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Composites: Part A: Kai Yang, Mingyuan Gu
Composites: Part A: Kai Yang, Mingyuan Gu
Composites: Part A: Kai Yang, Mingyuan Gu
Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa
a r t i c l e
i n f o
Article history:
Received 5 May 2009
Received in revised form 23 October 2009
Accepted 23 October 2009
Keywords:
A. Polymermatrix composites
B. Thermal properties
D. Thermal analysis
E. Surface treatments
a b s t r a c t
Multi-walled carbon nanotubes (MWCNTs) were rst treated by a 3:1 (v/v) mixture of concentrated
H2SO4/HNO3, and then triethylenetetramine (TETA) grafting was carried out. Nano-sized silicon carbide
particles (SiCnp) were modied by the silane coupling agent. Epoxy nanocomposites lled with hybrid ller system containing TETA-functionalized MWCNTs and silane-modied SiCnp were prepared. The investigation on the thermal conductivity of epoxy nanocomposites lled with single ller system and hybrid
ller system was performed. Chemical surface treatment is conducive to the enhancement of thermal
conductivity of epoxy composites. The thermal conductivity of epoxy composites with hybrid ller system is higher than that of epoxy composites with any single ller system (functionalized MWCNTs or
modied SiCnp), which is due to the effective combination of MWCNT-to-MWCNT and SiCnp-to-SiCnp
conductive networks. Hybrid ller system could provide synergistic effect and cost reduction
simultaneously.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
The development of polymer composites with nanoscaled
modiers has become an attractive new subject in materials science. The thermal conductivity of polymer composites is an
important material property for many applications [15]. Due
to the fact that most polymers show a rather low thermal conductivity, the introduction of conductive llers is an effective
method to enhance the thermal transport of polymer-based composites. Carbon nanotubes (CNTs) are considered to be a type of
very attractive ller for the improvement of thermal transport
property of polymer composites because of their extremely high
thermal conductivity (about 6000 W/mK for single-walled CNTs
(SWCNTs) [6] and about 3000 W/mK for multi-walled CNTs
(MWCNTs) [7]). According to this, a certain enhancement of the
thermal conductivity of polymer-based nanocomposites by an
incorporation of CNTs can be expected and have also been reported for CNT/polymer nanocomposites [812]. However, the
potential application of CNTs is hindered by manipulation difculties owing to their insolubility and poor dispersion in polymeric matrices [13,14]. In order to optimize the thermal
conduction of polymer-based CNT nanocomposites, it is essential
to modify the sidewalls of CNTs by chemical functionalization
* Corresponding author. Fax: +86 021 62822012.
E-mail address: kyang_80@yahoo.com.cn (K. Yang).
1359-835X/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2009.10.019
216
remarkable improvement in the thermal conductivities of polymer composites. Obtained thermal conductivity values by experiments are much lower than those estimated by a rule of mixture
approach. On the contrary, the aspect ratio of the ller is a more
important parameter dictating the thermal conductivity of a
composite, because the llers with large aspect ratios easily form
the bridges between them, known as conductive network. At this
time, conductive networks from llers will be more important for
the thermal conductivities of polymer composites. The formation
of random bridges or networks from conductive llers facilitates
phonon transfer leading to high thermal conductivities. CNTs
possess the large aspect ratios and easily form the bridges or networks. The tube-to-tube networks facilitate phonon transfer
leading to high thermal conductivities of polymer composites.
Bonnet et al. [19] have reported that the thermal conductivity
of SWCNT/PMMA composites is dominated by the SWCNT network contribution. Thick MWCNTs with a high aspect ratio are
suggested to be the most favorable type of nanotube for an
enhancement of a polymer composites thermal conductivity
[20]. On the other hand, the large nanotube volume fraction
may cause some problems, such as the agglomeration of nanotubes, the increase of composite melt viscosity and the corresponding mechanical performance degradation. This means that
hybrid ller system with large formation of conductive networks
is signicant for the fabrication of the next generation heat dissipation materials.
In this current study, we report the effectiveness of hybrid ller system consisting of triethylenetetramine (TETA)-functionalized MWCNTs and silane-modied nano-sized silicon carbide
particles (SiCnp) on the preparation of thermally conductive
epoxy nanocomposites. We attempt to efciently make tube-totube and particle-to-particle networks be combined to optimize
thermally conductive paths. In order to establish the comparison,
we also study the thermal conductivity of epoxy nanocomposites
lled with single ller system (functionalized MWCNTs or modied SiCnp). Additionally, unfunctionalized MWCNTs and unmodied SiCnp are also investigated in order to evaluate the effect of
the surface modication. Chemical surface treatment of the llers
would improve the interfacial interaction, which is conducive to
good wettability and homogeneous dispersion. Interfacial thermal resistance is closely correlated with the differences in the
phonon spectra of llers and epoxy matrix. Heat transport along
isolated MWCNTs occurs by phonons with a wide range of
frequencies; in MWCNT/epoxy nanocomposites, this requires
phonon transfer from tube to tube via the epoxy [7]. Due to
the difference in stiffness, the MWCNTs and the epoxy matrix
are coupled by only a small number of low-frequency vibrational
phonon modes in the absence of covalent bonds at the interface.
Accordingly, thermal energy contained in high-frequency phonon
modes within the nanotubes must rst be transferred to lowfrequency phonons through phononphonon couplings before
being exchanged with the surrounding medium. This is the origin
of the high interfacial thermal resistance in MWCNT/epoxy
nanocomposites [21]. The similar mechanism is also indicated
for the interface between SiCnp and epoxy matrix. Therefore,
the goal of chemical surface modication is to introduce the
covalent bonds at the interfaces between the llers and epoxy
matrix. This is very benecial to the improvement of llermatrix interfacial interaction. Simultaneously, it can enhance the
wettability of the llers and facilitate their good dispersion.
Homogeneous dispersion is a positive factor to form combined
MWCNT-to-MWCNT and SiCnp-to-SiCnp conductive networks.
More effective llerller thermal conduction in the case of good
dispersion state is conducive to the enhancement of thermal conductivity of epoxy nanocomposites (llermatrixller transfer
Fig. 1. (a) Scheme for the process of grafting TETA onto the MWCNT and (b) scheme for chemical modication of SiCnp.
217
218
Table 1
The ller volume fractions of epoxy nanocomposites lled with different types of
llers.
Systems
used to coat the fracture surface of the sample for better observation. Thermal conductivity measurement was conducted by
employing ASTM E1225-87, which was based on temperature difference between reference and specimens at steady state and room
temperature. A minimum of four individual measurements was
performed on bulk specimens. The detailed information about
these measurements (ASTM E1225-87) can be referred in Ref. [23].
MWCNTs and SiCnp were dispersed in chloroform and the corresponding dispersions were placed for 72 h to check the ller dispersibility. The functionalized MWCNTs usually present better
dispersion in solvents. A stable dispersion was obtained in the case
of TETA-functionalized MWCNTs when equal amounts of as-received MWCNTs and TETA-functionalized MWCNTs were respectively added to the same volume of chloroform and mechanically
mixed (shown in Fig. 2a). With respect to untreated SiCnp and treated SiCnp by silane coupler, the similar phenomenon could be observed (exhibited in Fig. 2c). Moreover, the surface analytical
characterization of the llers was carried out. The XPS survey spectra (revealed in Fig. 2b) of as-received MWCNTs and TETA-functionalized MWCNTs were recorded to identify the chemical
composition of the surfaces. All the spectra exhibit C 1s and O 1s
peaks, whereas the XPS spectrum of TETA-functionalized MWCNTs
shows the remarkable intensication of O 1s peak. The reason for
this phenomenon could be attributed to the great effect of
H2SO4/HNO3 treatment on the MWCNT surface. Additionally, a N
1s peak is also found in this spectrum, which indicates that TETA
has been successfully grafted onto the MWCNT surface. The FT-IR
spectra of unmodied and modied SiCnp are displayed in
Fig. 2d. The bands at 930.45 cm 1 and 1101.03 cm 1 are found in
Fig. 2. (a) Photograph of as-received MWCNTs (marked with 1) and TETA-functionalized MWCNTs (marked with 2) dispersed in chloroform and wait for 72 h; (b) XPS
survey spectra of as-received MWCNTs and TETA-functionalized MWCNTs; (c) photograph of untreated SiCnp (marked with 1) and silane-treated SiCnp (marked with 2)
dispersed in chloroform and wait for 72 h; (d) FT-IR spectra of untreated SiCnp and treated SiCnp by silane coupler.
these spectra. The former could be assigned to the SiC characteristic absorption peaks and the latter to the SiO antisymmetric
stretching vibrations, which denotes that the surface of unmodied
SiCnp has been partly oxidized in the ller manufacture. The band
at 474.86 cm 1 could be assigned to the SiO bending vibrations.
In the FT-IR spectrum of unmodied SiCnp, the intensity of the peak
at 930.45 cm 1 (SiC bonds) is greater than that of the peak at
1101.03 cm 1 (SiO bonds). However, in the spectrum of modied
SiCnp, the latter is greater and CH2 characteristic absorption peaks
(the wavenumbers at 28302960 cm 1) are remarkable, which
indicates that more SiOSi bonds appear in the surface of SiCnp
and a coating of silane coupler has been formed.
The microstructures of an as-received MWCNT and a TETAfunctionalized MWCNT were further characterized by HRTEM. In
Fig. 3a, the tube wall of the as-received MWCNT is rather smooth.
However, in Fig. 3b, the surface of the TETA-functionalized
MWCNT is rather rough, which could be due to a TETA layer
formed on its tube wall. Fig. 3c shows the TEM image of silanemodied SiCnp.
Optimization of the epoxy-ller interfacial interaction is
signicant for the enhancement of thermal transport of epoxy
composites. Fig. 4 reveals the thermal conductivity of epoxy nanocomposites lled with different types of llers (error bars are also
shown in Fig. 4). It can be observed that the thermal conductivities
of silane-modied SiCnp/epoxy composites are larger than those of
unmodied SiCnp/epoxy composites. Silane coupler treatment
could bridge the connection of SiCnp to the epoxy matrix and decrease the resistance to the heat ow caused by epoxySiCnp interface. TETA functionalization would make tube carbon atoms be
covalently attached to matrix molecules. These carbon atoms will
therefore act as scattering centers for the heat carrying wave packages (phonons) and reduce tube thermal conductivity. In addition,
H2SO4/HNO3 treatment would shorten the length of MWCNTs, and
thus the aspect ratio would decrease. These factors are adverse to
the enhancement of thermal conductivity of MWCNT/epoxy composites. However, it can be clearly seen that with respect to different nanotube volume fraction, the thermal conductivities of TETAfunctionalized MWCNT/epoxy composites are larger than those of
as-received MWCNT/epoxy composites. The phenomenon denotes
that TETA functionalization improves the interfacial heat transport
between the epoxy matrix and the MWCNTs and facilitates better
dispersion of MWCNTs in the matrix, which is benecial to the
enhancement of the thermal conductivity of MWCNT/epoxy composites. Therefore, in the case of single ller system, chemical surface treatment contributes to the improvement of the thermal
conduction property of epoxy nanocomposites. It is due to increasing wettability and dispersion of nano-llers in epoxy matrix.
With regard to the single ller system, there is another similar
phenomenon that large ller volume fraction may lead to the decrease of the thermal conductivity of epoxy composites due to
the formation of large agglomerates (when ller volume fraction
is large, the viscosity of the composite (pre-curing) is massive
and the mixing is very difcult. Therefore, large agglomerates easily form. In the consolidation of the composite, voids or air pockets
would exist in these large agglomerates and lead to lower thermal
conductivity of the composite). This phenomenon would be more
remarkable in the composites lled with nano-structured llers
because these inclusions are small in size and their surface-to-volume ratios are high. In an attempt to simultaneously obtain high
thermal conductivity and prevent the appearance of large agglomerates, we applied hybrid ller system to epoxy composites. Hybrid
ller system could mitigate large agglomerates. On the one hand,
the application of hybrid ller system relatively decreases the content of functionalized MWCNTs. On the other hand, the spherical
modied SiCnp is lled in the brous MWCNT-to-MWCNT network,
which indicates that the space formed in MWCNT-to-MWCNT net-
219
Fig. 3. (a) HRTEM image of an as-received MWCNT; (b) HRTEM image of a TETAfunctionalized MWCNT; (c) TEM image of silane-modied SiCnp.
220
Fig. 4. Thermal conductivity of epoxy nanocomposites lled with different types of llers.
Fig. 5. Scheme for epoxy nanocomposites lled with hybrid ller system.
Fig. 6. FESEM image of epoxy nanocomposites lled with hybrid ller system (the
total ller volume fraction is equal to 20%).
221
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