LMSB152212 LMSB_045_002 Techset Composition Ltd, Salisbury, U.K.

3/7/2006

Journal of Macromolecular Sciencew, Part B: Physics, 45:231–245, 2006

Copyright # Taylor & Francis Group, LLC
ISSN 0022-2348 print/1525-609X online
DOI: 10.1080/00222340500522299

Morphology and Crystallization Behavior of

HDPE/CNT Nanocomposite

STEPHEN L. KODJIE,1 LINGYU LI,1 BING LI,1

WENWEN CAI,1 CHRISTOPHER Y. LI,1
AND MIMI KEATING2
1
Department of Materials Science and Engineering and A. J. Drexel
Nanotechnology Institute, Drexel University, Philadelphia, PA, USA
2
Experimental Station, DuPont, Wilmington, DE, USA

Polymer carbon nanotube nanocomposites (PCNs) represent the first realized major
commercial application of carbon nanotubes (CNTs). In this study, high density poly-
ethylene (HDPE)/CNT PCNs have been prepared using a solution blending technique.
Both pristine single-walled nanotubes (SWNT) and polyethylene (PE) single crystal
decorated CNTs (so called nano hybrid shish kebabs, NHSKs) have been used as the
precursors for PCN preparation. Polarized light microscopy, transmission electron
microscopy, scanning electron microscopy, differential scanning calorimetry, and ther-
mogravimetry were used to study the morphology, crystallization behavior, and
thermal stability of the resulting PCNs. The PCNs from pristine SWNTs possess a
more dense morphology than do the PCNs prepared from NHSKs; PE single crystal
lamellae are perpendicular or oblique to the CNT axis, leading to relatively “open-
structured” PCNs. Heterogeneous nucleation occurred in both nonisothermal and iso-
thermal crystallization of PCNs and the crystallization kinetics are much faster than
that of the pure HDPE. Thermal stability of PCNs showed dramatic enhancement
(as high as 708C/1158C improvement of Tmax in N2/air atmosphere, respectively),
which is attributed to the formation of the free radical scavenging CNT network.

Keywords polymer carbon nanotube nanocomposites, carbon nanotubes, single-

walled nanotubes (SWNT), crystallization kinetics

Introduction
Due to their extraordinary mechanical, electrical and optical properties, CNTs have
attracted great attention in recent years.[1 – 6] As the structure and properties of the CNT
have been understood, there is a pressing need to transfer their outstanding properties
from nano- to micro-/macro-scales. One essential step towards this goal is assembling/
processing CNTs, which often involves dispersing them in an organic solvent/
polymeric matrix to form complex materials such as polymer CNT nanocomposites

Received 31 July 2005; Accepted 19 August 2005.

Dedicated to Prof. Phillip H. Geil’s seventy-fifth birthday.
Address correspondence to Christopher Y. Li, Department of Materials Science and Engineer-
ing and A. J. Drexel Nanotechnology Institute, Drexel University, Philadelphia, PA 19104, USA.
E-mail: Chrisli@drexel.edu

231
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232 S. L. Kodjie et al.

(PCNs). The PCNs represent the first realized major commercial application of CNTs.[6]
Incorporation of CNTs into polymers dramatically enhances the mechanical properties of
the polymer while it also imparts attractive properties such as conductivity, electromag-
netic interference shielding, and sensing capability to the otherwise inert polymer
matrix.[6] Multiwalled CNT (MWNT) and SWNT as well as carbon nanofiber (CNF)
have been used. Depending on the targeted properties, a variety of polymers have been
explored. These include amorphous polymers such as polystyrene,[7 – 9] poly (methyl
methacrylate),[10 – 13] rigid rod polymers such as poly(p-phenylene benzobisoxazole),[14]
cross-linkable polymers such as epoxy[15 – 17] and conducting polymers such as polyani-
line, polypyrrole, etc.[18 – 21]
Most of the studies regarding the crystalline polymer/CNT PCNs focused on their
crystallization behavior. It should also be noted that carbon materials, such as carbon
fibers (CFs) which are  10 mm in diameter, have been used to induce polymer crystalliza-
tion (transcrystallization). A number of polymers have been investigated including
isotactic polypropylene (iPP), polyethylene (PE), polyhexamethylene adipamide (Nylon
66), poly(phenylene sulfide), polyether ether ketone, etc.[22 – 24] In the case of iPP/CF
composite, the pitch-based CF induces a dense population of iPP crystal nuclei along
its surface.[22] As these nuclei grow, they impinge upon one another, such that crystal
growth occurs essentially perpendicular to the fiber axis. This leads to oriented growth
of iPP lamellae away from the fiber outward into the thermoplastic matrix, thus
forming a transcrystalline layer.[22] Epitaxial growth of polymers such as PE, Nylon 6,
polyethers, etc., on graphite surfaces has also been confirmed using scanning tunneling
microscopy (STM) and transmission electron microscopy (TEM) techniques.[25,26]
Polymer chains have been found to possess a trans conformation and align parallel to
the [100] or [110] direction of the graphite lattice. These previous studies suggest that
CNTs, as one type of carbon material, might promote polymer crystallization.
Recently, PCNs formed by CNTs and semicrystalline polymers such as iPP,[27 – 31]
[32]
PE, polyvinyl alcohol (PVA),[33] polyacrylonitrile (PAN),[34 – 36] thermoplastic
polyimide,[37] and conjugated organic polymer,[38] as well as thermoplastic elastomers
such as polyurethane systems[39 – 41] have been studied. Using DSC nonisothermal and iso-
thermal crystallization technique, it has been found that t1/2 decreases with increasing
CNT content in PCNs. Crystallization behavior of iPP/CNT PCNs was most extensively
studied. Grady et al.[28] reported that upon mixing with CNTs, the b form of iPP content
increases while Assouline et al.[30] showed that MWNTs could act as a nucleation agents.
Kelerakis et al.[29] studied the crystallization behavior of elastomeric ethylene/propylene
(EP) random copolymer (84.3 wt% P) in the mixture with modified carbon nanofibers
(MCNF).[29] The MCNF was found to nucleate a form iPP. They also reported that the
highly stretched PCN exhibited a higher amount of unoriented crystals, a low degree of
crystal orientation, and a higher amount of g crystals, indicating the effective load
transfer from the matrix to MCNFs. Chang et al.[27] reported that b form iPP formed in
the iPP/SWNT PCN under strain. In a series of thermoplastic elasotmers (Morthane)/
CNT PCNs, it was found that the strain induced crystallization was enhanced with the
addition of CNT (for 1 –5 vol.%), which led to the increase of the rubbery modulus by
a factor of 2 –5 and the shape fixity was also improved.[39,41] When near IR was used to
“heat” CNTs, leading to the melting of the physical cross-linking points (polymer
crystals) and 50% more recovery stress than the pristine resin were reported.[41]
We recently investigated CNT-induced Nylon 66 and HDPE crystallization.[42] Using
a solution crystallization method,[42,43] it has been found that a unique nano hybrid shish
kebab (NHSK) structure could be obtained. Polymer single crystals were formed around
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HDPE/CNT Nanocomposites 233

CNTs. In this paper, we report the morphology and crystallization behavior of PE/CNT
PCNs. A solution blending method was used to ensure exfoliation of CNT bundles. The
CNT-initiated polymer crystallization was evident. The resulting PCNs showed
dramatic improvement in thermal stability. A detailed mechanism will be discussed.

Experimental

Materials
The high density polyethylene pellets (density  0.937 g/cm3, MFI ¼ 12 g/10 min,
1908C/2.16 kg, ASTM D 1238) were purchased from Aldrich Co. The SWNTs were
purchased from Carbon Nanotechnologies Inc. and used as received. The MWNTs were
purchased from Aldrich and washed with 2.4 M nitric acid for 0.5 h to remove
amorphous carbon. The resulting MWNTs were then centrifuged, collected, and dried
in a vacuum oven. p-Xylene and methanol were purchased from Aldrich and used as
received.

Preparation of Coprecipitated HDPE/CNT Nanocomposite (CP-PCN)

The HDPE/SWNT nanocomposites with the following wt%: 0.0, 0.1, 0.25, 0.5, and 1.0
were prepared by initially sonicating a weighed amount of the SWNT in p-xylene for
about 2 h and adding the content to an already dissolved HDPE/p-Xylene solution in an
oil bath at 1208C. Finally a fibrous composite material was precipitated in methanol.
The precipitant was filtered, washed with excess methanol, and dried in a vacuum oven
at 608C overnight.

Preparation of HDPE/CNT Nanocomposite from NHSK (N-PCN)

For the solution-crystallized HDPE/SWNT nanocomposites, initially a 0.01 wt% SWNT-
HDPE NHSK was prepared by sonicating a known weight of SWNT in p-Xylene and
adding it to a dissolved HDPE-p-Xylene solution at 1208C. The mixture was crystallized
at 1048C for one hour to form the NHSK precursor.[42] Concentrated HDPE/p-Xylene
solution at 1208 was transferred to the oil bath containing NHSK at 1048C for 1 h. The
mixture was then transferred to an oil bath at 808C where crystallization of the nanocom-
posite took place for 1– 3 h. The contents were filtered and dried overnight in the vacuum
oven at 608C. The final SWNT contents were controlled to be 0.1, 0.25, 0.5, and 1 wt%.
The HDPE/MWNT N-PCNs were also prepared using a similar method.

Characterization
The TGA was carried out using a Perkin Elmer TGA 7 under air and nitrogen (N2) atmos-
phere with a flow rate of 40 mL/min. About 3– 6 mg of the sample was heated from 308C
to 6008C at a heating rate of 108C/min. The crystallization and melting behavior of the
different concentrations of SWNT in HDPE was studied by DSC using a Perkin Elmer
DSC 7 that had been calibrated with a standard indium and under a N2 flow rate of
20 mL/min. The cooling and heating rate of 108C/min was used. The sample were first
heated to 2008C and then cooled to 308C. The second heating curve was collected by
heating the sample at the same rate to 2008C. The crystallinity was determined using
the enthalpy of fusion of HDPE with 100% crystallinity as 293.6 J/g.[44] Isothermal
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234 S. L. Kodjie et al.

crystallization was carried out by quenching the PCNs from 1908C to the preset
crystallization temperatures at a rate of 4008C/min.
The PCN morphology was examined via polarized light microscopy (PLM) (Olympus
BX-51) coupled with a Mettler hot stage (FP-90). The image was captured using an Insight
digital camera. The film was prepared by melt pressing the PCN at 1908C.
The TEM experiments were conducted using a JEOL-2000FX microscope with an
accelerating voltage of 120 kV. THE SEM experiments were carried out using a FEI/
Phillips XL30 field emission environmental scanning electron microscopy (SEM) with
an acceleration voltage of 15 kV. The PCNs were placed on glass slides and sputtered
with platinum for 30 s to enhance the surface conductivity.

Results and Discussion

Morphology of HDPE/SWNT Nanocomposite

It has been recognized that the structure and morphology of PCNs critically depend on the
fabrication process. Solution blending of polymers and CNTs was employed in the present
study since it should provide better CNT exfoliation compared to the melt blending
method. Two types of precursors were utilized: pristine CNTs and PE single crystal –
decorated CNTs (PE NHSK), leading to CP-PCN and N-PCN samples, respectively.
Figure 1 shows a TEM micrograph of the unique NHSK precursor.[42] The SWNTs
formed small bundles and disc-shaped objects on the CNTs can be clearly seen,
spanning along the entire length of SWNTs with a periodicity of  50 –100 nm. These
disc-shaped objects are edge-on views of PE single crystal lamellae and the peculiar mor-
phology is similar to the classical polymer shish-kebab structures formed in an
elongation/shear flow field.[45,46] The CNT/polymer system in this case was not under
external flow during crystallization and it is the SWNT that induces nucleation of

Figure 1. TEM micrograph of HDPE/SWNT NHSK formed by crystallizing PE at 1048C in

p-Xylene at the presence of SWNT.
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HDPE/CNT Nanocomposites 235

polymer chains on the SWNT surface. This observation serves as direct evidence that
CNTs can promote heterogeneous nucleation of PE.
Figure 2 shows PLM micrographs of the CP-PCN and N-PCN from both SWNTs and
MWNTs. The samples were sandwiched between two glass slides, melt pressed at 1908C,
and then quenched to 1108C for observation. It is evident that 1) CNTs were uniformly
dispersed in the PE matrix and large size agglomeration was absent, indicating that
solution blending leads to better CNT dispersion compared to melt blending. 2) The PE spher-
ulites were not observed in all cases, a common case in crystalline PCN since CNTs (or other
inorganic fillers such as nano clay) prevent PE from growing into large size spherulites. The
crystalline nature of the PCN is, however, evident by the strong overall birefringence.
The detailed morphology of the PCN is revealed by SEM micrographs shown in
Fig. 3. Note that these samples were not melt pressed. Figure 3a shows the CP-PCN
sample. Rounded PE aggregates can be clearly seen, which is due to the precipitation/
phase separation process. The surface of the PE spheres is rough; small lamellae were
formed within the precipitated spheres. The lamellae are relatively densely packed in
each sphere. The average size of the spheres is  2– 3 micrometers. It should be noted
that these spheres are similar to the PE “globs” observed by Garber and Geil[47] by
rapid quenching of 0.05% of PE (Marlex 6050) in xylene to temperatures of 86 and

Figure 2. PLM of HDPE/CNT PCNs a) 0.5% SWNT CP-PCN, b) 0.25% SWNT N-PCN, and
c) 0.25% MWNT N-PCN.
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236 S. L. Kodjie et al.

Figure 3. SEM of HDPE/CNT PCNs a) 0.1% SWNT CP-PCN, b) 0.1% SWNT CP-PCN, and
c) 0.1% MWNT CP-PCN.

708C. These authors suggested that the formation of the globs was due to the phase sep-
aration occurred during the quenching process.[47] In the present case, CNTs are not
evident in the micrograph, indicating that the fast precipitation kinetics lead to rapid
phase separation of PE from the solution. Microspheres were formed and CNTs might
be buried inside the PE spheres. Figures 3b and 3c show the N-PCN samples of 0.1%
CNT content. Figure 3b was from the SWNT sample while Fig. 3c shows MWNT
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HDPE/CNT Nanocomposites 237

PCN. The morphology is clearly different from CP-PCN. The CNTs are wrapped with a
layer of PE single crystals. Although CNTs can not be directly seen, it is evident that in
N-PCNs, PE lamellae were formed on CNTs and the dotted lines in Fig. 3b represent
the orientation of the CNTs. Prominent PE single crystal lamellae can be seen perpendicu-
lar/oblique to the CNT axis. Figures 3b and 3c could thus be viewed as the overgrowth
from NHSK in Fig. 1. The unique orientation of the PE lamellae leads to the “open” mor-
phology of the PCN, which could play an important role in the PCN crystallization and
thermal properties, a topic that we will return to in the following section.

Crystallization of HDPE/CNT Nanocomposite

Nonisothermal crystallization behavior of HDPE and HDPE/CNT PCN were studied
using DSC. The HDPE, CP-PCNs, and N-PCNs were cooled from 2008C to 308C at
108C/min and heated up at the same rate; the results are presented in Fig. 4. Tables 1
and 2 list the onset temperature (Ton), peak temperature (Tpeak), and heats of fusion
(DH ) as well as the crystallinity (wc) data of CP-PCN and N-PCN. The cooling curves
show that pure HDPE crystallized at 110.88C and the inclusion of SWNT did not signifi-
cantly change the crystallization temperature (Tc). The 1.0 wt% composite increased the
onset of crystallization about 38C while Tpeak
c was increased by 1.838C. The increase of
Tc is attributed to the heterogeneous nucleation induced by CNTs. The corresponding
heat release during crystallization was reduced by 11 J/g, corresponding to a reduction
in percentage crystallinity of about 4%. Figure 4b shows the second heating curve. Pure
HDPE undergoes crystal melting at 1258C; it was observed that the melting points of
the composites did not change much, being recorded as 125.28C, 127.48C, 127.78C, and
126.28C, corresponding, respectively, to the 0.1, 0.25, 0.5, and 1.0 wt% samples. The cor-
responding heat of fusion that depends on the crystallinity was recorded as 176.2 J/g for
HDPE and 173.0, 173.2, 174.6, and 169.3 J/g for the 0.1, 0.25, 0.5, and 1.0 wt% PCNs.
The observed reduction in percentage crystallinity is different from some of the
reported data, in which case an increase of polymer crystallinity was claimed by adding

Figure 4. DSC thermograms of HDPE/CNT N-PCNs (a) first cooling, and (b) second heating.
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238 S. L. Kodjie et al.

Table 1
DSC data of HDPE CP-PCNs

Heat of
fusion Crystallinity
Sample Cycle Ton8C Tpeak8C DH, J/g (%)

HDPE 1st Heating 116.6 123.0 203.5 69.0

Cooling 112.5 110.8 157.5 54.0
2nd Heating 120.2 125.2 176.2 60.0

0.1wt% 1st Heating 116.6 124.3 189.2 64.4

SWCNT – HDPE Cooling 112.6 109.1 151.1 55.6
2nd Heating 121.0 125.2 173.0 59.1

0.25wt% 1st Heating 119.7 127.4 173.3 59.1

SWCNT – HDPE Cooling 114.7 112.0 151.4 51.5
2nd Heating 119.7 127.4 173.2 59.1

0.5wt% 1st Heating 121.5 127.7 186.9 63.3

SWCNT – HDPE Cooling 113.2 110.1 155.2 55.4
2nd Heating 120.6 127.7 174.5 59.3

1wt% 1st Heating 120.4 127.2 170.6 58.0

SWCNT – HDPE Cooling 115.2 112.6 148.1 50.5
2nd Heating 117.9 126.2 169.3 57.6

CNTs.[28] In the present case, we suggest that the reduction of the crystallinity is because
that the CNTs can break the continuity of the polymer matrix and large, uniform lamellae
can not be formed, as evidenced in Fig. 2. More grain boundaries as well as defects are
formed in the case of PCNs, leading to the crystallinity reduction. It should also be
noted from the DSC data, the HDPE sample that was used might contain a number of
branches per chain since the melting temperature as well as the crystallinity are relatively
low compared to linear HDPE.
For the N-PCN samples, which were prepared from PE-NHSK as shown in Table 2,
similar Tc, and Tm were observed. One noticeable difference is that the heat of fusion of the
first heating is much higher compared to the second heating while the Tm is lower. This
could be attributed to that the first heating curve shows the melting of solution crystal-
lized/precipitated samples while the second heating curve shows the melting of noni-
sothermal melt crystallized samples. Compared to melt crystallization, solution
crystallization/precipitation occurred in a more dilute environment, leading to more
complete crystallization (thus higher DH). Most of the crystals in solution crystallized/
precipitated samples, however, were formed during precipitation or crystallization at
808C. The Tc is relatively low compared to nonisothermal melt crystallization; a relatively
lower Tm was thus observed in the first heating curves as indicated in Table 2. Note that the
differences tends to diminish as CNT contents increase, possibly due to the CNT network
providing a nano confinement effect (Tm increases while crystallinity decreases with
increasing CNT contents).
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HDPE/CNT Nanocomposites 239

Table 2
DSC data of HDPE N-PCNs

Heat of
fusion Crystallinity
Sample Cycle Ton8C Tpeak8C DH, J/g (%)

HDPE 1st Heating 116.6 123 203.5 69

Cooling 112.5 110.8 157.5 54
2nd Heating 120.2 125.2 176.2 60

0.1wt% 1st Heating 113.9 121.5 206.5 70.1

SWNT– HDPE Cooling 114.0 112.0 157.4 54.1
2nd Heating 119.2 125.0 175.8 60.1

0.25wt% 1st Heating 115.9 121.2 207.5 70.2

SWNT– HDPE Cooling 115.0 112.0 157.2 53.3
2nd Heating 119.3 125.2 176.6 60.2

0.5wt% 1st Heating 117.0 122.8 206.0 70.4

SWNT– HDPE Cooling 114.3 112.1 155.9 53.3
2nd Heating 119.7 125.9 175.2 60.0

1wt% 1st Heating 118.9 127.8 181.2 61.6

SWNT – HDPE Cooling 114.7 112.0 153.6 52.5
2nd Heating 119.2 126.4 174.5 59.4

Compared to CP-PCN, there were no significant changes in crystallization and

melting temperatures in the case of N-PCN except that a slightly lower impact on crystal-
linity was observed with increasing SWNT. This is probably due to the more open mor-
phology of the PE/CNT hybrid structure as shown in Fig. 3. Since the lamellae in the
NHSK PCNs are perpendicular/oblique to the CNT axis, this open structure leads to
more free space for PE crystal growth and the crystallinity reduction due to the CNT con-
finement was, therefore, limited.
Isothermal crystallization was also carried out and Fig. 5 shows the isothermal crystal-
lization of HDPE and PCNs at 1158C and the plots of t1/2 with respect to CNT content. It is
evident that crystallization occurred at a much faster rate, for both CP-PCN and N-PCN.
The t1/2 decreased dramatically, from 233 s to 69 s for CP-PCN and 77 s for N-PCN
sample. Again, the slightly higher t1/2 of N-PCN compared to CP-PCN might be due to
the open structure of N-PCN. It is of interest that the Avarmi exponent n did not
change much for the CP-PCN, while it slightly increased for N-PCN (1.59 for HDPE,
1.55 for 1% CP-PCN, and 1.78 for 1% N-PCN), indicating that the growth dimension
of the PE crystal was not significantly affected by CNTs. Comparing the isothermal
curve shapes, one can immediately tell that the pure HPDE curve is very broad, indicating
multiple crystallization behavior, possibly due to the high polydispersity as well as the
nonlinearity of the sample. The isothermal curve of the PCNs, however, is much
narrower and uniform, suggesting that the heterogeneous nucleation is the overwhelming
crystallization mechanism and crystallization occurred at the same time, leading to the
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240 S. L. Kodjie et al.

Figure 5. Isothermal crystallization at 1158C a) CP-PCNs and b) N-PCNs. c) shows the plot of
t1/2 with respect to SWNT contents.

narrow distribution of the isotherm curve. Another feature of the isothermal crystallization
is that the crystallinity of the PCNs is lower than that of the pure HDPE, suggesting again
that the CNT network has dramatically hindered the crystal growth.

Thermal Stability of HDPE/CNT Nanocomposites

The degradation of pure HDPE as well as composites was analyzed in air and N2
atmosphere. The thermogarmetric analysis (TGA) curves of HDPE and CP-PCN
specimens in air and N2 are shown in Fig. 6 while the N-PCNs sample in air and N2
are depicted in Fig. 7. In air HDPE maintained a constant weight until about 240 8C
and the onset of maximum weight loss (Ton) was recorded as 346.98C. The differential
curves showed a single peak at 350.88C, which can be correlated to the temperature of
maximum weight loss (Tmax) of the neat polymer (not shown). The temperature of 5%
sample weight loss (T5%) was found to be  315.68C. In N2, the Ton, T5% and Tmax were
found to be at 405.88C, 369.08C, and 446.98C, respectively, much higher than when
recorded in air atmosphere. At temperatures above 4908C, HDPE had completely
degraded and the weight of the residue remained constant. For both CP-PCN and
N-PCN samples, in air or N2, it is evident that the Ton, T5%, and Tmax have been dramati-
cally increased. Figure 8 shows the plots of Ton, T5%, and Tmax with respect to the CNT
contents for CP-PCN and N-PCN in N2 and air. All three temperatures were dramatically
increased with a small amount of CNT and they then tended to reach a plateau. In air, the
Tmax was increased by 1158C for the CP-PCN while the increase was  658C for N-PCN.
For all the samples in air atmosphere, the differential curves of the decomposition process
showed several peaks, indicating that the degradation process involves a multistaged
process of separate chemical reactions as a result of carbon-oxygen bond formation and
subsequent decomposition of the bonds at higher temperatures to form carbon
monoxide and carbon dioxide. Regardless of this multistage process,  65– 1158C
increase of the degradation temperature is evident. Single peaks were found for the
derivatives of the TGA curves for the PCNs in N2 (not shown). With increasing the
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HDPE/CNT Nanocomposites 241

Figure 6. TGA of CP-PCNs in (a) air and (b) N2.

CNT contents, the degradation temperature shifted upward for both CP-PCN and N-PCN.
As high as a 708C increase has been achieved for both samples in N2 atmosphere.
It is known that the thermal degradation of HDPE occurs by random chain scission to
form radicals of alkyl and alkyl peroxyl that are susceptible to inhibition reagents capable of
trapping the radicals. The CNTs have high electron affinities similar to C60; as such they have
been proposed to acts as scavengers of free radicals.[48] By incorporating CNTs in polymers
the thermal stability of polymers could be enhanced. Watts et al.[48] recently reported
an  188C increase of the degradation temperature of PE in N2 at a much higher CNT
content (14% CNT). In the present case, as high as 708C improvements were achieved.
The difference could be attributed to two factors: 1) MWNT were used in Watts’ study
while SWNT were used in our case; and 2) melt blending was used in the previous study
and a solution blending technique was used in our case. In order to further confirm which
is the major reason for the thermal stability enhancement, MWNT were also used for
solution blending. It was found that for 0.25% MWNT/HDPE N-PCN in N2, a Tmax of
5058C was achieved, indicating a  598C increase, which is much higher than the previously
reported 188C improvement. Therefore, more complete CNT exfoliation might hold the key
to the present observation of the high PCN thermal stability.
Solution blending technique ensures more complete CNT exfoliation and less CNT
bundle formation in the PCNs. The radical scavenging efficiency, therefore, can be dra-
matically enhanced at very low CNT content. Figure 8 indicates that Ton, T5%, and Tmax
increase dramatically as small amounts of CNT are added. The temperatures then
reached a plateau. This indicates that the percolative network of CNTs was achieved
and further increasing CNTs, therefore, did not alter the degradation behavior signifi-
cantly. The threshold CNT content is  0.2%, a very low value due to the high CNT
aspect ratio.
It should be noted that the Ton, T5%, and Tmax of coprecipitated CP-PCN samples are
slightly higher than that of the N-PCNs from NHSK (a few degrees difference). This could
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242 S. L. Kodjie et al.

Figure 7. TGA of N-PCNs in (a) air and (b) N2.

be attributed to two possible reasons: 1) since the CP-PCN were prepared immediately
after sonication, CNTs might be dispersed more uniformly while in N-PCNs, 0.5 – 1 h crys-
tallization time was allowed, which might result in certain CNT agglomeration. 2) From
Fig. 3, it is evident that N-PCNs possess a more “open” morphology and PE, therefore, is

Figure 8. Ton, T5%, and Tmax vs. CNT contents for CP-PCNs in (a) air, (b) N2, and for N-PCNs in (c)
air, and (d) N2.
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HDPE/CNT Nanocomposites 243

not as intimately contacted with CNT as in CP-PCN. The radical scavenging efficiency
might be relatively low, which could lead to a slightly lower degradation temperature.
It is, therefore, again clear that uniform dispersion of SWNT holds the key to the
thermal property enhancement and we are currently investigating using other solvents
(such as 1,2 dichlorobenzene which is a better solvent for SWNT) to achieve better
CNT exfoliation. An even higher degradation temperature of HDPE PCN is envisaged.

Conclusion
The HDPE/SWNT PCNs were prepared using a solution blending technique. Both
pristine SWNT and the unique NHSKs were used as precursors for PCN preparation.
Uniform SWNT dispersion was achieved in both cases. SEM shows that CP-PCNs from
the pristine SWNT possess denser structures while in N-PCNs from NHSK precursors,
single crystal lamellae are perpendicular/oblique to the CNT axis, creating open space
in the PCNs. Crystallization temperatures were found to be slightly increased and the
t1/2 in isothermal crystallization decreased; both suggest that CNTs initiated PE crystal-
lization. Thermal stability of HDPE was dramatically enhanced and as high as 1158C
increases in Tmax were achieved. The thermal stability enhancement was attributed to
the formation of the radical scavenging SWNT network.

Acknowledgment
This work was supported by the National Science Foundation (NSF CAREER award,
DMR-0239415), DMI-0508407, ACS-PRF, 3M, and DuPont. The ESEM was purchased
through the support of NSF (BES-0216343).

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