International Communications in Heat and Mass Transfer 78 (2016) 207213

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International Communications in Heat and Mass Transfer

journal homepage: www.elsevier.com/locate/ichmt

Thermophysical and optical properties of SWCNTs nanouids

Z. Said
Department of Sustainable and Renewable Energy Engineering (SREE), University of Sharjah, PO Box 27272, Sharjah, United Arab Emirates
Department of Engineering Systems and Management (ESM), Masdar Institute of Science and Technology, Abu Dhabi, United Arab Emirates

a r t i c l e i n f o a b s t r a c t

Available online 30 September 2016 The aim of this experimental study is to measure and analyze the thermophysical properties (density, thermal
conductivity, viscosity, and specic heat) and optical properties (transmittance, extinction coefcient) of
Keywords: SWCNTs nanouids. Different concentrations of 0.1, 0.25, and 0.5 vol.% were investigated. SWCNTs-based
Thermophysical nanouids exhibit signicant enhancement compared to water at low volume concentration. The favorable sta-
Optical properties
bility, thermophysical, and optical properties of SWCNTs nanouids are promising for solar thermal applications.
SWCNTs
They can be utilized as working uids for DASCs and volumetric solar collectors.
Extinction coefcient
Nanouid
2016 Elsevier Ltd. All rights reserved.

1. Introduction
Nanouids have improved favorable thermophysical properties,
such as thermal conductivity [15], lower specic heat, and enhanced
heat transfer coefcients [69] in comparison with conventional uids.
Furthermore, they also have favorable optical properties [1017] and,
when used as HTFs, they don't cause clogging in the pipes. [11]. Das
et al. [18] experimentally showed that thermal conductivity of a
nanouid can be augmented up to 4-fold by increasing the temperature.
Xuan and Li [19] also found that the heat transfer coefcient could be
enhanced by the use of nanouids, particularly when increasing the
ow or volume fraction. Different results on the density of nanouids
have been reported by the researchers and most of them are for a par-
ticular temperature or for a particular nanouid [2,20]. Obtaining the
viscosity of nanouids is of importance for establishing sufcient
pumping power. Besides the convective heat transfer coefcients,
Prandtl and Reynolds numbers are also reliant on viscosity.
The concept of direct absorption solar collector proposed by Minardi
et al. [21], is a promising new type of solar collector. The working
uid that functions as the absorber and the transporter are critical for
DASCs. However, the previously used working uids for DASCs are
black dyes or inks which were not efcient enough due to the
lower thermal conductivity and photo-induced instability. Therefore,
it is very important to develop new working uids with better
thermophysical properties, higher optical properties and stable at the
same time for DASCs and other solar collectors. Recently, nanouids
have gained attention, which mainly focuses on the theoretical predic-
tion and experimental efciency evaluation of nanouid-based DASCs
[13,2224] as well as optical properties of nanouids [11,2527].
Communicated by W.J. Minkowycz.
E-mail addresses: zaffar.ks@gmail.com, zsaid@sharjah.ac.ae.
The nanouid mix must be very cautiously selected to match its use
in order to see improvement. This is particularly true for the nanouid
optical properties. The optical properties of the base uid can be ex-
traordinarily improved by the addition of nanoparticles in base liquid
[28,29]. The properties are greatly reliant on the particle shape, size,
and the optical properties of the base uid [28]. Scattering and absorp-
tion can be signicantly improved by applying small changes in these
parameters. With the high volume fractions of the nanoparticles, all
the incoming thermal energy is absorbed in a thin surface layer, where-
as with lower volume fractions of the nanoparticles, all the incoming
solar radiation might not be absorbed. Therefore, these parameters
must be chosen very preciously to enhance the optical properties of
the uid or the nanouid could end up damaging instead of improving
the optical properties. Optical and thermal properties of single wall car-
bon nanohorns (SWCNHs) nanouid as DASCs was investigated [30].
Less energy was scattered away by MWCNTs nanouids compared to
Al- or CNPs-based nanouids [31]. A full characterization of the optical
properties of nanouids consisting of single-wall carbon nanohorns of
different morphologies in aqueous suspensions was carried out using
a novel spectrophotometric technique and was used to characterize
the optical properties of SWCNHs-based nanouids [32]. The extinction
index of water, ethylene glycol, propylene glycol, and Therminol VP-1
were achieved experimentally for solar thermal applications [33]. The
scattering and absorption properties of SWCNHs-based nanouids
were studied by L. Mercatelli et al. [34]. Unquestionably, nanouids
with improved thermophysical properties and higher optical properties
are highly necessary for enhanced efciency of DASCs.
Carbon nanotubes (CNTs) are one of the most amazing ndings of
the last era [35,36]. CNTs have achieved an abundant deal of devotion
for their thermal properties [3745]. High thermal conductivities of
CNTs have been reported in the literature, both numerically and exper-
imentally [4650]. Therefore, higher thermal conductivity is reported
using CNTs in nanouids compared to other nanoparticles. Nonetheless,

http://dx.doi.org/10.1016/j.icheatmasstransfer.2016.09.017
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208 Z. Said / International Communications in Heat and Mass Transfer 78 (2016) 207213
this unusual higher thermal conductivity could not be supported by
subsequently reported studies [44,5155]. Exceptional mechanical,
electrical and structural properties are reported for SWCNTs, which
have attracted the attention of the researchers in the eld [56,57].
SWCNTs possess outstanding thermal and chemical stabilities with
high-tensile strength and extreme light weight [58,59]. The specic
heat of SWCNTs has also been investigated by several researchers
[3840,60,61]. Limited data has been reported on the thermophysical
and optical properties of SWCNTs. Therefore, this study was carried
out to enrich the data based on the thermophysical and optical proper-
ties using SWCNTs at different volume concentrations.
2. Methodology
2.1. Materials and data collection
Short SWCNTs (90% CNTs, 60% SWCNTs) were purchased from
Nanostructured & Amorphous Materials, Inc., USA. Sodium dodecyl
sulfate (SDS, 92.5%100.5%, Sigma-Aldrich) was used as a surfactant
together with distilled water as a base uid. The properties of SWCNT
nanoparticles nanoparticle used in this experiment are listed in Table 1.
The characterization of SWCNTs nanoparticles and the density mea-
surements were performed using transmission electron microscope
(TEM) and Density Meter DA-130N, respectively.
2.1.1. Preparation of SWCNTs-based nanouids
The two-step method was used for preparing three volume concen-
trations (0.1, 0.25, and 0.5 vol.%) in this study. The stability of nanouids
is extremely important for the experiment. Therefore, two approaches
were used to prepare a stable nanouid. The rst approach involved a
mechanical process to separate agglomerated nanoparticles, and sec-
ondly stabilizing the suspensions. A high-pressure homogenizer was
used to overcome the strong cohesion force between the SWCNTs. The
nanouids in distilled water segregate and settle down under gravita-
tional forces due to their hydrophobic nature. Therefore, a surfactant
SDS was used which added hydrophilic character to the SWCNTs and
water. By the combination of a strong shear force and cavitation pro-
duced by the high-pressure homogenizer, agglomerated nanoparticles
were easily segregated. The SWCNTs nanouid preparation details are
listed down in Table 2. The nanouids were sonicated for 1 h at a
power output of 500 W and frequency of 50 kHz with a 2 s pulse.
2.2. Measurement setup
This sections consists of the measurement approaches used to obtain
the stability of nanouids, thermophysical properties of nanouids
(thermal conductivity, viscosity, and specic heat), and the optical
properties using transmission spectrum.
2.2.1. Stability
The stability of a nanouid is determined by the quality of dispersion
and the suspension of nanoparticles in the mixture. Furthermore, these
characteristics directly affect the thermophysical and optical properties
of nanouids. Another important parameter is the surface charge that
inuences the stability of a nanouid. The zeta potential can be used
to quantify the surface charge. A stable nanouid must have high zeta
Table 1
Properties of SWCNT nanoparticles.
Parameter SWCNT
Average particle diameter (nm) 12 nm diameter, 500 nm length
Purity (%) 90% CNTs, 60% SWCNTs
Density (kg/m3) 2100 at 20 C
Thermal conductivity (W/m K) 6000 [62]
Specic surface area (m2/g) 360400
Color Black
Table 2
Preparation of SWCNT nanouids.
Base uid Water
Nanoparticle SWCNTs (cylindrical)
Surfactant SDS
Volume concentration (vol.%) 0.1, 0.25, 0.5
Sonicator time (min) 60
Power (W) 500
Frequency (kHz) 50 (pulse 2 s)
potential enabling strong electrostatic repulsion between particles.
Whereas an unstable nanouid has lower values of zeta potential, and
thus, weaker electrostatic repulsion. A nanouid with a zeta potential
greater than 30 mV is considered a stable nanouid [63], whereas less
than 20 mV indicates limited stability. Moreover, a nanouid is highly
stable if the zeta potential is greater than 60 mV [64]. A Zetasizer
Nano Zs manufactured by Malvern Instruments Ltd. was used to obtain
the zeta potential value at 25 C. Fig. 1 shows the absolute value of zeta
potential with respect to the volume concentration of SWCNTs
nanoparticles. The error bars indicate the minimum and maximum
errors in the measurements. The measured values of zeta potential are
53.1, 54.4, and 55.8 for 0.1. 0.25, and 0.5 vol.%, respectively.
SWCNTs nanoparticles in SDS surfactant are negatively charged, thus,
the values of zeta potential are also negative.
Fig. 2 presents the average particle size of the three different volume
concentrations of nanouids. The 0.1 vol.% has an average particle size
in the range of 122130 nm, whereas the average particle size in the
0.25 and 0.5 volume concentrations were comparatively larger. This
results from the agglomeration of SWCNTs nanoparticles.
The morphology of the SWCNTs nanouid, shown in Fig. 3, was de-
termined through TEM (transmission electron microscope). SWCNTs
are cylindrical in shape and are well dispersed with no sign of agglom-
eration as observed from the TEM image. Nevertheless, the presence of
some clusters was noticed.
The density reported for the studied volume concentrations of
SWCNTs nanouids are (1007, 1021, and 1036 kg/m3) for (0.10, 0.25,
and 0.50 vol.%), respectively, and the density of water is 998.8 kg/m.
2.2.2. Thermal conductivity
The thermal conductivity of nanouids was measured using the KD2
Pro thermal property analyzer (Decagon Device, USA). It works on the
principle of Transient hot wire method (THWM) (write full form of
THWM) and has a maximum deviation and accuracy of 5.0% and
0.001%, respectively. The thermal conductivity of samples were mea-
sured at the temperatures ranging from 20 C to 60 C. A water bath was
used for controlling the temperature. In order to ensure temperature
equilibrium between the water bath and nanouid, the data was re-
corded after 10 min. All the measurements were carried out three
times to ascertain the accuracy of the experimental data. The recorded
Fig. 1. Average zeta potential w.r.t. to volume concentration.
 Z. Said / International Communications in Heat and Mass Transfer 78 (2016) 207213
Fig. 2. Average particle size w.r.t. to volume concentration.
data for the thermal conductivity were compared against the model de-
veloped by Nan et al. [42], Haris et al. [3], and Timofeeva et al. [44],
which are discussed in the Results and discussions section.
2.2.3. Viscosity
The viscosity of the nanouid was measured using the Brookeld
viscometer (DV-II + Pro Programmable Viscometer) that was connect-
ed to a temperature-controlled bath. In this study, the shear rate range
and spindle rotation were between 24.46 and 293.5 s 1 and 20 and
240 rpm, respectively. The experimental results were compared against
the models proposed by Brenner and Condiff [45] and Timofeeva et al.
[44]. These models investigated the particle shape effect on the viscosity
suspension and are suitable for tubular shape particles. Both the above
models are suitable for tubular-shaped particles.
2.2.4. Specic heat
Heat capacity is the measurable physical quantity of heat energy re-
quired to change the temperature of an object by a given amount. A heat
ux-type differential scanning calorimeter (PerkinElmer's DSC 4000)
was used to measure the nanouid's specic heat capacities. The differ-
ential scanning calorimeter (DSC) measures the heat ux into a sample
as a function of temperature for a user-prescribed heating regime. The
specic heat of SWCNTs nanouids was determined for a temperature
range of 20 C to 60 C. The values were recorded for every 10 C in-
crease in temperature, and it was repeated three different times to es-
tablish the accuracy of the measured data. Moreover, the experimental
Tubular shape
Fig. 3. TEM image of SWCNTs nanouid.
209
Fig. 4. Thermal conductivity of SWCNTs nanouid as a function of temperature and
volume concentrations.
results are then compared with the theoretical models. The specic
heat capacity of nanouids, calculated at any particle concentration,
which is valid for homogeneous mixtures [65], is given by
1C P bf C P P
C Pnf 1
1bf P
2.2.5. Transmission spectrum
A double beam UVVisNIR spectrophotometer (PerkinElmer Lambda
950), with the wavelength range from 200 to 2500 nm, is used to measure
the transmittance of SWCNTs nanouids. The cuvette has an optical path
length of 10 mm. According to the effective medium theory, higher order
reections at various interfaces can be ignored for small volume concen-
trations of uid. In this study, the aforementioned assumption is applied
[66]. The uncertainty of the wavelength is reported as 0.02 nm.
According to the BeerLambert law, the intensity of light at a dis-
tance r in a medium can be written as the following relation [14]:
Ir I0 e ext 2
where is the propagation length within the medium, i.e. 10 mm for
this study. The extinction coefcient (ext) was calculated from the ex-
perimentally determined values of the spectral transmittance from UV
Clusters
Tubular shape
210 Z. Said / International Communications in Heat and Mass Transfer 78 (2016) 207213
Fig. 5. Thermal conductivity ratio compared to present correlations.
to visible light using Eq. (2). Each measurement was repeated for
several times to achieve the best precision.
3. Results and discussions
3.1. Thermophysical properties
3.1.1. Thermal conductivity
The thermal conductivity of water and SWCNTs nanouids with dif-
ferent volume percentages (0.10 to 0.50 vol.%) are plotted at various
temperatures ranging from 20 C to 60 C, shown in Fig. 4. The thermal
conductivity of SWCNTs nanouids changes much rapidly after 30 C as
compared to that of water. The increase in the thermal conductivity
with an increase in temperature is due to Brownian motion of the par-
ticles [67]. And SWCNTs nanouids exhibit higher thermal conductivi-
ties due to higher heat transfer capacity of SWCNTs nanoparticles. At
60 C, the enhancement in thermal conductivities as compared to
water are 23%, 37%, and 62% for 0.10, 0.25, and 0.50 vol.%, respectively.
This high enhancement in thermal conductivity is due to Brownian mo-
tion of the micro- or nano-convection, formation of a nanolayer around
particles, and near-eld radiation [68]. Moreover, an increase in the
cluster size has also been reported as one of the main contributing fac-
tors for high thermal conductivity [69,70]. However, extreme clustering
results in sedimentation, which negatively affects the system. An in-
crease in thermal conductivity was observed for increasing volume con-
centrations, shown in Fig. 4, whereas an increase in cluster size was
observed for increasing volume concentration, shown in Fig. 3.
The obtained experimental results are compared with those report-
ed by Haris et al. [43] and are presented in Fig. 5. A similar trend with an
increase in volume concentration for thermal conductivity was ob-
served. A maximum increment of 16% for 0.3 vol.% was reported by
Haris et al. [43], whereas, in our case, we observed an increment of
Fig. 6. Variation of thermal conductivity over a period of time.
Fig. 7. Viscosity of SWCNTs nanouid w.r.t. temperature and vol.%.
37% for the same temperature (60 C) at a particle loading of 0.25
vol.%. This enhancement in the thermal conductivity could possibility
be due to the use of surfactants as well as the purity of SWCNTs.
Patel et al. [71] considers the thermal conductivity of carbon nano-
tube CNT which is much larger than the thermal conductivity of the
base uid, and Timofeeva et al. [72] developed a model to investigate
the effect of the particle shape on the thermal conductivity. It can be
seen in Fig. 5 that Patel et al. [71] overestimated the thermal conductiv-
ity of SWCNTs nanouid, whereas the model of Timofeeva et al. [72]
shows good agreement with the obtained results.
Fig. 6 shows the thermal conductivity at different volume concentra-
tions for a period of 15 days. The thermal conductivity was measured at
an interval of two days for a total of 15 days. The results are shown in
Fig. 6. The SWCNTs nanouids at different concentrations remained sta-
ble even after a period of 15 days with minor changes noticed in the
thermal conductivity.
3.1.2. Viscosity
Fig. 7 shows the viscosity of SWCNTs nanouids with different vol-
ume concentrations at temperature ranging from 20 C to 60 C. The vis-
cosity increases with an increase in particle loading and decreases with
an increase in temperature. Viscosity reduces due to the weak intermo-
lecular forces between the particles and uid. A signicant decrease of
viscosity with an increase in temperature is reported in the literature
[32,5457].
The experimental results from this study are compared with the the-
oretical models presented by Timofeeva et al. [72] and Brenner and
Condiff [73], shown in Fig. 8. The experimental results of SWCNTs
nanouids at different volume concentrations are higher compared
with both the theoretical models considered. The higher value of
Fig. 8. Experimental data compared to present correlations for relative viscosity.
 Z. Said / International Communications in Heat and Mass Transfer 78 (2016) 207213
Fig. 9. Viscosity w.r.t. to shear rate for SWCNTs nanouid.
viscosity could be due to the addition of SDS surfactant as the models
only considered the viscosity of nanoparticles immersed in uid.
Fig. 9 shows the effect of viscosity with respect to shear rate at differ-
ent volume concentrations. Rheological behavior of nanouid has a
noteworthy inuence on the ow behavior of the uid and stability.
Progressive decrease in viscosity is observed with the increasing shear
rate resulting in a shear thinning behavior for the different volume
concentrations. Similar trends were reported by Garg et al. [54] and
Nanda et al. [74].
The rheological behaviors of SWCNTs nanouid at different volume
concentrations is presented in Fig. 10 to prove the relation between
the shear stress and shear rate. From the gure, it can be observed
that the shear stress increases almost linearly with the increasing
shear rate for the different particle loading.
3.1.3. Specic heat
The effect of temperature on the specic heat with different volume
concentrations of SWCNTs nanouid is presented in Fig. 11. It is ob-
served from the results that the specic heat increased with the increase
in temperatures, whereas it reduced with the increase in the volume
concentration. Lower values of specic heat were observed for SWCNTs
nanouids compared to water. The reduction in specic heat is ob-
served due to the lower value of specic heat of SWCNTs nanoparticles
[58]. The experimental values for 0.50 vol.% of SWCNTs nanouid are
2.49, 2.60, 2.72, 2.86, and 3.02 kJ/kg C, at temperatures ranging from
20 C to 60 C, with an increment of 10 C. At a xed temperature of
20 C, the specic heat values are 4.17 kJ/kg C for water and 3.43,
2.96 and 2.49 kJ/kg C for volume concentration of 0.10, 0.25, and
0.50 vol.%, respectively. It can be observed that the specic heat is
reduced with an increase of volume concentration and it increased
with rising temperature.
Fig. 10. Shear stress w.r.t. to shear rate for SWCNTs nanouid with different vol.%.
211
Fig. 11. Specic heat of SWCNTs nanouid w.r.t. to temperature.
Fig. 12 shows the comparison between the experimental results and
theoretical results. Eq. (1) is used for specic heat. The experimental
results were found to be lower compared to the theoretical results. No
model has yet been developed that can account for tabular shape of
CNTs nanouid. Eq. (1) was used to calculate the specic heat of
SWCNTs nanouid, and does not consider the effect of surfactant, parti-
cle size, and shape; this could be a possible reason for the deviation in
the results.
3.2. Optical properties
3.2.1. Transmittance
The characteristics which distinguish direct absorption solar collec-
tors (DASCs) from the surface absorbers is its ability to synchronize
with the solar radiation spectrum. In this section, SWCNTs nanoparticles
dispersed in the base uid, and its effect on optical properties was
studied, because the volume concentration of the nanoparticles can be
attuned in such a way that the total solar energy can be absorbed by
the nanouids. Fig. 13 below shows the transmittance of water and
SWCNTs nanouids at different volume concentrations.
As noticed from Fig. 14, the amount of absorbed light is increased as
the SWCNTs nanoparticles in water reduce the transmittance coefcient
considerably. Different volume concentrations of SWCNTs are dispersed
in water and investigated due to its importance for absorbing the
solar energy [11,17]. It can be noticed from Fig. 14 that 0.50 vol.% of
SWCNTs nanouid absorbs almost all the emitted light, using a volume
concentration above this would not result in much enhancement. The
evaluation of the spectrum with the sum spectrum suggests further en-
hancement is possible using SWCNTs nanouids in DASCs. Water is
seen to be almost transparent in the visible light range (400800 nm).
It can be noticed from these results that adding SWCNTs nanoparticles
to water can improve the optical properties. Therefore, SWCNTs
Fig. 12. Existing correlations compared to experimental data.
212 Z. Said / International Communications in Heat and Mass Transfer 78 (2016) 207213
Fig. 13. Transmittance spectrum of water and SWCNTs nanouids.
nanouid with lower volume fraction show promising results for
DASCs.
3.2.2. Extinction coefcient
The extinction coefcients of water and SWCNTs nanouids with
different volume concentrations are presented in Fig. 14.
As it can be observed from the trend of the extinction coefcient that
as the volume concentration is increased, the extinction coefcient in-
creases signicantly as well. All three concentrations of SWCNTs
nanouid follow the same trend, showing an increase in extinction co-
efcient from 200 nm to 830 nm, and then a sudden drop is noticed at
834 nm. From 880 nm onwards, the extinction coefcient increases
with a sudden rise at 1120 nm, reaching a peak at 1190 nm and then
again dropping. The same trends were noticed at each different volume
concentration studied. The SWCNTs nanouid with 0.05 vol.% showed
the highest extinction coefcient, and the water showed the lowest.
The extinction coefcient of water was found to be very small, which
is 0.01 cm 1 in the visible range (400 nm800 nm). The extinction
coefcient of the SWCNTs increased by several orders of magnitudes
compared to water, demonstrating that the optical properties of the
nanouids were improved signicantly by the addition of SWCNTs
nanoparticles. The highest extinction coefcient value of about
9.48 cm 1, has been achieved by the addition of 0.05 vol.% of SWCNTs
nanouid, whereas 8.20 cm 1 and 4.98 cm 1 values of extinction
coefcient were observed for 0.25 vol.% and 0.10 vol.%, respectively.
4. Conclusion
This study investigated the stability, thermophysical, and optical
properties of SWCNTs nanouids at three (0.10, 0.25, and 0.50 vol.%)
different volume concentrations. SWCNTs nanouids showed good
Fig. 14. Extinction coefcient of water and SWCNTs nanouids.
stability by using SDS surfactant, which resulted in high electrostatic re-
pulsion force among the particles. The density of nanouids increased
slightly with the addition of SWCNTs nanoparticles. SWCNTs nanouids
in comparison with water as a base uid shows highest thermal conduc-
tivity (62% increment), which increases with the addition of volume
concentrations and rising temperature; however, the reliance of ther-
mal conductivity on temperature is much more noteworthy. The ther-
mal conductivity remained the same with minor deviations for a
period of 15 days. The viscosity of SWCNTs nanouids increased with
rising volume concentration but reduced with rising temperature. For
rheological behaviors, shear stress increased almost linearly with the in-
creasing shear rate for the different particle loading. Specic heat
decreased with the increasing volume concentration of SWCNTs nano-
particles, but increased with the rising temperature. SWCNTs nanouids
demonstrated their outstanding aptitude to absorb emitted light energy
along with the highest extinction coefcient compared with water. The
dominance of SWCNTs nanouids in thermophysical properties
and optical properties makes them ideal candidates to be used for
high-performance HTFs in solar thermal applications as working uids
for DASCs and volumetric solar collectors.
Acknowledgement
This research is supported by UM High Impact Research Grant
UM-MOHE UM.C/HIR/MOHE/ENG/40 from the Ministry of Higher
Education Malaysia. The author would also like to thank Masdar
Institute for its support.
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