ARTICLE IN PRESS

Journal of Physics and Chemistry of Solids 69 (2008) 1395–1398

www.elsevier.com/locate/jpcs

Mechanical and electrical properties of multi-wall carbon

nanotube/poly(lactic acid) composites
Chen-Feng Kuana,, Hsu-Chiang Kuana, Chen-Chi M. Mab, Chia-Hsun Chena
a
Department of Chemical Engineering, Far East University 744, Tainan, Taiwan
b
Department of Chemical Engineering, National Tsing Hua University 300, Hsin-Chu, Taiwan
Received 26 June 2007; received in revised form 28 September 2007; accepted 30 October 2007

Abstract

The preparation of multi-walled carbon nanotube (MWCNT)/polylactide (PLA) composites is described. High electrical conductivity
can be achieved at a low carbon nanotube loading. When only 0.5 parts per hundred parts of resin (phr) modified multi-walled carbon
nanotube was added to low-crystalline PLA (LC-PLA), the surface resistance of the composite fell from 5.46  1015 to 2.61  102 O (by
1013 order). The degree of crystallinity of PLA can influence the electrical property of MWCNT/PLA composites apparently. MWCNT
dispersion was enhanced by covalent or hydrogen bonding between modified multi-walled carbon nanotube and PLA. The flexural
strengths of pristine LC-PLA and 4 phr modified multi-walled carbon nanotube/LC-PLA composites are 102.3 and 120.2 MPa,
respectively (representing a difference of 17.5%).
r 2007 Elsevier Ltd. All rights reserved.

Keywords: A. Interface; D. Electrical properties; D. Mechanical properties

1. Introduction improve the compatibility between carbon nanotubes and

Carbon nanotubes have excellent electrical, mechanical
and thermal properties. They exhibit low density, high
strength, high toughness, a large surface area, flexibility,
etc. Several investigations have been conducted on the
carbon nanotubes and their polymer composites. Recently,
polylactide (PLA) has attracted considerable interest, for
its use in polymers and co-polymers, or in blends with
other polymers. Some methods have been reported to
improve the physical properties, including the addition of
natural or synthetic fibers, layered clay or carbon
nanotubes [1,2] and others.
Carbon nanotubes were added to high-crystalline PLA
(HC-PLA) and low-crystalline PLA (LC-PLA) to compare
the electrical and thermal properties of their polymer
composites. The resulting composite can generally be
utilized in biodegradable electronics or packing materials
to prevent electromagnetic interference (EMI). A new
modification technique displayed in Fig. 1 was presented to
Corresponding author. Tel.: +886 6 5977111x55; fax: +886 6 5977115.
E-mail address: cfkuan@cc.feu.edu.tw (C.-F. Kuan).
PLA matrix. The maleic anhydride-grafted multi-walled
carbon nanotube (MA-g-MWCNT) can generate some
chemical and physical bonding with the PLA matrix,
increasing the interfacial bonding between carbon nano-
tubes and the PLA matrix. The effect of carbon nanotube-
induced crystallinity on the PLA composite was also
carefully studied herein.
2. Experimental
2.1. Materials
Two types of PLA, low- and high-crystalline resins, were
purchased from the Cargill-Dow, Inc. (USA), trade name:
Nature Greens 2002D (LC-PLA, D% comonomer of up
to 4.2570.55%; low crystalline) and 2100D (HC-PLA,
D% comonomer of up to 1.470.2%; high crystalline).
Before being extruded, the PLA samples were dried in a
vacuum oven at 40 1C for 24 h to remove water and other
volatile components. The multi-walled carbon nanotube
(MWCNT) was supplied by the CNT Co. Ltd., Incheon,
Korea. This was 40–60 nm in diameter, 5–20 mm in length.

0022-3697/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2007.10.060
 ARTICLE IN PRESS
1396 C.-F. Kuan et al. / Journal of Physics and Chemistry of Solids 69 (2008) 1395–1398
O
C
BPO/THF/Acetone
O
80°C / 4 hr
C
O
O Covalent bond
C CH3
O H O C C OH
C H O n
O O
PLA
Fig. 1. The reaction mechanism of CNT grafted with maleic anhydride (MA).
2.2. Sample preparation
The 0.5 g MWCNT was functionalized by refluxing with
1.3 g maleic anhydride dissolved in 25 ml acetone and 25 ml
THF at 80 1C for 4 h. The free radical reaction is initialed
by benzoyl peroxide (BPO). Modified MWCNTs (MA-g-
MWCNT) were washed by anhydrous acetone for several
times.
MWCNT and PLA (high- and low-crystalline) were
compounded by a co-rotating type twin screw extruder;
with L/D ¼ 43.5, and a high shear rate configuration.
The rotation speed is 100 rpm and barrel temperatures
are from 150 to 190 1C. Extruded material was cut
into small pellets in a granulator. Dumb-bell shaped
specimens were then injection moulded using a Battenfeld,
Ba750 CDPLUS injecting molding machine from dried
pellets at a mould temperature of 160–190 1C. The
maximum injection pressure was 100 bar and the hold
pressure was 10 bar.
3. Results and discussion
3.1. FTIR spectroscopy analysis of MWCNT/PLA
composites
Fig. 2 shows the FTIR spectra of melaic anhydride
modified MWCNT and maleic anhydride. The changes of
FTIR absorption peak are due to actual changes in the
chemical reaction between MWCNT and MA. From Fig.
2, the transmittance band appears at 1750, 1214, 1228 and
1365 cm1, apparently associated with CQO bonds,
C–O–C bonds and –COO bonds, introduced on the carbon
nanotubes during the grafting process. Moreover, the
transmittance band appears at 2848 and 2947 cm1
associated with the formation of –CH bonds, and the
CQC bond of MA (at 3129 cm1) and carbon nanotubes
(at 1600–1475 cm1) disappeared at the same time. It
represents that maleic anhydride was linked to the
MWCNT.
O
C
O
C
O
O
C O PLA OH
C OH
HO-PLA-OH
Hydrogen bond
3.2. Mechanical properties
Fig. 3 depict the mechanical properties of MWCNT/
PLA composites with various MWCNT contents. Adding
MWCNT enhanced the tensile strength and flexural
strength of MWCNT/PLA composites. Blending 0.5 parts
per hundred parts of resin (phr) MWCNT in PLA, which is
high crystalline, slightly increased the tensile strength from
60 to 63.5 MPa (an increase of 5.8%). However, when
0.5 phr MWCNT was blended with PLA, which is low
crystalline, the tensile strength was elevated from 59.9 to
68.5 MPa (an increase of 14.4%), which exceeds that of
HC-PLA with the same MWCNT content. The greater
improvement in tensile strength may be caused by the
better dispersion of MWCNT in LC-PLA. Restated, the
homogeneous distribution of MWCNT in LC-PLA in-
crease the interface bonding and increases the shear
stress between MWCNT and the polymer matrix. With-
out interfacial adhesion, between the fiber and the
plastic, the tensile strength would decrease as the fiber
contents increased, as indicated by various authors [1,3].
MWCNT were surface-grafted with maleic anhydride
(Fig. 1) and further blended with LC-PLA to improve
the bonding between MWCNT and PLA and thereby
improve the mechanical properties of the MWCNT/
PLA composite as potential bone substitute material. Its
tensile strength exceeded that of the untreated composite.
The tensile strengths of pristine LC-PLA and 4 phr
modified MWCNT/LC-PLA composites are 59.9 and
76.2 MPa, respectively (representing a difference of
27.2%). Moon et al. [1] showed that the tensile modulus
of the CNTs/PLLA composite increased as the CNT
content increased, but the tensile strength and ultimate
elongation decreased. Oksman et al. [4] indicated that when
30 wt% flax fiber was used to reinforce PLA, the tensile
strength of the composite was increased only by 6%.
Composites with coupling agents exhibit greater tensile
strength than untreated ones, because interfacial bonding
was improved. The results indicate that modifying the
surface of the carbon nanotubes enhances the compatibility
 ARTICLE IN PRESS
C.-F. Kuan et al. / Journal of Physics and Chemistry of Solids 69 (2008) 1395–1398 1397

56 Pristine MWCNT
O
54 C
CH2 O
CH
C
MA-g-MWCNT

T%
52 O

C-H
50
-COO- -C-O-C-
1740 1365 1228, 1214
48
4000 3500 3000 2500 2000 1500 1000
O
C
120
O
100 Maleic Anhydride C
O
80
T%

60 -CH-
3121, 3129
40
20
0
4000 3500 3000 2500 2000 1500 1000
Wavenumber ( cm-1)

Fig. 2. FT-IR spectrum of MA-g-MWCNT and maleic anhydride.

80 LC-PLA / MWCNT 122 LC-PLA / MWCNT

HC-PLA / MWCNT HC-PLA / MWCNT
78 LC-PLA / MA-g-MWCNT 120 LC-PLA / MA-g-MWCNT

76 118

74 116
Flexural Strength ( MPa )
Tensile Strength ( MPa )

72 114

70 112

68 110

66 108

64 106

62 104

60 102

58 100
-1 0 1 2 3 4 5 -1 0 1 2 3
MWCNT Contents ( phr) MWCNT Contents ( phr)

Fig. 3. Tensile and flexural strength of MWCNT/PLA composites.

between the polymer and the filler, increasing the tensile 3.3. Surface resistance of MWCNT/PLA composite
properties.
Moreover, dispersion was enhanced by covalent or Fig. 4 presents the electrical surface resistance of
hydrogen bonding between MA-g-MWCNT and LC- MWCNT/PLA composite. The surface resistance dropped
PLA. The flexural strengths of pristine LC-PLA and as the MWCNT content increased. However, the disper-
4 phr modified MWCNT/LC-PLA composites are 102.3 sion of MWCNT in the PLA polymer matrix importantly
and 120.2 MPa, respectively (representing a difference governs the extent of the decline in the surface resistance.
of 17.5%). When the MWCNT content exceeded 0.5 phr, the surface

1398
16
14
log(Surface Resistivity) (Ω/sq.))
12
10
8
6
4
2 cause the electrical conductivity and mechanical character-
0.0 0.5 1.0 1.5 2.0 2.5 3.0
MWCNT Contents ( phr )
Fig. 4. Effect of MWCNT contents on the surface resistance of MWCNT/
PLA composites.
resistance in LC-PLA composites differed greatly from that
of HC-PLA composite, since the dispersion of functiona-
lized MWCNT in the PLA matrix differs considerably.
CNT has a high aspect ratio and many p-bonds (CQC
bond), so the electrons may be transferred through the p-
bond of CNT. The surface conductivity improved mark-
edly when CNT was added and well dispersed. From DSC
study, the crystalline region of PLA did not disappear
when 0.5 phr MWCNT was added, suggesting that
MWCNT was not intercalated in the crystalline region of
PLA, so most MWCNT dispersed out of the crystalline
region of PLA. Accordingly, most carbon nanotubes
aggregate mainly in the amorphous region of the PLA
matrix, indicating that the dispersion of MWCNT in HC-
PLA matrix was worse than that in the LC-PLA matrix.
ARTICLE IN PRESS
C.-F. Kuan et al. / Journal of Physics and Chemistry of Solids 69 (2008) 1395–1398
LC-PLA / MWCNT Consequently, electron transfer in crystalline HC-PLA
HC-PLA / MWCNT composites is less efficient than that in LC-PLA composite.
LC-PLA / MA-g-MWCNT Moreover, dispersion was enhanced by covalent or
hydrogen bonding between MA-g-MWCNT and LC-
PLA. When only 0.5 phr modified MWCNT was added
to LC-PLA, the surface resistance of the composite fell
from 5.46  1015 to 2.61  102 O/& (by 1013 order).
4. Conclusions
Comparisons of carbon nanotubes-reinforced HC- and
LC-PLA composites were discussed. Carbon nanotubes
istics of LC-PLA to be better than those in HC-PLA.
3.5 4.0 4.5
Acknowledgement
The authors greatly appreciate the financial support for
this research from Plastics Industrial Development Center
(PIDC) in Taichung, Taiwan, ROC.
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