Materials Science and Engineering A 457 (2007) 287291

Study on polycarbonate/multi-walled carbon nanotubes composite

produced by melt processing
Li Chen a, , Xiu-Jiang Pang b , Zuo-Long Yu c,
a

Key Lab of Rubber-Plastics, Qingdao University of Science & Technology (QUST), Ministry of Education, Qingdao 266042, China
b Department of Chemistry & Molecular Engineering, QUST, Qingdao 266042, China
c Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China
Received 9 October 2006; received in revised form 6 December 2006; accepted 26 January 2007

Abstract
Multi-walled carbon nanotubes (MWCNTs) were filled into polycarbonate (PC) by large scale extruder, and some studies were carried out on
as-produced composite. The results showed PC composite containing 1 wt.% of MWCNTs had a tensile strength 4.5% higher than neat PC, and
the elastic modulus of PC/MWCNTs composite increased obviously with MWCNTs loadings. The electrical resistivity measurements indicated a
percolation of MWCNTs near 5 wt.% (3.4 vol.%) for the composite. Either the decrease in the fluidity of the composite melts with the increase of
carbon nanotubes (CNTs) loadings or the unexpected shortening of CNTs in extrusion was supposed to have weakened the effects of CNTs as a
reinforcing agent or a conductive filler.
2007 Elsevier B.V. All rights reserved.
Keywords: Carbon nanotubes; Polymer-matrix composites (PMCs); Electrical properties; Mechanical properties; Electron microscopy

1. Introduction
Carbon nanotubes (CNTs) have diverse electrical properties [1,2], and have modulus and strength in the range of
2001000 GPa and 200900 MPa, respectively [3,4]. So, CNTs
has been regarded as a good filler for producing new functional
polymer-based composite. Since the discovery of carbon nanotubes (CNTs), polymer-based CNTs composite have attracted
considerable attention in the research and industrial communities, due to their good electrical conductivity and high strength
at relatively low CNTs content [510].
A key issue in producing polymer/CNTs composite is how to
achieve a homogeneous dispersion of CNTs in target polymer
base. Currently, three methods are commonly used to introduce
CNTs into polymers, i.e. solution processing [11], in situ polymerization of CNTspolymer monomer mixture [12], and melt
mixing of CNTs with polymers [13]. In context with industrial applications of polymerCNTs systems, melt mixing is
the preferred method of composite preparation. The tendency

Corresponding author. Tel.: +86 532 8402 2950; fax: +86 532 8402 3977.
Corresponding author.
E-mail address: chl5590@163.com (L. Chen).

0921-5093/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2007.01.107

of nanotubes to form aggregates may be minimized by appropriate application of shearing force during melt mixing and
studies using melt processed thermoplastic polymer are increasing gradually. For example, Haggenmuller et al. [11] applied a
method combining solvent casting and melt processing together
to produce films of poly(methyl emthacrylate) (PMMA) containing single walled carbon nanotubes (SWCNTs). And the films
obtained by this melt processing technique had a more uniform
nanotube distribution than the cast film and led to much better
mechanical properties. Ferguson et al. [14] reported on kilogram
quantities of polycarbonate (PC)-based nanotube formulations
produced in a Buss Kneader. The results showed a better dispersion of the fibrils in as produced composite. Potschke et al.
[15] examined the rheological properties of MWCNTs filled PC
nanocomposite formed by melt extrusion.
Here we produced PC based composite incorporating MWCNTs by traditional large scale polymer manufacturing machines
like screw extruder. The electrical, mechanical, melt flowing
properties and microstructures of as-produced composite and
length change of CNTs before and after processing were examined. In the paper, the emphasis is put on the interrelationship
between properties and microstructures based on melt flowing
rate, and the influence of the length change of CNTs in melt mixing on the properties of composite. Although the properties of

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L. Chen et al. / Materials Science and Engineering A 457 (2007) 287291

the composite were not as ideal as those expected theoretically,

some useful results were obtained.
2. Experimental
2.1. Materials
MWCNTs used were synthesized from methane via catalytically chemical vapor deposition (CCVD). The as-produced
MWCNTs were treated with hydrochloride (6 M) acid to remove
the remained catalyst particles and the support of catalysts. The
purified MWCNTs were dried in an oven at 150 C for 24 h. The
pristine MWCNTs existed as agglomerates and curved intertwined entanglements [16] with an average diameter of 20 nm
and a mean length of 50 m. The PC resin pellets were Panlite K-1300 obtained from Teijin and were dried at 120 C in a
hopper dryer for at least 6 h prior to use.
2.2. Production of PC/MWCNTs composite
The production of the PC-based composite containing MWCNTs in a two step route was as follows: Firstly, PC composite
masterbatch pellets containing 15 wt.% MWCNTs was produced in a TSSJ-25 co-rotating inter-meshing twin-screw
compounding extruder (D = 25 mm, L/D = 33). The barrel temperature from the entrance to the exit was 220 C, 250 C,
270 C, 285 C, 285 C, and 285 C, respectively; Then, some
PC pellets were melt mixed with PC/MWCNTs masterbatch pellets in the twin-screw extruder to produce 1 wt.%, 3 wt.%, 5 wt.%
and 8 wt.% PC/MWCNTs composite pellets, respectively.
2.3. Characterizations
The morphology of MWCNTs was characterized by transmission electron microscope (TEM) using a JEM-100cx
instrument with an accelerating voltage of 20 kV. The samples
were ultrasonicated in ethanol suspensions with a ultrasonic
bath and then the dispersion was dropped on a copper grid
to observe the morphology. In order to study the dispersion
of MWCNTs in the PC/MWCNTs composite, examination of
scanning electron spectroscopy (SEM) was also carried out on
the cryofractured surfaces of the PC/MWCNTs composite by
using a JSM-5900LV instrument with an accelerating voltage
of 20 kV. All the surfaces were examined after being gilded to
avoid electrostatic charging and poor image resolution.

on a CS-127 MFR tester (Atlas Electric Devices Co.). The

test temperature and the applied load were 300 C and 1.2 kg,
respectively. The volume resistivity (V ) was measured by the
two-terminal method through the vertical thickness of the composite specimens using a multimeter (for V < 108  cm) and a
high resistivity meter (for V > 108  cm) [17]. The composite
were compression molded at a pressure of 10 MPa for 20 min
at 220 C into 4.0 mm thick plaques. And the sample dimensions for low and high resistivity were 4 mm 8 mm 35 mm
and 4 mm 100 mm 100 mm, respectively. Before the measurement, the sample surfaces were coated with silver
paint to reduce contact resistance. For each composite, the
results reported was averaged from at least five experimental
result.
3. Results and discussion
3.1. Morphology of purified MWCNTs
Most pristine CNTs contain some impurities such as amorphous carbon, fullerenes, nanocrystalline graphite and catalyst
particles, which were a serious impediment for CNTs to be
directly used as functional filler in polymer base. Fig. 1 shows
the TEM image of purified MWCNTs in which the long intertwined CNTs with a diameter of about 20 nm were very clean and
almost all impurities have been removed. According to our XPS
studies about MWCNTs [18], in addition to the CC groups, the
surface of purified MWCNTs still contained many other carbonbased polar oxygenated groups such as CO, C O and OC O,
which were beneficial to the its combination with PC matrix
through either van der Waals force, H bond or other forms of
covalent bond. So, the purified CNTs were directly used without
any other surface modification.
3.2. Properties of PCMWCNTs composite
3.2.1. Tensile properties
It can be found from Table 1 that the results were not as ideal
as expected theoretically, and the change in the elastic modulus,
tensile strength and elongation at break of PC composite did not
follow the same rule. Modulus of the composite was estimated

2.4. Properties measurement of PC/MWCNTs composite

Tensile test was conducted on the standard dumbbell specimens (150 mm 10 mm 4 mm) at the constant crosshead
speed of 50 mm/min by using a Shimadzu AG-10TA tensile instron machine. The standard dumbbell specimens were
molded from PC/MWCNTs composite pellets in a PS40E5ASE
injection molding machine (Nissin Co., Japan). The barrel temperature from the entrance to the nozzle was 255 C, 280 C,
285 C, and 280 C, respectively and the mold was at room
temperature. The melt flowing rate (MFR) test was carried out

Fig. 1. TEM image of as-purified MWCNTs.

L. Chen et al. / Materials Science and Engineering A 457 (2007) 287291

289

Table 1
The tensile properties of PC composite with different contents of MWCNTs
Specimen

Content of CNTs (wt.%)

Tensile strength (MPa)

Elastic modulus (MPa)

Elongation at break (%)

a
b
c
d
e

0
1
3
5
8

2350
2495
2641
2798
4183

60.84
63.60
54.83
43.32
25.55

105.00
39.750
4.087
1.9620
1.013

to obey the following equation:

Ecomposite = EPC VPC + EMWCNT VMWCNT

(1)

where EPC and EMWCNT are the elastic moduli of the two components, VPC and VMWCNT are their volume fractions. In other
words, the elastic modulus of PC composite increased with the
content of MWCNTs. This might result from the restrictions of
the stronger interfacial adhesion to the movement of PC chains.
For example, the elastics modulus of the 8 wt.% composite was
78% higher than that of neat PC. The tensile strength of PC
composite with 1 wt.% MWCNTs was 4.5% higher than that of
pure PC, but when the content of MWCNTs exceeded 3 wt.%,
the tensile strengths of PC composite became lower and lower.
The elongation at break of PC/MWCNTs composite decreased
with the increase of CNTs content. The decreases in either tensile strength or elongation at break of the PC composite might
be due to that the dispersion of MWCNTs in PC matrix became
less and less uniform when the content of CNTs became more
and more.
3.2.2. Electrical resistivity
In case of conductive fillers, electrical measurements are
suitable to detect the percolation composition unequivocally.
Fig. 2 shows the logarithm of volume resistivity (V ) for the
PC/MWCNTs composite as a function of the MWCNTs concentration. In our studies the percolation was roughly estimated
at about 5 wt.% (3.4 vol.%) MWCNTs in PC composite from the
curve in Fig. 2. Near this value the volume resistivity changed
greatly. The great decrease in the volume resistivity of the
PC/MWCNTs should, presumably, result from the formation
of the conductive 3D CNTs network, and the composite with
CNTs contents higher than 8 wt.% (5.5 vol.%) can be regarded

Fig. 2. Influence of CNTs contents on PC composites volume resistivities.

as electrically conductive. The percolation threshold and volume resistivity were not advantageous compared to the results
reported for PCMWNT composite produced by melt mixing
in a small scale twin-screw extruder using a higher molecular
weight PC [15]. This may be due to the relatively uneven dispersion of CNTs in the PC/MWCNTs composite resulting from
both the melt mixing process and the features of the MWCNTs
used in this study. Besides that, the small scale extruder used
in this literature was kind of different in mixing efficiency from
the larger scale extruder we used. What is more, the electrical
conductivity and the percolation threshold of composite varied
with host polymer [6]. It can be expected that the introduction of
some processing additives, the optimization of the mixing conditions, the proper surface modification of CNTs might lower
the electrical resistivity and the percolation threshold value.
3.2.3. MFR of PCMWCNTs composite
You can also find the answer to the above phenomena from
the results of MFR in Fig. 3. With the content of CNTs increasing from 1 wt.% to 8 wt.%, the MFR of the PC composite
decreased from 59.1 g/10 min to 0.5 g/10 min. Generally speaking, the higher the MFR values of composite were, the less the
fluidity of the melts in the course of processing. Thus, compared
with the PC composite with a lower CNTs content, the PC composite with a higher CNTs content were supposed to have less
uniform dispersion of CNTs, lower tensile strengths and higher
volume resistivities.
3.3. Dispersion of MWCNTs in composite
In order to make out the dispersion state of MWCNTs in
the PC matrix, SEM characterization was performed on the

Fig. 3. MFR of PC composite pellets with different contents of MWCNTs.

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L. Chen et al. / Materials Science and Engineering A 457 (2007) 287291

Fig. 5. TEM images of shortened MWCNTs in melt extrusion.

3.4. Length change of MWCNTs in melt mixing

Fig. 5 shows the TEM images of MWCNTs washed from
their PC composite pellets containing 5 wt.% MWCNTs. It
was found unexpectedly that the most of the MWCNTs were
much shorter than those in Fig. 1 and the shortest MWCNTs
in Fig. 5 were only about 400 nm long. The image of shorter
CNTs appeared straighter due to the release of bending stress
coming from the entanglements of the pristine long CNTs. It
can be assumed that the MWCNTs were seriously shortened
by the violent rubbing forces and strong shearing forces
existing in producing PC/MWCNTs composite pellets via
melt extruding. Although the shortening of CNTs may exist
in other melt mixing processes as well, it would become more
serious especially for a melt mixing process without adding
any additives. The composites with more CNTs loadings were
supposed to result in more shorter CNTs after melt processing
[19]. This phenomenon could be used to explain the poor
strength and the higher volume resistivity of the PC/MWCNTs
composite we produced. In other words, the considerable
reduction in CNTs length during extruding broke the large
aspect ratios of MWCNTs and weakened the effects of CNTs
as either a reinforcing agent or a conductive filler.
4. Conclusion

Fig. 4. SEM images of PC/MWCNTs composite: (a) PC/MWCNTs masterbatch

with 15 wt.% MWCNTs, (b) PC/MWCNTs pellets with 1 wt.% MWCNTs, and
(c) PC/MWCNTs pellets with 5 wt.% MWCNTs.

PC/MWCNTs composite pellets. As could be observed that

MWCNTs in Fig. 4a showed an uneven distribution in the
PC/MWCNTs masterbatch pellet. After diluting with PC, the
PC composite with 1 wt.% MWCNTs (Fig. 4b) showed an more
even distribution than that with 5 wt.% MWCNTs (Fig. 4c). Individual CNTs (white dot) in Fig. 4b could be distinguished from
each other and the fracture surface was rather rough, while in
Fig. 4c some CNTs agglomerated and the fracture surface was
smooth, which was in good agreement with the above results of
tensile tests.

Generally speaking, the PC/MWCNTs composite could be

produced through traditional large scale plastics processing
machines. The composite containing 1 wt.% of MWCNTs
showed some improvement in tensile strength. With the increase
of content of MWCNTs in composite, there were significant
increases in elastic modulus and obvious decreases in either
tensile strength or elongation at break. In the meantime, electrical resistivity measurements indicated a percolation of MWNT
near 5 wt.% (3.4 vol.%) for the composite. Besides that, the
decrease in the fluidity of the composite melts with the increase
of CNTs loadings became an obstacle to form a uniform
microstructure through the composite and the inhomogeneous
microstructure in return lowered the mechanical strengths and
electrical conductivities of the composite.
Especially, MWCNTs in PC composite pellets were found to
be shortened due to the strong rubbing forces and shearing forces
involved in melt extrusion. It was supposed that the shortening
of CNTs further weakened the effects of CNTs as a reinforc-

L. Chen et al. / Materials Science and Engineering A 457 (2007) 287291

ing agent or a conductive filler. It is also an important issue to

protect CNTs from being cut short in producing polymer/CNTs
composite on a large scale. The optimization of the melt conditions like screw speed and mixing time and so on could make the
commercialization of polymer/CNTs composite with excellent
performances more promising.
Acknowledgement
The support from the Doctoral Fund of Qingdao University
of Science and Technology is gratefully acknowledged.
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