Influence of the Graphite Type on the Synthesis of Polypropylene/

Graphene Nanocomposites
Marc eo A. Milani,
1
Raul Quijada,
2
Nara R. S. Basso,
3
Ana P. Graebin,
3
Griselda B. Galland
1
1
Instituto de Qu mica, Universidade Federal do Rio Grande do Sul, Av. Bento Gonc alves 9500, 91501-970 Porto Alegre, Brazil
2
Departamento de Ingeniera Qu mica, Facultad de Ciencias Fsicas y Matem aticas, Universidad de Chile, Casilla 2777 y CIMAT,
Santiago, Chile
3
Faculdade de Qu mica, Pontif cia Universidade Cat olica do Rio Grande do Sul-Brasil, Av. Ipiranga 6681,
90619-900 Porto Alegre, Brazil
Correspondence to: G. B. Galland (E-mail: griselda.barrera@ufrgs.br)
Received 9 April 2012; accepted 18 April 2012; published online 25 May 2012
DOI: 10.1002/pola.26149
ABSTRACT: In this work, the synthesis of polypropylene (PP)/
graphene nanosheet (GNS) nanocomposites by in situ poly-
merization using metallocene catalysts was studied. Initial
reactions were performed using rac-Et(Ind)
2
ZrCl
2
and rac-
Me
2
Si(Ind)
2
ZrCl
2
catalysts to select the best one to obtain good
molecular weight, thermal properties, and tacticity. Subse-
quently, PP nanocomposites with different loadings of GNS
were obtained. GNS from two different sources [Graphite
Nacional (GN) and Graphite Aldrich (GA)] have been used, and
the differences between the obtained nanocomposites were
evaluated. The GNS and nanocomposites were studied by
scanning electronic microcopy, transmission electronic micro-
copy, and X-ray diffraction. They showed that the GN nano-
sheets had lower crystal size and diameter than the GA
nanosheets and dispersed better in the PP matrix. Differential
scanning calorimetry analyses of both types of nanocompo-
sites showed an increase in the crystallization temperature
with increasing graphite loading. The polymeric materials were
also characterized by GPC, thermogravimetric analysis, and
13
C
NMR. VC
2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym
Chem 50: 35983605, 2012
KEYWORDS: metallocene catalysts; nanocomposites; poly
(propylene) (PP); synthesis; X-ray
INTRODUCTION Isotactic polypropylene (PP) is one of the
polymers most commercially used in the world due to its
low cost, easy processability, and full recyclability.
1
PP has
good thermal, mechanical, and physical properties when
used at room temperature; however, its range of applicability
and its properties could be increased, when combined with
other materials in the form of nanocomposites.
2
Polymeric nanocomposites are new materials of great scien-
tific and technological interest, obtained from polymers and
organic or inorganic fillers with nanometric dimensions.
3
They combine the properties of both components in a single
material. On the nanometric scale, the fillers dramatically
increase the physical and mechanical properties of the poly-
mer, even when small amounts are incorporated.
3,4
This gain
is greater compared to traditional microcomposites, which
need a higher amount of filler to reach similar properties.
5
The interest in nanocomposites polymer/graphite comes
from the potential applications due to the graphite proper-
ties: excellent conductivity, lubricating action, antistatic,
chemical resistance, flame retardancy, and barrier properties,
besides being environmentally friendly and low cost.
6,7
Even
more interesting will be obtaining polymers/graphene
nanocomposites, as graphene properties are superior to
graphite.
8
Graphite is found naturally in the form of flakes, which are
composed of layers less than 100 nm thick. Each layer is di-
vided in aggregates of graphene sheets with about 12 nm
thick. The spacing of the aggregates is between 7 and 16
and between the sheets is 3.35 , as shown in Figure
1.
9,10,11
Graphene sheets are bound by Van der Waals forces,
and each sheet is composed of hybridized sp
2
carbon atoms
in a hexagonal structure.
9,12
Because of the small spacing
between graphenes, it is difficult to prepare graphene nano-
composites by direct intercalation, rather requiring the phys-
ical or chemical modification of graphite, with the objective
being to expand the layers. First, the graphite flakes undergo
an intercalation process with chemical species, as H
2
SO
4
and
HNO
3
, to form the graphite intercalated compounds (GIC).
When GIC is exposed to a rapid thermal treatment, the
expanded graphite (EG) can be obtained via the decomposi-
tion of the intercalation agents and the formation of gases
that expand the graphene sheets (Fig. 2).
11,14
The graphene
VC
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nanosheets (GNS) can be obtained by treating the EG with
an ultrasound bath.
15
Graphene or GNS that are well dispersed in a polymer ma-
trix could provide a nanocomposite with excellent properties.
This seems simple but there are enormous experimental
difficulties in obtaining a good dispersion of graphene in a
polymeric matrix due to the tendency of graphene to
agglomerate.
One of the methods to introduce nanofillers in a polymeric
matrix is by in situ polymerization; this technique leads to a
more uniform filler dispersion when compared to conven-
tional mechanical melt blending.
16
The in situ polymerization
of polyolefins is even more attractive when metallocene cata-
lysts are used because they have unique catalytic properties,
such as, high activity, molecular weight, and polydispersity
control, besides perfect control of the polymer microstruc-
ture, which is not observed in traditional catalytic systems.
17
In the literature, there are few studies related to the synthe-
sis of polymer/graphite or graphene nanocomposites by in
situ polymerization process. Among the polymers studied are
nylon,
11
polyaniline,
18
poly(methyl methacrylate) (PMMA),
12
PMMA/poly(vinyl chloride),
19
and polystyrene.
13,20,21
Recently, our research group succeeded in preparing polyeth-
ylene/GNS by in situ polymerization.
22
In the present work,
we studied the synthesis of PP/graphene nanocomposites. To
obtain PPs with good properties, it was necessary to select a
proper catalyst and conditions. For producing nanocompo-
sites with good dispersion of filler, different GNS sources
were also studied and evaluated.
EXPERIMENTAL
Materials
All manipulations were performed by using standard Schlenk
tube techniques under deoxygenated and dried argon. The
EG (Micrograf HC11) was provided by Nacional de Grafite
Ltda. (Brazil) and natural graphite flake (332461) acquired
from Sigma-Aldrich. Toluene was distilled from metallic
sodium and benzophenone. Methylaluminoxane (MAO) was
acquired from Chemtura (10 wt % Al solution in toluene).
The metallocene catalysts rac-Et(Ind)
2
ZrCl
2
(Sigma-Aldrich)
and rac-Me
2
Si(Ind)
2
ZrCl
2
(Chemtura) were used as received.
Preparation of the Graphene Nanosheets
Graphite Aldrich
The graphite in form of the flakes was treated as described in
literature.
12
First, the graphite was intercalated with HNO
3
and H
2
SO
4
, followed by an expansion in an oven at 1000

C
and finally suspended in ethanol (70%), treated with an ultra-
sound bath, filtered, and dried at 120

C for a period of 24 h.
Graphite Nacional
The EG was suspended in ethanol (70%) and the suspension
treated with an ultrasound bath for 8 h was filtered and the
GNS was dried at 120

C for a period of 24 h.
Polymerizations
The polymerization reactions were performed at a controlled
temperature using a 100-mL steel Parr reactor equipped with
mechanical stirring. Toluene was used as solvent, MAO as
cocatalyst (Al/Zr 1500) and rac-Et(Ind)
2
ZrCl
2
or rac-
Me
2
Si(Ind)
2
ZrCl
2
as catalysts (2 10
6
mol). The reactor was
fed continuously with propylene to maintain a constant pres-
sure of 3 bar during 0.5 h. Polymerizations were terminated
by the addition of 5 vol % HCl in ethanol solution. The poly-
mers were washed with water and dried until constant weight.
In the polymerizations to obtain nanocomposites, GNS were
added to the reactor as fillers at various amounts. Before the
reaction, the nanofillers were treated with 15 wt % of MAO
FIGURE 2 Schematic illustration of the production of expanded
graphite.
13
FIGURE 1 Schematic view of the graphite layer structure.
9
TABLE 1 Polymerization Results for Polypropylene from the Two Metallocene Catalysts
Samples Catalyst T
m
(

C) X
c
(%) M
w
(g/mol)
Tacticity,
m (mol %)
Activity
(kg PP/bar h mol)
1 rac-Et(Ind)
2
ZrCl
2
(I) 105 22 13,200 84.7 4100
2 rac-Me
2
Si(Ind)
2
ZrCl
2
(II) 126 39 23,700 92.2 4070
Reaction conditions: P 3 bar, T 70

C, [Zr] 2 lmol, Al/Zr 1500, t 30 min, V
tol
40 mL.
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during 0.5 h in toluene. The suspension was then introduced
into the reactor under inert atmosphere.
Characterization of the Graphenes and Polymers
Scanning electronic microcopy (SEM) analyses were carried
using a Phillips microscope, model XL30, operating at 20 kV.
Samples were prepared by material deposition in an alumi-
num stub and coated with gold.
Transmission electronic microcopy (TEM) analyses were per-
formed using a transmission electron microscope JEOL 1011
operated at 100 kV. Samples were prepared by deposition of
a solution drop on a copper grid of 300 mesh covered with
amorphous carbon.
X-ray diffraction (XRD) measurements were obtained on a
diffractometer Rigaku DMAX 2200 equipped with a Cu tube
and a secondary monochromator, the goniometer used was
Siemens D500, and the detector was the scintillator (NaI and
Tl). The samples were analyzed in the powder form at room
temperature.
Differential scanning calorimetry (DSC) curves were per-
formed using a Perkin-Elmer differential scanning calorime-
ter, model DSC Q20, operating at a heating rate of 10

C/min
and a temperature range from 25 to 160

C. Melting temper-
ature, T
m
, was determined in the second scan and the degree
of crystallinity was calculated from enthalpy of fusion data
obtained from the DSC curves (209 J/g was used for 100%
crystalline material).
The molecular weights were obtained with a Waters Alliance
GPC 2000 instrument equipped with tree Styragel HT-type
columns (HT3, HT5, and HT6E). 1,2,4-Tricholobenzene was
used as solvent, at a flow rate of 1 mL/min and at tempera-
ture of 135

C. The columns were calibrated with polysty-
rene standards.
Polymer microstructure was determined by
13
C NMR. The
spectra were obtained at 130

C in a Varian VNMRS 300
operating at 75 MHz. Solutions of the polymers were pre-
pared in o-dichlorobenzene and benzene-d
6
(20% v/v) in 5-
mm sample tubes. Spectra were taken with a 74

-flip angle,
an acquisition time of 1.5 s and a delay of 4.0 s. The tacticity
was determined from methyl that appear in the region from
19 to 22 ppm, indicating the meso (m) and racemic (r)
settings.
23
Thermogravimetric analysis (TGA) was performed on a SDT
(TGA-DSC) Q600 thermal analyzer at a scanning rate of 20

C/min in air with a temperature range from 25 to 1000

C.
RESULTS AND DISCUSSION
Optimization of Reaction Parameters
It was first necessary to choose the most appropriate cata-
lytic system to produce a PP with high crystallinity and mo-
lecular weight, which could be useful for further studies af-
ter the incorporation of the GNS. These characteristics are
necessary to have a polymer with good mechanical, chemical,
and thermal properties. So, studies of catalytic activity, mo-
lecular weight, thermal properties, and tacticity were done
using two metallocene catalysts that present different struc-
tures. Two metallocenes containing bridges between the
indenyl ligands to ensure the formation of polymers with
high degree of isotacticity were chosen.
24,25
The catalysts
used were rac-Et(Ind)
2
ZrCl
2
(I) and rac-Me
2
Si(Ind)
2
ZrCl
2
TABLE 2 Reactions with Catalyst II at Different Reaction Temperatures (T)
Samples T (

C) T
m
(

C) X
c
(%) M
w
(g/mol) PI
Tacticity,
m (mol %)
Activity
(kg PP/bar h mol)
2 70 126 39 23,700 1.3 92.2 4070
3 60 134 42 28,800 1.4 93.0 3870
4 50 138 46 38,500 1.4 94.9 3510
5 45 141 46 42,700 1.4 95.6 2650
6 40 144 49 67,300 1.3 96.9 1810
Reaction conditions: P 3 bar, [Zr] 2 lmol, Al/Zr 1500, t 30 min, V
tol
40 mL.
PI, polydispersion index.
FIGURE 3 X-Ray diffraction of Graphite Nacional and Graphite
Aldrich.
TABLE 3 Distances among Graphite Layers and the Crystal Size
of GA and GN
Samples d
002
(nm) C (nm)
GA 0.3356 33.02
GN 0.3359 28.25
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(II), both prereacted with the cocatalyst MAO to form the
catalytic species. In Table 1, the results on molecular weight
(M
w
), melting temperature (T
m
), and tacticity are presented.
It can be seen that the catalyst II showed superior results in
all parameters studied, such as, higher T
m
, crystallinity, tac-
ticity, and in particular, it has twice the molecular weight of
catalyst I. Therefore, catalyst II was adopted to perform the
polymerization reactions. As molecular weight is one of the
most important parameters that influence the mechanical
properties, it is necessary to study the conditions that can
increase it, such as the reaction temperature effect.
Table 2 shows that at lower reaction temperature, higher
values of T
m
, X
c
, M
w
, and tacticity were obtained, which is
expected for metallocene systems.
26
Even though the activity
was lower at that temperature, the values are reasonable for
the intended studies. Thus, the reaction temperature of 40

C was chosen for the synthesis of the nanocomposites.

Graphite
In this study, two graphites from different sources were
used: one in the flake form (Aldrich) which was converted
into GNS, as described in the Experimental section, and
another from a Brazilian company, which produces EG that
was only treated with ultrasound to obtain the GNS. Before
starting the synthesis of the nanocomposites, characteriza-
tion by XRD, SEM, and TEM of the GNS was performed.
XRD
XRD analysis was used to study the crystal structure of the
GNS, as shown in Figure 3. The diffractograms of the graph-
ites present a strong peak at 2h 26.5

, which is character-
istic of the spacing between graphene layers, corresponding
to the 002 plane.
Using Braggs law and Scherers equation, this technique also
allows to determine the distance between the graphenes that
composes the graphite (d
002
) and also the size of the crystal
(C) formed by them. Table 3 shows that the distance
between the graphene sheets corresponds to the value men-
tioned in the introduction (3.35 ), which means that the
corresponding treatments did not increase the distance
between the graphenes, but they remain the same that in
the initial graphite. On the other hand, it was found that the
crystal size was different between the two GNS. The GNS
from Graphite Aldrich (GA) presented a larger crystal, indi-
cating a higher stacking of graphenes that the one from
Graphite Nacional (GN).
FIGURE 4 SEM images (scale of 5 lm) of Graphite Nacional (a) and Graphite Aldrich (b).
FIGURE 5 TEM images of GN (a) and GA (b).
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SEM
Figure 4 shows the SEM micrographs of the GNS obtained
after treatment with ultrasound bath. Although both have
nanometer thickness, a difference in their morphologies can
be observed. For the Graphite Nacional [Fig. 4(a)], the nano-
sheets have smaller diameters and seem less aggregated
compared to the Graphite Aldrich [Fig. 4(b)].
TEM
Figure 5 shows the TEM micrographs obtained for the GNS.
It can be noticed that both GNS are formed by several layers
but GN has a lower number of graphenes in each aggregate
of sheets, confirming the XRD results.
Synthesis and Characterization of the Nanocomposites
Polymerization Reactions
Table 4 shows the results of the in situ polymerization of the
PP in the presence of different amounts of GNS. Values of
catalytic activity and the characterization of the nanocompo-
sites formed are given.
TABLE 4 Polymerization Reactions for the Nanocomposites PP/GA and PP/GN
Samples
GNS-Yield
a
(wt %)
GNS-TGA
b
(wt %) M
w
(g/mol) PI
Tacticity,
m (mol %)
Activity
(kg PP/bar h mol)
PP 67,300 1.4 96.9 1810
PP/GA-1 1.0 0.9 65,800 1.3 97.2 1770
PP/GA-2 1.3 1.8 67,100 1.4 n.d. 1600
PP/GA-3 2.2 2.4 64,100 1.3 n.d. 1433
PP/GA-4 5.0 5.2 66,000 1.3 n.d. 1150
PP/GA-5 13.0 11.6 69,300 1.4 n.d. 1100
PP/GN-1 1.0 0.9 71,500 1.4 96.4 1833
PP/GN-2 2.2 2.3 72,200 1.3 96.7 1667
PP/GN-3 3.5 3.8 68,400 1.4 96.1 1520
PP/GN-4 5.3 5.6 69,500 1.4 96.6 1220
PP/GN-5 8.3 7.6 67,900 1.3 96.6 1117
Reaction conditions: P 3 bar, T 40

C, [Cat.II] 2 lmol, Al/Zr
1500, t 30 min, V
tol
40 mL.
a
Graphite percentage calculated from the polymer yield.
b
Graphite percentage obtained by TGA residue.
TABLE 5 Thermal Properties of PP and its Nanocomposites
Samples Graphite (%) T
m
(

C) T
c
(

C) X
c
(%)
PP 144 108 49
PP/GA-1 0.9 145 112 47
PP/GA-2 1.8 145 112 48
PP/GA-3 2.4 145 114 46
PP/GA-4 5.2 146 117 45
PP/GA-5 11.6 146 118 46
PP/GN-1 0.9 145 115 50
PP/GN-2 2.3 146 115 45
PP/GN-3 3.8 146 116 46
PP/GN-4 5.6 146 117 49
PP/GN-5 7.6 147 118 47
FIGURE 6 X-Ray diffraction of (a) neat PP, Graphite Aldrich,
and PP/GA nanocomposites; (b) neat PP, Graphite Nacional
and PP/GN nanocomposites.
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The amount of GNS in the nanocomposites was determined
from the reaction yield and from the residue obtained by
TGA. It can be seen that both results are very close, which is
an indication of the homogeneity of the samples. It is
also possible to observe that no significant changes in the
properties of molecular weight, polydispersity, and tacticity
were obtained for the nanocomposites compared to the neat
polymer (PP). The catalytic activity of the polymerization
tends to decrease slightly with increasing graphene content,
probably due to polar groups on the graphene surface result-
ing from the graphite oxidation with acid treatment that
remain after the layers expansion, which might deactivate
the catalyst. All these results showed the same behavior for
GN and GA.
Through the determination of the tacticity by solution NMR,
a great difference was found for both types of nanocompo-
sites. For the PP/GA nanocomposites, the analysis was only
performed for the sample containing 0.9% GA. It was not
possible to analyze the nanocomposites with higher percen-
tages because the magnetic field was impossible to stabilize,
which is normally the case when solid particles are present.
However, for the PP/GN nanocomposites, NMR analysis was
possible to perform even for 8.3% of GN. This is an indica-
tion that the GNS are well dispersed in these
TABLE 6 Parameters of PP/GA and PP/GN Nanocomposites
from XRD Data
Samples GNS (%) d
002
(nm) C (nm)
GA 0 0.3356 33.02
PP/GA-1 0.9 0.3362 37.08
PP/GA-3 2.4 0.3360 38.16
PP/GA-4 5.2 0.3358 38.64
GN 0 0.3359 28.25
PP/GN-1 0.9
PP/GN-2 2.3 0.3359 28.37
PP/GN-4 5.6 0.3359 30.29
FIGURE 7 SEM images (5 lm) of neat PP (a,b), PP/GN 2.3% (c,d), and PP/GA 2.4% (e,f).
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nanocomposites. Most likely, the PP/GA presents some
agglomeration at higher loadings of graphene.
Thermal Properties
The most important result, shown in Table 5, was the
increase in crystallization temperature with increasing load-
ings of GNS, indicating that the graphite may act as nucleat-
ing agent for the nanocomposites. Page et al.
9
and Fu et al.
27
observed similar behavior when PP/graphite composites
were synthesized by extrusion and solution, respectively.
This increase of T
c
is desirable for PP processing. The melt-
ing temperature and degree of crystallinity showed no signif-
icant change.
Dispersion Study by XRD, SEM, and TEM
Figure 6 shows the diffractograms of neat PP, GNS, and
nanocomposites. Neat PP has the peaks expected for the
polymer at 2h: 14.2, 17.1, 18.7, and 21.8.
28
In this diffracto-
gram, there is no peak around 26.5 where the diffraction of
the graphene planes appears. However, this peak is observed
in some of the nanocomposites diffractograms.
In the PP/GA nanocomposites [Fig. 6(a)], the GNS diffraction
peak is strong and present in all the diffractograms. For the
PP/GN nanocomposites [Fig. 6(b)], it is possible to observe
the evidence of two significant differences: (a) the peak of
the GNS appeared only when 2.3% of GN or higher amount
is added; (b) this peak is smaller when compared to the one
presented by PP/GA nanocomposites, indicating that the GNS
should be more dispersed in the PP/GN nanocomposites.
Table 6 shows a significant increase in GNS crystal size in
the PP/GA, indicating that some sheets are agglomerating
during the formation of these nanocomposites. On the other
hand, the results obtained for the PP/GN nanocomposites
reinforce the evidence of a better dispersion of the filler in
the polymer matrix, as the increase in the crystal size was
not as significant as in PP/GA nanocomposites.
Figure 7 shows the SEM micrographs of neat PP and of both
nanocomposites with similar amounts of GNS. It is not
possible to observe any significant change in morphology in
PP/GN 2.3% (c,d) compared with the neat PP (a,b). However,
for the nanocomposites PP/GA 2.4%, a difference is evident
with the presence of some graphite agglomerates as can be
seen in Figure 7(f).
Finally, Figure 8 shows TEM images of the PP/GN 5.6%
nanocomposite. It is observed that the GNS (black lines) are
well dispersed in the polymer matrix corroborating previous
results.
CONCLUSIONS
PP with high tacticity, molecular weight, and good activity
was synthesized using the metallocene catalyst rac-
Me
2
Si(Ind)
2
ZrCl
2
, at a polymerization temperature of 40

C.
PP nanocomposites with different loadings of GNS were
obtained. The nanocomposites formed did not show altera-
tions in the M
W
, T
m
, and X
c
, compared to neat PP obtained
using the same conditions but showed a significant increase
of the crystallization temperature. XRD, SEM, and TEM analy-
ses showed that the GNS obtained from graphite flake
(Aldrich) presented higher crystal size and diameter than
the GNS obtained from Graphite Nacional. It was found that
agglomerates formed during the synthesis of the PP/GA
nanocomposites, whereas on the other hand, the PP/GN
nanocomposites presented a good dispersion. The inability
to perform NMR analysis on the PP/GA nanocomposites sup-
ports this hypothesis.
ACKNOWLEDGMENTS
The authors thank to CAPES, FAPERGS-PRONEX, and CNPq for
financial support. The authors also thank CNPq-PV for Raul
Quijadas grant and Nacional de Grafite Ltda./Brazil for the
Micrograf supply.
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