirms the direct attachment of amine groups to graphene
and its very low intensity indicates the presence of a very small amount of this sequence.
Moreover, the appearance of two new peaks at ~2853 and 2925 cm-1 for the f-TRG samples is
attributed to CH2-CH2 symmetric and asymmetric vibrations from APTS108.
Figure 3.1 FTIR spectra of the pure and f-TRGp and f-TRGs
42
While FTIR confirmed the attachment of APTS to graphene, a quantitative estimate of
the level of functionalization is provided by XPS analysis. The results shown in Table 3.1 reveal
that the functionalized graphene samples contain 7.4% Si and 6.9% N for f-TRGP and 8.0% Si
and 6.5% N for f-TRGS. Not only we are able to achieve such high yield without the use of any
catalyst but also the observed yield is higher than all previously reported for nanocarbons, e.g.,
graphene58 and CNT108. The Si/N ratio for f-TRGP is close to the stoichiometric APTS ratio of 1.
However, The Si/N ratio for f–TRGS is 1.2. Based on the stoichiometric ratio, Si/N ratio greater
than unity suggests the probability of side reactions in the presence of the solvent as will be
discussed later.
Table 3.1 Atomic composition of pure and f-TRG as obtained from XPS
Atomic %
C1s O1s N1s Si2p
TRG 89.1 10.9
f-TRGp 66.8 20.0 6.9 7.4
f-TRGs 67.4 18.2 6.4 8.0
In order to further explore the structure of f-TRG, high resolution C1s, O1s, N1s and Si2p
spectra were collected (Figure 3.2 and Table 3.2). In C1s spectra, all the samples exhibit the
same graphitic C=C peak whose area percentage decreases in the f-TRG due to the appearance of
new bands. The C-O peak58 in TRG decreased in f-TRGP and f-TRGS samples. Due to the
smaller electronegativity difference between C and N compared to between C and O, the peak
for C-N is observed at a lower binding energy (BE). The relative percentage of ~285 eV peak has
increased significantly in f-TRGP and f-TRGs. The peak for C=O carboxylic groups for f-TRGS
has a reduced intensity compared to the C=O peak in TRG, it vanishes in f-TRGP. Thus, C=O is
43
a potential attachment site for APTS on TRG (i.e, the carboxylic group on TRG). The
disappearance of C=O in f-TRGP suggests selective attachment of APTS onto the carboxyl
group. Meanwhile, two additional peaks are observed in C1s spectra of f-TRGP. The first peak at
286.16 eV is assigned to aliphatic C-N group58, 113

whereas the second peak at 288.85 eV is
attributed to either N-C=O or O-C=O108. Since APTS is a bi-functional silane, its grafting to
TRG can also take place through a linkage between the amine group in APTS and the carbonyl
or carboxylic functionalities on TRG. The small peak at 288.85 eV BE is attributed to such
linkage108. However, the relative area of this peak is very small indicating that fraction of APTS
that attaches to TRG through the amine linkage, is relatively small. Therefore, we conclude that
APTS reacts bi-functionally with TRG through attacking the phenolic and carbonyl groups on
the surface. εoreover, the π-π* interactions59 are observed in TRG and f-TRGS whereas no π-π*
interactions are observed in f-TRGP possibly due to the disappearance of C=O peak in f-TRGP.
Unlike C1s core level, where the assignment of the peaks to single and multiple C–O
bonds is quite straight forward, the assignment of O1s peaks is more difficult. The carbonyl
groups C=O are expected between 531 and 532 eV, C–O bonds in ethers and hydroxyls between
532 and 533.5 eV, whereas ether oxygen atoms in esters and anhydrides appears at 533.8–534.6
eV, or higher, and the carboxilates should originate a single component at BE similar to that of
C=O groups in the case of oxidized carbon surfaces. Although C=O is observed for TRG, f-
TRGP and f-TRGS, the relative intensity of C=O is lower in the f-TRG samples as a result of
APTS attachment in agreement with the analysis of the C1s spectra. The C-O-C/O-C=O band in
TRG appears at higher BE for TRGs showing the bonding with a more electronegative structure
at this point. The peak at ~ηγγ.ηeV originates from τ - contribution of TRG due to the presence
of O-2 ions.
44
The appearance of new Si-O bands in f-TRGP and f-TRGS is sign of APTS
functionalization and its intensity and relative contribution depend on the degree of APTS
functionalization114. Moreover, the carboxylic band observed for TRG at ~534 eV disappears in
the f-TRG samples in excellent agreement with the results from C1s XPS spectra and FTIR. The
prominent changes in O1s spectra of the pure and functionalized samples clearly indicate that the
silanization has changed the structure of the graphene sheets. Table 3.2 summarizes the results of
the high resolution C1s and O1s spectra. Furthermore, the details of high resolution N1s and
Si2p XPS spectra of f-TRG are provided in Appendix-A.
Figure 3.2 High resolution XPS spectra of pure and f-TRG samples
45
Considering the XPS data and the structure of f-TRG, the APTS may attach to graphene
through the phenolic as well as the carbonyl surface groups where a similar mechanism has been
reported by Gasper et al.108 for CNTs. However, this multiple functionality may differ from the
previously reported mechanisms for silylation where the aminosilanes are proposed to attack the
epoxy groups58 on the graphene surface. In addition, the second possibility of enhanced grafting
efficiency of APTS is NH2-silicon polymerization108 on the surface of TRG.
Table 3.2 High resolution fitting of C1s and O1s groups appearing in the XPS spectra of TRG, f-TRGp,
and f-TRGs
C1s O1s
C=C C-O/ N-C=O/ C-O-C/
C-N C=O π-π* C=O Si-O O-C=O
(sp2) C-N O-C=O O-C=O
TRG 284.57 285.86 - 287.26 - 290.54 531.56 - 533.55 534.84
f-TRGp 284.57 285.37 286.16 - 288.85 531.26 532.75 - -
f-TRGs 284.67 285.67 - 287.26 - 290.14 531.66 532.65 533.74 -
Previous reports demonstrated APTS grafting efficiency on MWCNT108 up to 4.5 Si
atomic%, and 3.4%109 and 4.1% for graphene58. The current method is able to generate much
higher yield of ~ 7.4% Si attachment in f-TRGP and ~ 8% Si in f-TRGS. The increase in Si
attachment can be attributed to the reaction of APTS with not only the surface functionalities of
graphene but also with the surface C-atoms. Schematics of possible mechanisms are also
discussed later.
The effect of silane attachment on the electronic structure of graphene is also confirmed
by EELS. The core-level energy losses of C, O, N and Si (Figure 3.3 and Figure 3.4) are
measured at the areas of minimum overlapping between the graphene sheets. All collected EELS
spectra are background corrected.
46
a) f-TRGs
b)
Intensity, a.u
Intensity, a.u
f-TRGp
f-TRGs
TRG
f-TRGp
280 300 320 340 360 520 535 550 565 580 595 610 625
Energy Loss, eV Energy Loss, eV
Figure 3.3 EELS Carbon K-edge a), and Oxygen K-edge b)
The carbon K-edge (Figure 3.3a) is the characteristic of graphene115. The sp2
hybridization of TRG is clearly observed as sharp peaks corresponding to the 1s  * and 1s
 * transitions at 289 and 294 eV, respectively. Interestingly, the hybridization state of
graphene is altered in the functionalized samples. In specific, the sp2 structure becomes less
dominant in the case of f-TRGP and f-TRGS in excellent agreements with FTIR, XPS and Raman
results. The ratio was calculated using the peak-ratio method116 and found to
be 98±1.5% , 94±1.1%, and 87±1.9% for TRG, TRGp, and TRGs, respectively. A plausible
explanation for this change in hybridization is attributed to the sp3 structure of carbon atoms in
silane. Based on the current information obtained from FTIR and XPS on the successful grafting
of APTS on graphene, the apparent change in hybridization most possibly represents the
combination between the sp2 structure of graphene and the sp3 structure of silane. The oxygen K-
edge region is presented in Figure 3.3b and exhibits an overall shape equivalent to that of the N
K-edge. Two * peaks can be observed at 530 and 535 eV which are attributed to the C-O bonds.
The dominating structure however, is the absorption beyond 541 eV with a particular triangular
shape. Similar findings were observed in literature117, 118, and the aforementioned structure was
47
attributed to the increased presence of Si-O bonds originating from the APTS-attachment on
graphene.
Figure 3.4a displays the nitrogen K-edge evolution, where a strong * absorption is
observed at ~399 eV and a structure-less * absorption of triangular shape is observed at ~410
eV.
a) b)
Intensity, a.u
Intensity, a.u
f-TRGs
f-TRGs
f-TRGp
f-TRGp
380 400 420 440 460 480 500 90 110 130 150 170 190
Energy Loss, eV Energy Loss, eV
Figure 3.4 Nitrogen K-edge a) and Silicon L2-3-edge b)
The *-transition is usually attributed to unsaturated C-N bonds119. Since this type of
bonds is not present in the silane molecule, the peak at ~399 eV can be attributed to a possible
loose attachment of the amine part of silane on the graphene surface in agreement with FTIR and
XPS spectra. Regarding the * absorption, this can be attributed in the Si-N bond present in
APTS. In the case of silicon L-edge (Figure 3.4b), the EELS spectra from the functionalized
samples are very similar to the spectrum of silicon oxide120. Peak at 99 eV corresponds to
elemental silicon (Si), at 105 eV to Si-N bond (Si1+) and peaks at 108 and 116 eV to Si-O (Si2+)
and Si=O (Si4+) bonds respectively121, 122. Regarding Si L1 edge at ~155eV, strong overlapping
48
with the threefold L2-3 edge prevents the acquisition of any useful information. Regardless,
silicon EELS strongly supports the presence of silane grafted on graphene.
The effect of APTS functionalization and the degree of exfoliation in TRG was also
examined by the Raman spectroscopy (Figure 3.5), which is known for its unambiguous
nondestructive identification123. For graphitic materials, the typical Raman bands are: a defect-
induced D band at 1350 cm-1, an in-plane vibration of sp2 carbon at 1580 cm-1 (G band), and a
two-phonon double-resonance process at ca. 2700 cm-1 (2D band).
The G-band position increases with decreasing number of layers in graphene124. Herein,
the G band centred at 1770 cm-1 for TRG has been upshifted to 1778 cm-1 on functionalization
(Figure 3.5a), thus revealing the decrease in the layer stacking125, mainly due to the presence of
APTS. Moreover, compared to TRG (Figure 3.5b), the characteristic 2D band for f-TRGs and f-
TRGP is observed to be blue shifted by about 28 cm-1 and accompanied with peak broadening,
confirming that the functionalization lead to better exfoliation of TRG and formation of few-
layer graphene flakes126.
Additionally, the appearance of D peak at 1339 cm-1 has been attributed to the presence
of structural disorder127. The D band arises from the activation in the first order scattering
process of sp3 carbons in graphene, and the intensity ratio of D and G bands (ID/IG) expresses the
sp2/sp3 carbon ratio, a measure of the extent of disorder128. The ID/IG for f-TRGS and f-TRGP has
increased from 0.677 for TRG to 0.903 and 1.026, respectively. The increased ID/IG ratio is
consistent with the functionalization of graphene through covalent bonding57, 129

and also in
agreement with the EELS results. In addition, the appearance of a new peak at lower frequencies
between 500-600 cm-1 is ascribed to the Si grafting on TRG 130

. Hence, overall the Raman
49
findings confirm the successful functionalization of TRG and the exfoliation state of TRG
remains unaffected by APTS attachment.
G-Band
D-Band
b)
Raman Intensity (a.u.)
a)
Raman Intensity (a.u.)

Si f-TRGs
f-TRGp
f-TRGp
Si
f-TRGs
TRG TRG
2500 2600 2700 2800

100 600 1100 1600
Frequency, cm-1 Frequency, cm -1
Figure 3.5 Raman spectra of TRG samples a) D and G band and b) βG (Gˈ) band
3.3.2 Morphological Analysis
TEM and EELS analyses are performed in order to understand the effect of functional
moieties on the morphology of graphene and to define the bonding between APTS and TRG
which can arise due the presence or absence of organic solvent. Pure TRG is composed of very
thin sheets, ranging in thickness between 3 and 6 nm and in lateral dimension from 0.5 to 1.5 m
(Figure 3.6).
These thin sheets are composed of overlapping graphene layers; the sheets are well
defined and separated. The inset in Figure 3.6a shows a selected area electron diffraction
(SAED) pattern collected from the center of the image, which verifies the crystallographic
identity of graphene.
High resolution TEM imaging (HRTEM) performed in areas where graphene was
“folded”, showed the thickness of the sheets ranges on between β.4 and θ.η nm corresponding to
50
number of overlapping layers between 4 and 10 (Figure 3.6b); based on graphene inter-planar
distance of 0.34 nm and sheet thickness of 0.314 nm). Finally, EDS results indicate the presence
of a small amount of chlorine impurity (< 0.5%), probably originating from the HCl washing
(Appendix-A).
a) b)
Figure 3.6 TEM images of pure TRG. (a) Graphene particle composed of overlapping graphene
sheers (inset: SAED pattern from the center of the graphene particle), (b) HRTEM image of two
overlapping graphene sheets
Although f-TRGp exhibits a structure similar to that of pure TRG, however, the sheets do
not appear as well separated as were in the pure TRG (Figure 3.7). The silane creates defects in
the graphene sheets (tears on the graphene surface) (see Figure 3.7a for f-TRGp). On the other
hand, no considerable change in the morphology of graphene sheets was observed for f-TRGs.
Instead, the sheets are very well defined and separated, (Figure 3.7b). The solvent appears to
soften the severe attack of APTS on graphene and hinders breaking down of sheets to smaller
ones. We infer that using organic solvent during the course of silane functionalization reaction
helps in maintaining the intrinsic morphology of graphene. The EDS analyses (Appendix-A)
from the two samples were in good agreement with the XPS elemental analysis: on average Si/N
51
ratio is found to be equal to 1.2 for f-TRGp, and 1.3 for f-TRGs (average of EDS spectra
collected at various points for each sample).
Furthermore, in order to understand the preferable attachment sites for silane on TRG,
EFTEM elemental mapping was performed on both f-TRGp and f-TRGS. To the best of our
knowledge, there is currently no publication on EFTEM mapping of the functionalized graphene
to determine the functionalization selectivity. However, the EFTEM elemental mapping,
completed here (Figure 3.8), can be a simple and versatile method for studying the local
functionalization. Bright spots in Figure 3.8(b, d) represent Si from EFTEM Si-elemental
mapping of Figure 3.8(a, c).
a) b)
`
Figure 3.7 TEM images of functionalized graphene: (a) f-TRGp, (b) f-TRGs
It is interesting to note that, in f-TRGP, Si (and N which is not shown here) is distributed
over the entire graphene surface (Figure 3.8b) representing a homogeneous distribution of the
grafted silane on f-TRGP surface. Thus, we infer that pure silane reacted homogeneously on the
graphene surface. A small amount of localized Si is also observed on the sheet edge. Thus, the
mode of silane grafting, when TRG is reacted with pure APTS, is with the surface functional
52
groups as well as the functional groups on the sheet edges. On the other hand, in f-TRGS, the Si
is observed to localize on the sheet edges. The homogeneous surface distribution of Si was not
observed as was seen in f-TRGP. Thus, it appears that in the presence of organic solvents like
toluene, the edge-functionalization of TRG can be the preferable mode of grafting. The
selectivity of edge-functionalization might further be increased by choosing appropriate solvents
and reaction conditions. In summary, solvent can play a vital role in the selective
functionalization of TRG. Further studies will evolve better control on its chemistry for selective
applications of silane functionalized TRG.
a) b)
c) d)
Figure 3.8 TEM bright field image (a) and corresponding EFTEM maps of silicon (b) for f-
TRGp; TEM bright field image (c) and corresponding EFTEM maps of silicon (d) for f-TRGs.
53
Based on the observations presented above, proposed reaction schemes for APTS with
TRG are elucidated (Scheme 1). The TRG oxy-functionalities are distributed over the surface
and sides of the sheets where the carboxylic groups are mainly located near the edges and most
of hydroxyl and epoxy groups are distributed over the surface. In f-TRGP, APTS reacts with
most of the surface groups and there is less reaction with the side carboxylic groups. In the case
of f-TRGS, the APTS molecules form covalent bonds with the carboxylic groups present on the
sides of TRG sheets. The use of various solvents assisting silane functionalization is not
uncommon. Toluene being a non-polar solvent with a dipole moment of 0.36 D has induced
significant effects on the functionalization selectivity. Owing to the non-polarity of toluene and
TRG being polar due to the presence of oxy-functional groups on its surface, the solvent helps
assisting preferable distribution of silane on TRG surface; leading silane molecules to more
reactive areas such as the edges. On the other hand, in the absence of any solvent, the silane
(being polar) is chemically adsorbed throughout the surface and edges. Increasing solvent
polarity in silylation reaction has already been proved to decrease the rate of silane reaction with
inorganic surfaces131, 132. Thus, using different non-polar solvents such as cyclohexane, benzene,
diethyl ether, chloroform,…etc can lead to discovering interesting aspects of effective solvents
for selective silane functionalization. Nevertheless, the probability and further quantification of
the attached functional groups depending on other solvents is beyond the scope of this article.
3.3.3 Thermal Stability and Conductivity
The thermal characterization of the pure and f-TRG by TGA provides a reliable
quantification of the relative amount of the introduced functionalities. As shown in Figure 3.9,
both TRGP and TRGS have lower thermal stability compared to the pure TRG.
54
NH2
OH
O
H2N
Si
OH
OH
O
Si O O
HO
OH
O
OH HO NH
OH
H2N O
No solvent OH Si
OH
HO O
APTS Si O
O
OH
OH
OH
HO O
OH NH2 HO
O Si
H5C2 HO
HO O O
NH2
O OH Si OH
O OH
O Si
O H5C2 O OH
OH C2H5 f-TRGp
HO HO
O H2N
O
OH
HO Catalyst H2N
O OH
TRG OH
NH2
Si
O
HO OH
O O
HO Si
HO
H2N O OH
Solvent O
OH
OH
O
O
Si O
O
HO
OH O
HO O O
OH
Si OH O
HO OH
Si
H2N
f-TRGs
H2N
Scheme 1 Reaction of APTS with TRG. TRG contains carboxylic functionalities on the sides
whereas hydroxyl and epoxy groups are mainly distributed over the surface
The lower thermal stability of f-TRG samples compared to pure TRG is attributed to the
full or partial detachment of the APTS groups from the graphene surface. The observed weight
losses in the temperature range of 50-500° C are 16, 22, and 25% for TRG, f-TRGS, and f-TRGP,
respectively.
As discussed earlier XPS results indicated that f-TRGP contains 7.4 atomic% Si, which
corresponds to 15 wt.% APTS and f-TRGS contains 8 atomic% Si corresponding to 16 weight%
APTS. Therefore, about 40% of APTS in f-TRGP and 55% of APTS in f-TRGS is lost between
50 and 500° C, respectively. Moreover, the higher weight loss for f-TRGS compared to f-TRGP
might be due to the most of the attached silane groups on the edges (as observed from the
elemental mapping), and in f-TRGP, the silane moieties are distributed over the surface and on
the edges of the sheets. Thus, it can be inferred that the end-functional groups are thermally less
stable as compared to the surface distributed labile groups.
55
The electrical resistance of pure and functionalized TRG samples has been investigated
using a custom made conductivity setup. The functionalization, as expected, has appeared to
increase the resistance of graphene. The measured room temperature resistance of TRG of 42
ohms slightly increases to 50.8 ohms for f-TRGP but increased significantly to 230 ohms for f-
TRGS. The increased resistance (decrease in conductivity) is expected due to the increase in sp3-
contents in the f-TRGS as indicated by ID/IG ratio in the Raman spectra (see Figure 3.5). The
edge distributed APTS in f-TRGS seems to have a more pronounced effect on the conductivity
compared to surface distributed groups in f-TRGP. This may be due to the effect of the group
distribution on the dispersion of sp2-electronic cloud of TRG.
100
Remaining Weight, %
90
80
70
60 Pure TRG
f-TRGp
f-TRGs
50
50 100 150 200 250 300 350 400 450 500
Temperature, C
Figure 3.9 Thermograms of TRG, f-TRGp, and f-TRGs. Samples were heated from 50-500° C at
10° /min under nitrogen
Conclusion
A simple catalyst-free method for synthesizing APTS-functionalized graphene was
successfully demonstrated along with the effective role of organic solvent in directing the
functionalities over the graphene surface and to the edges. The amount of APTS attached onto
graphene was determined by XPS and TGA and the covalent linkages were confirmed by FTIR,
56
XPS, EELS and Raman spectroscopy. TEM and EELS analyses show that no substantial change
in surface morphology of graphene was observed upon APTS functionalization in solution
whereas pure APTS has appeared to attack the graphene sheets adversely and changed the
morphology considerably.
The quantification of the f-TRG showed more than 7-8 atomic % attachment of Si, which
is higher than any previously reported functionalization. The method of APTS intercalation/
incorporation has a significant effect on the structure and properties of the resulting functional
material. Based on the EFTEM elemental mapping, it can be proposed that the selective end-
functionalization can be achieved using a suitable solvent during the course of the silylation
reaction. The f-TRG has shown good thermal stability over the temperature range of 50-500 °C
where only 16% weight loss is observed for pure TRG compared to 22% for TRGp and ~25%
for TRGs. The decrease in electrical conductivity (increase in electrical resistance) of TRG with
functionalization has been attributed to the increase in sp3-contents. Further studies can evolve a
better mechanism for selective functionalization of TRG with APTS.
Acknowledgements
We would like to thank Mr. Issam Ismail at the Department of Chemical Engineering and
Materials Science, University of Minnesota for the XPS measurements, Kelly Mason at National
Renewable Energy Laboratory (Golden, CO) for helping in the conductivity measurements, and
Dr. Sunil Lonkar at the Department of Chemical Engineering, The Petroleum Institute for his
valuable comments. This project has been supported by The Petroleum Institute in Abu Dhabi
through the Cooperative Research Partnership with Colorado School of Mines.
57
CHAPTER-4
SYNTHESIS AND CHARACTERIZATION OF POLYETHYLENE/OXIDIZED
POLYETHYLENE (PE/OPE) BLENDS AND ROLE OF OPE AS A VISCOSITY CONTROL
This chapter is modified from a paper published in the journal of
Applied Polymer Science1
Muhammad Z. Iqbal2, Ahmed A. Abdala3, Matthew W. Liberatore4
4.1 Introduction
Polymer blending is an economical way of designing new materials with unique
properties, such as high impact strength by leveraging the interactions between similar and
dissimilar polymer chains. The estimated consumption of polymer blends is more than 35% of
133
the total polymer consumption around the world and is continuing to increase . The properties
of pure polymers are important in predicting the resultant blend properties. Therefore, generating
new structure-property relationships between pure polymers and their blends can lead to new
133, 134
high performance materials . In general, the bulk properties of blends depend on its phase
morphology and interfacial structures.
Polymer blends are categorized as immiscible, miscible, or partially miscible. In
immiscible blends, one polymer can form a discrete phase dispersed in the other polymer
whereas in miscible blends, a single phase is observed. Also, partially miscible blend can exhibit
135
a single phase or multiple phases . Owing to the high molecular weight and small entropy of
1
Reproduced with permission Springer, (2016), 133, 43521-43532
2
Primary author and researcher
3
co-author and senior scientist at Qatar Environment and Energy Research Institute, Doha, Qatar
4
Author for correspondence and advisor
58
136
mixing, polymer blends usually exhibit immiscibility . Examples of commercial immiscible
137
blends include polystyrene with butadiene to produce high impact polystyrene or
poly(ethylene terephthalate) with poly(vinyl alcohol) for beverage bottles with better barrier
properties 138. Conversely, a small number of polymers shows miscibility when blended, such as
139 140
polystyrene with poly(phenylene oxide) , poly(vinyl chloride) with polycaprolactone , and
141, 142
poly(vinylidene fluoride) with poly(methyl methacrylate) . Usually, the miscibility is
observed when mixing polymers leads to molecular ordering. For example, when polystyrene is
blended with poly(phenylene oxide), the phenyl rings in both polymers overlap due to π-π
interactions creating miscible blends 139.
143, 144, 145, 146, 147

Polyolefins are used in packaging films , but due to their non-polar
148
nature, exhibit poor printability and dye-ability . Polyolefin blends with thermoplastics can
create new materials that impart polarity in polyolefins by mixing, allowing for dispersing fillers,
such as talc, carbon black, and graphene 148. Introducing a small amount of polar groups onto the
149 150
polymer backbone during polymerization or via post-polymerization process can
overcome the non-polar nature of polyolefins, but costs increase substantially. On the other hand,
blending polyolefin, such as linear low density polyethylene (PE), with another polar polymer to
prepare miscible blends can impart polarity in the blend matrix.
Oxidized polyethylene (OPE), commonly known as polymer wax, is often used as a

151, 152 153
processing aid or biodegradable PE . The OPE is synthesized by oxidizing PE by
154 155 156
thermal , radiation , or chemical methods . The oxidation process breaks the polymer
chains into segments of small molecular weight while introducing polar groups (e.g., acidic and
9, 157
ester groups) at the chain ends and along the chains . OPE is weaker and more brittle than
PE, but when mixed with PE, it can ease processing by decreasing viscosity. Durmus et al. 9 used
59
OPE as a compatibilizer in PE/clay nanocomposites and compared the properties of OPE
compatibilized nanocomposites with conventional PE-grafted-maleic anhydride compatibilized
nanocomposites. They reported ~120% reduction in oxygen permeability in the OPE
compatibilized nanocomposites at 15 wt% OPE loading, which was attributed to increased
exfoliation of clay. Also, OPE compatibilized nanocomposites improved barrier properties and
lowered the clay aspect ratio 8. Thus, PE/OPE blends show potential for packaging applications.
However, a more detailed understanding of the interactions of OPE with PE is needed to
engineer properties to create new products.
In this work, a comprehensive study of PE/OPE blends prepared by solution blending is
reported. The miscibility of the blend was determined by the Flory-Huggins parameter. The
rheological, mechanical, thermal and morphological properties of the blends were characterized.
Finally, the molecular morphology was correlated with the macroscopic properties.
4.2 Experimental
Details on synthesis procedures for PE/OPE blends are described below.
4.2.1 Materials
Linear low density polyethylene (LLDPE) with molecular weight of 3.6 × 106 g/mol
(determined via gel permeation chromatography) and bulk density of 0.97 g/cm3 was purchased
from Aldrich (428078, lot#07730MEV). Oxidized polyethylene (OPE) with an acid number of 7
and density of 0.94 g/cm3 (molecular weight ~ 1x103 g/mol) was supplied by Marcus Oil and
Chemicals (Texas). The Newtonian viscosity of LLDPE at 160°C is 1x104 Pa-s, and that of OPE
60
at 145°C is 0.02 Pa-s (viscosity versus temperature is provided in supporting information). The
solvent p-xylene (purity~99%, Sigma Aldrich, 134449) was used as received.
4.2.2 Preparation of Blends
PE and OPE at various compositions were dispersed in p-xylene (10 wt% solution) at
120°C for two hours. After the formation of homogenous and transparent solution, the solution
was drop cast on a heated glass plate at 120°C, and the solvent evaporated at that temperature for
two hours. The complete solvent removal was achieved by drying in a fume hood at ambient
conditions for 24 hours followed by drying for five hours at 80°C in a convection oven. The
samples were further vacuum dried overnight. The complete solvent removal was confirmed by
running thermal scans in a differential scanning calorimeter where no solvent evaporation peak
was observed. The dried samples were cut into pieces 3-5 mm wide, heated at 160°C for 10
minutes and hot pressed for 3 minutes under 5000 kPa pressure to prepare circular discs
(thickness ~ 1-1.3 mm and diameter ~ 25 mm) for rheological testing. Similarly, thin films (100-
β00 m) were prepared for mechanical and scattering testing by the same method using more
dilute solutions of PE and OPE in p-xylene and drop casting in a petri dish at 120°C and
following the same drying process.
The thermal transitions of the blends were investigated using DSC (TA Instruments Q20)
. About 5-10 mg sample was heated under nitrogen flow (20 mL/min) at 10°C/min from RT to
160°C, isothermally heated for 3 minutes to remove any previous thermal history, and cooled at
10°C/min to room temperature in order to record the crystallization temperature, Tc. The melting
temperature, Tm was determined from the second heating ramp at 10°C/min from room
61
temperature to 160°C. For the determination of equilibrium melting point, after removing
thermal history, the sample was rapidly cooled to a fixed Tc at a rapid rate of 60°C/min to avoid
premature crystallization, kept at Tc for 30 minutes, cooled to room temperature at 10°C/min,
and finally heated above the melting point at 10°C/min to record the apparent melting associated
with each Tc.
Thermal stability of the blends was determined by, TGA (TA Instruments Q50).
Approximately, 10-20 mg of the sample was loaded in TGA sampling pan, heated from room
temperature to 650°C at 20°C/min under nitrogen flow (60 mL/min).
The rheological properties of the pure and blend samples were studied using TA
Instruments AR-G2 rheometer equipped with a 20 mm parallel plate. Time sweeps were
conducted at 160°C at 1% strain and 1 rad/s angular frequency. For time sweep, the samples
were carefully loaded so that less than 80 s elapsed before data collection began. Samples were
equilibrated at 180°C for 2 minutes followed by 5 seconds at 160°C under static conditions,
pressed between the plates. The blends were subjected to time sweep experiments for 60
minutes. The linear viscoelastic region was determined by running stress sweep at each
temperature at 1 Hz. The time-temperature superimposed master curves were constructed by
conducting frequency sweeps at each temperature within the linear viscoelastic range using the
horizontal shift factors.
The mechanical properties of blend films were determined following ASTM D882, using
ARES-G2 (TA) extensional rheometer with Film & Fiber tool. Measurements were carried at
room temperature under a speed of 0.0167 mm/s using thin rectangular samples ~10 mm long
62
and ~ 5 mm wide, stretched at 0.166 mm/s-1 at room temperature. The reported mechanical
properties are the average of 5 samples.
Small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS)
experiments were performed at the X-ray Sciences Division, beamline 12-ID-B, at the Advanced
Photon Source at Argonne National Laboratory. Details of the measurement procedure and the
158, 159
temperature and humidity control can be found elsewhere . Wide angle X-ray diffraction
(XRD) was performed using a Phillips PW γ040/θ0 spectrometer using CuKα radiation at a scan
rate of 0.02 °C/s. The samples for SAXS, WAXS, and XRD were prepared following procedure
similar to that used for mechanical testing samples.
Fourier Transformed infrared (FTIR) spectra (32 scans at 4 cm-1 resolution) were
collected using a Nicolet FTIR with ATR. The FTIR spectra were taken from 5 different spots
on thin films and averaged.
The micro-images of the blends were obtained using JEOL-JSM-7000F field emission
scanning electron microscope (FE-SEM) at an accelerating voltage of 3 KV. The blends were
cryo-fractured in liquid nitrogen and spur coated with gold for 1-1.5 minutes.
This section contains characterization of the PE/OPE blends synthesized in this thesis.
4.3.1 Miscibility, Phase Behavior and Thermal properties
Monitoring chemical bonds via FTIR spectroscopy provided the first qualitative measure
of the interactions between PE and OPE. Neat OPE showed specific vibrations originating from
63
various O-containing groups (Figure 4.1a). In the carbonyl range (1600-1800 cm-1), symmetrical
C=O stretching was observed at ~1715-1780 cm-1, including the ketonic stretching at 1715 cm-1,
C=O stretch in esters at ~1740 cm-1, and carboxylic acid C=O stretch at ~1780 cm-1. The region
in the frequency range of 1400-1500 cm-1 was attributed to the combination of symmetric
carboxylate stretch and C-H mode 160. CH2- stretching was observed at 1470 and 1460 cm-1. C-H
rocking absorption appeared at 1380 cm-1 and C-O stretch in tertiary alcohols observed at ~1150
cm-1. Thus, OPE structure contained carbonyl C=O and ketonic C=O along with alcoholic C-O
groups. The spectral regions of OPE were consistent with the structure of OPE reported
elsewhere 9.
The spectra of neat PE and PE/OPE blends were also obtained at various compositions
(Figure 4.1b). Since neat PE does not contain oxygen, no change in transmission was observed in
the carbonyl region. Increasing the OPE concentration decreased the IR-transmission through the
carbonyl peaks (at 1715 and 1740 cm-1) in the blends, which is consistent with the location of the
OPE functional groups. Averaging over 5 spots across the films, no changes in spectral patterns
were observed, so the distribution of OPE within PE matrix appeared homogeneous.
Thermal properties of polymer blends describe application behavior of blends. Increasing
OPE decreased the melting point and melt enthalpy of the blends (Figure 4.2). The melting
temperature decreased from 123°C for pure PE to 119°C for 50/50 blend whereas there was no
pattern observed for the melt enthalpy (ΔHexp). ΔHexp was in the range of 99 J/g for neat PE to
111 J/g for 50/50 blends. The melting profile of OPE showed three consecutive melting
transitions in the range of 98-105°C indicating presence of low molecular weight fractions in the
commercial τPE samples, and ΔHexp for OPE was 75 J/g (see Appendix-B). In addition, the
64
crystallization temperature, and crystallization enthalpy are also provided in supporting
information.
The melting profile for neat PE exhibited a peak melting point of 123 °C. As OPE was
added into PE, a small shoulder appeared in the vicinity of PE’s melting peak. Since this
shoulder was less prominent in neat PE, the immiscible adsorption of OPE chains containing
functional groups onto PE might be inferred. The small shoulder in PE melting profile indicated
significant short chain branches that crystallize separately from the backbone of PE. The small
separation between two melting peaks in neat PE was an indication that some chains do co-
crystallize 145. Some of the OPE chains when blended with PE acted as diluents whereas the part
that did not mix completely in PE might create the shoulder near the melting peak of PE. The
shoulder increased with increasing OPE concentration in the blends whereas the melting peak of
PE decreased as OPE concentration increased (Appendix-B). Due to the small separation
between PE and the shoulder component, it is reasonable to believe the formation of single
endotherm, which is indication of the miscibility between PE and OPE 161.
PE
% Transmission
1780 1715 1415 1150

1380
1740
~1740
PE/OPE 0/100
a) 1470 1460
b)
~1715
1900 1800 1700 1600 1500 1400 1300 1200 1100 1760 1750 1740 1730 1720 1710 1700 1690
Wavenumbver, cm-1 Wavenumber, cm-1
Figure 4.1 FTIR spectra of OPE (a) and PE/OPE blends at various compositions
65
Furthermore, the percent crystallinity in PE varied significantly increased with increasing
the OPE loading. The percent bulk crystallinity was calculated by considering the enthalpy of
melting of a 100% crystalline PE (ΔH°PE) to be 293 J/g 162

by the formula crystallinity%
=ΔHexp/(ΔH°PE x φPE) x 100. The measured bulk crystallinity% was 34, 42, 42, 52, 56, and 76%
(±2%) for PE/OPE 100/0, 90/10, 80/20, 70/30, 60/40, and 50/50 blends, respectively. The
significant increase in crystallinity also indicates formation of high modulus materials.
The χ-parameter has been evaluated experimentally using melting point depression
following Hoffman-Weeks analysis (Figure 4.3) and Flory-Huggins theory (Figure 4.4). The
163
Hoffman-Weeks equation serves as the fundamental method of evaluating the equilibrium
melting temperature (Tmo). The theory assumes that 1) surface effects in formation of crystals are
negligible, 2) crystals at melting point exhibit equilibrium crystal perfections, and 3) the crystal
thickening is independent of the crystallization temperature. The Hoffman-Weeks equation is
expressed as:
 1 T
Tm  Tm o  1    c
  
The observed melting temperature (Tm) was measured after isothermal crystallization at
various crystallization temperatures (Tc).
A plot between Tm and Tc gives a line and the point where the line intersects the Tm=Tc
line, gives Tm° for each blend composition. In the above equation, is the thickening coefficient
equal to lc/lg* where lc is the thickness of grown crystal and lg* is the initial thickness of a chain-
folded lamellar crystal 163.
66
140
129
127 120
125
∆Hm (J/g)
100
T m ( C)
123
121 80
119
60
117
115 40
0 10 20 30 40 50 60
OPE wt%
Figure 4.2 Melting temperature and melt enthalpy of the blends
The Tmo of neat PE and in blends was determined (Figure 4.3a). A decrease in Tmo of PE
was observed with increasing OPE concentration in PE/OPE blends, an indication of the
141, 164
miscibility . The Tmo decreased from 129°C for pure PE to 124°C for the 50/50 blend
(Figure 4.3b). The decrease in Tmo is caused by the morphological and thermodynamic effects. In
terms of the thermodynamic effects, OPE acted as a miscible diluent that decreased the chemical
potential of a crystalline polymer, which in turn decreased Tmo value 164, 165.
130
129
(a) PE/OPE 129 (b)
80/20
128
126
127
Tm ( C)
T m ( C)
Tmo 126
123
125
120 124
123
117
Tm=Tc Line 122
114 121
114 117 120 123 126 129 0 10 20 30 40 50
Tc ( C) OPE wt%
Figure 4.3 Hoffman-Weeks plot of PE/OPE blends (a) and Tm° versus OPE concentration (b).
67
Thermodynamically, the chemical potential of a crystallizable polymer decreases with
addition of miscible diluents164. The decrease in chemical potential leads to reduction in Tm°,
which is caused by the morphological and thermodynamic effects. Considering only the
166
thermodynamic effects for Tm° depression, the Flory-Huggins theory modified by Nishi-
Wang 141 can be used to determine the Flory-Huggins interaction parameter, χ as followsμ
  R V2  ln 2  1 1  
 o  o        1  1 
1 1
 Tm ( pure ) Tm ( blend )  H V1  m2  m2 m1  
2
o
Here, the subscripts 1 and 2 refer to OPE and PE, respectively. Tmo(pure) and Tmo(blend) are
the equilibrium melting points of neat PE and that of PE in the blends, respectively. V 1 and V2
are the molar volumes of the repeating units of the components, R is universal gas constant, ΔH o
is the heat of fusion of a perfectly crystallizable polymer, m1 and m2 are the degrees of
polymerization, ϕ is the volume fraction of the OPE in the blend and χ is the polymer-polymer
interaction parameter (Flory-Huggins interaction parameter).
The ΔHo value for PE is 7870 J/mol 167. Molar volumes of PE and OPE repeat units were
168
calculated by the group contribution method . The calculated molar volume of PE is V1=32.2
cm3/mol. The molar volume of OPE was calculated based on the structure reported by Durmus et
9
al. where OPE structure contained ketonic and carboxylic groups. For calculating the molar
volume, two CH2- groups, one ketonic group (-CO-) and one -O- group were considered whereas
the end carboxylic functional groups (-COOH) were ignored. Thus, V2 was calculated to be 46.8
cm3/mol. Since both the components are polymers with large values of m 1 and m2, these terms
containing ‘m’ can be neglected. Thus, the simplified version of the Flory-Huggins theory is:
68
H o V1  1 
 o  o   1
R V2  Tm ( blend ) Tm ( pure ) 
1 2
A plot between the left hand side of the above equation and (1-ϕ2)2 should give a line
with an intercept of zero, whereas the χ can be obtained from the slope of the line. The χ
obtained, thus, is a single value, averaged over all the compositions. However, a critical analysis
of above equation by Rostami 169

shows that this χ is actually composition dependent (Figure
4.4). A highly negative value of χ indicated miscibility which decreased as OPE concentration
increased in the blends. Specifically, PE/OPE 90/10 exhibited χ = -2.3 that jumped to -0.6 for
80/20 composition, and was ~0 for 50/50 blend. The composition dependent χ has also been
164
found for polyacrylamide-poly(ethylene glycol) system and the blends of poly (ethylene
oxide) with different polymers 170

. Moreover, a negative value of χ indicates miscibility 168
whereas positive χ shows incompatible blends.
0.5
Interaction Parameter, χ
-0.5
-1
-1.5
-2
-2.5
0 10 20 30 40 50 60
OPE weight %
Figure 4.4 Composition dependence of the Flory-Huggins interaction parameter, χ
69
The pure PE showed a high thermal stability, losses 25% weight at 454°C, and
decomposes completely at 500°C. However, pure OPE exhibited low thermal stability, with
weight loss starting around 200°C, 25% weight loss by 389°C, and complete decomposition at
490°C. The thermal stability of the blend decreased with the inclusion of OPE (Figure 4.5).
Since miscibility produces blends with properties in between the two pure components, the
thermal stability of PE/OPE blends was in between that of neat PE and OPE. Due to the lower
thermal stability of OPE, the blends started losing weight at about 200°C and limited the
experimental window for the rheological measurements. Therefore, the TTS master curves were
constructed from 130°C (~10°C above the melting point) to 180°C.
In addition, SAXS and WAXS explored the effect of OPE inclusion on PE structure.
171
SAXS measures the shape and size of polymers between 5 and 25 nm of the repeat distances .
The scattering vector (q) probes different structural features at various length scales (length scale
~ βπ/q) in a polymer. Increase in power law decaying exponent (log(I) ~ log(q) -α) at lower q
indicates a larger size of scattering objects. A power law decaying exponent of α = β.γ for neat
172
PE (Figure 4.6a) indicated the presence of randomly branched ideal polymer chains in PE .
Increasing exponent reflect the scattering from the mass fractals in polymers. A small increase of
exponent to α = β.4 for 80/β0 blend showed a slight increase in mass fractals in blends, whereas
an exponent of α = β.8 for 70/γ0 compositions indicated a transition of morphology from ideal
173
polymer chains to larger mass fractals . A maximum exponent of 2.9 was observed for 50/50
blend, which showed stabilization of morphology between 30 to 50% OPE concentration.
70
100 100/0
90/10
Experimental 80/20
Weight Retained, %
80 Window 70/30
60/40
50/50
0/100
60
40
20
0
100 200 300 400 500 600
Temperature, °C
Figure 4.5 Thermal stability of PE/OPE blends
The Kratky-SAXS profiles (also known as Lorentzian corrected plots) of the PE/OPE
blends showed a maxima in the low q region (Figure 4.6b). This maxima is associated with the
periodicity resulting from the presence of macro-lattices formed by the centers of adjacent
174
lamellae . The arrangement of molecular chains in folded, unfolded, or partially unfolded
175
lamellae can also be obtained from a Kratky profile . Here, the long period, also called as
weight-average value of the long period, Lp, was calculated from the maxima intensity peak in
the Kratky plot. Lp decreased substantially from 180 Å for neat PE to 136 Å for 50/50 blends.
The decrease in Lp is also attributed to the increase in microcrystallinity in the PE/OPE blends as
confirmed by thermal analysis. This effect is further discussed in the mechanical properties
section.
PE showed two distinctive peaks in the high q-range in WAXS profile at 1.49 Å-1 and
1.64 Å-1 (Figure 4.7). The small domain size (called d-spacing hereafter) associated with these
peaks was calculated from d = βπ/q. A d-spacing of 4.2 Å and 3.8 Å for peaks were calculated.
71
Interestingly, the inclusion of OPE in PE did not change the d-spacing in blends, and the blends
exhibited a constant peak ratio of 1.1 across all compositions. Since, it was not possible to
perform WAXS on OPE because it does not form a film at its own, the crystal structure of OPE
was obtained through x-ray diffraction (XRD) (see Appendix-B).
PE showed two distinctive peaks in the high q-range in WAXS profile at 1.49 Å-1 and
1.64 Å-1 (Figure 4.7). The small domain size (called d-spacing hereafter) associated with these
peaks was calculated from d = βπ/q. A d-spacing of 4.2 Å and 3.8 Å for peaks were calculated.
Interestingly, the inclusion of OPE in PE did not change the d-spacing in blends, and the blends
exhibited a constant peak ratio of 1.1 across all compositions. Since, it was not possible to
perform WAXS on OPE because it does not form a film at its own, the crystal structure of OPE
was obtained through x-ray diffraction (XRD) (see Appendix-B).
The PE/OPE blends exhibited almost similar XRD patterns as were observed in neat OPE
or PE (also observed in WAXS). A nearly constant positions of crystalline peaks, and d-spacing
indicates that the PE and OPE crystals are not different from each other, and the possibility of
co-crystallization of PE and OPE. Further studies on the co-crystallization behavior of PE/OPE
blends under isothermal and non-isothermal blends could identify the nature and type of the
formed crystals, but is outside the scope of this work.
Based on thermal and scattering results discussed above, the structure of PE and PE/OPE
blends can be summarized as follows. PE consisted of lamellar structure containing the long
period order of ~ 180Å for neat PE, which reduced to ~136Å at 50 wt% OPE loading. The
substantial decrease in long period is directly associated with the increase in crystallinity of PE
with OPE addition.
72
(a) (b)
/0
-2.3
100
I(q) q , (a.u.)
/10
90
-2.4
20
80/
70/
-2.8 30
2
0
/4
-2.9 60
/20
50
0.2 0.4 0.6 0.8 -1

1.0x10
q, (1/Å)
200
Long period order, Lp, Å
(c)
180
160
140
120
100
Figure 4.6 log-log I vs q (a) and Kratky plots of PE/OPE blends (b) at 60°C and 0% relative
humidity with Y-offset, and long period order for blends (c)
The size of crystalline regions within the crystallites (d-spacing) remained unchanged,
which indicates that OPE chains could be crystallizing with PE to produce similar crystals.
Since, no quantitative argument could be made about the change in crystal size from WAXS, the
increased crystallinity indicates that both amorphous and crystalline fractions of the long period
are affected with OPE addition. This compact structure should exhibit higher modulus and
increased brittleness compared to neat PE, which will be discussed in the mechanical properties
section.
73
100/0
Intensity (a.u.)
90/10
80/20
70/30
60/40
50/50
1.3 1.4 1.5 1.6 1.7 1.8

-1
q, Å
Figure 4.7 WAXS patterns of PE/OPE blends with Y-offset
4.3.2 Melt Rheological Analysis
One important factor in designing new polymer blends is understanding their processing
properties. Melt rheology is one of the most useful techniques to assess the processing behavior
of polymers in the molten state to mimic the real time processing issues. Herein, time-dependent
rheological properties were measured to understand the blends’ thermal stability under
processing conditions and time-temperature master curves were constructed to observe the chain
dynamics over extended time scales.
The evolution of start-up transient rheological parameters is a common practice to
understand thermal stability of polymers. Here, the evolution of Gˊ was monitored with time at
160°C at constant frequency and strain. A slight increase in Gˊ was observed with time for neat
PE (Figure 4.8a). The 90/10 and 80/20 PE/OPE blends showed a similar small increase up to
~1000 s followed by a small level of thinning. At higher OPE concentration; the blends exhibited
a stronger thinning starting below 1000 s. The thinning effect was more pronounced when
74
reduced shear modulus, Grˊ (where Grˊ=Gˊ(t)/Gˊ(t=0)) was plotted against time (Figure 4.8b).
Neat PE showed about 20% increase in Grˊ and the increment decreased for 90/10 blend
followed by pure thixotropy with increasing OPE concentration in the blends. Thus, OPE acted
as a plasticizer. The critical time (time at which rheological properties such as Gˊ, G˝ and *
drop significantly) decreased with increasing OPE concentration in blends. The power law
exponent was evaluated as Gˊ~t where Gˊ was considered in the thinning regions only. The
evaluated shear thinning exponent, , values were -0.18, -0.30, -0.38, -0.55, -0.82, -0.85 for
100/0, 90/10, 80/20, 70/30, 60/40 and 50/50 blends, respectively. As increased, the blends
showed a stronger shear thinning behavior. In subsequent sections, all samples were equilibrated
at 180° C for 2 minutes followed by equilibrating for 1 minute at a specific temperature before
carrying out any measurement. The experiments were completed within 350 s at all temperatures
before the overshoot or shear thinning exceeded more than ±15%.
The plasticization effect of OPE on PE is more evident in Figure 4.9a. Significant
decrease in complex viscosity was observed with increasing OPE amount. For example, neat PE
showed a viscosity of 10,000 Pa-s (at 0.01 Hz) that was reduced by more than one order of
magnitude to 700 Pa-s for 50/50 blend.
The zero shear viscosity (ηo) of the blends at various temperatures is determined by
fitting the complex viscosity data with Cross model 176, which will be compared next.
1    
o
 ( )  1n
o
75
Where, o is the zero shear viscosity, o is the relaxation time related to the longest
relaxation time and n is the Cross-exponent. The Cross fitting parameters and fitting profiles are
given in the supporting information.
1.6
(a) (b)
10
4
PE/OPE 100/0 1.4
PE/OPE 100/0
Gr (G(t)/G(t=0)
90/10 1.2
3
10 80/20 90/10
1.0
G, Pa
70/30 0.8
2
80/20
10 60/40
0.6
50/50
70/30
10
1 0.4 50/50
60/40
0.2
0
10 1 2 3 4 10
1 2
10
3
10
4
10
10 10 10 10
Time, s Time, s
Figure 4.8 Start-up transient rheology of neat PE and PE/τPE blendsμ Evolution of Gˊ with
time (a), and reduced Gˊ versus time. Data reported at T = 1θ0°C, = 1 %, ω = 1rad/s.
The o decreased with increasing temperature and increasing OPE concentration, which
was consistent with a plasticization effect of OPE. The significant viscosity decrease might allow
little to no change in the processing condition of PE nanocomposites compared to neat PE.
Specifically, a substantial amount of nanofillers are needed to induce percolation within the non-
177
polar PE matrix . At high filler loadings, viscosity increases several orders of magnitude and
may cause processing issues. The inclusion of OPE in PE can be used to tune the viscosity of PE
nanocomposites. More importantly, the shear thinning behavior of PE remains unperturbed by
the incorporation of OPE in PE.
The zero shear viscosity, o changed with OPE loading in the blends at two experimental
temperatures tested, i.e. 180 °C and 130 °C (Figure 4.9-b). Small increase in ηo values (~70%)
with a 50°C change in temperature from 180 to 130° C indicated temperature insensitivity of the
76
blends within the accessible temperature range. A linear relationship between log- o and OPE
weight% (Figure 4.9-b) also showed the melt miscibility of OPE in PE 143, 144, 178, 179.
It is worth mentioning that the morphology of miscible blends is also considered as a
function of viscosity ratio and capillary number 180. Since, the viscosity of OPE at 145°C (~0.02
Pa-s, from Arrhenius relation) (see Appendix-B), the viscosity ratio (p = d/ m, where d is the
viscosity of dispersed phase, and m is the viscosity of matrix) becomes extremely low (p ~ 2x10-
6
). At such low viscosity ratios (p << 1), the droplet diameter essentially remains unchanged, and
180, 181, 182
will have no effect on the blend morphology and droplet break-up processes . In
addition, very low p has been shown to require a longer mixing time (~30-60 minutes) to form a
183
consolidated polymer morphology . However, above 60 minutes, miscible blends of any low
viscosity ratio (p ~ 10-6) should produce a stable morphology, which also applies in this study
(mixing time ~ 120 minutes).
Time-temperature superposition (TTS) provided master curves for Gˊ, G˝ for the linear
viscoelastic response of the nanocomposites (Figure 4.10-a,b). The validity of TTS was tested by
plotting dynamic moduli according to Han’s proposed method 184

, which showed only minor
fluctuations in the master curves of the blends. The Han’s plot and individual Gˊ~ƒ master curves
are provided in the Appendix-B. Due to the limitations of experimentally accessible temperatures
and temperature insensitivity of blends, the TTS could not be extrapolated over more than 200 s-1
frequency. Therefore, the viscoelastic data had been shifted horizontally only. The calculated
horizontal shift factor, a from the best fit was also plotted versus temperature, and is provided in
T
Appendix-B.
77
5
4
10
10
130°C
*, Pa-s
o, Pa-s
10
3
10
100/0 3 180°C
90/10
10
80/20
2
70/30
10 60/40
50/50
2
10
, s
-2 -1 0 1 2
10 10 10 10 10 0 10 20 30 40 50
-1
OPE wt%
Figure 4.9 Complex viscosity profiles of PE/OPE blends at 160°C. The black solid lines are the
Cross model fit (left panel) and zero shear viscosity as a function of OPE wt.% at two different
temperatures (right panel)
σo Gˊ, G˝ plateau was observed within the experimental range. In the low frequency
region, Gˊ and G˝ were expected to show εaxwell behavior (Gˊ~ƒ2, G˝~ƒ1). However, neat PE
exhibited an un-relaxed behavior at low frequencies (Gˊ~ƒ1.1), which was observed in similar
high molecular weight PE melts 8, 185

. The low frequency slope increased from Gˊ~ƒ1.1 for neat
PE to Gˊ~ƒ1.7 for 50/50 blend, which approached the relaxed Maxwell behavior attributed to the
plasticization effect of OPE. Similarly, at low frequencies, neat PE exhibited G˝~ƒ0.8 behavior
which increased to G˝~ƒ1 for 50/50 blends, which was an indication of formation of the relaxed
chains compare to the neat PE. Furthermore, the formation of relaxed polymer chains with
increasing τPE concentration was more evident in the master curves of over the reduced
frequencies (see Appendix-B). The delta values increased as OPE concentration increased,
approaching ~λ0° for the completely relaxed chains.
In the high frequency regions, PE showed Gˊ~ƒ0.5, G˝~ƒ0.3 behavior that changes to
Gˊ~ƒ0.8, G˝~ƒ0.7 for the 50/50 blend. In the glassy (high frequency) region, PE showed a Rouse
78
longest relaxation time with a general expression186 Gˊ~ƒ0.5. Thus, slopes near 0.5 for Gˊ in the
high frequency region indicated Rouse dynamics. Increase in high frequency slope, further
indicated that the chains did not respond as glassy chains in high frequency region, which
confirms the existence of rubbery chains in that region.
6 6
10 PE 100/0 10
(a) 90/10 (b) PE 100/0
90/10
5 80/20 5
10 10 80/20
4 4
10 10
G, Pa
70/30
G, Pa
3 3
10 10
low  slope
60/40
low  slope
70/30
2 2
10 10
60/40 100/0 1.1 50/50 100/0 0.8
1 1
10 90/10 1.0 10 90/10 0.8
50/50 80/20 1.1 80/20 0.8
0 70/30 1.2 0 70/30 0.9
10 60/40 1.2
10 60/40 0.9
50/50 1.7 50/50 1.0
-1 -1
10 10
aT  s aT  s
-1 0 1 2 -1 0 1 2
10 10 -1
10 10 10 10 10 10
-1
Figure 4.10 εaster curves for Gˊ (a), G˝ (b) over the reduced frequency. Insets in (a) and (b)
show slopes in the terminal regions (at low frequencies) averaged over all the temperatures
(circles 180°C, upper triangles 160°C, lower triangles 140°C, and squares 130°C).
4.3.3 Mechanical Properties
Another important factor that determines the practical applications of new polymeric
materials is their mechanical performance. Among mechanical properties, tensile properties are
considered more important in the initial design of new polymers. The inclusion of OPE reduced
the strain at break for the blends(Figure 4.11a). In agreement with SAXS (Figure 4.6), the
decrease in blends’ δp led to the formation of high Young’s modulus materials. The fraction of
OPE that decreased the melting point (see thermal analysis discussion earlier) also induced
plasticization. The plasticization effect of τPE was quantified by a decrease in Young’s modulus
from 1.6 MPa for neat PE to 0.94 MPa for 90/10 blends. Further inclusion of OPE chains
79
increased the Young modulus from 0.94 MPa for 90/10 blend to 2.0 for 50/50 blend (~210%
increase), which is a direct evidence of the reduced blend elasticity (Figure 4.11b) in agreement
with the decreased long period spacing (Figure 4.6). The change in Lp is also known to influence
the elongation at break and yielding strain. A direct consequence of the decreased Lp also
resulted in decreasing the elongation at break from 21.5 for PE to 0.18 for 50/50 blends (Figure
4.11d) 187, 188. The yield stress (Figure 4.11c) increased from 12 MPa for PE to 16 MPa for 60/40
blends (~74% increase) whereas the yield strain decreased ~90% for 60/40 blends (Figure
4.11d). In conclusion, OPE in PE decreased the elongation to break for the blends and increased
the Young’s modulus, consistent with the findings from scattering and thermal analysis.
4.3.4 SEM Morphology
The cryo-fractured surface morphology of neat PE shows a smooth surface upon fracture,
189
which is expected for PE (Figure 4.12a) . When OPE is added into PE and the sample is
fractured, some fibrous structures appear to be pulled out from the fractured surfaces (Figure
4.12b). Denser fibers are observed for 80/20 (see Figure 4.12c) and 60/40 (Figure 4.12e).
However, 70/30 composition shows a distinct morphology, i.e., more abundant fibrous elements
(Figure 4.12d). At this time, we do not have a specific explanation for this behavior, but the
unique morphology might account for the higher elongation in the 70/30 blend compared with
90/10 or 80/20 blends. However, the scattering results also indicate this peculiar behavior with
70/30 composition. On the other hand, the 60/40 blends show smooth surface, which is
consistent with the reduced viscosity. The 50/50 blend represents a similar surface to the 60/40
blend, but due to the even lower viscosity of that composition, some larger fibers appear after
cryo-fracturing.
80
18 3.0
Young's Modulus, MPa

(a) (b)
15 50/50 2.5
100/0 2.0
Strees,M Pa
12
9
15
1.5
6 10 1.0
5
3 0.5
0
0.0 0.2 0.4
0 0.0
0.01 0.1 1 10 100 0 10 20 30 40 50
Strain OPE wt%
Yield and Break Stress, MPa
100
Yield and Break Strain

25 (d) Strain@ Break
(c) Stress@ Break Yield Strain
Yield Stress
20
10
15
10
1
0 0.1
0 10 20 30 40 50 0 10 20 30 40 50
OPE wt% OPE wt%
Figure 4.11 Mechanical properties of PE/OPE blends: (a) Stress-Strain behavior, (b) Young’s
modulus, (c) yield and break stress, and (d) yield and break strains. Arrows in stress-strain data
indicate the break points. The inset in (a) shows stress-strain data on a linear scale.
81
(a) Neat PE (b) 90/10
2μm 2μm
(c) 80/20 (d) 70/30
2μm 2μm
(e) 60/40 (f) 50/50
2μm 2μm
Figure 4.12 SEM micro-images of PE/OPE Blends
Conclusion
A new type of PE/OPE blends has been prepared and the molten and solid state
properties of the blends are evaluated at different OPE content. All blends exhibited a negative
82
Flory-Huggins interaction parameter indicating miscibility between PE and OPE that decrease
with increasing OPE loading. Increasing OPE concentration in the PE/OPE blends from 0 to 50
weight% decreases the melt temperature from 123 °C to 119 °C and also reduces the thermal
stability. The SAXS analysis revealed that the OPE resides inside PE lamellae, and the lamellar
thickness decreases with increasing OPE inclusion, leading to increased brittleness that is also
confirmed by the increase in modulus and decrease in the strain at break.
Time-temperature superposition master curves showed the formation of relaxed polymer
chains with increasing OPE loading and the blends exhibited positive deviation from the Rouse
dynamics at higher frequencies. Moreover, incorporation of OPE reduced the zero shear
viscosity of the blends suggesting that OPE can also be incorporated as a processing aid. The
fractured surface morphology revealed interesting results exhibiting smooth surface of blends
with increasing OPE loadings, which is in agreement with the viscosity reduction in blends. In
addition, this type of blends with controlled viscosity can also be used to create PE
nanocomposites with high filler loadings and can still be processed on neat PE processing
conditions. This topic will be the subject of a future manuscript.
Acknowledgements
This project was supported by The Petroleum Institute, Abu Dhabi through the
Cooperative Research Partnership with Colorado School of Mines. The U.S. Army Research
Office (DURIP Grant No.W911NF-11-1-0306) is also acknowledged for partial financial
support. The authors would also like to thank Prof. John Dorgan for use of his lab facilities, Tara
Pandey and Soenke Seifert for assisting in SAXS experiments. Marcus Oils and Chemicals
(Texas) are acknowledged for supplying the OPE. The use of the Advanced Photon Source, an
83
office of Science User facility operated for the U.S. Department of Energy (D.O.E.) Office of
Science by Argonne National Laboratory was supported by the U.S. DOE under Contract No.
DE-AC02-06CH11357.
84
CHAPTER-5
PROCESSABLE CONDUCTIVE GRAPHENE/POLYETHYLENE NANOCOMPOSITES:
EFFECTS OF GRAPHENE DISPERSION AND POLYETHYLENE BLENDING WITH
OXIDIZED POLYETHYLENE ON RHEOLOGY AND MICROSTRUCTURE
This chapter is modified from a paper submitted in the journal
Polymer1
Muhammad Z. Iqbal2, Ahmed A. Abdala3, Sӧnke Seifert4, Andrew M. Herring5, Matthew
W. Liberatore6
5.1 Introduction
Due to the widespread interest in nanotechnology and its applications, polymer
nanocomposites, which are polymers with nano-scale fillers, have shown enormous potential.
For example, carbon nanotubes (CNTs) and graphene28, 48, 190, 191 are promising, conductive nano-
fillers used for reinforcement of polymers as well as inducing electrical and thermal conductivity
in the nanocomposites.
Graphene is a 1-atom thick layer of sp2-hybridized carbon atoms, consisting of
honeycomb-like assembly of C-atoms. Outstanding properties of graphene/polymer
nanocomposites include mechanical enhancement192, improved electrical conductivit43, 48, 191

,
thermal conductivity99, 109, 193

, gas barrier 48
, and flame retardancy194, 195
. To achieve
1
Permission will be obtained after the paper will be published
2
Primary author and researcher
3
Co-author and senior scientist at Qatar Environment and Energy Research Institute, Doha, Qatar
4
Scientist at Advanced Photon Source, Argonne National Laboratory, Chicago, IL, USA
5
Co-author and professor at Colorado School of Mines, Golden, CO, USA
6
Author for correspondence and advisor
85
combinations of practical properties in graphene/polymer nanocomposites, a homogenous
dispersion of graphene in polymer matrix is essential. In order to obtain good graphene
dispersion, graphene agglomerates must be broken down to single layers during processing (e.g.,
solvent, melt blending, or in-situ polymerization), or by surface functionalization of graphene, or
altering chemistry of the polymer matrix. Regarding the microstructure of graphene in polymer
matrices, two open questions need to be addressed: 1) Does graphene dispersion follow
traditional theories, such as the Brownian diffusion; 2) What is the structure of the graphene
network inside polymer matrix?
Single layer graphene has exceptionally high modulus of ~1,000 GPa in tension
compared to ~1-10 GPa for polymers, and 10-800 GPa for other fillers28, 196. Such high strength
of graphene enables graphene/polymer nanocomposites to carry the applied load. Because of its
high surface area and sheet structure, graphene can, in principle, significantly alter the properties
of the polymer matrix, e.g. polymer crystalline morphology197, chain conformation198, and
dynamics through confinement effects199. Thus, many factors are responsible for the property
changes offered by graphene, and better understanding of the property improvements requires
additional studies of the behavior of graphene inside the polymer matrix.
Translating graphene’s unique properties to nanocomposites is difficult, since graphene is
known to poorly disperse in polyolefins, including polyethylene43 and polypropylene200, 201, due
to the nonpolar nature of polyolefins. Several groups are attempting to develop strategies to
homogenously disperse graphene in polyethylene, since polyethylene is one of the most widely
used commodity thermoplastics. For example, Kim et al. reported high electrical percolation
threshold of graphene (12-15 wt%) nanoplatelets in polyethylene202, which is significantly higher
than many polar polymers28. High percolation is directly associated with poor dispersion and
86
larger graphene aggregates in polyolefins43, 203. Improved dispersion of graphene in polyethylene
was reported using amine functionalized graphene204. About 150% increase in elastic modulus
was achieved at 3 wt% loading using functionalized graphene, compared to graphene oxide.
Introducing functional groups onto the polymer can improve dispersion of the nano-
fillers in polyolefins. Maleic anhydride-grafted polyethylene205, and chlorinated-polyethylene206,

207
were reported as compatibilizers for graphene/polyethylene nanocomposites. However,
transmission electron microscopy showed that chlorinated polyethylene did not reduce graphene
stacking in the nanocomposites. Functionalized polyethylene containing cyano- and amino-
functional groups, showed improved mechanical properties, but the electrical conductivity of
functionalized polyethylene/graphene nanocomposites was less than neat polyethylene/graphene
nanocomposites43.
Also, poor dispersion was reported when polyethylene chains were in-situ polymerized
on graphene surface208. Despite the goals of attaining better dispersion and high conductivity,
nanocomposites with 10 vol% graphene loading exhibited electrical conductivity of 10-4 S/cm,
which is a strikingly low conductivity at such high loading. However, using such high loading of
graphene in a nonpolar polymer also increases the viscosity by several orders of magnitude200,
209
, which limits processing operations. In a report, Pang et al.102 reported a very low electrical
percolation threshold (0.07 vol%) for graphene/polyethylene nanocomposites via formation of a
segregated structure, but other thermomechanical properties were not provided. Therefore,
polyolefin nanocomposites having reduced graphene stacks, and with controlled processing
properties is highly desirable.
87
Commonly used as a processing aid151, 152
or biodegradable polyethylene153, oxidized
polyethylene (OPE) also improved the barrier properties of polyethylene/clay nanocomposites9.
Leveraging our earlier work on blending OPE with PE to produce high modulus materials with
controlled processing properties210, we combined blends of polyethylene and OPE with graphene
as nano-filler to create nanocomposites. Overall, the purpose of this study is to better understand
the origin of the reinforcement observed in PE/OPE/graphene nanocomposites with improved
dispersion. Graphene loading was varied to understand the filler microstructure. Linking the
thermo-mechanical properties of nanocomposites with their microstructure using scattering will
also be detailed. In addition, graphene nanocomposites will be compared with carbon black
composites.
This section describes the synthesis of TRG and its nanocomposites with PE/OPE blends.
5.2.1 Materials
Natural flake graphite (-10 mesh, 99.9% Alfa Aesar), carbon black(CB) (99.9%, bulk
density = 170-230 g/L, surface area = 75m2/g, Alfa Aesar), linear low density polyethylene
(LLDPE) with molecular weight 3.6 x 106 g/mol (determined via gel permeation
chromatography) and bulk density 0.97 g/cm3 (428078, lot#07730MEV, Aldrich), p-xylene
(99%, Sigma Aldrich), potassium permanganate (Fisher Scientific), sulfuric acid (95-97%, J.T.
Bakers), phosphoric acid (>99%, Aldrich), hydrogen peroxide (30% solution, BDH), HCl (37%,
Reidel-deHaen), were used as received. Oxidized polyethylene with an acid number of 7 and
density of 0.94 g/cm3 was supplied by Marcus Oil and Chemicals (Texas, USA).
88
5.2.2 Synthesis of TRG
TRG has been prepared by thermal exfoliation and reduction of graphite oxide (GO)37, 88,
110
. For synthesis of Gτ, Tour’s method211 was employed. Typically, 5 g of natural flake graphite
was dispersed in a mixture of H2SO4 (272 mL) and H3PO4 (33 mL), and stirred for 30 minutes.
About 27.8 g KMNO4 was gradually added into the mixture over the course of one hour to avoid
explosion. The mixture was stirred continuously using an overhead stirrer for three days at room
temperature. After the completion of reaction, H2O2 (30%, 17.5 mL) and deionized water (137.5
mL) were added to the reaction mixture, and stirred until the color of the mixture turned from
dark brown to bright yellowish, indicating high oxidation level of graphite. The GO was washed
three times with 1M HCl aqueous solution, and further repeatedly washed with deionized water
until a pH of 4-5 was obtained. The separation of the washed GO was carried out by a centrifuge
with a force of 10000 g followed by dialysis. The washed GO was dried under vacuum for two
days to remove any traces of water. The dried GO was thermally exfoliated and reduced by
heating rapidly at 1000° C for 30 s under nitrogen flow in a tube furnace to produce thermally
reduced graphene (TRG). The produced TRG was dried overnight under vacuum before using in
the composites.
5.2.3 Preparation of Composites
Low density polyethylene (PE) and OPE were dispersed in p-xylene at 120° C for one
hour under reflux. Meanwhile, TRG (or CB) was sonicated in p-xylene for one hour at room
temperature in a sonication bath. TRG dispersion was added into PE/OPE mixture, and solution
was further stirred for another hour to form a homogenous solution at 120° C. After the
formation of homogenous solution, the solution was drop cast on a heated glass plate at 80° C
89
and the solvent was allowed to evaporate for two hours. The complete solvent removal was
achieved by drying in a fume hood at ambient conditions for 24 h followed by drying in
convection oven at 80°C for 5 h. The complete solvent removal was confirmed by differential
scanning calorimeter, where no solvent peak was observed. The dried samples were cut into
pieces 3-5 mm wide, heated at 160°C for 10 min and hot pressed for 3 min under 5000 kPa
pressure to prepare circular discs (thickness 1-1.3 mm and diameter ~ 25 mm) for rheological
testing. Similarly, thin films (100-200 µm) for mechanical and scattering testing were prepared
by the same method using more dilute solutions of PE/OPE and TRG (or CB) in p-xylene, and
drop casting in a petri dish at 80°C, and following the same drying procedures.
For pure PE/OPE blends, the same procedure was used without TRG or CB. The PE/OPE
solution was stirred for 2 hours at 120°C under reflux before drop casting on a glass plate or in a
petri dish.
Wide angle x-ray diffraction (WAXD) was performed on a Phillips PW 3040/60 with
CuKα radiation at a scanning rate of 0.0β °/s to study exfoliation of graphite. Transmission
electron microscope (TEM) images were obtained using a FEI Phillips C200 at 200 kV to
confirm the production of TRG nanosheets. For TEM measurements, a dilute dispersion of TRG
(0.1 mg/20 mL acetone) was prepared by bath sonication for 10 minutes, and one drop of
solution was deposited on a 300-mesh Cu grid with holy carbon. The micro-images of blends and
composites were obtained using JEOL-JSM-7000F field emission scanning electron microscope
(FE-SEM) at an accelerating voltage of 3 KV. The blends and composites were cryo-fractured in
liquid nitrogen, and spur coated with gold for 120 seconds. Functional groups on TRG surface
90
were analyzed by Fourier transform infra red spectrometer (FTIR) (NicoletTM iSTM 10, Thermo
scientific FTIR) with 32 scan at a resolution of 4 cm-1 (TRG in KBr). Very dilute dispersions of
CB (0.1 mg/mL) and TRG (0.025 mg/mL) were dispersed in acetone via bath sonication at room
temperature, and dynamic light scattering (DLS) was performed using particle size analyzer
(NanoBrook 90Plus, Brookhaven) at 25°C.
Rheological measurements of blends and composites were performed at 160°C using TA
Instrument AR-G2 rheometer equipped with 20 mm parallel plate. Tests were conducted in air
while samples were covered with an aluminum solvent trap to avoid temperature fluctuations
during the run. Linear viscoelastic (LVE) region was determined by conducting strain sweep in
0.01-100% strain range at 1 Hz frequency. The frequency sweep experiments were performed in
the frequency range of 0.01-100 Hz at fixed strain within LVE region.
Mechanical properties of thin films were determined following ASTM D882, using
ARES-G2 (TA Instruments) rheometer with Film & Fiber tool. Measurements were carried out
at room temperature at a stretching speed of 0.0167 mm/s using thin rectangular samples ~10
mm long and ~5 mm wide.
The in-plane electrical conductivity was calculated using electrochemical impedance
spectroscopy (EIS) using the following equation:
Conductivity 
L
R.w .t
Where, R is the film resistance, L is the distance between the sense electrodes, w is the
width of film, and t is the sample thickness. The impedance spectra were obtained over a
frequency range of 0.3 Hz to 100 kHz using a four-electrode test cell connected to a multi-
91
channel potentiostat (Biologic VMP3, Knoxville, TN). All measurements were carried in an
environmental chamber to control sample temperature and humidity (TestEquity Model 1007H,
Moorpark, CA). The samples were polished using a 100-mesh grit paper before conductivity
measurements in order to remove thin polymer layer transported to the surface during the film
formation and drying process. Due to polishing, TRG and CB composites exhibited static current
build up, which was removed by conditioning the samples at 95% relative humidity and 50 °C
for one hour. The results reported are averaged over 3 samples at 25 °C temperature and 95%
relative humidity.
Small angle X-ray scattering (SAXS) experiments were performed using X-ray Sciences
Division, beamline 12-ID-C, at the Advanced Photon Source at Argonne National Laboratory.
Data have been collected at 60°C under dry conditions, and is averaged over three exposures
times. Details of the procedure and temperature/humidity control can be found elsewhere212, 213.
5.3 Result and Discussion
This section describes the characterization of nanofillers and nanocomposites.
5.3.1 Characterization of TRG and CB
Rapid heating of GO produced a substantial increase in volume, and GO was exfoliated
into TRG. Typically, GO has a bulk density of 0.5 g/cm3 (1 g with a bulk volume of ~2 cm3),
while the TRG product has a bulk density of ~10 mg/cm3 (1 g TRG with a bulk volume of 100
cm3). An exfoliated sheet-like structure was observed when TRG was deposited on a TEM grid
from a very dilute solution (Figure 5.1a). A paper-like morphology of graphene nano-sheets were
observed, and the graphene sheets were overlapping, extended to a few hundred nanometers. The
92
actual graphene sheets are extremely transparent to the electron beam, however, the folded edges
appeared dark, as observed by others88. The CB particles are clusters of almost spherical
particles, forming fractal structures extending over 2 µm (Figure 5.1b). The size of the individual
CB particles was ~60-80 nm. Although the TEM images were taken from extremely dilute
suspension of CB in acetone, the particles still formed large aggregates. The size of these
aggregates might increase with higher CB concentration in polymers. Complete characterization
of TRG, and CB particles by XRD, TEM, FTIR, and DLS is provided in the Appendix-C.
(a) (b)
Figure 5.1 TEM image of TRG (a), and CB (b).
5.3.2 Melt Rheological Analysis
The rheological properties and their analysis is provided in this section.
(i) Rheology of Blends and TRG-Nanocomposites
Melt rheology of polymers and polymer nanocomposites is essential for understanding
their processing and developing structure-property relationships. Viscoelastic (VE) response can
be connected to the intrinsic behavior of polymers, inter-particle, and polymer-particle
interaction. In general, rheological properties depend on the input strain, whether in the linear or
non-linear viscoelastic region. The dynamic strain sweep determines the strain dependent
93
viscoelastic response and the linear viscoelastic (LVE) region. The addition of OPE in PE led to
the formation of miscible blends, where OPE resided within the amorphous region of the long
period domains of PE210. Due to miscibility and plasticization, OPE decreased the complex
viscosity of PE (complex viscosity at 0.01 Hz, Figure 5.2). An approximately 7-fold decrease in
viscosity was observed for 60/40 blend compared to neat PE. This lower viscosity can be very
advantageous when processing polyolefin nanocomposites that require high filler loadings. The
complete rheological, thermal, and structural properties of PE/OPE blends can be found in our
previous work210. Also the complete rheological properties of PE/OPE blends are provided in
Appendix-C.
12000
f = 0.01 Hz
10000
η* (Pa-s)
8000
6000
4000
2000
0
PE 80/20 60/40
Figure 5.2 Processing control by PE/OPE blends
TRG-filled PE, PE/OPE 80/20, and 60/40 blends exhibited different rheological
responses at various TRG loadings (Figure 5.3). Adding TRG to PE increased Gˊ at all TRG
loadings (Figure 5.3a). With increasing TRG, an exponential increase in Gˊ was observed. Also,
the low frequency slope of Gˊ decreased, leading to asymptotic behavior that is nearly
independent of frequency. This asymptotic behavior indicates the development of a concentrated,
percolating network214. A similar trend was observed for 80/20/TRG nanocomposites (Figure
94
5.3b). Increasing TRG loading increased G' of 80/20/TRG nanocomposites, leading to
exponential growth in G' with increased loading.
A peculiar rheological behaviour was observed for 60/40/TRG nanocomposites at low
TRG loadings (Figure 5.3c). For TRG < 1 wt%, Gˊ decreased with TRG addition compared to
the unfilled blend. At higher TGR loadings, an exponential increase in G′ was observed, similar
to the PE/TRG and 80/β0/TRG nanocomposites. For θ0/40 blends, the decrease in Gˊ for dilute
TRG loadings might be attributed to the interlayer slipperiness between TRG and polymer layers
due to a low surface friction, and possible exfoliation of TRG sheets209. Exfoliation of TRG into
smaller stacks might lead to sheet alignment, which could decrease the viscoelastic response
from the nanocomposites. Further details of this slippery behaviour will be discussed in
conjunction with scattering results later.
The viscosity of nanocomposites plays a vital role in practical processing for mass
production and product formation. PE showed a typical non-Newtonian shear thinning viscosity
profile with increasing frequency (Figure 5.3d), which increased with TRG addition. Increasing
frequency (or correspondingly the shear rate according to Cox-Merz rule215) produced a similar
shear thinning profile, attributed to the alignment of graphene sheets in the shearing direction. At
higher TRG loadings (5 wt%), a rheological response typical of a highly filled percolated
network ( * ~ ƒ-1) was observed. Similar trends were observed for 80/20/TRG nanocomposites
(Figure 5.3e). The θ0/40/TRG nanocomposites exhibited similar peculiar behavior for the * as
was observed for Gˊ~ƒ data (Figure 5.3f). The viscosity decreased at low TRG loading, and a
continuous increase in viscosity was observed with increasing TRG loading above 1 wt%. The
three matrices (PE, 80/20 and 60/40) showed similar asymptotic behavior * ~ ƒ-1 at higher TRG
loading (5 wt%). However, due to the plasticization effect of OPE, the low frequency viscosity
95
for 60/40/TRG nanocomposites was even lower than that of 80/20/TRG composites, which was
lower than PE/TRG nanocomposite viscosity. The reduced viscosity of blend nanocomposites
provides ease of processing for PE nanocomposites.
Mackay72 reported the non-Einstein viscosity behaviour in nanocomposites with
nanoparticles smaller than the radius of gyration of the polymer. The TRG used in this study,
have approximately 5-6 nm thin, and 0.6-1 µm long particles. Due to highly non-polar nature of
polyolefins leading to insufficient filler/polymer interactions, TRG sheets tend to agglomerate
into a few hundred nanometer thick particles, becoming larger than the radius of gyration of
polyolefins, which do not exhibit slipperiness (Figure 5.3a). However, in 60/40/TRG
nanocomposites, OPE might be wetting the graphene surface, breaking down TRG agglomerates
to a few nanometer thin particles, leading to slipperiness. Therefore, we hypothesize that
particles with one dimension smaller than the radius of gyration of polymer might also exhibit
Mackay's non-Einstein behaviour. However, investigation of this behaviour is beyond the scope
of this study, and will be explored separately. The microstructure developed in nanocomposites
at lower TRG loading will be discussed in detail in the scattering section.
The rheological properties of CB-filled composites showed similar trends as observed for
TRG-filled nanocomposites (see Appendix-C). However, higher loading of CB (5-10 wt%) was
required to reach the percolation in the CB-composites. At dilute loadings, the complex viscosity
of 60/40/CB composites was lower than that of neat 60/40 blends, exhibiting a similar
slipperiness as was observed in 60/40/TRG nanocomposites. However, the slippery behaviour
was less prominent in CB-composites, which might be due to the highly fractal forming nature of
CB. More details on microstructure of CB-filled composites will be discussed in scattering
section.
96
(ii) Percolation and Scaling Analysis
The amount of filler needed to create an interconnected network within a polymer matrix,
called percolation threshold, is associated with polymer-particle interactions and particle
dispersion in the polymer matrix. In order to determine percolating volume fraction (Φp), we
analyzed the increase in Gˊ in the terminal region (at 0.01 Hz, Gˊ0.01), which is presented in
Figure 5.4. With increasing TRG loading, an exponential increase in G’0.01 corresponds to the
transition to solid-like behavior, which indicates Φp. Above Φp, the Gˊ0.01 exhibited a power law
dependence on TRG volume fraction as follows:
~   p 
' 
G0.01
where α is the power law exponent. The measured Φp values were 1, 0.7, and 0.3% for
PE/TRG, 80/20/TRG, and 60/40/TRG nanocomposites, respectively. The corresponding
percolation in weight% are 2.3%, 1.6%, and 0.7 wt%, respectively.
The substantial decrease in Φp for 60/40 blends indicated improved dispersion, likely due
to the increased graphene/matrix chain interactions. Fitting to percolation power law yielded the
α values of β.λ, β.η, and β.7 for PE/TRG, 80/β0/TRG, and θ0/40/TRG nanocomposites,
respectively (inset in Figure 5.4). Typically, a stress-bearing network produces α ranging from
β.1 to γ.7η. Here, α > β.1 may indicate the establishment of graphene-graphene bridging
network, which could derive from π-π interactions in graphene sheets at higher loadings.
Generally, an α < β.1 shows a network of particles bridged with polymer chains is formed,
whereas a direct particle-particle network is established for α > γ.7η216, 217, 218. However, a three
dimensional network exhibits α ≥ γ, to form a rigid percolating network219, 220, 221.
97
7
10
6
10
5 5
10 5
G  (Pa)
4 5
10
3
10 1
2 1
10 0.16
0.16 1
PE 80/20/TRG 60/40/TRG
1
10 PE/TRG 80/20
0
(a) (b) 60/40 0.16 (c)
10
7
PE/TRG 80/20/TRG 60/40/TRG
10 (d) (e) (f)
6
5
10
* (Pa-s)
5 5
10
1
0.16 1
4
10 0.16
PE 1
3 80/20 60/40
10
0.16
2
10
 (s )
-2 -1 0 1 2 -2 -1 0 1 2 -2 -1 0 1 2
10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
-1
Figure 5.3 Representative shear modulus and complex viscosity vs. frequency curves for
PE/TRG (a, d), PE/OPE 80/20/TRG (b, e) and 60/40/TRG (c, f), respectively. Solid lines
represent the polymer matrix in each box and numbers next to each curve correspond to weight
% of TRG
Furthermore, the aspect ratio of graphene in these matrices (Af) can be determined from
Φp. Af is the ratio of width to the thickness of the filler (l/d), and is considered as an indicative
parameter for exfoliation and dispersion. Af is equal to 1 for perfectly spherical filler. In case of
TRG/polymer nanocomposites, Af is maximum for completely exfoliated structures depending
on the lateral size of graphene layers. Ren et al.222 proposed a formula to determine the
relationship between the number of clay layers in each tactoid above percolation and clay
concentration. This expression was further simplified to calculate the average aspect ratio of
TRG191 as follows:
3pR
Af 
2p
98
where ΦpR is the percolation threshold volume fraction for randomly packed spheres, and
Φp is the experimentally determined percolating volume fraction. Combining ΦpR ~ 0.3, a
constant for the randomly packed spheres191, and measured Φp values (from Figure 5.4), the
aspect ratio was calculated for each nanocomposite. A more exfoliated structure exhibits higher
Af values. In TRG-filled systems, Af increased from 41 to 60 as the polymer matrix changed
from neat PE to PE/OPE 80/20 blend. However, an Af of 155 was obtained for PE/OPE 60/40
matrix, indicating better exfoliation and improved dispersion of TRG in the 60/40 blend (Table
5.1).
7
10

6
10
4

5 10
G
10 2
G0.01 (Pa)

10
p
3 -4 -3 -2 -1
10 10 10 10 10 PE/TRG
p=0.3%
80/20/TRG p=0.7%
1
10
p=1.0%
-1
60/40/TRG
10 -5
TRG volume fraction, 

-4 -3 -2 -1
10 10 10 10 10
Figure 5.4 Percolation analysis of TRG filled PE, PE/OPE 80/20 and 60/40 blends. Solid lines
are linear fit to experimental data. The point of intersection of two lines indicates the percolation
threshold, Φp. Inset shows power law fit to percolation law for PE, 80/20 and 60/40 blends-filled
with TRG, and the numbers next to each line are the power law exponents. Color schemes are
same in both panels.
By determining the power law dependences of Gˊ0.01 and critical strain ( c %) on TRG
volume fraction (Φ), δVE properties of nanocomposites can quantify the microstructure of fillers
99
in polymer nanocomposites. Critical strain ( c %) is defined as the strain ( %) at which G′
decreases to 90 % of its initial value in a strain sweep experiment. Shih et al.223 proposed a
scaling model for the elastic properties of fractal networks built up by filler aggregates above Φ p.
In nanocomposites, the fractal network is considered as elastically linked filler aggregates. A
decrease in the linear-elastic behavior with increasing filler volume fraction above Φp
(Appendix-C) can be explained by the physical links between the aggregates, called the strong-
link regime. In the percolation region, the power law dependence of c and Gˊ0.01 can be
described by the following equations:
 c ~  (1 x )/(3d )
f
'
G0.01 ~  (3 x )/(3df )
where, df is the fractal dimension of the filler aggregates, and x is an exponent related to
filler Φ, and aggregate size by giving dimension of aggregate backbone, which is responsible for
elasticity. The c and Gˊ0.01 (above percolation threshold) were plotted as a function of TRG Φ
(Figure 5.5), and exponents of Φ were evaluated. Both PE/TRG and 80/β0/TRG nanocomposites
exhibited similar exponent of c%, whereas the exponent decreased for 60/40/TRG
nanocomposites. The scaling exponent of G′ was lower for PE/TRG system (γ.8), than for
80/β0/TRG and θ0/40/TRG nanocomposites (4.γ). The higher value of G′ exponent further
indicates the formation of elastic network219, which is more efficient in storing elastic energy in
blend/TRG nanocomposites compared with PE/TRG nanocomposites. In addition, G′ scaling
exponents (3.8 and 4.3) in this study are higher than that reported for CNTs/polypropylene
nanocomposites (2.8)224. This difference in scaling exponents implies that the scaling can depend
on the fillers dimensionality, and the two-dimensional platelets, such as TRG nanosheets might
100
be more effective in enhancing the elastic contribution in polymers compared to the one-
dimensional nanotubes.
The exponents scaling for c and Gˊ0.01 above percolation can be expressed as:
c ~ 
m
'
G0.01 ~  mG
Combining the scaling equations, the power law exponents become:
df  3
2
m  mG
x 3
2mG
m  mG
The calculated values for df and x were 0.6 and 6.3 for PE/TRG, 1.4 and 3.7 for 80/20-
TRG, and 1.8 and 2.2 for 60/40-TRG nanocomposites, respectively. Surprisingly, df increased
with increasing OPE loading, which is different from other reports8, 219
. Usually, df decreases
with increasing Af, which is exhibited by various clay65 and graphene filled polymers219. A
relatively high value of x for PE/TRG system indicates that most sheets in TRG flocs contribute
to network elasticity, and the structural defects are elastically inactive such as dangling ends
which rarely exist216, 219

. The value of x decreased with increasing OPE loading in
nanocomposites. However, all three values of x are still large enough to confirm that the flocs are
elastically active in the three nanocomposites219.
101
c   (b)
-2.99
(a)
Gp  
3.81
Gp  
2 PE/TRG 5
Critical Strain, c (%)

10 10 4.25
c  
-2.98 PE/TRG
80/20/TRG
G0.01 (Pa)
1 80/20/TRG 10
4
10
0 3
10 10
c  
Gp  
-2.62
4.26
10
-1 60/40/TRG 10
2
60/40/TRG
TRG  TRG 
-3 -2 -1 -3 -2 -1
10 10 10 10 10 10
Figure 5.5 Scaling behavior of critical strain (a), and G′ (b) above percolation threshold
(iii) Mechanism of TRG Dispersion
The dispersion mechanism of nanoscale, hard, and rigid disks in a polymer matrix is
governed by either Brownian motion of particles or non-Brownian interactions. According to the
Stokes-Einstein equation225 for disk-shaped particles (of length L), particle rotary diffusion
coefficient (Dr, s-1) in dilute concentration regime in a suspending medium of viscosity ( o) is
given as:
Dr 
3kBT
4o L3
Where, kB is the Boltzmann constant, and T is the temperature in absolute scale.
Considering L~600 nm (longest dimension in Figure 5.1), the Dr calculated for PE/TRG, 80/20-
TRG, and 60/40-TRG at 160° C were 5x10-9, 1x10-8, and 1x10-7 s-1, respectively. Conversely, the
diffusion time, ~1/Dr was 108, 108, and 107 s, respectively, which represents the time needed for
nanosheets to travel a distance equal to their radii (300 nm) at the processing temperature (160°
C). The diffusion time, however, seems unrealistic, since a polymeric material would degrade if
kept at that high temperatures (160° C) for such extremely long time. Thus, the diffusion
102
coefficient or diffusion time alone cannot answer whether the diffusion of graphene inside a
polymer matrix follows Brownian or non-Brownian dynamics. Therefore, the concept of Dr is
further extended to describe the dynamics of disk-shaped particles via the universal Doi-Edwards
theory, originally developed for CNTs.
The Doi-Edwards theory226 describes the dispersion of nanorods of length L, and
diameter d, in liquid suspension in dilute and semi-dilute regimes. For nanorods, v is the number
of nanorods per unit volume, which is related to volume fraction of nanorods as Φ=d 2Lvπ/4.
Considering d as the thickness of graphene nanosheets (d=5 nm for TRG, since Raman analysis
indicated that our TRG was comprised of about four 1-atomic thick sheets88). According to Doi
and Edwards, the concentration dependence of the zero shear viscosity, o for dilute regime
obeys the following scaling law:
~  L3 
c
M
1
Here, C, M are viscosity of composites, and that of matrix, respectively. The rotary
diffusion of particles is hindered by neighboring particles in semi-dilute regime, and Dr is
predicted to follow the power law Dr ~ (vL3)-2. Consequently, the viscosity scales in the semi-
dilute regime as follows:
~  L3 
c
M
3
However, in the concentrated regime, the factors such as sheet flexibility, Brownian
motion, and van der Waals interactions are strongly affected by the viscosity of the matrix227.
The Doi-Edwards theory can be applied to any nanorods (or nano-sheets, in this case), provided
103
these particles behave as solid Brownian entities in the suspending medium on the nanometer
scale. Thus, from the equations derived by Doi and Edwards, the variation of the reduced
viscosity ( C/ M) with vL3 should follow a master curve. The Brownian motion of nanosheets
(similar to nanorods) should be universal and independent of their nature. Recently,
Cassagnaue228 reported the universal master curve of CNTs, cellulose whiskers, and polymer
nanofibers in different polymer matrices, which indicates that the rotary motion of these fillers
was dominated by the Brownian motion. It is worth mentioning that even extremely dilute
suspensions of nanorods were not able to produce c/ m ~ Φ1 behaviour 227, 228.
Following the Doi-Edward theory, a universal curve of log ( c/ M) versus the particle
concentration (vL3) was created for TRG-based nanocomposites (Figure 5.6). The successful
building of the universal curve indicates that TRG dispersion in these matrices is dominated by
Brownian forces227, c/ M
228
. The TRG nanocomposites showed ~ (vL3)3 behavior in the
concentrated regime. A downshift in the master curve was observed for 60/40/TRG
nanocomposites, attributed to the extremely low viscosity of 60/40 blends. Thus, the diffusion of
graphene sheets in polymers follows Brownian diffusion. However, further investigations in the
low viscosity polymers filled with graphene nanosheets should be carried out to claim the
universality of this behavior.
5.3.3 SAXS-Based Microstructure
The microstructural parameters, such as df and x, extracted from melt rheology scaling
are averaged for each matrix over all the compositions. However, each composition has its own
microstructure, which can be analyzed using scattering methods, including small angle x-ray
scattering (SAXS). SAXS measures the shape and size of polymers between 5 and 25 nm of the
104
repeat distances171. The scattering vector (q) probes different structural features at various length
scales (length scale ~ βπ/q) in polymers and polymer nanocomposites.
3.0
PE/TRG
2.5 80/20/TRG
60/40/TRG
log (ηC/ηM ) 2.0 ~3
1.5
1.0
~0
0.5
0.0 ~0
-0.5
0.0 0.5 1.0 1.5 2.0 2.5 3.0
log (vL3)
Figure 5.6 Universal behavior for TRG-filled matrices
Increase in power law decaying exponent (log(I) ~ log(q)-α) at lower q values indicates a
larger size of scattering objects. For clay minerals, Malekani et al.229 proposed that the decaying
exponent α was directly related to the fractal dimensions, df. For α ≤ γ, the particles form mass
fractals (a substance whose surface and mass are both characterized by the fractal properties). In
this case, α directly corresponds to mass fractal dimensions, dm. If γ ≤ α ≤ 4, surface fractals are
formed where the scattering is observed from a smooth surface. The surface fractal dimensions,
ds, is calculated from α as followsμ α ≡ θ - ds where 3 < 6 - ds ≤ 4229, 230. Thus, ds varies from 3 to
2, where ds ~ β indicates a smooth surface approaching Porod's scattering (α = 4)172, and ds ~ 3
indicates uneven concentration of scattering objects at the scattering surface231.
Pure PE exhibited α = β.γ, typical for randomly oriented polymer chains 172 (Figure 5.7a).
Inclusion of τPE in PE increased α to β.λ for PE/τPE θ0/40 blends (Figure 5.7b). In the absence
105
of any filler, higher α indicates increased mass fractal concentration in blends, which is attributed
to immiscibility of OPE at higher loadings210. Addition of TRG in PE showed smaller α values
(1.5 to 2.1) until a loading of 1 wt% (Figure 5.7a). The small α values at low TRG concentration
indicate the exfoliation of TRG sheets inside PE matrix. Increasing TRG loading to 5 wt%,
although α increased but it was still below 3, showing that TRG was forming the mass fractals.
The 80/β0/TRG nanocomposites exhibited a similar pattern of α increasing and only mass
fractals being observed (Appendix-C). However, 60/40/TRG nanocomposites showed a different
behaviour when TRG ≥ γ wt%; α > γ was observed. The increased α showed the formation of
surface fractals229, which was attributed to the better exfoliation, and high Af in 60/40/TRG
nanocomposites, which verifies the finding from rheology discussed earlier.
Scattering from the nanocomposites changes above the percolation threshold. The
PE/TRG nanocomposites exhibited the rheological percolation at ~1.0 vol% (2.2 wt%), whereas
the percolation for 60/40/TRG nanocomposites was observed at 0.3 vol% (0.7 wt%). Below
percolation, low α values were measured at 1 wt% for θ0/40/TRG system (1.λ) and PE/TRG
nanocomposites (2.1), which indicated better dispersion of TRG. Also, the slippery behaviour
observed in the rheological data for 60/40/TRG nanocomposites below percolation can be
associated with this small α values. Since, we did not observe the slipperiness in PE/TRG
nanocomposites, it might also be associated with relatively low viscosity of 60/40 blends, and
shear alignment of TRG sheets upon exfoliation.
Above the percolation threshold (TRG > γ wt%), the TRG formed surface fractals (α =
γ.η) in θ0/40 blend, whereas only mass fractals were observed for PE/TRG nanocomposites (α =
β.7). The large difference in α values further indicates markedly improved exfoliation and
dispersion of TRG in 60/40 blends.
106
(b)
60/40/TRG
3 wt% SPE40_29_00036_001
'6060TGR_016_00645_00001'
=3.5 '6040TGR_1_00647_00001'
'6060TGR_3_00648_00001'
1 wt%
=1.9
I(q) [a.u.]
60/40
=2.9
0.16 wt%
=1.4
5 6 7 8 2 3 4 5 6 7 8 2 3
0.01 0.1
q [1/Å]
Figure 5.7 I(q)~q log-log plots of PE/TRG (a), and 60/40/TRG nanocomposites (b). Note: The
lines in all panels are stacked in the same order with Y-offset for clarity.
Due to the fractal forming nature of CB particles, a relatively large α = β.1 was observed
at 0.5 wt% CB loading in 60/40/CB composites (Figure 5.8). A consistent increase in α was
observed with increasing CB loading. The arrangement of CB particles to form surface fractals
was observed at 10 wt%, which indicates the build up of strong network and a good dispersion of
CB in θ0/40 blend. However, the surface fractals (α > γ) were observed only in θ0/40/CB
composites, showing better dispersion of CB in 60/40 blends. The PE/CB, and 80/20/CB
composites showed similar increase in α with increasing CB concentrations, but no surface
fractals were observed (Appendix-C). In addition, secondary structure was observed in all CB-
filled composites, which could be seen as a shoulder appearing at low q values. With increasing
CB concentration, the shoulder shifted to higher q (smaller length scales). The calculated length
scales associated with this shoulder are shown later in this section.
The SAXS-knee in the range of 0.02 to 0.08 Å-1 corresponds to the lamellar thickness in
polymers (Figure 5.7). The lamellar thickness (Lp) or interparticle spacing can be extracted from
the maxima in the Kratky plots174, 175

, also called Lorentzian corrected plots, where I(q)q2 is
107
plotted versus the scattering vector (q). The maxima is converted into length scales by Lp ~ βπ /q.
The Lp is the sum of amorphous and crystalline fractions in polymers210.
60/40/CB
60/40/CB 0.55
60/40/CB 1.16
60/40/CB 4.3
60/40/CB 6.58
60/40/CB 10
I (q) [a.u.]
=2.1
9 2 3 4 5 6 7 8 9 2 3
0.01 0.1
q [1/Å]
Figure 5.8 I(q) ~ q log-log SAXS data for PE/OPE 60/40 Blends-CB composites. Note: The lines
in all panels are stacked in the same order with Y-offset for clarity.
The Lp was calculated for the TRG-filled nanocomposites, and CB-filled composites (see
supporting information for a representative Kratky plot). Inclusion of OPE in PE has already
been shown to decrease Lp from 180 Å for neat PE to 161 Å for 80/20 blends, which further
reduced to 147 Å for 60/40 blends210. Substantial decrease in Lp was observed with increasing
TRG in PE/TRG, and 60/40/TRG nanocomposites (Figure 5.9a). Similarly, the nanofillers (TRG
or CB) do not affect the WAXS patterns of the matrices (Appendix-C). Therefore, it is
reasonable to believe that the fillers reside inside the amorphous portion of the matrix, and due to
the packing of fillers inside lamellae, overall Lp decreased. The decrease in Lp has been reported
to have a direct effect on the macroscopic mechanical properties of polymers. Specifically, the
Young's modulus of polymers increases with decreasing Lp (see mechanical properties
108
section)187, 188, 210. A constant Lp with TRG ≥ γ wt% clearly indicated the percolation behaviour
in TRG-filled nanocomposites.
For CB-filled composites, the Lp also decreased with increasing CB loading in PE and
PE/OPE blends (Figure 5.9b). However, the decrease in Lp was not as significant as it was in
TRG-filled nanocomposites. The scattering also corroborates that high CB loading leads to lower
mechanical and rheological properties than TRG-filled nanocomposites. A constant Lp was not
observed for CB-filled composites at higher CB loading, which also indicates that these
composites do not achieve percolation.
5.3.4 Thermal Properties
Neat PE is thermally stable for a polymer, completely decomposing around 500°C. The
PE/OPE 60/40 blend showed lower thermal stability compared with neat PE, which is attributed
to miscibility and plasticization effects of PE and OPE, and oxygen contents of OPE 210. On the
one hand, addition of 5 wt% TRG in PE (Figure 5.10) did not affect the stability of the
nanocomposite (decomposition temperature ~ 474°C) compared to that of neat PE (473°C). The
unaffected thermal stability of PE/TRG nanocomposites indicates the absence of any favorable
interactions between graphene and PE. On the other hand, thermal stability of 60/40 blends at 5
wt% TRG was enhanced as the decomposition temperature increased from 472° C for neat 60/40
blend to 477° C for the nanocomposite, attributed to improved graphene-matrix interactions in
these nanocomposites. Similar patterns of thermal stability were observed for CB-filled
composites (see Appendix-C). The lack of interactions between CB and PE reduced the thermal
stability of PE/CB composites at 10 wt% loading. However, due the presence of OPE, and
interactions in blends, the stability of blend-CB composites was also improved.
109
200 180
Percolated regimes PE/CB
80/20/CB
PE/TRG 60/40/CB
180 80/20/TRG
60/40/TRG 160
Lp [Å]
160
Lp [Å]
140
140
120
120
(a) (b)
100 100
0 1 2 3 4 5 0 1 2 3 4 5 6 7 8
TRG wt % CB wt %
Figure 5.9 Kratky analysis of TRG-filled nanocomposites (a), and CB-filled composites (b).
Color schemes in (a) show percolation of each matrix.
5.3.5 Mechanical Properties
One of the advantages of adding nanofiller to a polymer matrix is improving the
mechanical properties. Mechanically robust nanocomposites can be used for a large number of
practical applications. Young's modulus of PE decreased from 1.6 MPa to ~1 MPa for 80/20
blends, and increased to 1.8 MPa for 60/40 blends. The increase in Young's moduli of blends
was directly associated with the decreased Lp187, 188, 210.
The superiority of TRG over CB as filler for polymers is evident by the comparatively
improved Young's modulus of filled matrices (Figure 5.11). The PE/TRG and PE/CB exhibited
similar Young's moduli, showing the poor dispersion of these fillers in PE in the absence of any
filler/polymer interactions. On the other hand, approximately ~3-fold increase in modulus was
observed for 60/40/TRG nanocomposites compared to PE/TRG nanocomposites due to the
increased filler/matrix interactions. The melt viscosity of 60/40 blends is ~7-fold lower than that
of neat PE, whereas the increase in the Young's modulus was 3-fold higher for 60/40/TRG
nanocomposites compared to that of PE/TRG nanocomposites.
110
100
2.5
Mass Retained, %
2.0
80
dW/dT, % / C
1.5
1.0
60 0.5
0.0
-0.5
40 350 400 450 500 550
PE
20 PE/TRG 5 wt %
60/40
60/40/TRG 5 wt%
0
0 100 200 300 400 500 600
Temperature, C
Figure 5.10 Thermograms for PE, PE+TRG 5 wt%, PE/OPE 60/40, and 60/40+TRG 5 wt%.
Inset shows derivative of TGA versus the temperature
This significantly lower processing viscosity and increased mechanical property indicates
the formation of processable and mechanically robust nanocomposites, which is very remarkable
to achieve as most nanocomposite that yield enhanced mechanical properties suffer from
significant increase in viscosity.
The elastic properties of fiber/flake polymer nanocomposites can also be predicted by
numerous micromechanical models232. Generally, the elastic properties in micromechanical
models depend on particle/matrix stiffness ratio (Ep/Em), particle volume fraction (Φp), particle
aspect ratio (Af), and orientation of particles in the matrix233.
In this study, both TRG and the matrices are assumed to be linearly elastic, either of
which can be taken as isotropic or transversely isotropic. Two widely-used models are the
233
Halpin-Tsai and Mori-Tanaka models . The Halpin-Tsai (H-T)234 equation gives reasonable
estimate for effective stiffness in nanocomposites, but the Mori-Tanaka model (M-T)235 is
111
considered more accurate for high aspect ratio fillers. Considering longitudinal stiffness (E11) of
nanocomposites (obtained from tensile testing), the H-T equation is given as:
E11( H T ) 1  2 Af  p

Em 1   p
( E p / Em )  1
E / Em   2 Af

p
and Mori-Tanaka (M-T) model is represented as:
E11( M T )

 f  2 m A3  1   m  A4  1   m  A5 A
1
1
Em
2A
10
CB 2.5 wt%
Young's Modulus (MPa)
TRG 3 wt%
PE 80/20 60/40
Figure 5.11 Comparison of the Young's moduli of TRG and CB filled composites
Here, vm, and vp are the matrix and particle Poisson ratios, and constants A, A3, A4, A5 are
calculated from matrix/particle properties and components of the Eshelby tensor236, 237
, which
depend on the particle Af, and dimensionless elastic constants of the matrix. For modeling, we
used Ep as 250 GPa for TRG sheets238, 239

, vp as 0.0006240, vm as 0.48 for PE241, whereas the
112
experimentally determined Em values are used throughout. The only variable fitting parameter in
the two models is the particle aspect ratio (Af).
The tensile moduli of nanocomposites normalized by the moduli are compared to the
loading to examine the model fits (Figure 5.12). PE filled with TRG at 2.14 vol% was
approximately 50% stiffer than neat PE. On the other hand, 80/20/TRG nanocomposites showed
~150% more stiffness compared to the neat 80/20 blend, and the 60/40/TRG nanocomposites
exhibited ~500% increased stiffness compared with the neat blend. Fitting based on the effective
medium models (H-T and M-T) were applied to moduli increase versus TRG concentration
(wt%), and the effective aspect ratio (Af) of the dispersed TRG sheets were estimated. Both the
H-T and M-T models produced similar Af of TRG for PE and 80/20 blends (Figure 5.12).
However, M-T model exhibited insensitivity for the 60/40/TRG nanocomposites due to large
increase in modulus. Only, H-T model was able to capture the Af for 60/40/TRG system, which
was ~460. A very large Ep/Em (~105) might be the reason for M-T model's insensitivity above Af
> 200. However, for small Ep/Em (~102), H-T model overestimates E11/Em compared with that
obtained from M-T model233.
5.3.6 Electrical Properties
The electrical properties of graphene/polymer nanocomposites are strongly dependent on
effective dispersion of graphene and its aspect ratio, whereas the dispersion is directly connected
to graphene-polymer and inter-graphene interactions. The electrical conductivity ( ) of PE/TRG,
80/20/TRG and 60/40/TRG nanocomposites (measured at 0.01 Hz) showed significant
improvement as the concentration of graphene was increased from 0 to 5 wt%. PE/OPE 60/40
113
blends exhibited a low rheological percolation threshold, and a similar transition was observed
for the electrical conductivity (Figure 5.13).
8.0
H-T M-T
PE/TRG 21 15
6.0 80/20/TRG 155 160
60/40/TRG 456
E11/Em
4.0
2.0
0.0
0.0 0.5 1.0 1.5 2.0 2.5
TRG vol%
Figure 5.12 Mechanical properties of TRG-filled nanocomposites. Solid lines are fit to Halpin-
Tsai model, and dashed lines represent Mori-Tanaka micromechanical model. Inset shows
estimated aspect ratio (Af) of TRG for nanocomposites from the best fit.
At almost same TRG loading, 60/40/TRG nanocomposites exhibited more than 1 order of
magnitude improvement in the electrical conductivity compared with PE/TRG, and 80/20/TRG
nanocomposites. The increase in is attributed to enhanced TRG-matrix interactions, and large
Af in blend-nanocomposites due to OPE. Also, at similar loadings, the TRG nanocomposites
exhibited better electrical conductivities compared to CB composites. The electrical conductivity
of TRG nanocomposites was ~2 orders of magnitude higher than that for CB composites (Figure
5.13).
A low electrical percolation threshold also signifies the improved interactions in
nanocomposites. The increased from 7.4x10-14 S/cm to 3.6x10-4 for PE/TRG as TRG
concentration was increased from 0 to 5 wt% (Figure 5.14). Similarly, the for 80/β0 blends
114
increased from 7.6x10-14 to 1.1x10-4 S/cm, and from 7.4x10-14 to 9.6x10-4 S/cm for 60/40 blends
for the same TRG concentration range.
-3
10 CB 2.5 wt%
-4
TRG 3 wt%
10
 [S/cm] 10
-5
-6
10
-7
10
-8
10
PE 80/20 60/40
Figure 5.13 Comparison of electrical conductivities of TRG-filled and CB-filled composites
The electrical percolation threshold values (Wp ) were 0.67, 0.45, and 0.3 wt% for
PE/TRG, 80/20/TRG, and 60/40/TRG nanocomposites, respectively. The rheological percolation
thresholds were higher than the electrical percolation for all composites. Similar to the
rheological percolation, the 60/40/TRG nanocomposites exhibited the lowest percolation, which
further signifies the increased graphene-matrix interactions, and high Af of TRG in the
nanocomposites. Moreover, the CB filled nanocomposites exhibited similar increase in electrical
conductivity with increasing CB loading. Expectedly, the electrical percolation thresholds for
CB-filled composites were higher than those obtained for TRG-filled nanocomposites. Higher
percolation threshold in CB-filled composites is attributed to highly fractal, and agglomerate-
forming nature of CB. The complete electrical conductivity data of CB-composites is provided in
the supporting information.
115
Again, a power law scaling relationship can be applied to the electrical conductivity data
as follows:
  W  Wp 
t
A log-log plot between and W-Wc should give a straight line with exponent t. The inset
in Figure 5.14 shows the power law fitting, and the power law exponents (t) are shown next to
each set of data (also see Table 5.1). The exponent, t, reflects the dimensionality of the system.
Typically, 1.6 < t < 2.0 is for three dimensional network, and 1 < t < 1.3 is exhibited by the two
dimensional network in nanocomposites242, 243, 244. In this study, t > 1.3, which showed a three
dimensional network was formed by TRG in all composites. Interestingly, the t-values for CB
composites were even higher than that for TRG nanocomposites, which can be attributed to the
fractal network forming nature of CB to construct a three dimensional network in composites
(Appendix-C). However, the electrical conductivity of CB composites are lower than that TRG,
which might be due to structural imperfections in the networks formed by the CB particles.
5.3.7 Morphology
The cryogenically fractured nanocomposites at 5 wt% loadings were used to study the
morphology via FE-SEM (Figure 5.15). The SEM images were taken at two different
magnifications. The PE/TRG nanocomposites (Figure 5.15 a, b) showed graphene being pulled
out during cryo-fracturing.
116
-2
10
-3
60/40/TRG
10
-4
10
 [S/cm]
-5
10 80/20/TRG
-6
10 10
-3
-7 10
-4
10

10 t~1.7
-5
-8
10 PE/TRG 10
-6
-7 t~2.6
t~1.5
-9 10 -1 0 1
10 10 10
W-Wp
10
-10
10
0 1 2 3 4 5 6
TRG wt%
Figure 5.14 Electrical conductivity of TRG-filled nanocomposites. Solid lines are to guide the
eye only. Inset shows the power law fit, the numbers indicate the power law exponents.
Table 5.1 Electrical and rheological percolation threshold and power law exponents for TRG-
based nanocomposites
Rheological Electrical
WpR% ΦpR% α Af Wpσ% Φpσ% t
PE/TRG 2.3 1 2.9 41 0.7 0.3 2.6
80/20/TRG 1.7 0.7 2.5 60 0.5 0.2 1.5
60/40/TRG 0.7 0.3 2.7 155 0.3 0.1 1.7
The graphene stacks were more visible in the high resolution image (Figure 5.15b).
Similar morphology was exhibited by 80/20/TRG nanocomposites. High Af of TRG in these
nanocomposites compared to PE/TRG system was evident in the high-resolution image (Figure
5.15d) as smaller graphene stacks are seen in these nanocomposites. The 60/40/TRG
nanocomposites exhibited morphology similar to PE/TRG in low-resolution images. However,
under high-resolution, 60/40/TRG nanocomposites showed very different, and exfoliated
morphology. The TRG stacks in these nanocomposites were either very small (seen at a few
117
spots), or not seen at all. These results are in agreement with the rheological, mechanical, and
scattering analysis, that better exfoliation was observed in 60/40/TRG nanocomposites compared
with the other two composite systems.
(a) (b)
(c) (d)
(e) (f)
Figure 5.15 SEM images of PE/TRG (a, b), 80/20/TRG (c, d), 60/40/TRG (e, f) at 5 wt%
loading. The arrows indicate TRG sheets located in these composites
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Conclusions
Dispersion of thermally reduced graphene (TRG) in PE, and PE/OPE blends was
investigated by thermomechanical, electrical, and scattering techniques. Reduced rheological and
electrical percolation thresholds in PE/OPE blends showed better dispersion, and exfoliation of
graphene sheets in the blends compared to neat PE. The universal behavior of TRG diffusion in
polymers followed the Doi-Edwards theory for CNTs dispersion, showing that TRG follows the
Brownian diffusion. The microstructure developed in TRG-filled nanocomposites by SAXS
showed the formation of mass and surface fractals in nanocomposites. At lower TRG loadings,
TRG showed better dispersion as indicated by small slope in I ~ q log-log plots. The dispersion
of TRG was fairly inconsistently similar at low TRG concentrations. However, a more detailed
study of SAXS with carefully synthesized nanocomposites is highly desirable to understand this
discrepancy in dispersion. The decrease in long period order (Lp) was linked with the mechanical
properties, where substantial decrease in Lp in blend nanocomposites showed remarkable
improvement in elastic moduli. Modeling and simulation of mechanical properties using
micromechanical models showed even higher exfoliation of graphene sheets in nanocomposites.
A ~3-fold increase in elastic properties of TRG-filled blends with a ~7-fold lower melt viscosity
indicates the formation of processable blend nanocomposites with improved filler/matrix
interactions. Higher electrical conductivity of blend-TRG nanocomposites than that of PE/TRG
nanocomposites is another indication of better dispersion and exfoliation of TRG in the blends.
Acknowledgements
This project has been supported by The Petroleum Institute, Abu Dhabi through the
Cooperative Research Partnership with Colorado School of Mines. Authors thank U.S. Army
119
Research Office (DURIP Grant No.W911NF-11-1-0306) for financial support in part of this
work. Prof. John Dorgan is acknowledged for his laboratory facilities. Authors also thank Tara
Pandey and Andrew Motz at Colorado School of Mines for helping with SAXS measurements,
and Marcus Oils and Chemicals (Texas) for supplying the commercial OPE samples used in this
study. Authors thank Travis Arnold for assisting with sample preparation and rheological
experiments. Use of the Advanced Photon Source, an office of Science User facility operated for
the U.S. Department of Energy (D.O.E.) Office of Science by Argonne National Laboratory, was
supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.
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CHAPTER-6
CONDUCTIVE POLYETHYLENE/GRAPHENE/CARBON BLACK HYBRID
NANOCOMPOSITES
Understanding the synergic effects of hybrid fillers in polymer reinforcement is an
exciting area in polymer nanocomposites. This chapter focuses on using commercial graphene
(called graphene nanoplatelets, GnP) and carbon black (CB) together to understand the hybrid
filler synergy in polyethylene (PE), and produce electrically conductive nanocomposites.
6.1 Introduction
Structural composite materials have attracted lots of attention due to high strength, high
or low thermal and electrical resistances, and low bulk density compared to metals1, 2, 3. One path
to composite materials is by incorporating a variety of fillers into polymer matrices, which
achieves the desired properties. In the past few decades, nanomaterial-reinforced polymers
(polymer nanocomposites) with high performance properties have attracted both academia and
industry. These advancements are likely to not only bring new technology into traditional
composite industry, but also offer cheaper and more environmentally benign production routes.
Electrically and thermally conductive polymer composites have introduced important
applications in areas such as adhesives, sensors, antistatic coatings and films, actuators, and
electromagnetic interference shielding materials for electronic devices.
Conventional micro-scale fillers such as metal powders245, 246, carbon black (CB)247, 248,
and graphite249 are required in large quantities (usually 10-50 wt%) to induce electrical and
thermal conductivities in insulating polymers. The conventional composite industry suffers from
processing and property issues when such large quantities of fillers are used. Currently,
121
nanomaterials, such as carbon nanotubes (CNTs) and graphene, are replacing conventional
micro-fillers due to their superior electrical properties, thermal conductivities, and reinforcing
effects in polymers. CNTs are 1D materials composed of sp2-carbons in the form of single or
concentric tubes, and graphene is a 2D, atomically-thick sheet of sp2-carbon atoms. A small
quantity of these nanofillers substantially alters the properties of polymers38. However, property
improvement in polymers largely depends on the characteristic nature of polymers, and that of
nanofiller28. For example, electrical percolation threshold of graphene in polar polymer/graphene
nanocomposites lies in the range of 0.05-1 wt% whereas it is higher (1-15 wt%) for the nonpolar
polymer/graphene nanocomposites. Specifically, polycarbonate191 showed rapid increase in
electrical conductivity at 0.6 wt% graphene, and thermoplastic polyurethane48 achieved the
percolation limit at 0.5 wt%. However, nonpolar polyolefins, such as polyethylene and
polypropylene, show electrical percolation at 2-12 wt% graphene loading202, 209

, which is
markedly higher than polar polymer nanocomposites.
In general, absence of sufficient filler/polymer molecular interactions in nanocomposites
results in the formation of large agglomerates of filler particles inside the polymers, which
eventually leads to high percolation limits. The polyolefin/graphene nanocomposites show
higher percolation because of graphene agglomeration which is a matter of great interest and
concern for researchers and industry around the world. Recently, we addressed the issue of poor
dispersion of graphene in polyethylene by synthesizing miscible blends of PE with OPE
(Chapters 4 and Chapter 5). The electrical percolation limit for graphene was substantially
reduced in PE/OPE blends (0.3 wt%) compared to neat PE/graphene nanocomposites (0.7 wt%).
In addition, remarkably improved mechanical properties were achieved in blend/graphene
nanocomposites, resulting from the high aspect ratio of the dispersed graphene in PE/OPE
122
blends. Herein, we address a new method of increasing graphene dispersion in polyethylene by
using CB as a synergic filler.
In the realm of polymer nanocomposites, besides manufacturing mechanically robust
materials, nanocomposites with unique electrical, thermal, magnetic, and optical properties has
become a new research highlight. Hybrid fillers250, 251, 252, consisting of two heterogeneous non-
elementary units with different properties can be used to prepare a new class of efficient,
functional, and multi-dimensional composite nanofillers. Incorporated in polymers through
different approaches, such as melt or solvent blending, these hybrid nanofillers can impart
important properties in polymers to manufacture high performance and multi-functional polymer
nanocomposites. Consequently, the next technological frontiers can evolve by designing and
optimizing the nanomaterial combinations and their synergic functions. In addition, expectedly,
the nanoparticles agglomeration and interfacial interaction issues in polymer nanocomposites
could also be reduced by using such functional hybrid nanofillers253.
Recently, in the last few years, a few reports have emerged on using hybrid nanofillers,
introducing various functional properties in polymer nanocomposites. Substantial improvement
in thermal conductivity of epoxy matrix was reported by Yang and Gu107 with modified CNTs
and silicon carbide (SiC) hybrid filler synergy. The thermal conductivity of epoxy
nanocomposites was almost doubled with CNT/SiC hybrids compared to CNTs alone. Ma et
al.254 reported CNT/CB hybrid filler in epoxy nanocomposites to improve the electrical
conductivity. A 50/50 ratio of CNT (0.2 wt%) and CB (0.2 wt%) showed synergic effects,
leading to electrical percolation in nanocomposites compared to percolation by CNTs at 0.3
wt%, and CB at 0.6 wt%, individually. In another report, marked improvement in mechanical
properties of nylon 6 was reported by Zhang et al.255 with CNT/silica hybrids at only 1 wt% of
123
the hybrid filler. However, to the best of our knowledge, no report has surfaced on using hybrid
filler to reinforce nonpolar polyolefins.
The current study is part of a larger research project focused on improving graphene's
dispersion in nonpolar polyolefins to produce electrically conductive, and mechanically robust
nanocomposites. Here, linear low density polyethylene (PE), one of the most widely used
polymers in the polyolefin family, was used as a matrix. The synergic effects of graphene and
CB were investigated by varying graphene/CB ratios and concentration in PE, mainly aiming at
improving the electrical conductivity of the nanocomposites. The study includes characterization
of the filler dispersion in nanocomposites by melt rheology, and microstructure of
nanocomposite investigated by small angle x-ray scattering.
Following section provides the information on materials and synthesis procedures
adapted in this study.
6.2.1 Materials
Graphene nanoplatelets (A12, Graphene Supermarket), carbon black (99.9%, bulk
density = 170-230 g/L, surface area = 75 m2/g, Alfa Aesar), linear low density polyethylene
(LLDPE) with molecular weight 3.6 x 106 g/mol (determined via gel permeation
chromatography), and bulk density 0.97 g/cm3 (428078, lot#07730MEV, Aldrich), and p-xylene
(99%, Sigma Aldrich) were used as received.
124
6.2.2 Nanocomposites Synthesis
Graphene nanoplatelets (GnP) and/or carbon black (CB) were dispersed in p-xylene via 2
h sonication at room temperature. The dispersion was also stirred for 30 minutes after the first
hour of sonication for better mixing, followed by sonication for another hour. Low density
polyethylene (PE) was added into the dispersion at room temperature, and stirred at 120 °C for 2
h under reflux. After complete homogenization, the composite dispersion was drop cast on a
heated glass plate at 80 °C, and dried for 2 h at the same temperature. The complete solvent
removal was assured by drying the cast films for 24 h inside a fumehood at room temperature.
The dried thin films were chopped into small pieces (3-5 mm wide), heated at 160 °C for 10
minutes, and hot pressed for 3 minutes under 5000 kPa pressure to prepare circular discs
(thickness 1-1.3 mm and diameter ~ 25 mm) for rheological testing. Thin films for scattering and
electrical testing were prepared following the similar procedure using more dilute solutions in p-
xylene, and drop casting on a glass plate at 80 °C, and following the same drying procedures.
X-ray diffraction patterns were obtained from a wide angle x-ray diffractometer (WAXD)
(Phillips PW γ040/θ0) with CuKα radiation at a scanning rate of 0.02 °/s. Transmission electron
microscope (TEM) images were obtained using a FEI Phillips C200 at 200 kV. For TEM
measurements, a dilute dispersion of GnP or CB or hybrid filler (0.1 mg/20mL acetone) was
prepared by bath sonication for 10 minutes, and one drop of the suspension was dried on a 300-
mesh Cu grid with holy carbon. Very dilute dispersion of CB (2.5 mg/mL), and that of TRG (1
mg/mL) were dispersed in acetone via bath sonication at room temperature, and dynamic light
125
scattering (DLS) was performed on a particle size analyzer (NanoBrook 90Plus, Brookhaven) at
25 °C.
Rheological measurements were performed at 160 °C using a TA instrument AR-G2
rheometer equipped with 20 mm parallel plate. Tests were conducted in air while samples were
covered with an aluminum shield to avoid temperature fluctuations during the run. Linear
viscoelastic (LVE) region was determined by running strain sweep in 0.01-100% strain range at
1 Hz frequency, and storage (Gˊ) and loss (G˝) moduli were recorded as a function of strain%.
The frequency sweep experiments were performed in the frequency range of 0.01-100 Hz under
a small amplitude oscillatory shear, = o sin(ωt) within the δVE region.
The in-plane electrical conductivity was calculated using electrochemical impedance
spectroscopy (EIS) using the following equation:
Conductivity 
L
R.w .t
Where, R is the film resistance, L is the distance between the sense electrodes, w is the
width of film, and t is the sample thickness. The impedance spectra were obtained over a
frequency range of 0.3 Hz to 100 kHz using a four electrode test cell connected to a multi-
channel potentiostat (Biologic VMP3, Knoxville, TN). All measurements were made in an
environmental chamber to control sample temperature and humidity (TestEquity Model 1007H,
Moorpark, CA). The samples were polished using a 100 mesh grit paper before conductivity
measurements in order to remove thin polymer layer transported on the surface during the film
formation and drying process. Due to polishing, composite films exhibited static current build
126
up, which was removed by conditioning the samples at 95% relative humidity and 50 °C for one
hour. The results reported here are averaged over 3 samples at 25 °C and 95% relative humidity.
Small angle X-ray scattering (SAXS) experiments were performed at the X-ray Sciences
Division, beamline 12-ID-C, at the Advanced Photon Source at Argonne National Laboratory.
Data has been collected at 60°C under dry conditions, and is averaged over three exposures
times. Details of the procedure, and temperature and humidity control can be found elsewhere 212,
213
.
This section provides details on the characterization of fillers and nanocomposites
synthesized in this study.
6.3.1 Characterization of GnP and CB
A typical paper-like morphology was observed for GnP (Figure 6.1a), where finely
separated graphene nanosheets were extended over a few microns in the lateral dimensions. In
addition, small overlapping areas (marked with arrows in Figure 6.1a) also showed the presence
of some smaller GnP sheets 200-300 nm wide and ~500 nm long. Thus, GnP is composed of two
types of particles. It is also worth noting that GnP sheets are not wrinkled indicating the absence
of any foreign element present on its surface88. On the other hand, CB particles are known for
their strong agglomerating nature256. Strong agglomeration/association of CB particles was also
observed in TEM (Figure 6.1b). The CB particles were spherical in nature, with a 50-60 nm
diameter (inset in Figure 6.1b). However, CB agglomerates were extended over a few microns
127
even when a very dilute suspension of CB particles was prepared in acetone, and deposited on
the Cu grid for TEM analysis.
(a) (b)
100 nm
Figure 6.1 TEM morphology of GnP (a) and CB (b). Inset in (b) shows high resolution image of
CB particles.
The quality of the commercial grade GnP and CB was also examined by XRD analysis
(Figure 6.2). Graphite showed the intrinsic (00β) peak at β ~ βθ.4°, corresponding to an
interlayer spacing of ~3.37Å. A single, sharp XRD peak in graphite further indicated the
presence of a perfectly stacked structure in graphite. The particle size of graphite was calculated
to be 145 nm from Scherrer analysis257. On the other hand, no diffraction patterns were observed
in GnP and CB compared to that in graphite. Inset in Figure 6.2 shows a small (002) peak in
GnP, corresponding to a particle size of ~35 nm. Assuming a perfect interlayer spacing of 3.37 Å
in graphene layers of ~1 nm thickness, a particle size of 35 nm shows approximately 24
graphene sheets stacked in one GnP particle. Generally, the graphene particle containing less
than 10 graphene sheets are considered high quality graphene258 for polymer reinforcement
applications. However, the large particle size indicates that this GnP might not be as effective as
high quality graphene produced by other methods; e.g., graphene synthesized by thermal
exfoliation and reduction of GO contains ~4-5 graphene layers28, 38.
128
CB
Intensity (a.u.)
GnP
26.4°
200
26.4°
100
0
20 22 24 26 28 30
Graphite
2 (°)
5 10 15 20 25 30 35 40
Figure 6.2 XRD patterns of graphite, GnP, and CB
6.3.2 Microstructure and Melt Rheology
Rheological properties of polymers are considered pertinent in designing new composite
materials. Understanding the flow behavior of nanocomposites gives direct insight into the
processing properties, and the dispersion of fillers. The rheological properties of PE/GnP
nanocomposites, and PE/CB composites were obtained within the LVE range (Figure 6.3). With
increasing GnP concentration in PE, the initial G' also increased. At 10 wt% GnP loading, a
quasi-asymptomatic behavior was observed where G' was nearly independent of the frequency.
Similarly, the initial G' increased with increasing CB loading. However, the increment was not as
significant as that was in PE/GnP nanocomposites. Strong network formation in PE/GnP
nanocomposites was observed at 10 wt% of GnP loading, and that in PE/CB composites
observed at 20 wt% of CB loading.
129
6 6
10 (a) 10 (b)
5 Increasing GnP wt% 5 Increasing CB wt%
10 10
G (Pa)
G (Pa)
4 4
10 10
Neat PE Neat PE
3 PE/GnP 0.5 wt% 3 PE/CB 0.5 wt%
10 PE/GnP 1.0 wt%
10 PE/CB 1.0 wt%
PE/GnP 1.5 wt% PE/CB 2.5 wt%
2 PE/GnP 2.5 wt% 2 PE/CB 4.3 wt%
10 PE/GnP 5.0 wt% 10 PE/CB 6.5 wt%
1 1
10 -3 -2 -1 0 1 2 10 -3
 (s )
-2 -1 0 1 2
 (s )
10 10 10 10 10 10 10 10 10 10 10 10
-1 -1
Figure 6.3 Rheological properties of PE/GnP nanocomposites (a), and PE/CB composites (b).
In order to understand the synergic effects of CB in PE/GnP nanocomposites, two
variables were selected: 1) GnP/CB ratio, and 2) total concentration of hybrid filler (Figure 6.4).
For the first variable, three representative GnP/CB ratios were used: a) 1:1, b) 1:5, and c) 1:10.
And, for the second variable, the concentration was varied from 0 to 15 wt%. The main objective
in varying the GnP/CB ratio was to fabricate conductive nanocomposites with least amount of
GnP.
Increasing concentration of nanofiller increases the rheological properties of
nanocomposites. An exponential increase in the initial G' defines the establishment of filler
network inside the polymers: an essential requirement in nanocomposites showing the effective
dispersion of filler and filler/polymer interactions. In GnP/CB 1:1 hybrid nanocomposites
(Figure 6.4a), incorporation of a small amount of the hybrid filler (1 wt%) increased the initial G'
at 0.01 Hz frequency from 42 Pa for neat PE to 191 Pa for the nanocomposites. The exponential
growth in G' was observed at 10 wt%, attributed to the network formation. In GnP/CB 1:5
(Figure 6.4b), and 1:10 (Figure 6.4c) hybrid nanocomposites, the initial increase in G' was not as
significant as that was in GnP/CB 1:1 nanocomposites at 1 wt% hybrid filler. However, the
130
rheological network formation was observed at 10 wt% hybrid filler in all the hybrid
nanocomposites. Thus, the network formation was not affected by changing GnP/CB ratio, and is
a function of filler concentration.
Since, incorporating nanofillers in polymers increases the viscosity of nanocomposites to
several orders of magnitude. The increased viscosity further indicates increased energy
requirements while processing these nanocomposites. For this purpose, the complex viscosity of
nanocomposites was compared to analyze the effect of hybrid filler on the processing properties.
Neat PE showed a non-Newtonian shear thinning viscosity profile where the viscosity
decreased with increasing frequency. Incorporation of 5 wt% GnP increased the complex
viscosity approximately 0.5 order of magnitude compared to that of PE at 0.01 Hz frequency.
Sine CB is a fractal filler which does not provide sufficient reinforcement effects, the complex
viscosity of PE/CB composites at 5 wt% CB loading was approximately double to that of neat
PE.
In hybrid fillers, the GnP:CB 1:1 hybrid/PE nanocomposites showed improved properties
where CB particles anchored to GnP sheets (later in Figure 6.6). The complex viscosity of
hybrid/PE nanocomposites was in between that of PE/GnP and PE/CB composites. Interestingly,
the viscosity of hybrid composites was closer to that of PE/CB composites which shows that
these composites can be processed at conditions similar to those for CB composites. The low
viscosity of hybrid nanocomposites was lower than that of PE/GnP nanocomposites which also
indicates ease of processing of these nanocomposites.
131
6 6
10 (a) 10 (b)
5 5
10 10
G (Pa)
G (Pa)
4 4
10 10
3 PE/Filler wt/wt 3 PE/Filler wt/wt
10 100/0 10 100/0
99/1 99/1
2 97/3 2 97/3
10 95/5 10 95/5
90/10 90/10
GnP/CB 1:1 85/15 1
GnP/CB 1:5 85/15
1
10 -3 -2 -1 0 1 2
10 -3 -2 -1 0 1 2
 (s )  (s )
10 10 10 10 10 10 10 10 10 10 10 10
-1 -1
6
10 (c)
5
10
G (Pa)
4
10
3 PE/Filler wt/wt
10 100/0
99/1
2 97/3
10 95/5
90/10
GnP/CB 1:10 85/15
1
10 -3 -2 -1 0 1 2
 (s )
10 10 10 10 10 10
-1
Figure 6.4 Effects of total filler concentration, and GnP/CB ratio on rheological properties of
PE/GnP/CB nanocomposites.
The arrangement of GnP sheets and CB particles in hybrid filler was further analyzed
using TEM imaging of the dried hybrid dispersions with different GnP/CB ratios (Figure 6.6). At
lower CB concentration in GnP/CB hybrid suspension, CB particles were observed being
anchored by the graphene sheets (Figure 6.6a). Increasing concentration of CB produced large
micron-scale agglomerates (Figure 6.6b). Interestingly, at GnP/CB ratio of 1:10, CB lost its
particle identity, and spread over graphene sheets like a viscous liquid.
132
5
10
GnP Total Filler = 5 wt%
1:1 Hybrid
CB
 , Pa-s
4
10
PE
*
3
10
, s
-2 -1 0 1 2
10 10 10 10 10
-1
Figure 6.5 Comparison of viscosity of composites
The morphology of GnP/CB hybrid suspensions is in agreement with the rheological
analysis (Figure 6.4). Due to the anchoring nature of CB particles at lower concentrations, the
initial increment in G' for GnP/CB 1:1 hybrid filler was higher compared to that in 1:5, and 1:10
hybrid filler/PE nanocomposites. However, increasing concentration of hybrid filler of any
GnP/CB ratio might produced agglomerates of CB. That’s why, the network forming
concentration of the hybrid filler was not affected by the GnP/CB ratio.
At this time, we do not have an explanation for the liquid-like merging behavior of CB
particles in GnP/CB 1:10 hybrid filler. More studies into the concentration stabilization of GnP
with varying concentration of CB might shed some light on this behavior.
The rheological analyses provide overall averaged microstructure in nanocomposites
below and above percolation65, 219. On the other hand, structural techniques such as small angle
x-ray scattering (SAXS) can show microstructure at individual compositions in nanocomposites.
SAXS measures the shape and size of polymers between 5 and 25 nm of the repeat distances 171.
133
The scattering vector (q) probes different structural features at various length scales (length scale
~ βπ/q) in polymers and polymer nanocomposites. In graphene-based nanocomposites, SAXS-
based morphology of nanocomposites can be correlated with the dispersion of graphene in
nanocomposites (Chapter 5).
(a) (b) (c)
1µm 1µm 1µm
Figure 6.6 TEM micro-images of GnP/CB suspensions with different GnP/CB ratios: a) 1:1, b)
1:5, and c) 1:10.
In the log-log intensity versus scattering vector plots, initial decaying exponent (α) at
lower q indicates the size of the scattering objects. The decaying exponent (α) is directly related
to the fractal dimensions, df of the scattering objects229. In general, for α ≤ γ, particles form mass
fractals (a substance whose surface and mass are both characterized by the fractal properties). In
mass fractals, α directly corresponds to fractal dimensions, dm. For γ ≤ α ≤ 4, surface fractals are
formed where the scattering is observed from a smooth surface. Fractal dimension, d s, is
calculated from α as followsμ α ≡ θ - ds where 3 < 6 - ds ≤ 4229, 230. Thus, ds varies from 3 to 2,
where ds ~ β is for a smooth surface approaching Porod's scattering (α = 4)172, and ds ~ 3
indicates the uneven concentration of scattering objects at the scattering surface231.
Pure PE exhibited α = β.γ, typical for randomly oriented polymer chains 172 (chapter 5).
We recently showed the increased dispersion of graphene in PE elucidated by decreasing
decaying exponent (α), where I ~ q-α log-log analyses hold for low q range. Two representative
nanocomposites were selected for SAXS analysis: below and above the rheological percolation
134
limit (Figure 6.7). For all nanocomposites, α > γ was observed, signifying the formation of
surface fractals. Using Malekani et al. analysis of fractal size, the surface fractal dimensions are
calculated as ds = 6 - α. GnP/CB 1μ1 hybrid showed ds similar to that for PE/GnP
nanocomposites. The ds increased for 1:5, and 1:10 hybrids (Figure 6.7a). Increased ds in
GnP/CB 1:5, and 1:10 nanocomposites might indicate the uneven agglomeration of CB particles
in these hybrid nanocomposites.
Increasing hybrid filler loading to 15 wt% (Figure 6.7b) showed slight decrease in α for
PE/GnP, and PE/CB composites compared to that at 5 wt% loadings (Figure 6.7a). Similarly, the
GnP/CB 1:1 showed the same exponent at 15 wt% filler loading as was observed at 5 wt% filler
loading. The exponent α decreased for GnP/CB 1μη nanocomposites from γ.4 at η wt% to γ.β at
1η wt%, whereas α increased from γ.η at η wt% to γ.θ at 1η wt% filler loading for GnP/CB 1:10
hybrid nanocomposites. However, the change in α is not significant compared to increased
concentration of fillers, and they might be indicating no change in dispersion state at two filler
loadings.
3
10 4
GnP:CB 1:5
10
(a) = 3.2 (b)
'8-PECB15_01596_00001'
'7-PEGnP15_01587_00001'
2 GnP/CB 1:10 3 '19-H15-15_01634_00001'
10 GnP:CB 1:10
= 3.5 10 = 3.6
'24-H110-15_01647_00001'
'14-H11-15_01619_00001'
1 GnP/CB 1:5 2
10 = 3.4 10
I (q) [a.u.]
PE/GnP
I(q) [a.u.]
1
0 10 = 3.0
10
0
-1 10
10 PE/CB
-1
10 = 3.0
-2 PE/GnP
10 = 3.1 -2
GnP/CB 1:1 10
-3 '5-PEGnP5_01585_00001'
= 3.2
10 '12-H11-5_01617_00001'
'17-H15-5_01627_00001' 10
-3
'22-H110-5_01649_00001'
-4 -4
10 5 6 7 2 3 4 5 6 7 2 3 10 5 6 7 2 3 4 5 6 7 2 3
0.01 0.1 0.01 0.1
q [1/Å] q [1/Å]
Figure 6.7 SAXS I~q log-log plot for PE/hybrid filler nanocomposites at a filler loading of a) 5
wt%, and b) 15 wt%
135
6.3.3 Electrical Conductivity
Electrically conductive polymer nanocomposites are used in a variety of applications.
The electrical conductivity is a function of dispersion of filler and its aspect ratio were the
effective dispersion depends on filler/polymer and inter-filler interactions. Significant
improvement in electrical conductivity of nanocomposites (measured at 0.01 Hz) was observed
as the filler concentration increased from 0 to 15 wt%. Neat PE is an insulating polymer with
conductivity ~ 7.4 x 10-14 S/cm. Incorporation of GnP increased the conductivity to ~10-3 S/cm at
15 wt% graphene loading. On the other hand, a gradual increase in electrical conductivity was
observed in PE/CB composites, where the conductivity reached its peak value at 10 wt% CB
loading, followed by a slight decrease at 15 wt%. The decreased conductivity might be
associated with the highly fractal forming and agglomerating nature of the CB particles.
In order to comment on the efficacy of GnP, a comparison between GnP and hybrid
nanocomposites is provided below. PE/GnP nanocomposites showed a conductivity of ~9x10-4
S/cm at 5 wt% GnP loading. The GnP/CB 1:1 hybrid/PE nanocomposites at 10 wt% total filler
loading exhibited conductivity of ~2x10-1 S/cm. It is worth noting that 10 wt% of 1:1 hybrid
filler contains 5 wt% GnP and 5 wt% CB. Thus, incorporating equal amounts of GnP and CB in
PE increased the electrical conductivity by about 3 orders of magnitude compared with that of
GnP and CB (Figure 6.9) at 5 wt% individual loading.
On the other hand, strong agglomeration of CB was observed in GnP/CB 1:10 hybrid/PE
nanocomposites. The conductivity of hybrid nanocomposites at GnP/CB ratios of 1:5 and 1:1
were very close, showing less agglomeration of GnP/CB in these nanocomposites.
136
1.E+00
Total Hybrid= 10 wt%
1.E-01
Conductivity, S/cm
1.E-02
1.E-03
1.E-04
1.E-05
1.E-06
1.E-07
1.E-08
PE/GnP 5 1:10 Hybrid 1:5 Hybrid 1:1 Hybrid
wt%
Figure 6.8 Comparison of electrical conductivities of GnP and GnP/CB hybrid nanocomposites
Increasing concentration of hybrid filler in PE increased the electrical conductivity of the
nanocomposites. However, the conductivity is observed to be a function of GnP/CB ratio (Figure
6.9). In GnP/CB 1:1 hybrid nanocomposites, a sharp increase in conductivity was observed
between 5 and 10 wt% total filler loading, showing the electrical percolation limit as ~7.5 wt%.
Similar observations were observed for GnP/CB 1:5 hybrid filler ratio. On the other hand, the
GnP/CB 1:10 hybrid filler showed no electrical conductivity at lower concentrations, whereas
sharp increase in conductivity was observed between 10-15 wt% showing the electrical
percolating limit at ~12.5 wt%. The high percolation concentration in GnP/CB 1:10
nanocomposites might be associated with high agglomeration of CB particles, and conversion of
CB into viscous liquid-like appearance on the GnP nanosheets (Figure 6.6). Further insights into
the liquid-like merging of CB on GnP might shed light on this behavior, and help find a better
explanation.
137
2
10
PE/GnP
0 PE/CB
10 1:1 Hybrid
1:5 Hybrid
 [S/cm]
-2 1:10 Hybrid
10
-4
10
-6
10
-8
10
-10
10
0 5 10 15 20
Total Filler wt%
Figure 6.9 Electrical conductivity of nanocomposites.
Conclusions
The concept of manufacturing conductive nanocomposites using graphene/CB hybrid
nanofiller in nonpolar polyolefin matrix is a new and technologically challenging area. This
study is the first report on producing hybrid filler/PE nanocomposites. Dispersion of hybrid filler
was studied using rheological properties, electrical conductivity, and small angle scattering. The
microstructure formed inside the nanocomposites showed that hybrid fillers formed surface
fractals inside the polymers. Rheological properties were largely unaffected by GnP/CB ratio at
higher hybrid filler concentrations, attributed to the agglomerating nature of CB particles. On the
other hand, at lower concentrations, significant improvement in rheological properties was
observed in GnP/CB 1:1 nanocomposites. The electrical percolation threshold was also observed
to be a function of GnP/CB ratio, where the percolation limit decreased with increasing GnP/CB
ratio.
138
Acknowledgement
This study is supported by The Petroleum Institute, Abu Dhabi through the Cooperative
Research Partnership with Colorado School of Mines. Authors thank U.S. Army Research Office
(DURIP Grant No.W911NF-11-1-0306) for partial financial support. Prof. John Dorgan is
acknowledged for his laboratory facilities. Authors also thank Tara Pandey and Andrew Motz at
Colorado School of Mines, and Sonke Seifert at Argonne National Laboratory for assisting with
SAXS measurements. Use of the Advanced Photon Source, an office of Science User facility
operated for the U.S. Department of Energy (D.O.E.) Office of Science by Argonne National
Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.
139
CHAPTER-7
CONCLUSIONS AND FUTURE RECOMMENDATIONS
This thesis is a fundamental study on synthesis and characterization of composites made
from nanoscale carbon structures, especially TRG. A number of open questions in
nanocomposites research were explored and raised some new questions. The overall summary of
the thesis is presented in this chapter. In addition, new insights for the future research in the field
of nanocomposites are also provided.
7.1 Summary and Conclusions
TRG was successfully synthesized and characterized for its physical and chemical
properties. The residual oxy-functional groups on TRG were utilized for attaching the amino-
silane on TRG surface. A simple method to attach silane onto TRG surface was demonstrated
which allowed the grafting of more than 7-8 atomic% silane on graphene surface, more than
what was reported earlier. A fundamental understanding of the attachment mechanism of amino-
silane on graphene surface was demonstrated with and without the use of an organic solvent. The
described method can be further used for selective edge-functionalization of TRG by selecting a
suitable organic solvent.
Since, polyolefins are comprised of highly nonpolar structure, the dispersion of
nanofillers such as graphene and carbon nanotubes in polyolefins is considered difficult. One
serious disadvantage of the poor dispersion is filler agglomeration, due to which the potential
reinforcements in nanocomposites cannot be achieved. In this thesis, rather than using the
functionalization approach to solubilise graphene in PE, blends of PE with OPE were
140
synthesized via solvent blending approach. OPE was found miscible in PE whereas the
miscibility decreased with increasing OPE concentration in the blends. In molten state, OPE
acted as a processing aid for optimizing the processing properties of PE; whereas in the solid
state, inclusion of OPE increased the mechanical properties of PE. Being amorphous in nature,
OPE resided within the lamellae of PE, and increased PE's crystallinity which eventually
attributed in increasing the mechanical properties of the blends.
TRG was also incorporated in PE/OPE blends to manufacture polymer nanocomposites
via solvent blending, and the dispersion of TRG was quantified. Remarkable processing and
mechanical properties were achieved when nanocomposites were manufactured with PE/OPE
blends compared to neat PE/TRG nanocomposites. The dispersion of TRG in PE/OPE blends
was substantially increased, marked by the significant reduction in rheological and electrical
percolation limits. Along with the reduction in percolation thresholds, viscosity of PE/OPE/TRG
nanocomposites was considerably lower than that of PE/TRG nanocomposites which was
remarkable since nanofillers such as graphene increase the viscosity of nanocomposites many
orders of magnitude. Higher viscosity, however, is a big disadvantage in the nanocomposite
industry since higher viscosity means more energy requirements in processing these materials.
The microstructure formed by TRG inside the nanocomposites investigated by SAXS
confirmed the formation of surface fractals when high dispersion was achieved (blends/TRG)
whereas only the mass fractals were observed when graphene was not uniformly dispersed inside
the polymer matrix (PE/TRG). The SAXS results were in excellent agreement with rheology,
mechanical and conductive properties. The contextualization of microstructure with the
performance properties of nanocomposites further helped in understanding the "slippery
behaviour" in graphene-based nanocomposites reported in many publications. In addition to
141
manufacturing mechanically robust and electrically conductive nanocomposites, fundamental
questions on the dispersion mechanism of graphene in polymers were addressed. This thesis (and
related publication) was the first report showing that TRG followed the Doi-Edwards theory of
dispersion in polymers, which was reported only for carbon nanotubes-based nanocomposites
previously.
Procuring small amounts of high quality graphene (less than 10 number of graphene
layers stacked in one graphene particle) being very costly and due to the large volumes of
graphene required in nanocomposites' mass productions, new methods to lower the overall cost
of nanocomposites were explored. Therefore, a commercial grade graphene called "graphene
nanoplatelets (GnP)" was also used in manufacturing conductive PE nanocomposites. Due to
large particles of size ~ 35 nm (~25 graphene layers stacked in one graphene particle), GnP was
not as effective as TRG for reinforcing PE (TRG is a highly quality graphene containing 4-5
graphene layers in one particle). CB was investigated as a synergic filler for GnP in PE
nanocomposites to understand the effects of GnP/CB ratio, and the total concentration of hybrid
filler on the dispersion. Higher electrical conductivities were achieved with GnP/CB 1:1 ratio at
15 wt% filler loading, compared to that of individual fillers or GnP/CB ratios of 1:5 and 1:10.
Overall, my hypothesis that TRG could be better dispersed in PE/OPE blends has proven
true. The new polyolefin matrix, PE/OPE miscible blend, proved better in manufacturing
mechanically robust, and electrically conductive nanocomposites at lower TRG loading
compared to that required for manufacturing PE/TRG nanocomposites. A fundamental
understanding was developed for the processing properties of PE/OPE blends and PE/OPE/TRG
nanocomposites. Moreover, a new concept of synergic effects of graphene and CB was tested.
The results indicate that CB could be used to increase graphene's dispersion in PE
142
nanocomposites. This idea can be very helpful in reducing the overall cost associated with
graphene-based polymer nanocomposites because CB is inexpensive and abundantly available. A
GnP/CB 1:1 ratio exhibited the best results in terms of electrical conductivity which shows that
approximately 50% cost of the filler can be reduced if CB is used along with graphene.
In addition to the work presented in this thesis, applications of TRG in environmental
science were also explored in collaborative research. The synthesis conditions for TRG
production were altered to change the residual C/O ratio, and other physical properties of TRG
such as the bulk density and surface area, and further used to adsorb spilled crude oil from the
water surface88. TRG showed an adsorption capacity of (~300 g-oil/g-TRG) for crude oil which
is the highest among the reported adsorbents so far. The adsorption behaviour was further
correlated with the physical and chemical properties of TRG. TRG was also used to remove the
harmful dyes from the colored wastewaters37. In another report, graphene oxide (graphite oxide
being exfoliated in water) was used as a thermal fluid for heat transfer applications34.
A comparison of the best results obtained in this thesis provided in Figure 7.1. The
electrical conductivity of PE was increased by approximately 1 order of magnitude when
PE/OPE 60/40 blend was used. The conductivity was substantially increased to ~1 S/cm when
GnP/CB 1:1 hybrid filler used in manufacturing nanocomposites.
7.2 Future Research Directions
Polymer nanocomposites are used in a variety of applications ranging from high-tech and
high performance materials to household daily appliances. Nanocomposites are a very rapidly
growing field, and there are many opportunities to pursue this field in future.
143
During the course of this thesis, a number of new alterations/ideas were identified to
improve the main goals delineated in the beginning. Due to the time constraints and instrument
limitations at the time, not all the ideas could be pursued properly. In the following sections, a
few strategies to improve the current research are discussed, and platforms the applications of
this research are suggested.
1
10
Conductivity, S/cm
0
10
-1
10
-2
10
-3
10
-4
10
15 wt%
5 wt%
5 wt%
-5
10
PE/TRG 60/40/TRG 1:1 Hybrid
Figure 7.1 Comparison of electrical conductivity of nanocomposite
In chapter 3, aminopropyl triethoxy silane (APTS) was attached onto TRG surface, and a
mechanism of APTS reaction with TRG was demonstrated with the help of various
characterization techniques. APTS has three ethoxy groups which were observed self
crosslinking on TRG surface; making the mechanism of attachment very difficult to understand
by inducing more structural complexities. APTS was selected in this work because APTS silane-
modified fillers have been reported in many published reports.
144
However, I believe a better structural understanding of the attachment mechanism of
silane can be developed if simpler silanes such as mono- and di-ethoxy silanes are used. The
monoethoxy silane represents the simplest member in the silane family. Also, TRG contains
residual hydroxyl, epoxy, and carboxylic acid functional groups on its surface. For clean
attachment, hydroxyl and epoxy groups may be caped so that only carboxylic acid groups would
be accessible for silane attachment. The availability of only one type of anchoring groups on
TRG surface will give single site for attaching monoethoxy silane. In addition, chapter 3
concluded that several organic solvents can be used for selective edge functionalization of TRG
with silane groups. Thus, a good starting point for doing research in this area will be to
synthesize carboxylated graphene, and use monoethoxy silane in the presence of various organic
solvents to study the silane attachment, quantitatively.
Later, PE/OPE miscible blends were synthesized via solvent blending where OPE acted
as a processing control agent. The OPE used in this study was a commercial product obtained
from the vendors directly. A first step in moving forward in this area will be to use melt blending
for fabricating PE/OPE blends, and ascertain that the results from solvent and melt blending are
similar or different. Another area to explore can be the synthesis of blends of PP with oxidized
PP (OPP) using the same methods to understand if PP/OPP blends show similar behaviour.
Since, PE and PP have structural similarities, creating miscible PP/OPP blends can also be
advantageous for nanocomposites applications.
The PE/OPE/TRG nanocomposites showed excellent rheological, electrical, and
mechanical properties. However, the nanocomposites were prepared by solvent blending which
is not as famous as melt blending for mass production of composite materials. Therefore,
corroborating solvent blending results with melt blended composites will be highly desired. A
145
facile application of this study can be in manufacturing nanocomposite packaging materials for
food and electronic packaging applications. Plate-like fillers are already established for
increasing the gas barrier of polymers259, and therefore, determining the gas barrier of
PE/OPE/TRG nanocomposites will be a very versatile area to look into. A pictorial
representation of the above suggestions is also provided in Figure 7.2260, 261, 262.
Micro-compounder
Melt
Graphene pressing
Solvent
Polymer casting
Mechanical
SAXS sample detector
Barrier Characterization
Properties
Monochromatic Beam 2ϴ q
~ 0.1-0.2nm
log (Intensity)
log (q), 1/nm or 1/Å
Figure 7.2 Schematics for future research plan in nanocomposites research
While, during the course of this thesis, several questions about the dispersion mechanism
of graphene in polymers were addressed; some new questions were also raised. For example, we
still do not understand the reasons for highly fibrous behaviour of PE/OPE 70/30 composition.
The peculiar behavior was also corroborated with other characterization techniques, but we could
not find any suitable explanation at the moment. Thus, focusing on the peculiarity of 70/30
blends might be very interesting.
146
In PE/OPE/TRG nanocomposites, 60/40 blend-TRG nanocomposites exhibited viscosity
lower than that of neat 60/40 blends, which was very unusual than what is expected in
nanocomposites. Generally, the nanocomposites' viscosity increases with gradual addition of
nanofiller. This kind of unusual behaviour is known as the non-Einstein behaviour in
nanocomposites71, 72. The non-Einstein behaviour is exhibited by filler particles having size less
than the radius of gyration of the polymer. In this thesis, TRG particles were comprised of 4-5
graphene layers (~3 nm thick) and extended over ~1µm in lateral dimensions. Incorporation of
TRG in polyolefins usually leads to the agglomeration of TRG, increasing the particle size, and
eventually no dimension of the agglomerate would be smaller than the radius of gyration of
polyolefins. Since, 60/40 blends showed highly improved TRG dispersion, individual graphene
particle might have one dimension smaller than the radius of gyration. In addition, the viscosity
of 60/40 blends was ~1 order of magnitude less than that of neat PE. That's why, 60/40 blends-
TRG nanocomposites showed the non-Einstein behaviour at very low loadings of TRG. Further
studies into the low viscosity model polymers such as PDMS, and incorporation of single sheet
graphene will be extremely helpful in understanding the non-Einstein behaviour of graphene in
polymer nanocomposites.
The synergic effects of graphene and CB in PE nanocomposites, and how CB affects
graphene's dispersion are some open questions not addressed in the published literature. The
main element in these questions is the packing of GnP and CB to produce highly conductive
nanocomposites. Higher loadings of GnP/CB hybrid fillers not only induce higher electrical
conductivity in nanocomposites, but can also produce thermally conductive nanocomposites.
Introducing thermal conductivity in nanocomposites will open up a new area of applications of
these materials. The next step in this research might be to understand thermal conductivity of
147
PE/hybrid filler nanocomposites, and correlate thermal conductivity with packing of GnP and
CB together inside PE. In addition, hybrid nanocomposites were fabricated via solvent blending.
Thus, using melt blending to manufacture hybrid nanocomposites, and quantifying filler
dispersion can be another way of moving forward in hybrid nanocomposites.
The percolation laws are used in rheological scaling analysis of nanocomposites (Chapter
5). The absence of the percolation laws dealing with packing of hybrid fillers offers a big gap in
hybrid filler nanocomposites research. The percolation laws stem from the solution rheology of
dispersions, and then applied to nanocomposites by assuming if nanoparticles are following
similar packing trends in nanocomposites as they were in colloidal assembly. Therefore, a certain
area of research can be investigating the colloidal assembly of GnP/CB hybrid assembly, and
applying these laws to hybrid nanocomposites.
Another important area of research that has not been explored in this thesis is the
extensional viscosity of nanocomposites. The uniaxial extension of thin nanocomposites films
under melt conditions is considered important for packaging applications. These experiments can
be easily performed on an ARES G2 extensional rheometer. Important parameters such as melt
strength having major importance in packaging material design can also be deduced from
extensional rheology, which could further be used to understand blowing mechanism of these
nanocomposites in manufacturing packaging films.
148
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171
APPENDIX-A SILANE MODIFIED GRAPHENE
Experimental details
The oxidation of graphite and the extent of exfoliation of GO is studied using X-ray
diffraction (XRDX’Pert PRτ εPD diffractometer, PAσalytical). Scans at β from 5 to 35° with
0.02 /sec step size at 40 KV voltage with an intensity of 20 Å using CuKα radiation of
wavelength 1.5406 Å was conducted.
Transmission Electron Microscopy (TEM) was performed using FEI Tecnai G20 with
0.11 nm point resolution and operated at 200 kV. Samples were prepared by dispersing
approximately 0.5 mg of graphene in 25 mL of dimethyl formamide by sonication at room
temperature for 5 minutes. Two drops of the suspension were deposited on 400 mesh copper
grids covered with thin amorphous lacey carbon film. The coupled Energy Dispersion
Spectroscopy (EDS) X-ray analysis is used for elemental composition of TRG and f-TRG.
Electron Energy Loss Spectroscopy (EELS) was acquired using post column energy filtered
camera (Gatan Quantum 963). The energy resolution was measured to be 0.9 eV FWHM at the
zero loss peak. Energy filtered TEM (EFTEM) mapping was applied to map the location of the
elements on the surface of f-TRG by measuring core, post-edge and pre-edge losses of the
respective elements using the “three-window method” technique263. EELS spectra of the
aforementioned elements were also recorded at their respective core losses and the type of bonds
were identified. Acquisition time necessary to obtain a good signal to noise ratio was 5 s for
silicon L2-3-edge, 10 s for carbon K-edge, 20 s for nitrogen K-edge and 30 s for oxygen K-edge.
172
XPS measurements were performed using SSX-100 system (Surface Science
δaboratories, Inc.) equipped with a monochromated Al Kα X-ray source, a hemispherical sector
analyzer (HSA) and a resistive anode detector. The base pressure was 4.0 x 10 -10 Torr. During
the data collection, the pressure was ca. 1 x 10-8 Torr. The X-ray spot size was 1x1 mm2, which
corresponded to an X-ray power of 200 W. Each sample was separately mounted on a sample
holder using a piece of double-sided carbon sticking tape. Care was taken to ensure the surface
was fully covered by the samples. The survey spectra were collected using 150 eV pass energy
and 1 eV/step. The atomic percentages were calculated from the survey spectrum using the
ESCA 2005 software provided with the XPS system. The high resolution spectra were collected
using 50 eV pass energy and 0.1 eV/step. For the high resolution data, the lowest binding-energy
C 1s peak (presumably, C-C/ C-H peak) was set at 285.0 eV and used as the reference for all of
the other elements. The curve fitting used a combination of Gaussian/Lorenzian function with the
Gaussian percentages being at 80% or higher.
The electrical conductivity was measured by a custom made conductivity cell at the
National Renewable Energy Laboratory (Golden, CO). A very small quantity of TRG (2-10 mg)
was dispersed in 10 mL of a 3 to 1 water to isopropanol solution via 20 minutes of bath
sonication followed by an additional 2 minutes of tip sonication to break any remaining clumps
of TRG. About 1 mL of the dispersion was placed on a copper stub at a time and dried at 40° C
in a drying oven (Despatch, model LBB1-23A-1). Subsequent layers of dispersed TRG were
developed in this way until copper stub is completely covered with TRG layers. The complete
coverage of the copper stub was obtained from ~8mL of pure TRG, and ~10mL of the f-TRG
samples. The copper stub covered with a sample is loaded carefully in the custom made
173
conductivity cell. The resistivity was measured using a multimeter (Wavetek 28XT,
Accuracy: ±1% + 0.1 Ohm).
Characterization of TRG
The evidence of the complete exfoliation of graphite oxide has been obtained by XRD
(Figure A.1a). The interlayer spacing in graphite has been observed to be 3.37Å from the single
only intrinsic 002-peak at  = 13.25. Due to the presence of polar groups on GO from oxidation
and because of the adsorbed water contents in GO, the 002-peak shifts to  = 5.7 (indicating the
interlayer d-spacing of 0.78Å). The increased d-spacing is a clear evidence of expansion of
graphite layers upon oxidation.
a) b)
TRG
GO
Graphite
2
5 10 15 20 25 30
Figure A.1 XRD spectra of graphite, graphite oxide (GO) and TRG (a), and TEM of pure TRG
(b)
In XRD of TRG, no interlayer spacing is observed indicating a complete exfoliation of
GO. This confirms the production of no stacked structure and that we are not dealing with
nanocrystalline graphite but with TRG. In addition, TEM image (Figure A.1b) evidences the
presence of overlapping layers of graphene. The transparent graphene sheets are clearly visible
174
confirming that GO has been successfully exfoliated. However, the elastic corrugations and the
scrolled or folded edges often result in different brightness in the surface of graphene 95.
XPS Spectra
Important insights into the reaction mechanism and the material structure come from the
core-level binding energies (BEs) obtained from XPS high resolution spectra. Figure A.2 shows
the overall survey data of the pure and f-TRG samples. Clear differences between pure and f-
TRG samples can be observed. The XPS spectra have been collected on dry TRG samples. In
TRG overall survey, there has been no Si and N detected. Usually, the Si 2p is detectable between
95-110 eV whereas N1s can be found between 400-407eV, depending upon the chemical
environment of the molecule. As compared with pure TRG, both the f-TRGp and f-TRGs show
the presence of Si2p and N1s originating from APTS, indicating the successful covalent
functionalization of TRG with APTS.
5000 3000 3000

C1s O1s O1s C1s
TRG C1s 2500 f-TRGs 2500
4000 f-TRGp
2000 2000
3000
Counts
Counts
Counts
1500 1500
Si2s Si2s
N1s Si2p
O1s 2000 N1s Si2p
1000 1000
1000 500 500

C12p
C12p
0 0 0
1000 900 800 700 600 500 400 300 200 100 0 1000 900 800 700 600 500 400 300 200 100 0 1000 900 800 700 600 500 400 300 200 100 0
Binding Energy, ev Binding Energy, ev Binding Energy, ev
Figure A.2 Overall XPS survey for the pure and f-TRG
The broad band in high resolution N1s spectra of f-TRGp and f-TRGs fitted with two
peaks at 399.95 eV (~400.0) and ~401.0 eV BE (Figure A.3). The lower BE peak is assigned to
aliphatic amine, imine or amide groups (R-NH2, C=N, N-C=O) and the higher energy peak is
assigned to positively charged quaternary nitrogen (R-NH3+). The latter peak might have resulted
from the amine protonation by acidic groups on the surface of TRG264.
175
1700
1450 f-TRGp N1s f-TRGs N1s
399.95 1500 399.95

1250
1300
1050
401.24 401.74
850 1100
650 900
450 700
396.5 398.5 400.5 402.5 404.5 396.5 398.5 400.5 402.5 404.5
Binding Energy, eV Binding Energy, eV
700
f-TRGs Si2p
600
500 102.9
103.5
400
300
200
100
0
95 98 101 104 107 110
Binding energy, eV
Figure A.3 N1s and S2p high resolution XPS scans for TRGp and TRGs
In Si2p region, the presence of bands confirms the grafting reaction of silane on TRG
(Figure A.3). The Si2p spectra of the two functionalized samples appear almost similar. The two
shoulders are observed exactly at the same position for the functionalized samples. One small
shoulder peak appears at 102.9 eV and the other at 103.5 eV. The peak at 103.5 eV is attributed
to the development of a strong cage-like Si-O4bonds114 or Si-O-Si structure due to lateral
polymerization, which affects the theoretical predictions of the product concentrations in
silanization reaction. However, due to anhydrous conditions during the reaction, the lateral
polymerization effects can be neglected108. The shoulder at 102.9 eV in both spectra can be
attributed to N bonding with the carbon surface. However, when deconvoluted, the two peaks
merge into one smooth peak at ~102-103 eV. This single peak contains the contributions from
Si2p3/2 and Si2p1/2 which cannot be resolved by non-monochromatic radiation as shown as inset
in Figure A.3 for Si in f-TRGp. And therefore the single deconvoluted peak around 103 eV BE is
176
assigned to Si-O bond. The relative contribution of each band in high resolution fitting is shown
in Table A.1.
Table A.1 High resolution fitting of functional groups in N1s and Si2p XPS scans
N1s peaks Si2p peaks

R-NH2 R-NH3+ N-C Si-O4
f-TRGp 399.95 401.24 102.9 103.5
f-TRGs 399.95 401.74 102.9 103.5
EDS analysis
The EDS analyses were performed on selected thin areas of graphene sheets (Table A.2).
However, EDS shows a qualitative picture of the attached moieties which can be taken as a
rough estimate for quantitative analysis.
Table A.2 Averaged EDS results
Atomic %
f-TRGp f-TRGs
C(K) 73.98 74.98
N(K) 4.53 4.10
O(K) 13.53 14.39
Si(K) 7.89 6.27
S(K) 0.04 0.14
Cl(K) 0.01 0.10
177
APPENDIX-B PE/OPE MISCIBLE BLENDS
-3
at 10 sec-1
Arrhenius Fit
-3.5
-4
lnη
-4.5
-5
-5.5
2 2.2 2.4 2.6 2.8
1000/T
Figure B.1 Arrhenius Plot of the viscosity of OPE (at shear rate = 10 1/s). Viscosity data was
obtained from performing steady state flow test on OPE after melting on the Peltier plate
130 120
120
90
∆Hc, J/g
110
Tc, C
60
100
30
90
80 0
0 10 20 30 40 50 60
OPE wt%
Figure B.2 Crystallization temperature and heat of crystallization of PE/OPE blends with
different OPE wt%.
178
16 (a)
50/50
14
12 70/30
Heat Flow, W/g 10 80/20
8
100/0
6
4
2
0
20 40 60 80 100 120 140
Temperature, C
Figure B.3 Thermograms of PE/OPE blends show the melting profiles of the blends. The inset
shows the melting profile of neat OPE
16
14
12
Heat Flow, W/g
10
2
20 40 60 80 100 120 140
Temprature, °C
Figure B.4 Melting profile of pure PE. This area has been used for calculation of melt enthalpy
and % crystallinity
179
4000 3500 3000 2500 2000 1500 1000 500

Wavenumbver, cm-1
Figure B.5 Complete FTIR spectrum of OPE
2.5
TPeak
2.0
dW/dT, %/°C
1.5
1.0
0.5
0.0
200 300 400 500 600

Temperature, °C
Figure B.6 Derivative of weight loss of PE/OPE Blends
180
Table B.1 Thermal stability of blends with different compositions
Tpeak Tonset Total

Blend T25% T50% T75% T95%
(°C) (°C) wt loss
100/0 473 442 454 467 480 493 98.9
90/10 478 449 453 470 478 490 99.2
80/20 478 444 449 468 480 491 99.4
70/30 467 428 434 459 470 483 98.6
60/40 471 426 427 456 472 486 99.1
50/50 467 417 416 450 468 483 98.9
0/100 460 407 390 445 465 483 99.8
The solid phase miscibility of OPE in PE was studied by WAXD. PE showed two main
prominent peaks at β ~ β1° and βγ.γ° corresponding to (110) and (β00), respectively (Figure B-
155, 157,
6). The oxidation of PE to OPE is known to break down higher molecular weight chains
160
. OPE exhibited the same peaks as those in PE with extra peaks above β ~γη°. Inclusion of
τPE in PE slightly shifts the β for (110) plane to lower value, but no other change was seen
with increasing OPE concentration. No distinguishable peaks were observed in PE/OPE blends
which indicated blend immiscibility. Thus, in the solid state, blends exhibited the complete
miscibility.
50/50
60/40
Intensity [a.u.]
70/30
80/20
90/10
OPE
PE
2
10 20 30 40 50 60 70
Figure B.7 WAXD patterns of neat PE, OPE and PE/OPE blends at 25°C with Y-offset
181
Figure B.8 Cross model fitting to different blend compositions at various temperatures
Table B.2 Cross model fitting parameters for PE/OPE Blends
ηo (Pa-s) τo (s) n
180° 160° 140° 130° 180° 160° 140° 130° 180° 160° 140° 130°
PE/OPE
100/0 1.01×104 1.35×104 1.88×104 1.01×104 0.51 0.63 0.78 0.82 0.63 0.64 0.66 0.66
3 3 3 4
90/10 6.21×10 8.49×10 9.85×10 1.09×10 0.60 0.90 0.73 0.74 0.57 0.56 0.60 0.61
80/20 2.81×103 2.87×103 3.38×103 3.95×103 0.23 0.23 0.20 0.24 0.57 0.56 0.58 0.57
70/30 1.23×103 1.43×103 1.72×103 1.81×103 0.13 0.14 0.16 0.21 0.54 0.55 0.56 0.51
60/40 6.09×102 7.17×102 8.25×102 7.47×102 0.08 0.10 0.12 0.14 0.58 0.57 0.55 0.49
50/50 1.29×102 1.21×102 1.41×102 1.00×102 0.02 0.02 0.03 0.02 0.85 0.73 0.54 0.61
182
6
10
5
10
4
10
G, Pa 10
3
2
10 100/0
1 90/10
10 80/20
0 70/30
10 60/40
-1 50/50
10
G, Pa
1 2 3 4 5 6
10 10 10 10 10 10
Figure B.9 Han plots for the blends
3.00
100/0
90/10
Horizontal shift factor, a T
2.50 80/20
70/30
60/40
2.00 50/50
1.50
1.00
0.50
0.00
100 110 120 130 140 150 160 170 180 190
Temperature, C
Figure B.10 Shift factor for time-temperature master curves for PE/OPE blends
183
1000000
1000000
100/0 90/10
100000
100000
10000
G', Pa
G', Pa
10000
1000
180 100 180

1000
160 160
140 10 140
130 130
100 1
0.1 1 10 100 1000 0.1 1 10 100 1000
Frequency, Hz Frequency, Hz
1000000 1000000
80/20 70/30
100000 100000
10000 10000
G', Pa
G', Pa
1000 1000
100 100
180 180
160 160
10 10
140 140
130 130
1 1
0.1 1 10 100 1000 0.1 1 10 100 1000
100000 100000
60/40 50/50
10000
10000
1000
G', Pa
G', Pa
1000
100
100
10
180 180
10 160 160
1
140 140
130 130
1 0.1
0.1 1 10 100 1000 0.01 0.1 1 10 100
Figure B.11 Time-temperature master curves for all blend compositions against the tested
temperatures
184
80
90
PE/OPE 90/10
80 70
180
70 160 60
60 140
delta, [ ]
delta, [ ]
50
130
50
40
40
30
30 180
20 160
20
140
10 10
PE/OPE 100/0 130
0 0
0.01 0.1 1 10 100 1000 0.1 1 10 100 1000
90 90
80 80
70 70
60
60
delta [ ]
50 delta [ ] 50
40
40
30
180 30
20 160 180
20
140 160
10 130 140
PE/OPE 80/20 10
PE/OPE 70/30
130
0
0.1 1 10 100 1000 0
0.1 1 10 100 1000
Frequency Frequency, Hz
90 90
80 80
70 70
60 60
delta [ ]
delta [ ]
50 50
40 40
30 30
180
180
20 20 160
160
140
10 140 10
130 PE/OPE 50/50
130 PE/OPE 60/40
0 0
0.1 1 10 100 1000 0.1 1.0 10.0 100.0
Figure B.12 Time-temperature master curves for all blend compositions against the tested
temperatures
185
APPENDIX-C PE/OPE/TRG AND PE/OPE/CB COMPOSITES
Graphite showed an intrinsic 00β diffraction peak at β ~ βθ.η°, corresponding to a d-
spacing of 3.37Å. The oxidation of graphite to GO shifted the 00β peak to β ~11.4°, and doubled
the interlayer spacing to a d-spacing of 7.8Å. It is worth mentioning that the 002 peak in graphite
was a narrow and high intensity peak, exhibiting ordered stacked structure, whereas in GO the
peak was broad and small in intensity. The broadness in 002 peak was attributed to intercalated
oxygen functionalities and water within the stacks of graphite resulted from oxidation. On the
other hand, no diffraction peak was observed in TRG, showing that the ordered structure was
completely dissolved, and GO was successfully converted into non-stacked, and unlayered
graphene by thermal exfoliation.
2=26.5°
(a)
d ~ 0.34 nm
2=11.4°
d ~ 0.78 nm
Graphite
GO
2
TRG
5 10 15 20 25 30
Figure C.1 XRD of graphite, graphite oxide and TRG
186
TRG, produced from exfoliating GO, typically contains some residual oxy-functional
groups, such as carboxylic, hydroxyl, and epoxy groups on the surface37. The FTIR spectrum of
TRG showed these functional groups in 800-2000 cm-1 IR range. The C-O-C stretching vibration
in epoxy groups was observed at 1018 cm-1, and -OH stretching vibration in hydroxyl groups
was seen at 1259 cm-1. A weak OH deformation vibration was also observed at ~1370 cm-1.
Typical carboxylic group stretching vibrations in C=O was observed at ~1770 cm-1. The region
marked with bracket in 1550-1680 cm-1 IR range was attributed to multiple stretching vibrations
from C=C graphitic carbon in graphene37.
(a) (b)
Transmission (a.u)
Transmission (a.u)
1767
Sp2 C=C 1259 1018
2000 1800 1600 1400 1200 1000 800

4000 3500 3000 2500 2000 1500 1000 500
Wavenumber, cm-1 Wavenumber, cm-1
TRG
OPE
Transmission (%)
OPE + TRG
(c)
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
Figure C.2 FTIR of TRG (a, b), and OPE+TRG (c).
187
The particle size distribution of CB particles showed that CB particles were in 300-500
nm, in agreement with TEM sizing. Moreover, the DLS of dilute TRG solution showed bimodal
distribution of TRG nanosheets: smaller sheets of size 600-800 nm, and some larger sheets of
size 2-5µm.
100 (f)
Intensity [a.u.]
CB TRG
80
60
40
20
0
2 3 4
10 10 10
Particle Size [nm]
Figure C.3 DLS of TRG and CB
Figure C.4 TEM of Carbon Black (CB)
Melt rheology of polymers, and polymer nanocomposites is considered central for
understanding processing properties, and structure-property relationships. Viscoelastic (VE)
188
response can be connected to the intrinsic behavior of polymers, inter-particle, and polymer-
particle interaction. In general, rheological properties depend on the input strain, whether in linear
or non-linear VE region. The dynamic strain sweep determines the strain dependent viscoelastic
response, and the linear viscoelastic (LVE) region. The frequency sweep experiments conducted
at a strain of = 1% (in δVE region) within the frequency range of 0.01 to 100 s -1 at 160°C are
shown in Figure C.5 (a, b). Due to plasticization with increasing τPE concentration, Gˊ and G˝,
and the complex viscosity, * decreased gradually in blends compared with neat PE. In polymer
dynamics, typically, Gˊ~ƒ2 and G˝~ƒ1 behavior is expected at low frequency by relaxed polymer
chains. Here, neat PE (PE/τPE 100/0) exhibited Gˊ~ƒ1.1 behavior, which relaxed to Gˊ~ƒ1.2 for
θ0/40 blends. Similarly, G˝~ƒ behavior changed from G˝~ƒ0.8 for 100/0 to G˝~ƒ0.9 for 60/40
blends. The increase in low frequency slope for 60/40 blend indicated formation of the relaxed
polymer chains, which was attributed to the plasticization, and miscibility effects of OPE in
PE210. Similar behavior was observed for * since * also decreased with increasing τPE
concentration. The three blend compositions showed excellent fit to the Cross model176 with zero
shear viscosity ( o) of 10,330 Pa-s for PE that decreased to 3,540 Pa-s for 80/20 and 1,499 Pa-s
for 60/40 blends. The Cross exponent, decreased from 0.64 for PE to 0.56 for 80/20 blends, and
slightly increased to 0.57 for 60/10 blends.
189
10
10 (a) 4 (b)
Closed-G
10 4 10 Cross Fit
Open-G
100/0
10
8
10
G G [Pa]
* [Pa-s]
6 80/20
100/0
10
10 0 3
10
o, Pa-s
4 60/40
10 80/20
2 100/0 10,330
10 80/20 3,540
60/40
60/40 1,499
2
10
, s , s
-2 -1 0 1 2 -2 -1 0 1 2
10 10 10 -1 10 10 10 10 10 -1 10 10
Figure C.5 Rheological properties of PE/OPE Blends: (a) shear and loss moduli vs frequency,
and (b) complex viscosity profiles as a function of blend composition at 160°C. (100/0 circles;
80/20 upper triangles; 60/40 lower triangles). Pre-factors in (a) were used to shift G′~ƒ curves
vertically for clarity.
Complex Viscosity, *, Pa-s
6 5
10 10
(a) (b) PE
Shear Modulus, G , Pa
0.5
5
10 1
2.5
4.3
4 6.5
10 4 10
PE 10
0.5
3
10 1
2.5
4.3
2 6.5
10 10
3
10
1
10 -3
Frequency, , Hz Frequency, , Hz
-2 -1 0 1 2
10 10 10 10 10 10 10
-3
10
-2
10
-1
10
0
10
1
10
2
6
5
10 10
PE/OPE 80/20
(c)
(d) CB 0.55 wt%

5 CB 1.16 wt%
10 CB 2.57 wt%
4
CB 4.3 wt%
4 10 CB 10 wt%
10
3
10 PE/OPE 80/20 3
CB 0.55 wt% 10
CB 1.16 wt%
2
10 CB 2.57 wt%
CB 4.3 wt%
CB 10 wt%
1 2
10 -3 10 -3
-2 -1 0 1 2 -2 -1 0 1 2
10 10 10 10 10 10 10 10 10 10 10 10
Figure C.6 Rheological data of CB-filler composites
190
6 4
10 10
PE/OPE 60/40
(e) (f) CB 0.55 wt%
5 CB 1.16 wt%
10
CB 2.57 wt%
CB 4.3 wt%
4
10
3 3
10 10
2
10 PE/OPE 60/40
CB 0.55 wt%
1 CB 1.16 wt%
10 CB 2.57 wt%
CB 4.3 wt%
0 2
10 -3 10 -3
-2 -1 0 1 2 -2 -1 0 1 2
10 10 10 10 10 10 10 10 10 10 10 10
Figure C.6 Continued
5
10
4 Pure PE
8x10 PE/TRG 1 wt%

4
6x10
4
4x10
4
2x10
-2 -1 0 1 2
Strain, , %
10 10 10 10 10
Figure C.7 Representative strain sweep on PE/TRG nanocomposites at 160°C. Arrows point out
the limit of linearity used for scaling argument
191
4.0 3.3
PE/TRG
80/20/TRG
3.1
decaying exponent, α
3.5 60/40/TRG
decaying exponent, α
2.9
3.0
2.7
2.5
2.5
3.0
2.0
2.5
2.3
2.0 PE/CB
1.5 1.5
80/20/CB
2.1
1.0
0 0.1 0.2 0.3 0.4 0.5 60/40/CB
1.0 1.9
0 1 2 3 4 5 6 0 2 4 6 8 10 12
TRG wt% CB wt%
Figure C.8 Power law decaying exponent for TRG-filled nanocomposites, and CB-filled
composite, obtained from SAXS I ~ q log-log plot
2
10
1
10
10
0 1
I(q) [a.u.]
10
I(q) [a.u.]
-1 0.1
10
-2 PE/CB 0.5
10 0.01
PE/CB 1.0 80/20/CB 0.55
PE/CB 2.5 80/20/CB 2.57
-3
10 PE/CB 4.3 80/20/CB 4.3
0.001
PE/CB 6.5 80/20/CB 6.58
-4 PE/CB 10 80/20/CB 10
10
9 2 3 4 5 6 7 8 9 2 3 0.0001
0.01 0.1 9 2 3 4 5 6 7 8 9 2 3
0.01 0.1
q [1/Å] q [1/Å]
60/40/CB 0.55
10 60/40/CB 1.16
60/40/CB 2.57
60/40/CB 4.3
1 60/40/CB 6.58
60/40/CB 10
I [q]
0.1
0.01
0.001
9 2 3 4 5 6 7 8 9 2 3
0.01 0.1
q [1/Å]
Figure C.9 SAXS patterns for CB-filled composites
192
I(q)xq [a.u.]
wt%
t%
1
2
5w
TRG
TRG
/4 0
PE 60
PE/O
0.05 0.10 0.15 0.20

q [1/Å]
Figure C.10 Representative Kratky plot for SAXS data
100 (a) Mass Retained, % 100 (b)

Mass Retained, %
80 80
60 60
40 40
80/20
PE 20
20
PE/TRG 5 wt % 80/20/TRG 5 wt%
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature, C Temperature, C
100 (c) 100 (d)

Mass Retained, %
Mass Retained, %
80 80
60 60
40 40
60/40 PE
20 20
60/40/TRG 5 wt% PE/CB 10 wt%
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
100 (e) 100 (f)

Mass Retained, %
80
Mass Retained, %
80
60 60
40 40
20 80/20 20
60/40
80/20/CB 10 wt% 60/40/CB 10 wt%
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Figure C.11 Thermal stability of TRG-filled, and CB-filled composites
193
1.E+08 1.E+08
Breakage Strain, % Breakage Strain, % Breakage Stress, Pa
(a) (b)
Breakage Stress, Pa
1.E+07 1.E+07
1.E+06 1.E+06
1.E+05 1.E+05
1.E+04 1.E+04
1.E+03 1.E+03
1.E+02 1.E+02
1.E+01 1.E+01
1.E+00 1.E+00
0.03 0.07 0.16 0.5 1 3 5 0.03 0.07 0.16 0.42 1 2 3 5
1.E+08
(c) Breakage Strain, % Breakage Stress, Pa
1.E+07
1.E+06
1.E+05
1.E+04
1.E+03
1.E+02
1.E+01
1.E+00
0.03 0.07 0.16 0.42 1 3 5
Figure C.12 Strain at break and breakage stress of PE/TRG (a), 80/20/TRG, and 60/40/TRG (c)
nanocomposites
194
1.E+08 1.E+08
(b) Breakage Strain, % Breakage Stress, Pa
(a) Breakage Strain, % Breakage Stress, Pa
1.E+07 1.E+07
1.E+06 1.E+06
1.E+05 1.E+05
1.E+04 1.E+04
1.E+03 1.E+03
1.E+02 1.E+02
1.E+01 1.E+01
1.E+00 1.E+00
0.5 1 2.5 4.3 6.5 10 0.55 2.57 4.33 6.58 10
1.E+08
(c) Breakage Strain, % Breakage Stress, Pa
1.E+07
1.E+06
1.E+05
1.E+04
1.E+03
1.E+02
1.E+01
1.E+00
0.55 1.16 2.57 4.33 6.58 10
Figure C.13 Strain at break and breakage stress of PE/CB (a), 80/20/CB (b), and 60/40/CB (c)
composites
195
5.0
PE/TRG
80/20/TRG
4.0 60/40/TRG
3.0
Ec/Em
2.0
1.0
0.0
0 1 2 3 4 5
CB vol%
Figure C.14 Young's modulus of CB-filled composites, normalized by matrix moduli. Straight
lines are linear fit to experimental data with intercept 1.
0
10
-2
PE/CB
10
-4
60/40/CB
10
 [S/cm]
-6
10 10
-1
-8 -3 ~3.0
10 10
10 ~3.4
-10 -5
10 80/20/CB
-7 ~2.4
-12 10 -1
10 10 10
0
10
1
-14
W-Wp
10
0 3 6 9 12
CB wt%
Figure C.15 Electrical conductivity of CB-filled composites. Inset shows the power law fit to the
experimental data
196

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STRUCTURE-PROPERTY RELATIONSHIPS IN GRAPHENE/POLYMER

All rights reserved

Graphene’s unique combination of excellent electrical, thermal, and mechanical

properties can provide multi-functional reinforcement for polymer nanocomposites. However,

nanocomposites and develop processing-structure-property relationships.

crystallinity. In addition, the miscibility of OPE in PE substantially reduced the viscosity of

Using thermally reduced graphene (TRG) produced by simultaneous thermal exfoliation

and reduction of graphite oxide, electrically conductive nanocomposites were manufactured by

percolations decreased substantially to 0.3 and 0.13 vol% of TRG in PE/OPE/TRG

of only mass fractals.

manufacturing electrically conductive PE nanocomposites. Smaller fractals were observed at

lower CB concentration whereas increasing CB concentration produced large CB agglomerates

ABSTRACT ................................................................................................................................ iii

LIST OF FIGURES ....................................................................................................................... ix

LIST OF TABLES .........................................................................................................................xv

ACKNOWLEDGEMENT ........................................................................................................... xvi

CHAPTER-1 INTRODUCTION TO POLYMER NANOCOMPOSITES ...................................1

1.1. Polymer Nanocomposites ....................................................................................... 1

1.2. Conductive Nanocomposites .................................................................................. 3

1.3. Graphene ................................................................................................................. 6

1.3.1. Graphene/Polymer Nanocomposites ......................................................... 10

1.3.2. Dispersion of Graphene in Polymers: Issues and Answers ...................... 12

1.4. Nanocomposites Characterization ........................................................................ 17

1.4.1. Melt Rheology .......................................................................................... 17

1.4.2. Small Angle X-Ray Scattering (SAXS) .................................................... 20

1.5. Thesis Overview ................................................................................................... 22

CHAPTER-2 GRAPHENE: SYNTHESIS AND CHARACTERIZATION ...............................25

2.1. Thermally Reduced Graphene (TRG) ................................................................... 25

2.1.1. Introduction ............................................................................................... 25

2.1.2. Experimental Details ................................................................................. 27

2.1.3. Results and Discussion ............................................................................. 29

2.1.4. Summary ................................................................................................... 33

2.2. Graphene Nanoplatelets (GnP) ............................................................................. 34

3.1 Introduction ........................................................................................................... 36

3.2 Experimental Details ............................................................................................. 38

3.2.1 Materials ................................................................................................... 38

3.2.2 Preparation of TRG ................................................................................... 39

3.2.3 Silylation Reaction .................................................................................... 39

3.2.4 Characterization ........................................................................................ 40

3.3 Results and Discussion ......................................................................................... 41

3.3.1 Chemical Analysis .................................................................................... 41

3.3.2 Morphological Analysis ............................................................................ 50

3.3.3 Thermal Stability and Conductivity .......................................................... 54

CHAPTER-4 SYNTHESIS AND CHARACTERIZATION OF

4.1 Introduction ........................................................................................................... 58

4.2 Experimental ......................................................................................................... 60

4.2.1 Materials ................................................................................................... 60

4.2.2 Preparation of Blends ................................................................................ 61

4.2.3 Characterization ........................................................................................ 61

4.3 Results and Discussion ......................................................................................... 63

4.3.1 Miscibility, Phase Behavior and Thermal properties ................................ 63

4.3.2 Melt Rheological Analysis ........................................................................ 74

4.3.3 Mechanical Properties ............................................................................... 79

CHAPTER-5 PROCESSABLE CONDUCTIVE GRAPHENE/POLYETHYLENE

5.1 Introduction ........................................................................................................... 85

5.2 Experimental Details ............................................................................................. 88

5.2.1 Materials ................................................................................................... 88

5.2.2 Synthesis of TRG ...................................................................................... 89

5.2.3 Preparation of Composites ........................................................................ 89

5.2.4 Characterization ........................................................................................ 90

5.3 Result and Discussion ........................................................................................... 92

5.3.1 Characterization of TRG and CB .............................................................. 92

5.3.2 Melt Rheological Analysis ........................................................................ 93

5.3.3 SAXS-Based Microstructure .................................................................. 104