Polymer 52 (2011) 1837e1846

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Polymer
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Graphene/polyethylene nanocomposites: Effect of polyethylene functionalization

and blending methods
Hyunwoo Kim a,1, Shingo Kobayashi b, Mohd A. AbdurRahim c, Minglun J. Zhang a, Albina Khusainova a, 2,
Marc A. Hillmyer b, Ahmed A. Abdala c, **, Christopher W. Macosko a, *
a
Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN 55455-0331, USA
b
Department of Chemistry, University of Minnesota, Minneapolis, MN 55455-0431, USA
c
Chemical Engineering Program, The Petroleum Institute, United Arab Emirates

a r t i c l e i n f o a b s t r a c t

Article history: Since its recent successful isolation, graphene has attracted an enormous amount of scientific interest
Received 29 December 2010 due to its exceptional physical properties. Graphene incorporation can improve electrical and mechanical
Received in revised form properties of polymers including polyethylene (PE). However, the hydrophobic nature and low polarity of
9 February 2011
PE have made effective dispersion of nano-fillers difficult without compatibilization. Graphene was
Accepted 14 February 2011
Available online 23 February 2011
derived from graphite oxide (GO) via rapid thermal exfoliation and reduction. This thermally reduced
graphene oxide (TRG) was blended via melt and solvent blending with linear low density PE (LLDPE) and
its functionalized analogs (amine, nitrile and isocyanate) produced using a ring-opening metathesis
Keywords:
Polymer nanocomposites
polymerization (ROMP) strategy. TRG was well exfoliated in functionalized LLDPE while phase separated
Graphene morphology was observed in the un-modified LLDPE. Transmission electron micrographs showed that
Polyethylene solvent based blending more effectively dispersed these exfoliated carbon sheets than did melt com-
pounding. Tensile modulus was higher for composites with functionalized polyethylenes when solvent
blending was used. However, at less than 3 wt.% of TRG, electrical conductivity of the un-modified LLDPE
was higher than that of the functionalized ones. This may be due to phase segregation between graphene
and PE, and electrical percolation within the continuous filler-rich phase.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction Graphene is an atomically thin, 2-dimensional network of sp2-

Polyethylene (PE) is one of the most important commodity
polymers [1]. Within the PE family, linear low density PE (LLDPE) has
grown most rapidly [2] due to the good balance between rigidity and
strength, and more flexible processing compared to low density or
high density PE. As well as modifying the chain structure, mechan-
ical properties of PE can be improved by reinforcing with rigid nano-
particles. When graphitic carbons are incorporated, electrically and
thermally conductive polymer composites can be produced [3,4].
Electrically conductive PE has potential for applications such as
electromagnetic-reflective materials, static charge-dissipative
materials and semiconductor layers in high voltage cables.
* Corresponding author. Tel.: þ1 612 625 0092; fax: þ1 612 626 1686.
** Corresponding author. Tel.: þ971 2 607 5584.
E-mail addresses: aabdala@pi.ac.ae (A.A. Abdala), macosko@umn.edu
(C.W. Macosko).
1
Present address: The Dow Chemical Co., Midland, MI 48667, USA.
2
Present address: Synthetic Rubber Department, Institute of Polymers, Kazan
State Technological University, Russia.
hybridized carbons. One of the potential applications of graphene is
reinforcement for polymers. Significantly improved electrical,
mechanical and gas barrier properties of graphene/polymer nano-
composites have been reported [3,5e9]. Graphene can be derived
from naturally abundant, low cost graphite via a two step approach.
First graphite is converted to graphite oxide (GO) via strong acids
and oxidizing agents. Then GO is exfoliated by rapidly heating to
w1050
C [10]. The decomposition product, CO2, mechanically
splits apart GO layers bound by van der Waals forces [11], yielding
substantial volume expansion (100e300 times), very high surface
area (w1700 m2/g) and high electrical conductivity (10e20 S/cm) of
the produced sheets [10]. Residual oxygen groups on this thermally
reduced graphene oxide (TRG) improve interaction with polar
polymers, which leads to polymer composites with significant
increase in stiffness [9].
Although dispersion of graphene into polar polymers such as
poly(methyl methacrylate), polycarbonate, and poly(ethylene
naphthalate) has been very successful [3], dispersion of TRG in
relatively non-polar polymers has not been extensively explored.
Steurer et al. reported electrical percolation of TRG at w5 wt.% in

0032-3861/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2011.02.017
1838 H. Kim et al. / Polymer 52 (2011) 1837e1846
polypropylene (PP) [12] which is significantly higher than that for
many polar polymers. Transmission electron micrographs (TEM) by
Steurer et al. showed the presence of stacks with a significant
number of graphene layers. Their non-polar nature makes poly-
olefins incompatible with polar nano-fillers and their effective
dispersion is much more challenging. Miscibility between non-polar
polymers and organic nano-fillers can be improved by introducing
functional groups on the polymers. When maleic anhydride (MA)
grafted polyolefin was added as a compatibilizer, dispersion of
organically modified layered silicates [13e15] and expanded
graphite [16] could be enhanced significantly. Gopakumar and Page
[17] demonstrated that addition of maleated PP along with GO aided
dispersion of graphite in PP. In addition to post-polymerization
grafting of functional groups, functionalized polymers can be
prepared by polymerization of olefins and co-monomers with
functional groups. Seppala and colleagues used metallocene cata-
lysts to prepare PE functionalized with hydroxyl [18,19], carboxylic
acid [19] and silane [20] groups. They found these ethylene copol-
ymers to perform better than conventional compatibilizers like PE-
g-MA for dispersion of metal hydroxides and layered silicates in PE.
In addition to thermodynamic compatibility with polymers,
processing has a significant influence on the dispersion and prop-
erties of graphene reinforced polymer composites. In situ poly-
merization, melt compounding and solvent blending are the three
most commonly used blending techniques for polymer composites
with nano-particles including graphene [3]. Of the three common
methods, melt compounding is most economically and environ-
mentally viable since it does not require solvents and can be
performed using scalable melt extrusion. However, in situ poly-
merization generally results in more homogeneous particle
dispersion and more pronounced property enhancement for PE
[21,22] and other polymers [7] than melt compounding. Moreover,
melt blending is particularly difficult for TRG because of the
extremely low bulk density (w3e10 mg/cm3) which makes feeding
TRG into melt extruders more difficult. Another widely used com-
pounding method is solution blending. Due to facilitated material
transport in low viscosity solvents, facile particle dispersion is
expected. Nonetheless, due to the low solubility of polyolefins in
common solvents, blending must take place at elevated tempera-
ture in a limited number of solvents. To date, for polyolefin/gra-
phene nanocomposites, there have been no direct comparisons of
solvent blending and melt compounding in terms of particle
dispersion and properties of produced composites.
Here we report processing and properties of graphene/LLDPE
nanocomposites. Throughout this paper, we will discuss the effects
of PE functionalization and blending methods on graphene disper-
sion and composite properties. LLDPE’s with amino, cyano and
isocyanate functional groups were synthesized via ring-opening
metathesis polymerization (ROMP) of functionalized cyclooctene
and denoted as PE-f. The polymers were prepared using a strategy
based on our recently reported model synthesis of LLDPE via ROMP
of 5-hexyl substituted cyclooctene as a co-monomer [23]. This
method allows good control over the number of functional groups
along the polymer backbone and molecular weight. TRG sheets were
produced via rapid thermal expansion of GO. Dispersion of TRG in
un-modified and functionalized LLDPE is investigated via morpho-
logical characterization with TEM and electrical and mechanical
property measurements. Graphene was also dispersed into
commercial LLDPE analogs (Dow Affinity EG-8200 and MA grafted
EG-8200 (EG-8200-MA)) either in a solution or by melt extrusion.
Morphology and properties of solvent- and melt-processed TRG/EG-
8200 composites are compared. In order to ease the feeding of the
very low bulk density TRG into melt extruders, we have developed
a novel densification procedure for TRG. The effect of TRG densifi-
cation on TRG dispersion is also discussed.
2. Experimental
2.1. Materials
The functionalized LLDPEs containing cyano- [24,25] (PE-CN),
primary amino- (PE-NH2), and secondary amino- (PE-NHEt) groups
used in this study were synthesized through ring-opening metath-
esis copolymerization of cyclooctenes (COEs) having functional
groups (FCOE) and hexyl branches (HexCOE) [23], followed by
hydrogenation and deprotection reactions as shown in Scheme 1.
Synthesis and experimental details of the involved monomers and
polymers will be described in more detail in a forthcoming publi-
cation [26]. Values for hexyl branches and functional groups per
1000 backbone carbons, molecular weight of polymers, and
molecular weight distributions are summarized in Table 1. Molec-
ular characterization methods are described in Electronic
Supplementary Material 1 as well as the synthesis procedure for
isocyanate functionalized PE (PE-NCO) from PE-NH2.
Commercial LLDPE resins, Affinity EG-8200 was obtained from
the Dow Chemical Co. EG-8200 is a low density PE copolymer of
ethylene and octene (24 wt.% octene content, density: 0.87 g/cm3,
melt flow index: 5 g/10 min at 190
C) [27]. Its weight (Mw) and
number (Mn) averaged molecular weight are 201 and 67 kg/mol,
respectively. The same PE, but grafted with MA (EG-8200-MA,
0.8 wt.% MA content) was also provided by the Dow Chemical Co.
MA grafting was conducted in reactive extrusion with peroxides.
Mw and Mn of EG-8200-MA are 176 and 71 kg/mol, respectively. For
TRG synthesis, natural flake graphite (10 mesh, 99.9%) was
purchased from Alfa Aesar.
2.2. TRG synthesis and characterization
TRG was synthesized following the procedure reported by
Schniepp et al. [10], i.e. oxidation of graphite using Staudenmaier’s
method [28], followed by rapid pyrolysis in an oven preheated at
w1000
C. 5 g of graphite was placed in an ice-cooled flask con-
taining a mixture of H2SO4 (90 mL, 95e97%, J.T. Bakers) and HNO3
(45 mL, 65% Riedel-deHaen). Potassium chlorate (55 g, 99% Fluka)
was added slowly to the cold acid mixture. After the reaction pro-
ceeded for 96 h, the reaction was stopped by pouring the reaction
mixture into 5 L of de-ionized water followed by filtration (What-
man No.1 filter paper, Qualitative). The remaining GO was washed
with 5% hydrochloric acid (Riedel-deHaen) until no sulfite ions
were detected using a BaCl2 test. The mixture was then washed
with water until no chloride ions were detected by AgNO3. Graphite
Scheme 1. Synthesis of Functionalized PE.
 H. Kim et al. / Polymer 52 (2011) 1837e1846 1839

Table 1
Molecular characteristics of functionalized PEs.

Sample code Mna kg/mol Mw/Mna 1-Octene contentb Hexyl branches/1000 Functional groups/1000 Crystallinityc
mol% backbone carbonsb backbone carbonsb
PE-NH2 31.0 1.30 5.6 26.2 0.25 0.20
PE-NHEt 28.8 1.32 6.3 31.5 0.82 0.17
PE-CN 23.9 1.34 6.3 31.5 0.63d 0.19
PE-NCO NA NA 5.6 27.8 0.34e NA
PE 22.7 1.38 7.1 35.3 NA 0.18
a
Absolute molecular weight determined before the hydrogenation and deprotection reactions by size exclusion chromatography including multiangle laser light scattering
detector using tetrahydrofuran as an eluent at 30
C.
b
Measured in benzene-d6 at 75
C.
c
Determined by dividing the heat of fusion by 293 J/g [29].
d
Measured in tetrachloroethane-d2 at 100
C.
e
Observed as PE-NHCO-Imd (see Electronic Supplementary Material 1).

oxide was dried at 50
C in a vacuum oven overnight. 1 g of dried GO
was placed into a quartz tube with an inert gas inlet and outlet.
After purging the tube with N2 for 5 min, the tube was rapidly
inserted into a heated (w1000
C) tube furnace (Model 21100,
Barnstead Thermolyne) and maintained for 30 s. A densified form
of TRG (bulk density w100e200 mg/cm3) was made by dispersing
TRG in acetone (0.5 g TRG/100 mL acetone) followed by filtration
and drying in a vacuum oven at 60
C overnight. Throughout this
article, density of TRG is assumed to be 2.28 g/cm3, the density of
crystalline graphite [3].
Wide-angle X-ray diffractograms of graphite, GO, as-synthe-
sized and as-densified TRG powders were obtained using a Bruker-
AXS (SIEMENS) D5005 X-ray diffractometer (CuKa radiation, 45 kV
and 40 mA) in the 2q range of 5e40
at the scan rate of 0.02
/s.
operated in an accelerating voltage of 100 kV. We also used an
optical microscopy (Electronic Supplementary Material 6) to
investigate the macroscopic TRG dispersion in PE samples.
The degree of crystallinity of PE was determined by differential
scanning calorimetry (DSC, TA Instruments Q1000). 5e10 mg of
thin films was loaded into non-hermetic aluminum pans. Scanning
was performed from 100
C to 250
C at the rate of 10
C/min.
Degree of crystallinity was estimated by dividing the heat of fusion
calculated by integrating the area under the melting endotherms
located between 40 and 90
C using TA Universal Analysis software
by the heat of fusion value of 100% crystalline PE, 293 J/g [29].
dc surface resistance of the composite films was measured with
an 11-probe meter (PRS-801, Prostat). In order to ensure sample

2.3. Dispersion

TRG was dispersed into PE, PE-NH2, PE-NHEt, PE-CN and PE-NCO
in 1,2-dichlorobenzene (DCB). Up to 30 mg of TRG was stirred in
10 mL of DCB for up to 48 h at room temperature. Then w1.0 g of
polymer was added and temperature was raised up to 80
C. After
blending for 2 h, TRG/LLDPE mixtures in DCB were cast on a heated
glass plate at 80
C, which produced composite films containing
TRG at 0, 1.0, 3.0 and 5.0 wt.%. TRG was also blended into
commercial LLDPE resins, EG-8200 and EG-8200-MA using DCB to
yield 0, 0.5, 1.0, 2.0 and 3.0 wt.% samples. Blending procedure was
similar except higher temperatures were used: mixing was at
130e140
C in a refluxing DCB and 130
C for film casting
temperature. After film casting, solvent removal continued for 3 h
at 150
C and for 48 h at room temperature. Cast films were dried in
a vacuum oven at room temperature for 72 h.
EG-8200 and EG-8200-MA composites were also prepared via
melt compounding using a recirculating, vertical, twin screw extruder
(Microcompounder, DACA Instruments). TRG/polymer pre-blends
were vacuum dehydrated at room temperature then fed into DACA
compounder at 180
C. Note that for melt blending, the densified
version of TRG was mainly used since its higher bulk density allowed
easier feeding into the extruder. Compounding was conducted at 200
RPM for 8 min under nitrogen purge. Extrudates with 0, 1.0, 1.5, 2.0
and 3.0 wt.% TRG were processed into w 0.1 mm thick films by
compression molding at 250 kPa and 180
C before testing.

2.4. Composite characterization

Transmission electron microscopy (TEM) was used to investi-

gate the dispersion of TRG in different PE samples. Composite films
embedded in an epoxy matrix (TRA-BOND 2115, Tra-Con) were
microtomed (Leica Ultracut) at 90
C into 85e100 nm thick slices
using a diamond knife and transferred onto 400 mesh copper grids.
Micrographs were obtained using a JEOL 1210 electron microscope Fig. 1. Volume of w150 mg of (a) graphite, (b) GO, (c) TRG and (d) densified TRG.
1840
Fig. 2. Wide-angle X-ray diffraction patterns of (from top to bottom) graphite, GO, TRG
and densified TRG.
uniformity, geometric averages of the resistance measured from 3
to 4 different spots from each side of the films are reported.
Conductivity values measured from both sides of the composite
films were consistent implying sample uniformity.
Tensile stiffness of the composites was evaluated with Rheo-
metrics Solids Analyzer (RSA II, TA Instruments). 3e4 mm wide
strips cut from the solvent cast or compression molded films were
mounted between the film fixtures of RSA II. Tensile deformation at
Fig. 3. Films cast from DCB solutions of 1 wt.% TRG in (a, b) PE, (c) PE-NH2 and (d) PE-NCO.
H. Kim et al. / Polymer 52 (2011) 1837e1846
0.0005/s was applied to the specimen and static Young’s modulus
was determined from the slopes of stressestrain responses of the
composites at 0.5e1.5 %strain.
3. Results and discussion
Complete exfoliation of GO through rapid pyrolysis was
confirmed by X-ray diffraction. TEM was used to probe dispersion
of TRG sheets solvent and melt blended in ROMP synthesized LLDPE
and commercial EG-8200. TRG filled composites were tested for
electrical conductivity and tensile stiffness.
3.1. Exfoliation of graphitic derivatives
Fig. 1 compares the apparent volume of 150 mg of natural flake
graphite, GO, TRG and densified TRG. While graphite (Fig. 1a) does
not show appreciable volume change through oxidation to GO
(Fig. 1b), GO expands more than w100 times during rapid thermal
treatment (Fig. 1c). This low bulk density (3e10 mg/cm3) of TRG
impeded feeding into the melt compounder. However, after
densification (100e200 mg/cm3), TRG possesses a notably reduced
volume (Fig. 1d) which eases TRG handling especially during melt
processing.
Wide-angle X-ray diffraction patterns of graphite, GO and TRG
(as-synthesized and as-densified) are provided in Fig. 2. Upon
oxidation, X-ray diffraction of graphite located at 2q ¼ 26.4
shifts
to 2q w 11.2
, indicating increase of the interlayer spacing from 0.34
to w0.72 nm due to the incorporation of the oxygen functional
 H. Kim et al. / Polymer 52 (2011) 1837e1846
groups and the intercalation of water molecules. Unlike graphite
and GO, TRG does not display any prominent diffraction in
2q ¼ 5e40
in their X-ray diffractograms. Lack of X-ray diffraction
signifies loss of the periodic order in GO upon layer exfoliation. The
diffraction pattern was not significantly affected by densification,
which implies the exfoliated structure remained intact. However,
a weak reflection centered at 2q ¼ 23 w 25
from the densified TRG
may stem from a presence of a small fraction of restacked graphene
or “turbostratic” graphite [30]. Rare occurrence of sheet restacking
was confirmed by TEM analysis of densified TRG embedded in PE
(Electronic Supplementary Material 2).
3.2. Dispersion of graphene into the PE matrix
TEM of the different composites reveals the morphology of TRG
dispersed in PE. Based on TEM micrographs, the role of PE func-
tionalization and use of different blending routes in TRG dispersion
is discussed in the next few sections.
3.2.1. Solvent cast films
Optical images of solvent cast PE, PE-NH2 and PE-NCO films
containing 1 wt.% TRG are shown in Fig. 3. Strong segregation of
TRG in transparent PE is evident in the case of the PE composite
(Fig. 3a and Fig. S6). This phase separated morphology appears to
have been induced during solvent evaporation and may be attrib-
uted to poor miscibility between oxygen functionalized graphene
and the un-modified PE. Interestingly, graphene-rich domains
seem inter-connected throughout the film as shown in the higher
magnification image (Fig. 3b). Surface segregation of graphene
Fig. 4. TEM micrographs of solvent blended 1 wt.% TRG in (a, b) PE and (c, d) PE-NH2.
1841
aggregates in un-functionalized PE was not observed. Macroscopic
distribution of graphene is significantly improved in PE-NH2 and
PE-NCO (Fig. 3c and d). This substantiates compatibilization of the
blends by PE functionalization.
3.2.2. PE functionalization
TEM micrographs of 1 wt.% TRG solvent blended with PE and PE-
NH2 are compared in Fig. 4. Micrographs of PE-NHEt, PE-CN and PE-
NCO composites can be found in Electronic Supplementary
Material 3. Consistent with visual observation of the cast films
(Fig. 3), TRG is not homogeneously dispersed into the un-modified
PE matrix (Fig. 4a and b). Apparent localization of TRG aggregates
signifies phase separation due to intrinsic incompatibility. In
contrast, PE modification with amine functionality enhances the
dispersion of the thin TRG sheets into the PE matrix as shown by
the uniform dispersion of TRG in the matrix, Fig. 4c and d. Similar
exfoliated morphology of TRG can be seen in the TEM images of PE-
NHEt, PE-CN and PE-NCO composites (Fig. S3). Improved graphene
dispersion via PE functionalization is also confirmed by comparing
solvent mixed TRG dispersion in EG-8200 and EG-8200-MA. While
morphology of TRG in the EG-8200 matrix can be described as
partially exfoliated with significant occurrence of graphene aggre-
gation (Fig. 5a and b), TRG is well dispersed throughout the EG-
8200-MA matrix (Fig. 5c and d).
3.2.3. Blending methods
TRG was incorporated into EG-8200 via solvent blending and
also melt compounding. It can be inferred from the TEM analysis
that state of dispersion of TRG may differ significantly depending
1842 H. Kim et al. / Polymer 52 (2011) 1837e1846
Fig. 5. Morphology of 1 wt.% TRG in (a, b) EG-8200 and (c, d) EG-8200-MA prepared by solvent blending.
on the blending route. Electron micrographs of melt blended EG-
8200 and EG-8200-MA containing 1 wt.% TRG are provided in Fig. 6.
Unlike fully isolated, single graphene sheets blended in solution
(Fig. 5a and b), complete exfoliation is rarely observed for the melt
compounded TRG/EG-8200 (Fig. 6a and b). In Fig. 6a and b, areas
highly concentrated with graphene stacks are distinguished from
regions which lack graphene suggesting local concentration fluc-
tuation. In melt compounding, graphene dispersion could not be
improved by MA grafting on PE. In contrast to TRG layers well
exfoliated in solvent blended EG-8200-MA (Fig. 5c and d), melt-
processed samples appear predominantly phase separated (Fig. 6c
and d). Steady increase in melt viscoelasticity during annealing at
180
C (Electronic Supplementary Material 4) implies possible
chain cross-linking of EG-8200-MA in a melt state, which can make
dispersion more difficult and also cause phase separation. Note the
morphology of melt compounded TRG/EG-8200 is distinguished
from that of solvent blended TRG in un-functionalized PE. While
TRG aggregates formed after solvent mixing with PE or EG-8200
show some degree of inter-particle connectivity (Figs. 4 and 5a),
aggregates in melt blended EG-8200 are mostly isolated from one
another (Fig. 6). This morphological difference may explain differ-
ence in electrical conductivity trends as discussed in Section 3.3.1.
Better dispersion via solvent blending agrees with our previous
observation for polyurethane/TRG composites [7]. In addition to the
intrinsic low miscibility between PE and TRG, limited material
diffusion and compressive flow fields in high viscosity polymer
melts may lead to poor macroscopic distribution in melt com-
pounded samples. It should also be noted that TRG was melt
blended with PE after pre-densification. While we did not observe
significantly improved dispersion when as-synthesized TRG was
used, stacks formed during densification could not be fully sepa-
rated even by ultra-sonication in DCB, a good solvent (Electronic
Supplementary Material 2).
3.3. Properties of TRG/LLDPE composites
PE can become electrically conductive and mechanically robust
by reinforcing with graphene. Results are summarized in Table 2
(TRG/PE) and Table 3 (TRG/EG-8200). Dispersion of TRG in PE
inferred from property enhancement correlated with morpholog-
ical characterization by TEM. For weight to volume fraction
conversion, density data provided in the Experimental section
(TRG: 2.28 g/cm3, PE: 0.87 g/cm3) are used.
3.3.1. Electrical conductivity
Sample spanning pathways for electrical conduction can be
formed via percolation of graphene in the polymer matrix. Surface
resistance of 0.4 vol % (1.0 wt.%) TRG in PE and in functionalized PE
is compared in Table 2 and Fig. 7a. It is surprising that resistance of
TRG/PE is lower than that of other composites based on function-
alized PE despite the high degree of phase separation observed by
visual observation (Fig. 3 and Fig. S6) and TEM (Fig. 4). PE-NH2, PE-
NHEt and PE-NCO composites, which all showed good graphene
dispersion, did not become electrically conductive at 1 wt.% of TRG
as their resistance remained as high as that of un-filled PE
(1012e1013 Ohm). Fig. 7b summarizes surface resistance of TRG
filled PE and PE-NH2 as a function of TRG concentration. Conduc-
tivity of PE changes sharply even below 0.4 vol % (1.0 wt.%) of TRG.
 H. Kim et al. / Polymer 52 (2011) 1837e1846 1843

Fig. 6. TEM images of 1 wt.% TRG with (a, b) EG-8200 and (c, d) EG-8200-MA prepared by melt compounding.

However, for PE-NH2, a more gradual decrease in resistance sets in
only above 0.4 vol %.
Similar rather negative influence of PE functionalization on
conductivity improvement can be detected from EG-8200
composites. In Fig. 8, a greater decrease in electrical resistance by
TRG incorporation was achieved with EG-8200 than EG-8200-MA
for solvent blended samples. Even with seemingly better dispersion
from TEM analysis, TRG in EG-8200-MA resulted in higher electrical
1.2 vol % (3.0 wt.%) for TRG/EG-8200. Electrical percolation of TRG at
2e3 wt.% in melt blended EG-8200 is comparable to percolation
threshold of the same samples determined using melt rheology
(Electronic Supplementary Material 4).
Table 3
Properties of TRG/EG-8200 composites.

resistance than for TRG in EG-8200 throughout the entire Sample Surface Tensile
concentration. For melt blended samples, TRG/EG-8200-MA did not resistance modulus
Matrix TRG loading
(Ohm) (MPa)
become electrically conductive up to 1.2 vol % (3.0 wt.%) while
wt.% vol %
appreciable decrease in resistance occurred between 0.8 (2.0) and
EG-8200 Solvent blend 0 0 4.8  1011 6.2  2.1
0.5 0.2 1.7  1010 7.0  1.7
Table 2 1.0 0.4 1.4  106 10.0  0.7
Properties of TRG/PE composites. 2.0 0.8 1.8  105 11.7  0.3
3.0 1.2 1.4  104 14.1  0.6
Sample Surface resistance Tensile modulus
Melt blend 0 0 2.3  1012 7.1  0.8
(Ohm) (MPa)
Matrix TRG loading 1.0 0.4 5.1  1011 9.6  0.9
1.5 0.6 e 9.6  0.2
wt.% vol % 2.0 0.8 3.5  1011 10.1  0.2
PE 0 0 2.5  1013 5.6  0.4 3.0 1.2 1.2  107 11.4  0.9
1.0 0.4 2.0  108 5.1  0.4 EG-8200-MA Solvent blend 0 0 2.3  1012 7.0  0.2
3.0 1.2 4.0  106 7.1  0.7 0.5 0.2 1.6  1010 6.8  0.8
5.0 2.0 1.0  105 9.0  0.3 1.0 0.4 4.7  109 12.6  1.1
PE-NH2 0 0 9.1  1012 6.0  0.6 2.0 0.8 4.3  106 15.2  0.9
1.0 0.4 1.7  1012 7.7  2.0 3.0 1.2 1.1  106 17.3  1.2
3.0 1.2 2.3  108 7.9  0.8 Melt blend 0 0 6.0  1012 6.8  0.1
5.0 2.0 1.2  106 10.1  0.3 1.0 0.4 1.3  1013 9.9  1.2
PE-NHEt 1.0 0.4 3.0  1012 7.0  0.4 1.5 0.6 2.8  1011 11.5  0.2
PE-CN 1.0 0.4 1.6  109 6.2  0.5 2.0 0.8 6.0  1011 11.4  0.4
PE-NCO 1.0 0.4 1.0  1012 9.7  0.5 3.0 1.2 3.9  1012 12.3  0.2
1844 H. Kim et al. / Polymer 52 (2011) 1837e1846
Fig. 7. dc surface resistance of (a) 0.4 vol % TRG in PE, PE-CN, PE-NH2, PE-NHEt and PE-
NCO and (b) PE and PE-NH2 at different TRG concentration.
Fig. 8 also implies that conductivity increase by graphene
depends on how composites are produced. While melt blended
composites do not display notably improved electrical conductivity
nearly up to 1.2 vol % TRG loading, solvent blended TRG can reduce
the surface resistance of EG-8200 and EG-8200-MA at even as low
as 0.2 vol % (0.5 wt.%). This agrees with the TEM observation which
indicated better TRG dispersion via solvent than melt blending.
Note that TRG is also poorly dispersed in un-functionalized PE via
solvents but effectively improved electrical conductivity even
below 0.4 vol % (Fig. 7). Phase separation of TRG during solvent
removal formed an inter-connected network (Figs. 3b, 4a and 5a)
for electrical conduction while TRG aggregates in melt com-
pounded samples are mostly isolated from one another (Fig. 6).
3.3.2. Tensile modulus
Tensile properties of many polymers [5] have been enhanced
significantly by dispersion of TRG. Tensile moduli, measured with
Fig. 8. dc surface resistance of melt blended and solvent mixed TRG/EG-8200 and TRG/
EG-8200-MA composites.
Fig. 9. Tensile modulus of solvent blended 0.4 vol % TRG in PE and functionalized PE.
RSA II, of 0.4 vol % (1.0 wt.%) TRG in PE and functionalized PE are
shown in Table 2 and Fig. 9. Even at the same filler concentration,
the modulus of the TRG composites differs considerably depending
on TRG-matrix compatibility. Although they differ in degree of
functionalization, the highest modulus was achieved with PE-NCO
(9.7 MPa) and functionalization with eNH2 also led to a consider-
able modulus increase (7.7 MPa). The modulus of 0.4 vol % TRG/PE,
5.1 MPa, is even lower than that of neat PE, 5.6 MPa, possibly due to
inhomogeneous dispersion of graphene (Fig. 3a and b), although its
electrical conductivity was improved significantly (Fig. 7). Note that
stiffness of base PE polymer was not affected by functionalization.
Young’s modulus of PE-NH2 is 6.0 MPa which is close to that of PE
(see Table 2).
Young’s moduli of TRG reinforced PE and PE-NH2 at higher TRG
volume fraction are given in Table 2. Consistent with the prediction
of better dispersion by the TEM images (Fig. 4), TRG sheets
dispersed in PE-NH2 led to slightly higher increase in stiffness than
those in PE.
Tensile moduli of solvent and melt blended TRG/EG-8200 and
TRG/EG-8200-MA are listed in Table 3 and data normalized by
modulus of the un-filled polymers are plotted in Fig. 10. Irrespective
of blending method and matrix type, TRG is capable of stiffening
EG-8200 significantly. PE filled with 1.2 vol % (3.0 wt.%) TRG is at
Fig. 10. Tensile modulus, normalized by modulus E0 of un-filled polymer, of solvent
blended or melt blended TRG/EG-8200 and TRG/EG-8200-MA. Straight trend lines
based on the Mori and Tanaka model [31] and particle aspect ratio Af are also shown.
 H. Kim et al. / Polymer 52 (2011) 1837e1846
least 60% stiffer than that of neat PE. In agreement with TEM
analysis and electrical conductivity improvements, higher modulus
increase is observed from solvent blended composites than melt
compounded ones for both EG-8200 and EG-8200-MA. However,
despite less pronounced conductivity increase for TRG/EG-8200-
MA, MA grafting yielded higher modulus increase for both melt and
solvent blended TRG/EG-8200. Improved graphene dispersion and
interfacial load transfer from better adhesion between TRG and PE
might help increasing tensile modulus further. It should be also
noted for EG-8200-MA, chain cross-linking might influence the
mechanical properties especially for melt blended samples.
Increase in polymer modulus by rigid ellipsoidal nano-particles
including graphene can be modeled with micromechanical
composite theories [5e7]. Fitting based on an effective medium
model proposed by Mori and Tanaka [31], and later adopted by
Tandon and Weng [32] was applied to the modulus increase versus
TRG concentration, and effective aspect ratios Af (ratio of particle
diameter to thickness) of dispersed graphene were estimated. The
fitting and aspect ratio estimation for TRG in solvent and melt
Fig. 11. (a) Phase separated and (b) randomly distributed morphology of graphene/
polymer nanocomposites.
1845
blended PE and PE-MA are shown in Fig. 10. The model assumes
polymers filled with mono-dispersed, ellipsoids perfectly aligned in
tensile direction. Formulas and material parameters used can be
found in Electronic Supplementary Material 5.
Mechanical properties of semi-crystalline polymers including
PE can be affected by degree of crystallinity. Crystallinity in LLDPE
and TRG composites was estimated by DSC measurements. Crys-
tallinity of EG-8200 was w16% for both solvent cast and melt
pressed films and was not appreciably influenced by either gra-
phene dispersion or functionalization with MA. PE has slightly
higher crystallinity (w18%) and it is even higher (20%) for the eNH2
functionalized version. %Crystallinity, and number of hexyl
branches and functional groups determined by 1H NMR for func-
tionalized PE are summarized in Table 1. Higher crystallinity in the
PE-NH2 can be attributed to less hexa-alkyl side branches
compared to PE (5.6 versus 7.1 mol% of 1-octene units relative to
ethylene units). Nonetheless, degree of crystallinity remained
nearly unchanged after TRG addition, implying that mechanical
reinforcement with graphene is solely responsible for the improved
tensile stiffness of the composites.
3.3.3. Influence of graphene segregation
Although TRG seemed poorly dispersed in un-functionalized
LLDPE, it improved electrically conductivity more effectively than
that in functionalized matrices. As noted in Section 3.2.1, segrega-
tion of graphene to the film surface during solvent evaporation was
not observed. Therefore, local enhancement of electrical conduc-
tivity due to surface segregation may not be the case. Note despite
strong segregation between graphene and PE, graphene aggregates
formed a co-continuous structure in solvent cast PE films (Fig. 3b).
If TRG/PE phase segregation driven by intrinsic incompatibility
leads to a bi-continuous structure depicted in Fig. 11a, a sample
spanning conductive network can form exclusively in the gra-
phene-rich phase at small volume fraction of TRG. Otherwise
percolation may require considerably higher incorporation of more
homogeneously distributed graphene as illustrated in Fig. 11b. In
fact, morphology of graphene dispersed in PE (Figs. 3b and 4a, see
also Fig. S6 in Electronic Supplementary Material) and EG-8200
(Fig. 5a) resembles the structure depicted in Fig. 11a.
4. Conclusions
In this study, we attempted to disperse thermally reduced gra-
phene oxide (TRG) into LLDPE via solvent blending and melt
compounding. Dispersion of this functionalized graphene can be
difficult when the matrix is as highly hydrophobic and non-polar as
polyethylene. In order to improve miscibility with TRG, LLDPE
functionalized with eNH2, eNHEt, eCN and eNCO groups were
synthesized using a ROMP strategy. TRG was blended into the PE
matrices in DCB and composite films were obtained by solvent
casting. Graphene composites were also produced from commer-
cial LLDPE analogs (EG-8200 and EG-8200-MA) using solvent
blending and also via melt compounding.
Visual observation of cast films and electron microscopy
revealed more homogeneous distribution of exfoliated carbon
sheets in functionalized PE than un-functionalized ones implying
PE compatibilization helped dispersion. Also, solvent blending
yielded better dispersion than melt compounding, which agrees
with our previous observations on polyurethane/TRG composites
[7]. Regardless of blending methods, graphene increased the tensile
modulus of functionalized LLDPE more than that of un-modified
one. Modulus increased more for solvent mixed blends than when
they were melt blended. However, surprisingly electrical conduc-
tivity enhancement was more pronounced for TRG/PE composites
than TRG in functionalized PE. For example, although TRG/PE-NH2
1846 H. Kim et al. / Polymer 52 (2011) 1837e1846

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