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Energy Procedia 69 (2015) 699 705

International Conference on Concentrating Solar Power and Chemical Energy Systems,

SolarPACES 2014

Effects of surface modification on the suspension stability and

thermal conductivity of carbon nanotubes nanofluids
P. Zhanga, W. Honga, J. F. Wua, G. Z. Liua, J. Xiaoa, Z. B. Chena and H. B. Chenga*
a
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 430070,
Wuhan, China

Abstract

The composite carbon nanotubes (CCNTs) were synthesized by surface modification of the as-synthesized carboxyl-
functionalized carbon nanotubes (f-CNTs) with the polyethylene glycol, and the composite carbon nanotubes-based nanofluids
(CCNTs-based nanofluids) were prepared with the as-synthesized CCNTs and ethylene glycol. The surface molecular structure,
surface morphology of the CCNTs were characterized by Fourier Transform Infrared Spectroscopy, Field Emission Scanning
Electron Microscope and Transmission Electron Microscopy. The suspension stability and thermal conductivity enhancement
ratio of the CCNTs-based nanofluids were characterized via the thermal conductivity variation method. The results show that
suspension stability of the CCNTs-based nanofluids was greatly improved by surface modification of the carbon nanotubes; the
thermal conductivity of the CCNTs-based nanofluids was further enhanced and became more stable by surface modification.

2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
2015 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer review by the scientific conference committee of SolarPACES 2014 under responsibility of PSE AG.
Peer review by the scientific conference committee of SolarPACES 2014 under responsibility of PSE AG
Keywords: carbon nanotubes nanofluids; surface modification; suspension stability; thermal conductivity.

1. Introduction

Carbon nanotubes-based nanofluids (CNTs-based nanofluids) are very promising composite fluids applied in
solar thermal power generation to enhance heat transfer capabilities [1], because of their enhanced thermal
performance [2], stable chemical property and high temperature stability [3]. However, pristine carbon nanotubes
have strong tendency to rapidly aggregate and precipitate to the bottom of the container, which can clog any flow

* Corresponding author. Tel.: +86-13349878089; fax: +86-27-87879468.

E-mail address: chenghbok@163.com

1876-6102 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer review by the scientific conference committee of SolarPACES 2014 under responsibility of PSE AG
doi:10.1016/j.egypro.2015.03.080
700 P. Zhang et al. / Energy Procedia 69 (2015) 699 705

channels, seriously decay heat transfer effectiveness, and render practical engineering applications infeasible [4,5].
Therefore, improving suspension and heat transfer enhancement stability of CNTs-based nanofluids is the key
challenge to enable successful engineering applications of these CNTs-based nanofluids [6]. To efficiently mitigate
these disadvantages, a novel method has been developed to controllably modify the surface characteristics of CNTs
through in-situ grafting organic molecular chains on the surface of CNTs, so that composite CNTs (CCNTs) and
CCNTs-based nanofluids have been prepared using ethylene glycol carrier fluid. The effects of surface modification
on the suspension stability and thermal conductivity enhancement ratio of CCNTs-based nanofluids were
investigated. Moreover, the mechanisms that increase the suspension stability, or reduce sedimentation rate, were
studied.

Nomenclature

f base fluid
nf nanofluid
k nf thermal conductivity of nanofluids
kf thermal conductivity of the base fluid ethylene glycol
k=k nf -k f thermal conductivity enhancement of nanofluids
k/k f thermal conductivity enhancement ratio
volume fraction of CCNTs
T temperature

2. Experimental procedure

2.1. Preparation of the CCNTs-based nanofluids

Firstly, carboxyl-functionalized carbon nanotubes (f-CNTs) were synthesized with carbon nanotubes and a mixed
acid composed of nitric and sulfuric acid for 5 hours [7,8]; then the composite carbon nanotubes (CCNTs) were
synthesized via esterification reaction between the as-synthesized f-CNTs and polyethylene glycol. Finally, CCNTs-
based nanofluids were prepared by suspending CCNTs in ethylene glycol for five different volume fractions (0.1,
0.3, 0.5, 0.7 and 0.9 vol%) by means of mechanical agitation and ultrasonic mixing.

2.2. Characterization of CCNTs-based nanofluids

The structure and properties of both CNTs and CCNTs were characterized by Fourier Transform Infrared
Spectroscopy (FT-IR), Field Emission Scanning Electron Microscope (FE-SEM), and Transmission Electron
Microscopy (TEM). The suspension stability of the CCNTs-based nanofluids was evaluated via the thermal
conductivity variation method [9]. Thermal conductivity of nanofluids were measured using a thermal properties
analyzer, which complies with ASTM and IEEE Standards [10].

3. Results and discussion

3.1. The surface molecular structure of CCNTs

To judge whether the surface modifier polyethylene glycol was successfully grafted onto the surface of the as-
synthesized CCNTs, the surface molecular structure of the as-synthesized CCNTs and pristine CNTs were analyzed
by FT-IR spectra, because the FT-IR spectra can reflect the changes of the surface molecular structure of the CCNTs
as the organic surface modifier polyethylene glycol (PEG) 200 was grafted on the surface [11]. So the FT-IR spectra
of as-synthesized CCNTs and pristine CNTs (for comparison) were collected, as shown in Fig. 1. The infrared
characteristic absorbing peaks of the CCNTs can be assigned to -COO-stretch (1642.48 cm-1), -OH stretch (1383.49
cm-1), and CH 2 stretch(702.72 cm-1). In contrast, FT-IR spectrum of the pristine CNTs does not exhibit these
 P. Zhang et al. / Energy Procedia 69 (2015) 699 705 701

absorption bands. These results show that the surface molecular chain has the characteristic groups of polyethylene
glycol: -COO-, -OH, and CH 2 ; that is, the surface modifier polyethylene glycol was successfully grafted onto the
surface of composite carbon nanotubes. Thereby, the surface properties of the CCNTs would be modified by the
grafted organic molecular chains [12].

Fig. 1. FT-IR images of CCNTs and pristine CNTs.

3.2. Surface morphology of CCNTs

The surface morphology of the CCNTs was characterized by SEM (as shown in Fig. 2 A), and the surface
morphology of the CNTs was characterized by TEM for comparison (as shown in Fig. 2 B). The radial dimension of
CCNTs ranged from 25 to 35nm, and the radial dimension of CNTs ranged from 12 to 18 nm. The increment (13-
17nm) of the radial dimension of CCNTs may be contributed to the grafted organic molecular chains polyethylene
glycol. In addition, the intertwining of CCNTs can be clearly observed, which implies that homogeneously
dispersing carbon nanotubes in carrier fluid is still a key technique for to prepare stable CCNTs-based nanofluids
[13].

Fig. 2. (A) SEM image of CCNTs; (B) TEM image of pristine CNTs.

3.3. The effect of surface modification on the stability of CCNTs-based nanofluids

To investigate how surface modification impacts the suspension stability of CCNTs-based nanofluid, 0.3 vol%
CCNTs-based nanofluid and 0.3 vol% CNTs-based nanofluid were respectively prepared; and their suspension
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stability was assessed by the thermal conductivity variation method [9]. Thermal conductivities of the base fluids
ethylene glycol (k f ) and the CCNTs-based nanofluids (k nf ) were measured by a transient short hot wire method [14].
In order to reduce the error due to the limit of measurement precision, and increase the sensitivity of surface
modification on the thermal conductivity of CCNTs-nanofluids, normalization processing was adopted by taking
k/k f (=(k nf -k f )/k f ) describing the thermal conductivity enhancement ratio of CCNTs-based nanofluids. The data
are shown in Fig. 3 A and B. The thermal conductivity enhancement ratio of 0.3 vol% CCNTs-based nanofluid (A)
was about 12.8 %, and exhibited no measurable decline over a 1000 hours period. In contrast, the thermal
conductivity enhancement ratio of 0.3 vol% CNTs-based nanofluid (B) was about 7.9 %, smaller than that of 0.3 vol%
CCNTs-based nanofluid by 38.3 %, which shows that surface modification further improved the thermal
conductivity enhancement effect of nanotubes. In addition, the thermal conductivity enhancement ratio of the 0.3 vol%
CNTs-based nanofluid degraded sharply from 7.9 % to about 0 % after 26 hours. These results clearly demonstrated
that the surface modification of CNTs not only increased the thermal conductivity enhancement, but also markedly
improved the stability of thermal conductivity enhancement effect [15].
Fig. 3 A inset and Fig. 3B inset are the photo of the 0.3 vol% CCNTs-based nanofluid and the 0.3 vol% CNTs-
based nanofluid after standing for 1000 hours and 26 hours, respectively. As shown in Fig. 3 A inset, there was no
observable sedimentation in the CCNTs-based nanofluid even after standing for 1000 hours (a). However, rapid
sedimentation occurred in the CNTs-based nanofluid after standing for 26 hours (As shown in Fig. 3B inset b), the
formation of the mud line separating clarified fluid above the mud line, and fluid with high solids loading fluid
below the mud line can be clearly observed. Obviously, the suspension stability of the 0.3 vol% CCNTs-based
nanofluid is much higher than that of the 0.3 vol% CNTs-based nanofluid, that is, the stability of CNTs-based
nanofluid can be markedly improved by surface modification of CNTs, which in this case was achieved by grafting
organic molecular chains polyethylene glycol on the surface of carbon nanotubes. Because grafted organic
molecular chains polyethylene glycol has similar molecular structure, based on the principle of the dissolution in the
similar material structure, the grafted organic molecular chains polyethylene glycol could stretch into the carrier
fluid molecule ethylene glycol to increase the buoyant force of the nanotubes, and surface modification could endow
carbon nanotubes with compatibility with the carrier fluid, so that suspension stability has been markedly improved
[16]. Thereby, we believe that surface modification is an effective way to improve the stability of nanofluids. The
mechanism of surface modification on the thermal conductivity of nanofluids is very complicated, needs to be
deeply investigated; according to this experimental results, keeping the CNTs nanoparticles uniformly dispersed in
carrier fluid and no sedimentation is of greatest importance.
 P. Zhang et al. / Energy Procedia 69 (2015) 699 705 703

Fig. 3. (A) Thermal conductivity enhancement ratio of 0.3 vol% CCNTs-based nanofluid; (B) 0.3 vol% CNTs-based nanofluid as a function of
time. Insets are photos of sedimentation of CCNTs-based nanofluid (a) after standing for 1000 hours, and CNTs-based nanofluid (b) after
standing for 26 hours.

3.4. The effect of volume fraction and temperature on the thermal conductivity enhancement ratio of CCNTs-based
nanofluids

In order to further seek for more suitable CCNTs-based nanofluids with high stability and high thermal
conductivity enhancement effect for applied in heat transfer engineering, the effect of volume fraction on the
thermal conductivity enhancement ratio was investigated by preparing five CCNTs-based nanofluids with different
volume fractions (0.1, 0.3, 0.5, 0.7 and 0.9 vol%), and measuring thermal conductivity enhancement ratio. Thermal
conductivities of the base fluids ethylene glycol (k f ) and the CCNTs-based nanofluids (k n f ) were measured by a
transient short hot wire method. k/k f and refer to the thermal conductivity enhancement ratio of CCNTs-based
nanofluids ( k=k nf -k f ) and the volume fraction of CCNTs, respectively. As shown in Fig. 4, the thermal
conductivity enhancement ratio increased with the volume fraction of CCNTs, from 5.9 % up to 21.03 % as the
volume faction increased from 0.1 to 0.9 vol%. The results show the effect of the volume fraction on the thermal
conductivity enhancement ratio of CCNTs-based nanofluids is in accordance with that reported in the literatures
[17,18], so the thermal conductivity of the CCNTs-based nanofluids can be further enhanced by increasing the
volume fraction of CCNTs.
704 P. Zhang et al. / Energy Procedia 69 (2015) 699 705

Fig. 4. Thermal conductivity enhancement ratio of CCNTs-based nanofluids as a function of CCNTs volume fraction.

3.5. The effect of temperature on the thermal conductivity enhancement ratio of CCNTs-based nanofluids

The nanofluids are different from traditional fluids that the thermal conductivity of nanofluid increases with the
temperature, while the thermal conductivity of traditional fluids decreases with the temperature. To expand the
applications of the nanofluids at high temperatures, the thermal conductivity enhancement ratio of 0.3% CCNTs-
based nanofluid was investigated as a function of temperature. As shown in Fig. 5, within the scope of the test, a
linear relationship was obtained, k/k f =1.065T-13.825, which showed that the thermal conductivity enhancement
ratio increased with the temperature, from 12.8 % up to 55.4 % as the temperature increased from 25 to 65 . The
results show that compared with the thermal conductivity of CuO-based nanofluids at different temperature,
reported in the literature [19], the CCNTs-based nanofluids have an advantage on the heat transfer applications
under high temperature. So the CCNTs-based nanofluids can be as more promising nanofluids used in heat transfer
applications by increasing the temperature of CCNTs to enhance the thermal conductivity.

Fig. 5. Thermal conductivity enhancement ratio of CCNTs-based nanofluid as a function of temperature.

 P. Zhang et al. / Energy Procedia 69 (2015) 699 705 705

4. Couclusion

In this study, CCNTs were synthesized via in-situ grafting polyethylene glycol chains onto the CNTs, and the
CNTs-based nanofluids were prepared by suspending CCNTs in ethylene glycol. The stability of suspension and
thermal conductivity enhancement ratio of CCNTs-based nanofluids had been investigated. The results show that
the stability of thermal conductivity enhancement effect of the CCNTs-based nanofluids was also much better than
that of the CNTs-based nanofluids of comparable volume fraction; the thermal conductivity enhancement ratio of
the CCNTs-based nanofluids increased with the volume fraction of CCNTs and the temperature, which indicated
that the thermal conductivity could be tuned by adjusting the volume fraction and the temperature. Thereby, it can
be concluded that surface modification can significantly improve the suspension stability and stabilize thermal
conductivity enhancement effect to meet the needs of heat transfer applications in solar thermal power generation.

Acknowledgements

This work is financial supported by state key development program of basic research of china (2010CB227105)
and Natural Science Foundation of China (51372189).

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