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Solar Energy 105 (2014) 82–90
www.elsevier.com/locate/solener

High temperature and long-term stability of carbon nanotube

nanofluids for direct absorption solar thermal collectors
Nathan Hordy ⇑, Delphine Rabilloud, Jean-Luc Meunier, Sylvain Coulombe
Plasma Processing Laboratory, Department of Chemical Engineering, McGill University, 3610 University St., Montréal, Québec H3A 0C5, Canada

Received 22 November 2013; received in revised form 24 January 2014; accepted 10 March 2014

Communicated by: Associate Editor H.-M. Henning

Abstract

Stable dispersions (nanofluids) are produced using plasma functionalized multi-walled carbon nanotubes (MWCNTs). To our knowl-
edge, this study presents a first quantitative demonstration of nanofluid stability over extended periods of time (currently tested up to
8 months) and after intense heating. No agglomeration is found to occur in the water and glycol-based nanofluids after heating at 85
and 170 °C, respectively. Significant agglomeration does occur for suspensions produced using the non-polar TherminolÒ VP-1 heat
transfer fluid. Optical characterization of the nanofluids demonstrates that the MWCNTs are highly absorbing over the majority of
the solar spectrum, allowing for close to 100% solar energy absorption, even at low concentrations and small collection volumes. These
absorption properties coupled with the stability of the nanofluids make them ideal candidates as direct solar thermal collectors.
Ó 2014 Elsevier Ltd. All rights reserved.

Keywords: Solar absorber; Carbon nanotube; Nanofluid; Solar thermal

1. Introduction of the working fluid. Unfortunately, India Ink, as well as

Solar thermal collectors, which capture the Sun’s rays as
heat, are currently used world-wide in applications ranging
from hot water heating to large scale electricity production.
As demand for cleaner energy continues to grow, solar
thermal processes are expected to play an increasingly
significant role in our global energy future (Philibert,
2011). The concept of direct solar thermal collectors, in
which solar radiation is absorbed and transported directly
by the working fluid, was first introduced by Minardi and
Chuang (1975). As most heat transfer fluids (water, glycols,
oils, etc.) are transparent over the majority of the solar
spectrum (Otanicar et al., 2009), additives, such as India
Ink, can be added to improve the absorption characteristics
⇑ Corresponding author. Fax: +1 5143986678.
E-mail address: nathan.hordy@mail.mcgill.ca (N. Hordy).
other organic and inorganic chromophores have been
shown to experience light- and temperature-induced degra-
dation (Burke et al., 1982), which can lead to reduced
absorption and fouling of surfaces over time, thus limiting
their use, especially at high temperatures. Rather than
using dyes, the use of nanoparticles, as dispersed and solar
ray-absorbing phase in the heat transfer fluid, represents an
interesting alternative. Once dispersed in a host heat trans-
fer fluid, the nanofluid can pass through pumps and pipes
without adverse effects, such as clogging and fouling. Such
unique properties make the nanofluids ideal candidates for
direct solar thermal energy absorption applications (Taylor
et al., 2011a).
Nanofluids, which can be defined more formally as sta-
ble suspensions of nanoparticles (particles with one dimen-
sion <100 nm in size) in a host liquid, have gained a great
deal of attention over the past 15 years. Initially considered

http://dx.doi.org/10.1016/j.solener.2014.03.013
0038-092X/Ó 2014 Elsevier Ltd. All rights reserved.
 N. Hordy et al. / Solar Energy 105 (2014) 82–90
as revolutionary in the heat transfer community, the actual
heat transfer enhancements (heat conductivity and heat
transfer coefficient) fell short of expectations. Recent works
have demonstrated that more promising and scientifically-
sound applications may stem out of nanofluids, in particu-
lar applications utilizing their highly-tunable optical
properties (Taylor et al., 2013). Indeed, the use of nanofl-
uids as both a volumetric solar collector and heat transfer
fluid is now seen as a method of improving efficiencies and
reducing costs in solar thermal devices (Mahian et al.,
2013). Given the high surface-to-volume ratio of nanopar-
ticles, quantities on the scale of mg/L can be used to obtain
close to 100% absorption over relatively short distances
(mm range). Furthermore, the concentration of nanoparti-
cles can easily be controlled such that the incident radiation
is absorbed over the entire volume of nanofluid, instead of
over a thin surface layer, thus limiting heat losses to the
surroundings (Otanicar et al., 2011). Several different types
of nanoparticles in various base fluids have been modeled
and tested experimentally for this purpose. These include
metallic nanoparticles (He et al., 2011; Kameya and
Hanamura, 2011; Lenert and Wang, 2011; Otanicar
et al., 2010; Taylor et al., 2011a), carbon nanotubes
(CNTs) (He et al., 2011; Meng et al., 2012; Otanicar
et al., 2010; Taylor et al., 2011a), graphite (Otanicar
et al., 2010; Taylor et al., 2011a, 2011b), carbon black
(Han et al., 2011; Sani et al., 2011), and carbon nanohorns
(CNHs) (Sani et al., 2011). All of these materials have been
shown to be effective solar absorbers, but graphitic parti-
cles, such as CNTs, are seen as the most promising for
low to medium temperature applications (<400 °C) due
to their high spectral absorptivity over the entire solar
range (Taylor et al., 2011a). From an economic standpoint,
cost is not seen as a prohibitive factor, as the CNT additive
only adds around a dollar per liter of nanofluid produced.
One of the main obstacles to the large-scale use of nano-
fluids, in all applications, is the stability of the nanoparti-
cles in suspension (Taylor et al., 2013; Yu and Xie, 2012).
The unique properties of the suspension, attributed to
small size and homogeneous dispersion of the particles,
are lost if the nanoparticles agglomerate and settle out over
time. The stability of nanofluids has, up to now, been
essentially described qualitatively with little consistency
for defining a “stable nanofluid”. More often than not,
studies claim that stable nanofluids are produced without
any quantitative evidence being reported. Photographs of
the nanofluids are often provided as proof of stability.
However for concentrated nanofluids, particularly those
containing CNTs, the suspension is often too dark to deter-
mine if settling has occurred (Yu and Xie, 2012). In addi-
tion, even if sedimentation is not present, agglomeration
of nanoparticles may still have taken place (Fedele et al.,
2011). Agglomerated particles that remain in suspension
may provide the appearance of a stable suspension over a
short period of time, but the available surface area of the
particles to achieve the specific purpose (absorb light,
transfer heat, etc.), may have decreased significantly. For
83
direct solar thermal energy collectors, agglomeration of
nanoparticles translates directly into a decrease in absorp-
tion. Thus, it is essential that nanofluid stability (i.e. nano-
particles dispersion) be maintained over extended periods
of time (years).
Analytical techniques involving spectral absorbance
(Hwang et al., 2007; Jiang et al., 2003; Yu et al., 2007),
zeta-potential (Huang et al., 2009; Jiang et al., 2003), par-
ticle-sizing (Fedele et al., 2011), and analytical centrifuga-
tion (Harel et al., 2013; Krause et al., 2009) have been
used as ways to quantify nanofluid stability. All of these
techniques can provide initial indications if agglomeration
has occurred, however testing must be conducted over long
time scales if stability quantification on the order of
months or years is needed. Using an analytical centrifuge
to examine the transmittance of the nanofluid over time
can provide accelerated stability measurements, as larger
agglomerates will settle quicker than under normal gravita-
tional forces (Krause et al., 2009). However, the extent of
agglomeration, unlike sedimentation, is not directly pro-
portional to the applied gravitational force (Melik and
Fogler, 1984). Long-term testing may still be required. In
addition, suggesting that low sedimentation velocities are
an indication of nanofluid stability, as has been recently
proposed by Lamas et al. (2012), is somewhat questionable.
A nanofluid that contains well-separated supernatant (par-
ticle-free fluid) and a sediment phase prior to testing should
not be considered a stable and uniform system. If enough
agglomeration has already occurred to create a heteroge-
neous fluid, then most likely the suspension that remains
no longer contains particles that are “nano” in size.
Temperature stability of the nanofluid is another key
aspect for all heat transfer applications. Typically, nano-
particles in a host fluid are stabilized through the use of a
surfactant (Yu and Xie, 2012). Unfortunately, most surfac-
tants decompose upon modest heating and can lose effec-
tiveness at temperatures as low as 70 °C (Wen and Ding,
2004). Direct solar thermal collectors will require operating
temperatures from 60 °C for solar water heating, to values
as high as 400 °C for concentrated solar power (Taylor
et al., 2011b). To date, very few studies have tested the sta-
bility of nanofluids at high temperatures and those that
have made such tests reported significant agglomeration
and irreversible nanofluid degradation (Tavares and
Coulombe, 2011; Taylor et al., 2011b). Sani et al. (2011)
did report good stability of ethylene glycol-based nanofl-
uids up to 150 °C, but no evidence was provided to support
their claim. To the best of our knowledge, no study has
been done to quantify the temperature stability of a
nanofluid.
The purpose of this work is to quantitatively examine
both the long-term and high-temperature stability of
CNT nanofluids for use in direct solar absorption. The
optical properties of three base fluids that are commonly
used in solar thermal applications, namely ethylene glycol,
propylene glycol and TherminolÒ VP-1, are characterized
along with a range of concentrations of corresponding
84 N. Hordy et al. / Solar Energy 105 (2014) 82–90
nanofluids. Aqueous based nanofluids are also included for
comparison, given that nanoparticle–water dispersions are
by far the most common in the literature.
2. Material and method
2.1. Nanofluid synthesis
The carbon nanotubes (CNTs) used in this study were
grown directly from stainless steel (SS) 316 mesh using a
thermal chemical vapor deposition (T-CVD) process. A
detailed description of the growth process has been previ-
ously described (Hordy et al., 2013b). The CNTs produced
using this procedure are multi-walled (hereafter referred as
MWCNTs) with an average diameter and length of
approximately 30 nm and 4 lm, respectively, and form a
dense forest on the growth substrate. Following the synthe-
sis, the MWCNTs are surface-functionalized using a
low-pressure capacitively-coupled radio frequency
(13.56 MHz) glow discharge plasma sustained in an
argon/oxygen/ethane gas mixture (Hordy et al., 2013a).
This plasma treatment has been shown to covalently graft
oxygenated functionalities, such as carboxylic groups, onto
the surface of the MWCNTs, thus rendering them polar
and highly dispersible in water. The various nanofluids
are produced by placing the MWCNTs-covered SS sub-
strate into a 30 mL glass vial with approximately 20 mL
of the base fluid. The vial is then put into an ultrasonic
bath (Bransonic 2510) and sonicated for 15 min, causing
the MWCNTs to fracture at their roots and become sus-
pended within the base fluid. The mass of the sample is
measured using a Sartorius MC1 analytical balance (AC
210P, 0.1 mg precision) before and after in order to deter-
mine the amount of MWCNTs removed. The four base flu-
ids used in this work are: water (treated via reverse
osmosis), ethylene glycol (Fisher Scientific, >95%), propyl-
ene glycol (Fisher Scientific, 99%), and TherminolÒ VP-1
heat transfer fluid (Solutia Inc., 73.5% diphenyl oxide
and 26.5% biphenyl). The initial samples generated, with
concentrations up to 100 mg/L, were used to produce dilu-
tions corresponding to the concentrations shown in Table 1.
Concentrations of two of the trials using TherminolÒ VP-1
(labeled b* and e*) are slightly higher than the correspond-
ing samples for the other base fluids, as the dilutions were
Table 1
MWCNT concentration of various nanofluids produced.
Label MWCNT concentration (mg/L)
a 0
b 5.6 ± 0.4
b* 6.5 ± 0.5
c 11.0 ± 1.0
d 17.0 ± 1.4
e 27.0 ± 2.3
e* 33.0 ± 2.4
f 53.0 ± 5.6
made prior to knowing the exact mass of MWCNTs pres-
ent in suspension.
2.2. UV–Vis characterization
The various nanofluids were characterized using a
double-beam UV–Vis spectrophotometer (Cary 5000,
175–3300 nm). The samples were enclosed in a SuprasilÒ
quartz cuvette with a pathlength of 1 cm. All trials were
conducted at room temperature with an empty reference
path. To account for the difference between the refractive
index of quartz and air, the acquired spectra were corrected
by treating the filled cuvette as a three-slab system, thus
transmittance data presented represent only the nanofluid
and not the cuvette. The details of this procedure are
described in Otanicar et al. (2009 and references therein).
Measurements were taken over the 200–1500 nm range
for the water, ethylene glycol and propylene glycol based
nanofluids, and from 200 to 2300 nm for the TherminolÒ
VP-1 based ones. Transmittance spectra of the pure base
fluids (a) were also measured for reference. These two spec-
tral ranges account for, respectively, 85% and 95% of the
total incident solar energy at air mass 1.5. Spectra were
not taken above 1500 nm for water and the glycols, as
strong absorption bands in the IR mask any change due
to the addition of the MWCNTs. However, for direct solar
collection purposes, one can assume that the base fluid
would absorb the majority of the solar irradiation above
1500 nm. As this is not the case for TherminolÒ VP-1,
spectra were acquired up to 2300 nm. For all fluids the
concentration of MWCNTs was limited to 52 mg/L as
the transmitted signal for higher concentrations was below
the detection limit for the spectrophotometer and
pathlength used. If a higher concentration is needed, one
could estimate the required concentration using the Beer–
Lambert law (Section 3.1).
3. Results and discussion
3.1. Optical characterization
MWCNT nanofluids of various concentrations were
prepared using four base fluids commonly used in solar
thermal applications. Fig. 1 shows a series of MWCNTs-
ethylene glycol nanofluids with (a: pure ethylene glycol
control, b)f: increasing MWCNT concentration). UV–
Vis transmittance spectra were acquired at regular time
intervals following synthesis. The extinction coefficient,
a(k, c) (cm1), which is a function of MWCNT concentra-
tion, c (mg/L), and wavelength, k (nm), was calculated
using Eq. (1), where the transmittance, T(k), is logarithmi-
cally proportional to the extinction coefficient for a given
path length, l (cm) (Perrin, 1948).
T ðkÞ ¼ eaðk;cÞl ð1Þ
 N. Hordy et al. / Solar Energy 105 (2014) 82–90
a b c d e f
Fig. 1. Ethylene glycol-based nanofluids of various MWCNT concentra-
tions photographed eight months after synthesis. Labels a–f refer to
concentrations given in Table 1.
Fig. 2 shows the extinction coefficients (a) of as-pro-
duced MWCNT nanofluids for the four base fluids (concen-
tration levels are listed in Table 1). All produced nanofluids
show an absorption peak centered around 260 nm followed
by broadband absorption across the measured spectral
range. This absorption behavior is characteristic of
MWCNTs and can be attributed to 1D van Hove singular-
ities (Yu et al., 2007). Extinction coefficients larger than
7 cm1, which correspond to transmittance below 0.1% at
a path length of 1 cm, led to transmitted intensity levels
below the resolution of the detector in the near-infrared
Fig. 2. Extinction coefficient (a) of MWCNT nanofluids measured soon after synthesis. Base fluids are: (A) water, (B) ethylene glycol, (C) propylene glycol
and (D) Therminol VP-1.
85
(NIR) and as a result, some noise can be seen above
1400 nm. This is due to the strong NIR absorption bands
of the various base fluids used and not to absorption from
the MWCNTs.
The extinction coefficient, also referred to as the attenu-
ation coefficient, includes both scattering and absorption
effects. However due to the small size of the MWCNTs,
it has been shown that scattering effects are very low, and
thus attenuation of the incident electromagnetic energy
from the MWCNTs will be primarily caused by absorption
(Gan and Qiao, 2012; Mercatelli et al., 2011). Given that
the four base fluids are essentially transparent over the vis-
ible range (400–700 nm), all of the observed absorption in
this range can be attributed to the MWCNTs. Moreover,
in this work optical saturation effects are neglected. As a
result, the MWCNT concentration and optical absorption
coefficient, a0 (k) (L mg1 cm1), can be decoupled to obtain
the equation commonly referred to as Beer–Lambert law
(Eq. (2)).
0
T ðkÞ ¼ ea ðkÞcl ð2Þ
Eq. (2) predicts that the transmittance should be loga-
rithmically proportional to the MWCNT concentration,
and thus for perfectly dispersed MWCNTs, the absorption
coefficient, a0 , should not vary as their concentration
86 N. Hordy et al. / Solar Energy 105 (2014) 82–90
Fig. 3. Stored energy fraction as a function of penetration distance for various concentrations of MWCNTs and for the four base fluids: (A) water, (B)
ethylene glycol, (C) propylene glycol, and (D) Therminol VP-1.
increases. If, on the other hand, the MWCNTs start to
agglomerate as their concentration increases, the absorp-
tion coefficient will effectively vary with concentration.
DLVO theory, which describes the interaction of particles
within a liquid medium, predicts that an increase in
agglomeration, caused by van de Waals attraction, will
occur at high concentrations as the inter-particle distance
decreases (Amrollahi et al., 2008; Missana and Adell,
2000). Extracting the absorption coefficient (data not
plotted) from the spectra collected in the visible range
(400–700 nm), one can determine if agglomeration occurs.
The standard deviation of the absorption coefficient for
each of the three polar nanofluids (water, ethylene and pro-
pylene glycol) was found to be less than 2%, suggesting that
little to no agglomeration has occurred. The TherminolÒ
VP-1 nanofluids, on the other hand, had a mean standard
deviation of 17%, indicating that agglomeration had taken
place within hours of synthesis. It should be noted that
concentrations higher than 32 mg/L were not tested for
the TherminolÒ VP-1 based suspensions as severe agglom-
eration occurred. It was expected that the plasma function-
alized MWCNTs may not disperse as well nor remain as
stable in TherminolÒ VP-1 as it is a non-polar solvent
(dielectric constant of diphenyl oxide is 3.9 (Knovel,
2008)). The plasma functionalization treatment covalently
bonds polar functionalities such as carboxylic groups onto
the MWCNT surface, which is why the MWCNTs are
easily suspended in the three polar solvents (Hordy et al.,
2013a). In addition, deprotonation of the carboxylic
groups leads to a negative surface charge on the
MWCNTs, thus limiting agglomeration. As this is not
the case with TherminolÒ VP-1, agglomeration begins to
occur immediately after synthesis.
Using the extinction coefficient from each of the nanofl-
uids, a solar spectrum-weighted stored energy fraction (Am)
can be calculated (Drotning, 1978).
R
S m ðkÞ½1  eaðk;cÞx  dk
Am ðx; cÞ ¼ R ð3Þ
S m ðkÞ dk
This quantity represents the fraction of solar energy that
is absorbed by the nanofluid over a given penetration
distance, x (cm). Once again it should be noted that given
the low amounts of scattering from MWCNTs, extinction
coefficients are used as an approximation for absorption
coefficients. Ignoring the effects of scattering, even though
small, would not be ideal if one was trying to use the
absorption coefficient to precisely model a direct solar
 N. Hordy et al. / Solar Energy 105 (2014) 82–90 87

Fig. 4. Transmission spectra for various concentrations of nanofluids, immediately after synthesis (dash) and after 3 months (solid). (A) Water, (B)
ethylene glycol, (C) propylene glycol, and (D) Therminol VP-1. Absorption pathlength was 1 cm.

0.8
Relative Concentration

0.6

0.4

0.2

0
0 30 60 90 120 150 180 210 240
Time (Days)
PG EG Water T VP-1
Fig. 6. Calculated effective MWCNT concentration in Therminol VP-1
Fig. 5. Relative concentration of the nanofluids over time, as determined based nanofluids over an 8 month period, as determined from optical
by absorption spectroscopy. Error bars represent ±1 standard deviation. measurements.

thermal collector. However, as the focus of this work is to

demonstrate the stability and general absorption ability of
the produced nanofluids, this assumption is seen as
acceptable.
The spectral distribution of the solar irradiation, Sm(k)
(W m2), was taken at an air mass of 1.5 and the bounds
of integration were set from 200 to 1500 nm, so that the
results could be compared to those found in literature
(ASTM, 2012). The stored energy fraction at 1 cm fluid
thickness was within 1.2% of the values reported by
Otanicar et al. (2009) for each of the base fluids. The stored
88 N. Hordy et al. / Solar Energy 105 (2014) 82–90

Fig. 7. Transmittance spectra for various concentrations of nanofluids, after synthesis (dash) and after heating for 1 h at approximately 85% of the base
fluids’ boiling temperatures (solid). (A) Water (80 °C), (B) ethylene glycol (170 °C), (C) propylene glycol (170 °C), and (D) Therminol VP-1 (220 °C).
Absorption pathlength was 1 cm.

energy fractions, calculated using the extinction coefficients quantitative demonstration of a stable nanofluid to date.
reported in Fig. 2, are presented in Fig. 3 for a range of Fig. 4 displays the nanofluids transmission after synthesis
fluid thicknesses that is representative for solar thermal col- and after a 3 month storage period; a clear shift in trans-
lector geometries. It can be clearly seen by comparing mittance can be observed in cases where agglomeration
curves (b)–(f) with curve (a) that the addition of MWCNTs occurs. Using Eq. (2), this increase in transmittance can
has a significant effect on the energy storage ability of the be represented by a decrease in effective MWCNT concen-
nanofluid. At 10 cm of fluid thickness, even the least- tration. As can be seen from Fig. 5, only a small change
concentrated MWCNT nanofluids have a stored energy occurred for both ethylene and propylene glycol-based
fraction of 1. Using these results, one can easily tailor the nanofluids after 8 months (8.6% and 4.4% in effective
nanofluid concentration to obtain close to 100% absorp- concentration, respectively), and a gradual decrease
tion for any particular fluid thickness. occurred for the aqueous nanofluids (approx. 5% per
month). Error bars in Fig. 5, representing ±1 standard
deviation, were not included for the TherminolÒ VP-1
3.2. Long term stability based nanofluid due to the fact these suspensions were
Stability is one of the most critical issues preventing
nanofluids from making the transition from the laboratory Table 2
bench to large-scale use for which years of operation are Temperature to which each nanofluid was heated and boiling temperature
required for direct solar absorption applications. As a test of the corresponding base fluid.
of long-term stability, transmittance spectra of the different Base fluid Heating temp. (°C) Boiling temp. (°C)
nanofluids at various MWCNT concentrations were Water 85 ± 5 100
acquired over an 8-month period. The nanofluids were Ethylene glycol 170 ± 5 197
stored at room temperature and left without any agitation. Propylene glycol 170 ± 5 188
Therminol VP-1 220 ± 5 257
To the best of our knowledge, this is the longest
 N. Hordy et al. / Solar Energy 105 (2014) 82–90
Fig. 8. Effective MWCNT concentration in Therminol VP-1 nanofluids
after 5 heating cycles at 220 °C (1 h each), as determined from optical
measurements.
inherently instable. Fig. 6 illustrates the effect of agglomer-
ation on the effective MWCNT concentration in Thermi-
nolÒ VP-1 nanofluids for various times following
synthesis (up to 240 days). As can be seen the rate of
agglomeration is significant for all concentrations, however
more pronounced with the most concentrated sample. We
calculated an 87% effective MWCNT concentration loss
for the highest concentration (e*), as opposed 51% for the
least concentrated sample (b*). As discussed in Section 3.1,
this increased rate of agglomeration at higher concentra-
tions is predicted by the DLVO theory. It should be noted
that as the other nanofluids (EG, PG and H2O based) are
relatively stable, no concentration dependence on agglom-
eration was observed thus far for a period up to 8 months.
3.3. High temperature stability
The previous section examined nanofluid stability over
extended periods of time at room temperature. An addi-
tional constraint for a nanofluid to be used in a solar ther-
mal application, or any heat transfer application for that
matter, is its stability at high temperatures. As a prelimin-
ary investigation of this aspect, a second batch of nanofl-
uids was heated in a loosely capped vial sitting on a
temperature-controlled hot plate for 1 h to approximately
85% of each base fluid’s respective boiling temperature
(Fig. 7). These temperatures were chosen to limit any pres-
sure build-up during heating. They are given in Table 2
along with the corresponding atmospheric boiling temper-
atures of each base fluid. Since the vials were capped, these
experiments resulted in no net loss of the base fluid. The
fluid volume per sample was low (approx. 10 mL), thus
limiting the thermal stratification within the fluid. In total,
each heating experiment took 2–3 h. As can be seen in
Fig. 7, little to no change occurs for the water- and
glycol-based nanofluids. This indicates that the plasma-
introduced functionalities preventing the MWCNTs from
agglomerating are not damaged at high operating
89
temperatures going up to 170 °C for the glycols. In addi-
tion, the electrostatic repulsion caused by the deprotona-
tion of the carboxylic functionalities is sufficient to
overcome the increased number of high velocity collisions
between the MWCNTs that occur at high temperatures
(Amrollahi et al., 2008). This was not the case for the Ther-
minolÒ VP-1 based nanofluids, which experience significant
agglomeration after heating to 220 °C (Fig. 7D). As with
the long-term stability testing, the observed rate of agglom-
eration with the TherminolÒ VP-1 based nanofluids
increases with MWCNT concentration. Fig. 8 illustrates
the effect of heating cycles on a nanofluid which suffers
from agglomeration. All three TherminolÒ VP-1 trials
show significant agglomeration after 5 heating cycles. Once
again it should be noted that these are preliminary heating
experiments conducted to give an indication of the stability
of the nanofluids at high temperatures. A more rigorous
study of the effect of temperature on the nanofluids and
the plasma-grafted functionalities is currently underway.
4. Conclusions
This study describes the synthesis and solar energy
absorption properties of nanofluids made up of a wide con-
centration range of plasma-functionalized MWCNTs dis-
persed in water, ethylene glycol, propylene glycol, as well
as TherminolÒ VP-1 heat transfer fluids. Most importantly,
this study reports for the first time a quantitative demon-
stration of the high temperature and long-term stability
of ethylene glycol and propylene glycol-based MWCNT
nanofluids intended for use in solar thermal energy collec-
tors. Long-term, room temperature stability (currently
tested up to 8 months) has been demonstrated for the gly-
col-based nanofluids, while a gradual MWCNT agglomer-
ation was observed with the water-based nanofluids. Given
the polar nature of the oxygen functionalities bonded to the
surface of the MWCNTs, high levels of agglomeration
were found to occur for the non-polar TherminolÒ VP-1
based nanofluids. In the high temperature tests, no agglom-
eration was found to occur after heating to 85 and 170 °C
for the aqueous and glycol based nanofluids, respectively.
Optical characterization of various concentrations of the
nanofluids demonstrates that the MWCNTs are highly
absorbing over the majority of the solar spectrum, allowing
for close to 100% solar energy absorption, even at low con-
centrations and small collection volumes. These absorption
properties, coupled with the long-term and high tempera-
ture stability of the glycol-based nanofluids, make them
ideal candidates for direct solar thermal energy absorption.
Acknowledgements
The authors gratefully acknowledge the financial sup-
port provided by the Natural Sciences and Engineering
Research Council of Canada, the Fonds de recherche du
Québec – Nature et technologies and McGill University.
90 N. Hordy et al. / Solar Energy 105 (2014) 82–90
The authors also acknowledge Solutia Inc., for providing a
free sample of TherminolÒ VP-1 heat transfer fluid.
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