Carbon 42 (2004) 2329–2366

www.elsevier.com/locate/carbon

Letters to the Editor

Nanofiber toughened polyethylene composites

Karen Lozano *, Shuying Yang, Robert E. Jones
Mechanical Engineering Department, The University of Texas-Pan American, Edinburg, TX 78541, USA
Received 28 October 2003; accepted 10 March 2004
Available online 13 April 2004

Keywords: A. Carbon nanotubes; D. Elastic properties, Mechanical properties

Nanofiber/nanotube (NF/NT) reinforced polymer
composites have been widely studied because of their
potential high-technological applications. Attractive re-
sults in the electrical and physical fields have been ob-
tained while the potential of structural enhancements is
still considered a major technological challenge and
therefore of high interest in the research and industrial
communities [1–5]. Most of the reported work shows
small (not as expected) improvements in strength and
stiffness with loss of strain to failure [6–12]. Recently,
the search for high performance NF/NT polymer com-
posites produced successful results in relation to
toughness enhancements. Dalton et al. [13] published
‘‘super-tough’’ carbon-nanotube (CNT) fibers associ-
ated with polyvinyl alcohol through a coagulation-based
spinning method. Here, we show extremely high exten-
sibility, high toughness, moderate strength, carbon
nanofiber (CNF) reinforced polyethylene bulk compos-
ites. The total tensile elongation of more than 1600% is
higher than any published value for nanoreinforced
composites and higher than the upper bound (
1000%)
for any given material [14].
We developed a high-density polyethylene (HDPE)
matrix reinforced with purified vapor grown CNFs.
HDPE with a density and melt flow index of 0.95 g/cc
and 10 g/10 min respectively was obtained from Phillips,
Inc. NFs (Pyrograph III PR-19-raw with diameters
ranging between 40 and 150 nm) were kindly supplied by
Applied Sciences, Inc. and used as a model system for
CNT given their wider availability and lower cost.
CNFs consist of a highly graphitic structure that is
composed of an inner filament (diameter of 10 nm)
thickened by a carbon chemical vapor deposition pro-
*
Corresponding author. Tel.: +1-956-316-7020; fax: +1-956-381-
3527.
E-mail address: lozanok@panam.edu (K. Lozano).
0008-6223/$ - see front matter  2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.03.021
cess. The length of CNFs can vary between 50 and 100
lm, therefore high aspect ratios can be obtained [15].
The NFs, as previously reported, were purified and
functionalized to remove amorphous carbon and to
open the highly tangled fibers [16]. The composite with 8
wt.% of nanofibers was repeatedly subjected to shear
forces in the melt through mixing, extrusion, and com-
pression molding. Dispersion and distribution of the
CNFs in the HDPE was achieved by mixing the com-
ponents in a Haake Rheomixer 600 miniaturized inter-
nal mixer at 180
C, with a speed of 60 rpm and a mixing
time of 10 min. The composite was pressed at 200
C at
a pressure of 27 MPa for 1.5 min and pelletized. The
pellets were extruded using a single screw extruder with
a slit capillary die. The extrudate was re-pressed under
the same conditions and cut for tensile testing. Tensile
properties were measured according to ASTM D882
where dumbbell specimens of 5.08 cm in gage length and
0.56 mm thick were tested in a MTS Sintech 65/G at a
crosshead speed of 50.8 mm/min.
We developed isotropic sheets with extremely well
wetted fibers as verified in scanning electron micro-
graphs (Fig. 1A and B). Exact values for tensile elon-
gation and toughness (area under the stress–strain
curve) of the composites were not obtained since the
samples reached the maximum capacity of our tensile
tester (66 cm) without failure. Results of 1300% for
strain to failure and 151 kJ/m2 for toughness, with yield
strength of 25 MPa and elastic modulus of 800 MPa
were obtained. Pieces of the elongated samples were cut
and retested. The samples were able to elongate an
additional 24% with a toughness of 6.5 kJ/m2 , a mod-
ulus of 1600 MPa and yield strength of 232 MPa. By
comparing our developed system with pure HDPE
samples (Fig. 2), increases of at least 220% in elonga-
tion, 60% in modulus and 290% in toughness were ob-
tained. When compared to our previous prepared
2330 Letters to the Editor / Carbon 42 (2004) 2329–2366

strain to failure values reported by Dalton et al. [13] are

in between 10% and 700% depending on the degree of
initial pre-draw. It should be noted that the CNFs in our
samples were isotropically dispersed since samples cut
in x- and y-direction from the pressed sheets yielded
the same results.
The HDPE and NFs acted in a synergistic manner to
yield such results. The NFs behave as crack arrestors
rather than crack initiators as in most reinforced poly-
meric systems [5]. Composite fracture was similar to an
unfilled HDPE where voids grow and coalesce creating a
fibrillar structure though, fibril failure and crack prop-
agation was arrested by the nanofibers. Elongated pieces
of coupon gage section were fractured in liquid nitrogen.
Electron micrographs of fracture surfaces revealed ex-
tremely large damage zones compared to those usually
observed in polymeric fractures [18–20]. Cavitation
developed within these localized zones producing very
large stable voids (40 lm in diameter) as can be ob-
served from Fig. 3. These voids confirm the ductile
fracture behavior of the composite. We attribute the role
of CNFs in this process to the excellent dispersion and

Fig. 1. Tensile fractured scanning electron micrographs where well-

embedded nanofibers are observed. The samples were gold sputtered
and observed in a LEO435-VP scanning electron microscope (SEM).

samples and other systems of randomly oriented NF/NT

reinforced polymers, increases of at least 20,000% in
toughness (are under the strain–stress curve) and
16,000% in strain to failure are observed. This is the first
report that shows such a substantial enhancement
in strain to failure on nanofiber/nanotube-reinforced
polymers either in bulk or fiber form. Ruan et al. [17]
showed for the first time enhancements in ductility of a
Fig. 3. Fractured surface morphology showing a fibrillar structure as a
CNT reinforced ultrahigh molecular weight PE though result of the coalescence of large stable voids (up to 40 lm). Samples
their strain to failure values on the pre-drawn films were were taken from compression-molded plaques after elongation. The
of 100% and of 8–12% on the drawn thin films. The samples were submerged and fractured in a liquid nitrogen bath.

Fig. 2. Measured tensile stress versus strain behavior for nanofiber reinforced PE and neat PE. A picture of the elongated sample (66 cm) without
failure (the wood ruler length is 31.75 cm, sample gage initial length was 5.08 cm) is also shown.
 Letters to the Editor / Carbon 42 (2004) 2329–2366
interfacial bonding produced by the high shear history
of the samples. Thermogravimetric analysis showed
negligible effects on thermal stability due to thermal
history and shear forces when compared to pure HDPE.
Nanotube reinforced systems are being studied under
the same conditions to provide further insight into the
threshold size at which the reinforcement acts as supe-
rior crack arrestor.
This composite is promising for use in ‘‘cold-formed
parts’’ as described by E.V. Barrera where the material
will provide flexible/strong applications. The combina-
tion of mechanical properties, solvent resistance and
added benefit of electrical conductivity (107 X cm for the
as made samples, volume resistivity of HDPE is 1017
X cm), provides a new material for a vast number of
applications given the ease of processability and low
cost of the NFs. Potential application of the developed
system could be in the area of prosthetics, biomaterials,
high-performance packaging materials, permeable
membranes, and smart materials where commonly used
plastics possess similar strength, and modulus but far
less toughness and extensibility. Considering that the
NF/NT reinforced polymer area is new and developing
fast, further substantial improvements are expected.
Acknowledgements
We sincerely thank M. Eastman for useful comments,
SEM facilities of the Biology Department at UTPA, and
technical assistance from Krystal Hernandez. Support
from National Science Foundation under grant number
CMS 0092621 is gratefully acknowledged.
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