Sok Wan Kim 284 KURUS2005

Thermal Properties of Multi-Walled Carbon

Nanotube-Reinforced Polypropylene Composites
Sok Won Kim
uou
Department of Physics, Ulsan 680-749, KOREA
Abstrucr -The thermal conductivity and thermal
diffusivity of chemically surface treated multi-walled carbon
nanotube (MWCNT) reinforced poly-propylene (PP)
composites were measured using 3 0 method in 90 - 320 K
and photoacoustic (PA) spectroscopy at roomtemperature,
respectively. Nine kinds of samples were prepared by the
melt-blending of PP resins with the addition of 0.1, 0.5, and
2.0 wt% of not treated, nitric acid @NO3) treated, and
potassiumhydroxide (KOH) treated nanotube contents, and
compression-molded at l S0c into about 0.5 mm thickness
composite films using the hot-press. The thermal
conductivity was in the range between 0.05 to 0.6 W.m-.K-
and increases as the temperature increases and the CNT
concentration increases. By the chemical treatment, the
thermal conductivity of 0.5 and 2.0 wt% samples were
enhanced about 2 times, however the sampk of 0.1 wt%
didnt changed. These can beexplained qualitatively by the
effects of chemica1 treatment on reinforcing ability for
CNTs/poIymer composites.
I. INTRODUCTION
Since the discovery of carbon nanotubes (CNTs) in
1991 [I] and the realization of their unique physical
properties, including mechanical, thermal, and electrical,
many investigators have endeavored to fabricate
advanced CNT composite materials that exhibit one or
more of these properties [2]. For example, as conductive
filler in polymers, CNTs are quite effective compared to
traditional carbon black micro-particles. CNTs possess
one of the highest thermal conductivities known more
than 600 Wmk- , which suggests their use in
composites for thermal managements [3]. A better
understanding of the relationships between processing,
interfacial optimization, and composite properties is a
major goal of this area of research, which may lead to
optimal reinforcement of polymer matrices with CNTs [4].
From the surface chemistry point of view, the
formation of oxygen functional groups on CNT surfaces
as well as the improvement of diversity in the polymeric
matrix by chemical treatment plays an important role in
reinforcing ability for CNTdpolymer composites [5-71.
Therefore, in this work, we performed chemical
surface treatment with different solutions, such as HNO,
and KOH to study the effect of acid-base interaction
between the MWCNT filters and the polymeric matrix on
thermophysical properties of the CNTs/polymer
composites, and measured the thermal conductivity and
thermal diffusivity of the chemically treated CNT-
reinforced poly-propylene composites.
11. THEORETICAL CONSIDERATIONS
A. 3aMethod
The thermal conductivity was measured by the 3 0
method. The 30 method has been widely utitized for the
thermal conductivity measurement of bulk and film type
samples. This method for the thermal conductivity
measurement of thin films uses a single metal-line as both
the heater and thermometer. An ac driving current at
angular frequency w heats the surface of the dielectric
film at a frequency 2w. Since the resistance of a pure
metal increases with temperature, these temperature
osciilations also produce an oscillation of the electrical
resistance at a frequency of 2 0 . Consequently, the
voltage drop across the metal-line has a small component
at 3w that can be used to measure the temperature
oscillations and therefore the thermal response of the
dielectric film and substrate as Fig. 1 [SI.
Fig. 1. The Schematic diagram of the 30 thermal conductivity apparatus
The thermal conductivity of 3 0 apparatus was
calculated from [ 9]
where V;W is the in-phase 3 0 voltage at frequency o.
TCR(temperature coefficient of resistance)is defined as
R dT
heaterhhemometer line, V the voltage across the metal
line at o, and Y30 the measured voltage at 3 w. TCR was
-- I dR . R is the average resistance of the
0-7803-8943-3/05/$20.00 Q 2005 IEEE Natural Sciences
KOR US'2005 285 Sok Won Kim
measured by a four-probe method prior to 3 0
measurements.
B. Photoacoustic (PA) Spectroscopy
There are two kinds of modes in FA measurements,
namely, front surface excitation (FSE) and rear surface
excitation (RSE). In general, the PA signal from RSE
mode is weaker than that from FSE; therefore,
especially for the case of thin film sample which
requires high frequency modulation, FSE is more
sensitive than RSE [IO].
For the PSE mode of an opaque film on a backing
material, the expressions for the amplitude variation of
the PA signal can be derived fromR-G theory as follows
11 11;
+
A, [{(I +g)eY +(1 - g)e-Y}2 cos2 Y +
{(I +g)eY -(I - g ) P- y cos* Y +
AB =-
2Y2
where
g =q I E j (3)
(subscripts band f refer to backing material and film
sample)
i "hi/& (4)
(hi , ai : thermal conductivity and diffusivity)
Y =4 - ( f =modulation frequency) ( 5)
j , =a/ i $ ( tl =thickness of film sample) ( 6)
where A. i s the amplitude constant which is independent
of modulation frequency, ei is the thermal effusivity, f,
is the characteristic frequency of the sample, and g is the
effusivity ratio of backing to sample.
111. EXPERIMENTAL PROCEDURE
A. Sample Preparation
Commercially obtained MWCNTs were purified by
following method before use. The purification was based
on a mixture of concentrated nitric (HNO,) and sulphuric
acids (H,S04) in a ratio of 1:3, respectively. In a typical
experiment, a 1 g portion of raw MWCNTs was added to
40 cm3 of the acid mixture in a round-bottomed flask, and
refluxed for 30 minutes. On cooling, the mixture was
washed with distilled water on a sintered glass filter until
the washings showed no acidity.
For the modification of MWCNT surfaces and
diversity, the chemical surface treatment was performed
with 10 wt% HN03 and KOff solutions at room
temperature for 1 h using an apparatus, which were
denoted to BCNT and CCNT, respectively (not treated
normal one was denoted as ACNT). Prior to use them, the
residual chemicals used were removed by Soxhlet
extraction by boiling with acetone at 800 for 2 h. Finally,
the MWCNTs were washed with 'distilled water for
several times and dried in a vacuum oven at 900 for 12 h.
For composite production, PP was melt-blended with
the addition of several nanotube concentrations specified
as wt% in the polymer: 0.1, 0.5, and 2.0%. The
temperature of the mixing system was estimated by a
thermocouple regulation of I900 and the blending time
was 10 minutes. The mixed samples were then
compressed into about 0.5 mm thickness under a pressure
of about 8 MPa at 2 l Of l for 10 minutes using a hot-press.
The samples were cut into pieces to measure thermal
conductivity and diffusivity in the thickness direction of
the MWCNTs/PP composites.
We embedded 0.1, 0.5,Z.O wt% ofeach CNTs (ACNT,
BCNT, and CCNT) into PP matrix, therefore 9 kinds of
composite samples were prepared.
3. Thermal Conductivity and DifJirsivity Measurements
As shown in Fig. 2, the thermally evaporated gold
metal strip line for heater and thermometer is about 20
pm wide and 3 mmlong. The electrical resistance of gold
layer was controlled about 10 R- 30 R by controlling the
evaporation time. The metal strip line is functioning as
both the heater and the thermometer for detecting 3w
signal. The thermal conductivity of chemically surface
treated MWCNT-reinforced composites was measured
in the temperature range between 90 and 320 K by
the nearly same process shown in our previous
experiments [9 J .
Fig. 2. Schematics of the deposited metal ship for thormal heating and
seusor on the S~ITIPIE
The experimental setup for PA thermal diffbsivity is
shown in Fig. 3 [12]. The heating beam from an Ar' laser
is absorbed by the sample placed in the PA cell. The
beam is modulated by an acousto-optic modulator (AOM)
whose modulation frequency can be varied from a few Hz
to 350 Hz. The beam size on the sample surface is fixed
by a condensing lens and iris to be 10 mm.
For detection and amplification of the PA signal, we
used a half-inch microphone (B&K 2639) whose
sensitivity is 40 mV.Pa-' and amplifier, respectively. A
dual-phase lock-in amplifier (EG&G 5302) is used to
analyze the phase and amplitude of the signal. Figure 2
also shows the design of the PA cell. To minimize the
stray effect and other background noise, the cell was made
Natural Sciences
Sok Won Kim 286 KORUS'2005
w PA CELL
Fig. 3. Schematic diagram of the experimental setup of the PA
spectroscopic method and the design of a PA cel l
of plexiglass, whose absorption is negligible. There are
two chambers in the cell, one for the sample and the other
for the microphone. The two chambers are connected by
a narrow channel. The amplitude of the PA signal was
measured by changing the modulation frequency of
AOM.result and discussions.
For detection and amplification of the PA signal, we
used a half-inch microphone (B&K 2639) whose
sensitivity is 40 mV.Pa-' and amplifier, respectively. A
dual-phase lock-in amplifier (EGBrG 5302) is used to
analyze the phase and amplitude of the signal. Figure 2
also shows the design of the FA cell. To minimize the
stray effect and other background noise, the cell was
made of plexiglass, whose absorption is negligibfe. There
are two chambers in the cell, one for the sample and the
other for the microphone. The two chambers are
connected by a narrow channel. The amplitude of the PA
signal was measured by changing the modulation
frequency of AOM.
IV. RESULTS AND DISCUSSION
The measured thermal conductivities of chemically
surface-treated and non-treated MWCNT-reinforced
composites are shown in Fig. 4. We measured 5 times for
each sample and the reproducibility and accuracy was
within I 0 %. As the temperature increases, the thermal
conductivity of all the samples increases. This is the
common trends in most of all the dielectric and polymer
materials because the dominant thermal carrier is a
phonon, however the unique difference is that the thermal
conductivity was enhanced by CNT fillers,
The thermal conductivity of the sample also increases
as the concentration of nanotube increase, therefore when
the CNT concentration is 0.1 wt%, the thermal
conductivity is minimum and becomes maximum at 2.0
wt%. These can be explained by the model of Choi et al.
[ 131 and Nan et al. [ 141 which calculate the enhancement
of thermal conductivity with the addition of CNT on
polymer matrix. From them, the addition of 0.1 wt% does
not change the thermal conductivity, however for
addition of 0.5 wt% and 2.0 wt%, the thermal
conductivity increases abruptly more than several times
and it depends on the ratio of thermal conductivity of
CNT and matrix material h, l h, ( X c and h, are thermal
50 100 150 200 250 300 350
Temperature, K
(4
0.01 . ' ' ' . ' I
50 100 150 200 250 300 350
Temperature, K
Fig. 4: Thermal conductivity of MWCNT-reinforced
composites (a) no treatment (ACNTs), (b) HNOj
treated (BCNTs), (c) KOH treated (CCNTs)
conductivity of composite and matrix material,
respectively). For our case, we can assume that h, 2 600
W.m-'.K',h, =0.4 W.m'*.K-', andh, l h, 2 1500,
therefore the thermal conductivity will be enhanced 3
times and 12 times at 0.5 wt% and 2.0 wt%, respectively
[14]. But, the figures show that it was enhanced about
twice at 0.5 wt% and 2.0 wt%. The trends are
qualitatively similar and the stight differences could be
due to interfacial thermal resistance between the PP
matrix and nanotubes, and local aggregation and twist of
the nanotubes in the composites. For further quantitative
investigation, microscopic study will be required.
Since CNTs are chemically inert, activating their
surface by the formation of oxygen functional groups is
Natural Sciences
KO R US'2005 287 Sok Won Kim
HNOl
mated
Uo treated
an essential prerequisite for tight binding to matrix. The
activated CNTs had several times specific surface area
and pore volume than those of the normal CNT, therefore
the acid and base treated CNT composites show at least 2
times larger thermal conductivity than not treated CNT at
higher CNT concentration composites. The samples
treated by HNO, and KOH shows no large differences
and this also needs microscopic study and chemical
approaches.
From these results, the chemical treatment of CNTs
surface enhances the thermal conductivity and diffusivity
as well as the thermo-mechanical properties of CNT-
reinforced composites.
In order to obtain the thermal diffisivity of the
samples, amplitude variation of the PA signal for each
sample was measured by changing the modulation
frequency from a few Hz to 350 Hz (Fig. 3). Figure 5
shows the measured amplitude variation of the PA signat
for 3 kinds of HN03 treated samples by changing the
modulation fiequency. As the modulation frequency
increases, the signal from all the sampres quickly decreases
and approaches to zero, and the signal behavior of other
not treated and KOH treated samples was similar.
The measured amplitudes were analyzed using
parameter estimation (PE) technique. The parameter
estimation procedure was used to find optimum values of
three-parameters (Y, g, and &) from Eq. (2). From the
value of Y, the characteristic frequency can be obtained
and the thermal diffusivity can be calculated from Eq. (6)
for a known thickness of the sample. A nonlinear PE
algorithm NL2SOL developed by Dennis et al. 115, 163
was used in this work.
KOH
treated
I '. . ' ' ' . ' ' ' . ' . ' ' 1
0.1 WPh
0.5 wt%
2.0 wt%
"I 30 I
r
I I
0.757 1.25 I I 1.149
0.769 I 1.530 I 1.348
0.814 1.888 1 1.495
0 50 100 150 200 250 MO 350
Fmquency, k
Fig. 5. Amplitude variation of the FA signal as a function
of modulation frequency
Table 1 shows the obtained thermal diffusivities of all
the MWCNT samples by PA spectroscopy. As was seen
above, the thermal diffisivity shows the same trends as
the thermal conductivity and this can be explained by the
relation of k =paCp where p is the density, a is the
thermal diffusivity and C, is the specific heat capacity of
the sample because pandC, can be assumed to be
constant for all the sample. As thermal conductivity,
thermal diffusivity was also enhanced by the embedding
of the nanotubes into the PP matrices.
TABLE 1
OBTAINED THERMAL DIFFUSIVITY (CM2S' )OF THE SAMPLES BY
PHOTOACOUSTIC APPARATUS
V. CONCLUSIONS
The thermal conductivity and thermal diffusivity of
surface treated CNT-reinforced poly-propylene
composites were measured by 3w method and photo-
acoustic method, respectively. By increasing the
concentration of CNTs, the thermal conductivity and
difisivity also increase. Both the acid treated and base
treated samples show twice larger diffusivity and
conductivity than the not treated samples. More detail and
microscopic investigation will be studied soon.
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