Microstructure and Mechanical Properties of Carboxylated-CNT-PLA Comp

Journal of Composite Materials
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Microstructure and Mechanical Properties of Carboxylated Carbon

Nanotubes/Poly(L-lactic acid) Composite
Jiangtao Feng, Jiehe Sui, Wei Cai and Zhiyong Gao
Journal of Composite Materials 2008; 42; 1587
DOI: 10.1177/0021998308092208
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Microstructure and Mechanical

Properties of Carboxylated Carbon
Nanotubes/Poly(L-lactic acid) Composite
JIANGTAO FENG, JIEHE SUI, WEI CAI* AND ZHIYONG GAO
School of Material Science and Engineering
Harbin Institute of Technology, Harbin, China
ABSTRACT: Poly(L-lactic acid) (PLLA)/MWNTs composites were prepared by

mixing solubilized PLLA with solutions of MWNTs treated by four kind of acids.
Fourier transform infrared (FT-IR) spectra revealed that carboxyl groups were
grafted to the surface of MWNTs. The water solubility showed that the MWNTs
treated by HNO3/H2O2 and HNO3/H2SO4 could suspend in the air at room
temperature for more than 100 days. Thermogravimetric analysis (TGA) showed
that MWNTs treated by HNO3/H2O2 and HNO3/H2SO4 obtained relatively high
COOH content. Mechanical properties of composites showed that the Youngs
modulus of the carboxylated MWNTs/PLLA composites increased compared to the
pure PLLA. Scanning electron microscopy (SEM) images of fracture morphology
confirmed that the dispersion of carboxylated MWNTs was more homogeneous than
the pristine MWNTs in polymer matrix. MWNTs treated by HNO3/H2O2 could get
more COOH group and less damage.
KEY WORDS: carbon nanotubes, poly(L-lactic acid) (PLLA), composite materials,
mechanical properties.
INTRODUCTION
INCE THE CARBON nanotubes (CNTs) were discovered by Iijima 1991 [1], they have
been considered as ideal reinforcing fillers for polymer matrixes to achieve high
performance and multi-functions because of their nanometer size, high aspect ratio,
extraordinary mechanical strength, and high eletrical conductivity [24].
Considering the practical applications of carbon nanotubes, it is predicted that the area of
largest consumption of carbon nanotubes will be as one of the most promising candidates
for the design of novel polymer composites [5]. CNTs/polymer composites could be used
as a scaffold for the tissue engineer in osteoblast proliferation and, bone formation [6,7].
Li et al. [8] fabricated the composite based on CNTs/polycarbonate microfibrils reinforced
polyethylene, and the results showed that the tensile strength increased from 20 to
*Author to whom correspondence should be addressed. E-mail: weicai@hit.edu.cn

Figures 14 appear in color online: http://jcm.sagepub.com
Journal of COMPOSITE MATERIALS, Vol. 42, No. 16/2008

0021-9983/08/16 15879 $10.00/0
DOI: 10.1177/0021998308092208
SAGE Publications 2008
Los Angeles, London, New Delhi and Singapore
1587
J. FENG ET AL.
1588
22.6 MPa and the elastic modulus increased from 766 to 1197 MPa. Kuan et al. [9] reported
that the tensile strength of multiwalled carbon nanotubes reinforced polyurethane increased
by 370% compared to pure polyurethane. Blake et al. [10] functionalized MWNTs with
chlorinated polypropylene (CPP), the following addition of the CPPMWNTs to the CPP
polymer matrix resulted in a significant increase of mechanical properties.
Poly(L-lactic acid) (PLLA) is a linear aliphatic thermoplastic polyester, which has good
thermal plasticity, biodegradabililty, and biocompatibility. There is great interest in the use
of PLLA in implant materials, drug delivery systems, and packaging [11,12]. However, one
of the drawbacks for PLLA is that the mechanical properties alone are insufficient for high
load bearing applications [13]. To overcome the drawback, many approaches were carried
out to improve the mechanical properties of PLLA. Biphasic calcium phosphate (BCP) was
used as reinforcement to increase the mechanical properties of PLLA [14]. Shikinami et al.
[15] have applied hydroxyapatite (HA) as filler to improve the mechanical properties of
PLLA. Zhang et al. [16] prepared PLLA/bioglass composites by phase separation of
polymer solutions, and the elastic modulus of composites increased with the increase of glass
content. The concept of adding fillers as reinforcement has been applied in an endeavour to
produce high strength composite. In this article, CNTs were used as filler in an attempt to
improve the mechanical properties of PLLA. At present, the liquid oxiation method (usually
refluxing in nitric acid) is used to functionalize CNTs for attaching a variety of functional
groups to increase the solubility in the organic solvent or polymer matirix [1719]. Considering that the pristine CNTs easily entangle, different acids were used to treat the CNTs for
obtaining fine dispersion of CNTs in polymer matrix. The CNTs/PLLA composites were
prepared by solution casting. The corresponding characterization and mechanical properties were investigated by FT-IR, SEM, and tensile test. The dispersion of CNTs in polymer
matrix and the interaction between carbon nanotubes and PLLA were also clarified.
METHOD
Materials
Multi-walled carbon nanotubes (MWNTs) were purchased from the Nanotech Port
Company, Shenzhen, China. (The diameter is 510 nm, the length is 510 mm, and specific
surface area is 40300 m2/g). L-Lactic acid (PURAC Biochem.Spain) was used as received.
Stannous octoate (Shanghai Chemical Reagent Company, China) was used as a catalyst.
Chloroform and methanol were purchased from Kermel of China as analytic reagent.
Preparation of MWNTsCOOH/PLLA Composites
POLYMERIZATION OF PLLA
L-Lactide was prepared by polycondensation of L-lactic acid to give low molecular weight
poly (L-lactic acid) which was subsequently depolymerized under vacuum to yield the raw
lactide [20]. The lactide was purified by recrystallization from ethyl acetate. PLLA was
synthesized by ring-opening polymerization of L-lactide in the melt using stannous octoate
as initiator. A typical procedure was followed: the prepared lactide (7 g) was placed into
a flask. 0.006 mol stannous octoate was injected into the flask using a syringe. Then, the
flask was sealed under vaccum and heated in an oil bath at 1308C for 48 h. The resulted
product was dissovled in chloroform, precipitated in methanol, and dried under vacuum.

Properties of Carboxylated Carbon Nanotubes/Poly(L-lactic acid) Composite
1589
CARBOXYLATION OF MWNTs
Typically, 40 mL of HNO3 was injected into a 500 mL flask loaded with 50 mg pristine
MWNTs. And then, the mixture was stirred for 30 min, sonicated in an ultrasonic bath
(100 kHz) for 1 h and refluxed at 908C for 8 h to obtain MWNTs suspenstion solution. The
solution was washed with deionized water until pH approaching approximately 7, and
dried under vaccum at 608C for 8 h to obtain carboxylated MWNTs (MWNTsCOOH).
The other MWNTsCOOH, where pristine MWNTs were treated by HNO3/H2SO4 (1 : 1
by volume), HNO3/H2O2 (1 : 1 by volume) and HNO3/HCl (1 : 3 by volume), were
prepared in the same way.
FABRICATION OF MWNTsCOOH/PLLA COMPOSITES
Composites were prepared by solution casting. A typical proceture for the MWNTs
COOH/PLLA composite was described as follows: PLLA was mixed with 3 wt% of
MWNTsCOOH in chloroform at room temperature. The mixture was ultrasonicated for
30 min, then cast into glass mold and dried extensively at room temperature. As a
comparation, the composite of pristine MWNTs/PLLA and pure PLLA were fabricated
by the same way.
Characterization
FT-IR spectra of MWNTs and MWNTsCOOH were recorded on a Perkin Elmer
Spectrum One in the 4504000 cm1 region using KBr pellets. To investigate the
hydrophilic property, the MWNTsCOOH and pristine MWNTs were ultrasonicated in
deionized water for 30 min, then remained at room temperature. The mechanical
properties of composites as well as PLLA were performed by using a microcontrol
electronic tensionmeter (model WDW3100) according to the Chinese GB/T 5281998
standard. The sample used was a dog-bone type dumb-bell sample. The gauge length and
strain rate were 16 mm and 2.4 mm/min, respectively. The dispersion of MWNTs in
polymer matrix was observed by SEM.
RESULTS AND DISCUSSION
Carboxylated MWNTs
Figure 1 shows the FT-IR spectra of pristine MWNTs and the MWNTsCOOH. Except
the MWNTsCOOH (treated by HNO3/HCl), the peaks of MWNTsCOOH at 1714 and
3439 cm1 are attributed to CO stretching mode and OH stretching of carboxylic acids
with intermolecular hydrogen bonds, respectively [21], as shown Figure 1(b), (d) and (e).
Even if the peaks of the HNO3/HCl treated MWNTs at 3439 cm1 are not obvious,
the presence of COOH groups are also manifested by the peak of 1714 cm1. Therefore,
the presented spectrospcopic data makes clear that the COOH groups have been
introduced onto the surface of MWNTs by different acids treatment.
The Hydrophilic Property of MWNTsCOOH
Figure 2 shows the hydrophilic property of MWNTsCOOH and pristine MWNTs in
deionized water. The pristine MWNTs and MWNTsCOOH treated by HNO3/HCl begin

1590
J. FENG ET AL.
a: Pristine MWNTs
b: MWNTs (HNO3/H2O2)
c: MWNTs (HNO3/HCl)
d: MWNTs (HNO3)
Transmittance
e: MWNTs (HNO3/H2SO4)
a
b
c
d
e
1714 C=O
2000
3439 OH
2500
3000
3500
4000
Wavenumber (cm1)
Figure 1. FTIR spectra of pristine MWNTs and MWNTsCOOH.
(a)
(b)
(c)
HNO3
HNO3 and HCl
HNO3 and H2SO4
HNO3 and H2O2
CNT
HNO3
HNO3 and HCl
HNO3 and H2SO4
HNO3 and H2O2
CNT
HNO3 and HCl
HNO3 and H2SO4
HNO3 and H2O2
CNT
HNO3
Figure 2. Hydrophilic property of pristine MWNTs and MWNTsCOOH, (a) 8th; (b) 10 days and (c) 100 days.

1591
to precipitate at the eighth hour. Then, 10 days later the MWNTsCOOH treated by
HNO3 also precipitate. The MWNTsCOOH treated by HNO3/H2SO4 and HNO3/H2O2
could suspend homogeneously in the deionized water for more than 100 days. It can be
inferred from the following:
1. The existence of carboxy group. The COOH content of carboxylated MWNTs is
determined by TGA (Figure 3). As shown in Figure 3, there is a continuous weight loss
of all the carboxlated MWNTs, and the weight loss happens in the temperature range
from 200 to 5008C.The contents of COOH for MWNTsCOOH (HNO3/H2O2) and
MWNTsCOOH (HNO3/H2SO4) are 17 and 16%, respectively.
2. The different length of MWNTsCOOH after being processed in different acid
solutions also lead to the difference in solubility.
Mechanical Properties
The stressstrain curves of pure PLLA, pristine MWNTs/PLLA, and MWNTsCOOH/
PLLA composites are shown in Figure 4 and the characterized values of mechanical
properties are listed in the Table 1. We prepare and measure three samples for each kind of
acid treated MWNTs/PLLA composite, pristine MWNTs/PLLA composite, as well as pure
PLLA, and calculate the average value. Except for the composite of pristine MWNTs/
PLLA, the Youngs modulus of PLLA is increased with the addition of MWNTsCOOH in
contrast to the pure PLLA. Specifically, the MWNTsCOOH (HNO3/H2SO4)/PLLA
composite and MWNTsCOOH (HNO3/H2O2)/PLLA composite have a relatively high
Youngs modulus with a value of 394 and 388 MPa, separately. The ultimate tensile strength
Weight loss (%)
100
50
pristine MWNTs
MWNTs (HNO3/HCl)
MWNTs (HNO3)
MWNTs (HNO3/H2SO4)
MWNTs (HNO3/H2O2)
0
0
100
200
300
400
500
600
Temperature (C)
Figure 3. TGA traces of pristine MWNTs and MWNTsCOOH.

700
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J. FENG ET AL.
50
MWNTs (HNO3/H2SO4) /PLLA
MWNTs (HNO3) /PLLA
45
MWNTs (HNO3/H2O2) /PLLA
MWNTs/PLLA
40
MWNTs (HNO3/HCl) /PLLA
PLLA
Stress (MPa)
35
30
25
20
15
10
5
0
0
50
100
150
200
250
Strain (%)
Figure 4. Stessstrain curve of PLLA, pristine MWNTs/PLLA and MWNTsCOOH/PLLA composites.
Table 1. Mechanical properties of PLLA and

MWNTs/PLLA composites.
Composite
PLLA
PLLA/CNTs
PLLA/CNTs(HNO3/H2SO4)
PLLA/CNTs(HNO3/H2O2)
PLLA/CNTs(HNO3/HCl)
PLLA/CNTs(HNO3)
Ultimate tensile
strength (MPa)
Modulus
(MPa)
40.9
27.5
36.6
38.8
36.5
35.4
234
138
394
388
381
320
for the pristine MWNTs/PLLA composite and MWNTsCOOH/PLLA composites are not
improved, compared to the pure PLLA. Whereas, the ultimate tensile strength of MWNTs
COOH (HNO3/H2O2) reaches 38.8 MPa, which is the highest value except the pure PLLA.
It is possible that the acid treatment changes the physical structure of MWNTs and deduces
the intrinsic mechanical properties of MWNTs, although the COOH on the surface of
MWNTs could anchor the polymer matrix. Alternatively, it can be inferred that MWNTs
COOH (HNO3/H2O2) has less damage and more carboxy.
The state of dispersion of MWNTs in PLLA matrix observed by SEM is shown in
Figure 5. The pristine MWNTs disperse randomly and are entangled on the fracture surface
in the PLLA matrix (Figure 5(a)), which leads to the decrease of Youngs modulus of
pristine MWNTs/PLLA composite. Figure 5(be) show that MWNTsCOOH disperse
homogeneously in PLLA matrix, which result in higher Youngs modulus than that of pure
PLLA. It can be inferred that carboxy groups on the MWNTs reduce the surfacial free


(a)
(b)
(c)
(d)
1593
(e)
Figure 5. SEM of fracture morphology of (a) pristine MWNTs/PLLA composite, (b) MWNTsCOOH (HNO3/
H2O2)/PLLA composite, (c) MWNTsCOOH (HNO3/H2SO4)/PLLA composite, (d) MWNTsCOOH (HNO3/HCl)/
PLLA composite and (e) MWNTsCOOH (HNO3)/PLLA composite.
energy of MWNTs through steric effect. It can be seen from Figure 5 that MWNTsCOOH
are pulled out from the PLLA matrix in the process of tensile testing and the weak
interactions between fillers and polymer matrix always lead to a decrease of tensile strength.
CONCLUSIONS
The carboxyl groups have been successfully introduced onto the surface of MWNTs by
acid treatment. The MWNTsCOOH treated by HNO3/H2SO4 and HNO3/H2O2 could
suspend homogeneously in deionized water for more than 100 days. The acid treated

1594
J. FENG ET AL.
MWNTs could get good dispersion in the PLLA matrix, while the interaction force is
weak between PLLA and MWNTsCOOH. The acid of HNO3/H2O2 has relatively
positive effects on the dispersion of MWNTs and interaction between MWNTs and
polymer matrix.
ACKNOWLEDGMENT
The authors acknowledge the financial support for the research from the National Basic
Research Program of China (No. 2006CB708609).
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