International Communications in Heat and Mass Transfer 32 (2005) 1202 – 1210

www.elsevier.com/locate/ichmt

Enhancement of thermal conductivity with

carbon nanotube for nanofluidsB
Min-Sheng Liu a, Mark Ching-Cheng Lin b, I-Te Huang a, Chi-Chuan Wang a,T
a
Energy Resources Laboratories, Industrial Technology Research Institute, Hsinchu, Taiwan, ROC
b
Materials Research Laboratories, Industrial Technology Research Institute, Hsinchu, Taiwan, ROC
Available online 13 June 2005

Abstract

Thermal conductivity enhancements in ethylene glycol and synthetic engine oil in the presence of multi-
walled carbon nanotubes (MWNTs) are investigated. CNT nanofluids are prepared using a two-step method.
The volume concentration of CNT–ethylene glycol suspensions is below 1.0 vol.% and that of CNT–
synthetic engine oil suspensions is below 2.0 vol.%. The thermal conductivities of the CNT suspensions are
measured with a modified transient hot wire method. The results show that CNT–ethylene glycol suspensions
have noticeably higher thermal conductivities than the ethylene glycol base fluid without CNT. The results
for CNT–synthetic engine oil suspensions also exhibit the same trend. For CNT–ethylene glycol suspensions
at a volume fraction of 0.01 (1 vol.%), thermal conductivity is enhanced by 12.4%. On the other hand, for
CNT–synthetic engine oil suspension, thermal conductivity is enhanced by 30% at a volume fraction of 0.02
(2 vol.%). The rates of increase are, however, different for different base fluids. The CNT–synthetic engine
oil suspension has a much higher enhanced thermal conductivity ratio than the CNT–ethylene glycol
suspension.
D 2005 Elsevier Ltd. All rights reserved.

Keywords: Nanofluids; Thermal conductivity; Carbon nanotube

B
Communicated by J.P. Hartnett and W.J. Minkowycz.
T Corresponding author. D400 ERL/ITRI, Bldg. 64, 195~6 Section 4, Chung Hsing Rd., Chutung, Hsinchu 310, Taiwan,
ROC.
E-mail address: ccwang@itri.org.tw (C.-C. Wang).

0735-1933/$ - see front matter D 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.icheatmasstransfer.2005.05.005
 M.-S. Liu et al. / International Communications in Heat and Mass Transfer 32 (2005) 1202–1210 1203

1. Introduction

The thermal conductivity of heat transfer fluid plays an important role in the development of energy-
efficient heat transfer equipment including electronics, HVAC&R, and transportation. Development of
advanced heat transfer fluids is clearly essential to improve the effective heat transfer behavior of
conventional heat transfer fluids. Nanomaterials have been extensively researched in recent years.
Emerging nanotechnology shows promise in every aspect of engineering applications. Recently, there
has been interest in using nanomaterials as additives to modify heat transfer fluids to improve their
performance [1–13]. The new class of heat transfer fluid is termed nanofluids which are formed by
combining nanomaterials with heat transfer fluids. The nanofluids are shown to improve thermal
conductivity and heat transfer considerably. Dispersion or suspension of nanomaterials of high thermal
conductivities into base fluids gives rise to higher thermal conductivity of the mixtures [1–5], thereby
increasing the heat transfer coefficient. However, the significant increase of thermal conductivity cannot
be solely attributed to the addition of nanomaterials [10]. This is because the predictions of effective
thermal conductivity of solid/liquid suspensions by conventional models significantly underpredict the
measured results. Some subsequent studies are trying to explore the fundamental mechanisms [14–16] to
gain further insight of this unusual transport phenomenon. But it seems still a long way to finalize the
true mechanisms behind.
Compared with millimeter- or micrometer-sized particle suspensions, nanofluids possess better long-
term stability and rheological properties, and can have dramatically higher thermal conductivities. In
addition to enhanced heat transfer performance, it is found that nanofluids can have a 200% increase of
the CHF in pool boiling application [17]. Again, the actual mechanism for this enhancement is unclear.
In essence, despite the promising features of nanofluids, the actual enhancement mechanisms are still
under investigations. Hence, more experimental data are needed for further analyzing. In this study,
thermal conductivity enhancements of ethylene glycol and engine oil in the presence of multi-walled
carbon nanotubes (MWNTs) are presented. The carbon nanotubes are dispersed in ethylene glycol or
engine oil. The thermal conductivities of the CNT suspensions are measured with a transient hot wire
method.

2. Experiments

Carbon nanotube (CNT) nanofluids were prepared using a two-step method. CNTs were prepared first. Multi-
walled carbon nanotubes (MWNTs) were produced by a catalytic chemical vapor deposition method (Nanotech
Port Co., Shenzhen, China). The specific surface areas of multi-walled carbon nanotubes were in the range of 40–
300 m2/g as received. The crystalline phases of the CNT were determined by X-ray diffraction (XRD).
The carbon nanotube powders were then added to ethylene glycol or synthetic engine oil base fluids. After
being mixed in the ethylene glycol base fluid, CNTs were dispersed by magnetic force agitation; the suspensions
were then homogenized by intensive ultrasonics. No surfactant was used in carbon nanotube–ethylene glycol
suspensions. On the other hand, N-hydroxysuccinimide (NHS) was employed as the dispersant in carbon
nanotube–synthetic engine oil suspensions. NHS is in the solid particle form. NHS was added into CNTs directly.
The mixture was blended by a magnetic stirrer. Synthetic engine oil was then filled into the CNTs–NHS mixture.
The mixture was mixed up by an ultrasonic homogenizer. The volume concentrations of carbon nanotube–ethylene
glycol suspensions are in the range from 0.2 to 1.0 vol.%. On the other hand, those of carbon nanotube-engine oil
suspensions are from 1.0 to 2.0 vol.%. The NHS is in 5 vol.% for all carbon nanotube–synthetic engine oil
1204 M.-S. Liu et al. / International Communications in Heat and Mass Transfer 32 (2005) 1202–1210

suspensions. The carbon nanotubes were measured for size and morphology before being dispersed in liquids.
CNTs were measured with scanning electron microscopy (SEM) and high-resolution transmission electron
microscopy (HRTEM) to determine microstructure.
The thermal conductivity (k) of CNT nanofluid was measured with a special designed computer-controlled
equipment as described in detail elsewhere [4]. Thermal conductivities were measured as a function of nanotube
volume fractions at room temperature. For the transient hot wire system, platinum wire was immersed in the fluid
using a vertical, cylindrical glass container. The diameter of platinum wire was 76.2 Am. The platinum wire was
simultaneously used as a heater and as an electrical resistance thermometer for the nanofluid. The surface of
platinum wire was coated with a thin electrical insulation epoxy for preventing the platinum wire from short
circuitry. The platinum wire’s temperature variation is obtained by the change in the electrical resistance with time.
The thermal conductivity is then estimated from Fourier’s law. The thermal conductivity of the nanofluid is
inversely proportional to the slope of the temperature versus time response of the platinum wire. The transient hot
wire system was calibrated using deionized water and ethylene glycol at room temperature. Uncertainty of the
measurement is less than 2%.

3. Results and discussion

A typical SEM micrograph of CNTs is shown in Fig. 1(a). The randomly oriented fiber-like CNTs are clearly
seen. An individual CNT is several microns long. Small catalytic, metallic nanoparticles are observed at the tip
of the CNT with diameters of 20–30 nm. Fig. 1(b) shows a typical HRTEM micrograph of CNTs. The HRTEM
image clearly shows the characteristic features of a multi-walled carbon nanotube (MWNT). The CNT core is
hollow with multiple layers almost parallel to the CNT axis. Its inner diameters are about 5 nm to 10 nm, and
outer diameters are about 20 nm to 50 nm, respectively. The CNT’s crystal structure was studied by X-ray
diffraction. Fig. 1(c) displays the XRD patterns of CNTs. The (002) peak indicates the graphitic structure of the
CNTs. They display considerable broadening X-ray diffraction lines. This observed line broadening can be used
to estimate the average size of the nanocrystals. The CNT size can be calculated from a single diffraction peak
using Scherrer’s formula. The size of CNT is 13.4 nm for the (002) peak. The CNT size is in good agreement
with HRTEM results.
The allotropes of carbon materials include graphite, diamond, fullerene, and carbon nanotube (CNT). The
fullerenes and carbon nanotube are both new and discovered recently [18]. This discovery has a strong impact
extending far beyond the restrictions of academia and marks the beginning of a new era in materials. Further, it has
generated extraordinary excitement in scientific communities all over the world.
The CNTs disperse in ethylene glycol and synthetic engine oil well. For carbon nanotube–ethylene glycol
suspensions, surfactant is not employed. On the other hand, N-hydroxysuccinimide (NHS) is used to disperse
carbon nanotube in synthetic engine oil. Both suspensions are subjected to high frequency ultrasonic vibration. The
two suspensions are black-colored liquid. The sedimentation of the suspensions is not visible. In order to
characterize the suspensions further, scanning electron microscopy (SEM) is used to inspect. However, it is
difficult to get the SEM images of carbon nanotube–synthetic engine oil suspensions. This may be due to higher
viscosity accompanied with the synthetic engine oil. The dispersion and stability of CNT nanofluids will be
discussed later.
For the measurement of thermal conductivity, the carbon nanotube–ethylene glycol suspensions or carbon
nanotube–synthetic engine oil suspensions are filled into the vertical, cylindrical glass container of transient hot
wire system. The long glass container has a inner diameter of 19 mm and a length of 240 mm. It is observed that
thermal conductivity enhancements for CNT nanofluids are approximately linear with the volume fraction. This
indicates that, in such a long cylindrical container, stable nanofluids are successfully prepared. The CNTs disperse
in ethylene glycol and synthetic engine oil well. The CNT–ethylene glycol suspensions are stable and the CNT–
 M.-S. Liu et al. / International Communications in Heat and Mass Transfer 32 (2005) 1202–1210 1205

Fig. 1. Characteristics of the carbon nanotubes. (a) Typical SEM micrograph of carbon nanotubes. (b) Typical HRTEM
micrograph of carbon nanotubes. (c) The XRD patterns of carbon nanotubes.
1206 M.-S. Liu et al. / International Communications in Heat and Mass Transfer 32 (2005) 1202–1210

engine oil suspensions are also stable. The stable CNT suspensions are prepared for thermal conductivity
measurement.
Figs. 2(a) and (b) show the thermal conductivity enhancements of CNT–ethylene glycol and synthetic engine
oil suspensions as a function of the volume fraction of CNTs. The results clearly show that CNT–ethylene glycol
suspensions have noticeably higher thermal conductivities than ethylene glycol base fluids. The results for CNT–
synthetic engine oil suspensions also exhibit the same trend. For CNT–ethylene glycol suspensions at a volume
fraction of 0.01 (1 vol.%), thermal conductivity enhancements of up to 12.4% is observed. On the other hand, for
CNT–synthetic engine oil suspension, thermal conductivity is enhanced by 30% at a volume fraction of 0.02 (2
vol.%). Conductivity of CNTs nanofluid is enhanced approximately linearly with the volume fraction of CNTs.
The rates of increase are, however, different for different base fluids. Experimental data is shown in Tables 1 and 2.
In the present experiment, small amount of CNT dispersion results in a significant increase in the thermal
conductivity of the base fluid. On the other hand, for CNT–ethylene glycol suspension, thermal conductivity

(a)
0.3
thermal conductivity ke (W/m.K)

0.29

0.28

0.27

0.26

0.25
0 0.2 0.4 0.6 0.8 1 1.2
volume fraction (vol. %)
(b)
0.2
thermal conductivity ke (W/m.K)

0.19

0.18

0.17

0.16

0.15

0.14
0 1 2 3
volume fraction (vol. %)

Fig. 2. (a) The thermal conductivity of carbon nanotubes–ethylene glycol nanofluids as a function of volume fraction. (b) The
thermal conductivity of carbon nanotubes–synthetic engine oil nanofluids as a function of volume fraction.
 M.-S. Liu et al. / International Communications in Heat and Mass Transfer 32 (2005) 1202–1210 1207

Table 1
Enhanced thermal conductivities of CNT–ethylene glycol nanofluid
Volume fraction (vol.%) Thermal conductivity increase ratio (%)
0.2 1.6
0.4 3.6
0.5 7.6
1.0 12.4

enhanced by 12.7% at a volume fraction of 0.01 (1 vol.%) has been reported [19]. Moreover, for CNT–synthetic
poly oil suspensions, the measured enhancement in thermal conductivity with 1 vol.% nanotubes in oil is 160% as
reported previously [10]. The results clearly indicate that the enhanced thermal conductivity ratios increase with
the increase of volume fraction of CNTs. The increase is nearly linear. The rates of increase are, however, different
for different base fluids. The results for CuO nanofluid with different volume fractions also exhibit the same trend
[20].
For ethylene glycol-based nanofluids containing CuO nanoparticles and CNTs, the experimental results show
that these nanofluids have substantially higher thermal conductivities than the liquids without addition of CuO
nanoparticles or CNTs. Considerable increases in thermal conductivity of up to 4% and 22% for CuO–ethylene
glycol suspensions at 1 and 5 vo1.%, respectively, were observed in previous study [20].
Furthermore, the CNTs have a much higher thermal conductivity enhancement when compared with CuO
nanoparticles dispersed in the same base fluid. The CNT increases up to 12.4% at the same volume fraction of 1
vol.% for ethylene glycol fluid. Therefore, CNT can improve nanofluids’ thermal conductivity significantly more
than CuO nanoparticles.
CNT has substantially higher thermal conductivity [21,22]. The typical value of thermal conductivity is 2000
W/md K for MWCNT and 33 W/md K for CuO. It can therefore be expected that their respective nanofluids’
thermal conductivities behave similarly. The high conductivity and high aspect ratio of CNT make it especially
suitable for heat transfer in a nanofluid. Notice that the thermal conductivity of carbon nanotube–synthetic engine
oil suspensions is higher compared with that of same suspensions without the addition of NHS surfactant.
Therefore, the presence of NHS has positive effect on the carbon nanotube–synthetic engine oil suspensions. The
impact of the NHS or other surfactants on the CNT suspension deserves further investigation. The enhancement of
thermal conductivity with the addition of CNT is not solely attributed to the contribution of CNT alone. In Fig. 3 a
remarkable difference between the measured thermal conductivity ratios to some models [23–25] is seen. The
predictive equations are shown in Table 3. For instance, for CNT–oil nanofluids, the measured thermal
conductivity is about 3–5 times higher than the existing models. Despite the thermal conductivities of solid/liquid
suspensions that have been studied for nearly a century, one can clearly see a significant underprediction of the
existing models. Choi et al. [10] pointed out the departure between the measured results and the predictions is from
the fundamental limits of conventional models. They further interpret this enhanced thermal conductivity as two
consequences of the presence of nanotubes in the liquid: the nature of heat conduction in nanotube suspensions,
and an organized structure at the solid/liquid interface.
The Brownian motion [26] on the nanoparticles at the molecular and nanoscale levels is a main mechanism
controlling the thermal conductivity of nanofluid. A theoretical model for the role of dynamic nanoparticles in

Table 2
Enhanced thermal conductivities of CNT–engine oil nanofluid
Volume fraction (vol.%) Thermal conductivity increase ratio (%)
1.0 8.5
2.0 30.3
1208 M.-S. Liu et al. / International Communications in Heat and Mass Transfer 32 (2005) 1202–1210

1.4

thermal conductivity ratio (ke / kf)

Maxwell
1.3 Hamilton-Crosser
Jeffery
MWNT/EG
MWNT/oil
1.2

1.1

1
0 0.5 1 1.5 2
volume fraction (vol. %)

Fig. 3. Comparisons of enhancement ratios of nanofluids relative to the predictive equations.

nanofluid has been proposed [15]. The fundamental difference between solid/solid composites and solid/liquid
suspensions is identified. This model is very helpful for nanofluids in the industrial applications of high efficiency
heat transfer. Similar to the nanoparticles, the characteristics of interface between CNT solid and base liquid need
to be exploited for better understanding of the role of CNT on the nanofluid.
The morphology measured by SEM and TEM shows that the CuO nanoparticles are typically spherical and
CNTs are fiber-like. The CuO nanoparticles are zero-dimensional nanomaterials and the CNTs belong to one-
dimensional nanomaterials with a high aspect ratio (approximately 100:1). CNT dispersed in base fluid can form
extensive three-dimensional CNT networks that facilitate thermal transport. On the other hand, it is observed
that the enhanced thermal conductivity ratio decreases with the increase of thermal conductivity of the base
fluid. CNT–synthetic engine oil suspension has a much higher enhanced thermal conductivity ratio than CNT–
ethylene glycol suspension. This indicates that the CNT nanofluids are affected by the property of base fluid.
The two suspensions are black-colored liquid. At present, it is difficult to get the SEM images of carbon
nanotube–synthetic engine oil suspensions. This may be caused by the synthetic engine oil with higher viscosity
relative to water.
For CNT–oil suspension with a surfactant, a much higher thermal conductivity enhancement of up to 160% at 1
vol.% is reported [10]. In the present study, CNTs from different sources are tested and surfactant is added to the
oil host liquid. Therefore, it is likely that lower thermal conductivity enhancement would be obtained with the
same concentration of CNTs. The highest thermal conductivity enhancement is seen from CNT nanofluids. This
application of CNT in nanofluid is very important for thermal management. It certainly deserves further intense
study.

Table 3
Conventional models of effective thermal conductivity of solid/liquid suspensions
Models Expressions
ke 3ða  1Þ/
Maxwell [23] ¼1þ
kf ða þ 2Þ  ða  1Þ/
ke a þ ðn  1Þ  ðn  1Þð1  aÞ/
Hamilton-Crosser [24] ¼
kf a þ ðn  1Þ þ ð1  aÞ/
 
ke 2 3b3 9b3 a þ 2 3b4
Jeffery [25] ¼ 1 þ 3b/ þ 3b þ þ þ 6 þ N /2
kf 4 16 2a þ 3 2
 M.-S. Liu et al. / International Communications in Heat and Mass Transfer 32 (2005) 1202–1210 1209

4. Conclusions

The thermal conductivities of nanofluids containing CNTs dispersed in ethylene glycol and synthetic
engine oil are improved significantly compared to pure fluids. Randomly oriented fiber-like CNTs are
clearly seen from SEM and TEM. An individual CNT is several microns long. Its inner diameters are
about 5 nm to 10 nm, and outer diameters are about 20 nm to 50 nm, respectively. The (002) peak
indicates the graphitic structure of the CNTs. The thermal conductivity enhancement for CNT nanofluid
increases almost linearly with the volume fraction of CNT. For CNT–ethylene glycol suspensions at a
volume fraction of 0.01 (1 vol.%), thermal conductivity increased up to 12.4%. On the other hand, for
CNT–synthetic engine oil suspensions, thermal conductivity increased by 30% at a volume fraction of
0.02 (2 vol.%). The higher thermal conductivities and the larger specific surface area of CNT have big
impacts on thermal conductivity. The CNT dispersed in base fluid can form an extensive three-
dimensional CNT network that facilitates thermal transport. The highest thermal conductivity
enhancement is seen in CNT nanofluids. This application is essential for thermal management.

Nomenclature
ke effective thermal conductivity of solid/liquid suspensions
kf thermal conductivity of base fluid
kp thermal conductivity of particle
a k p / k f, thermal conductivity ratio
b (a  1) / (a + 2)
N particle shape factor, n = 3 for spheres, n = 6 for cylinders
/ particle volume fraction

Acknowledgements

Support of this research through a grant from Bureau of Energy is greatly acknowledged. The authors
also wish to express their great appreciation to Dr. Choi of Argonne National Laboratory for his help.
The SEM performed by Mr. Kai-Liang Hsieh is also very helpful.

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