International Journal of Thermal Sciences 76 (2014) 168e189

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International Journal of Thermal Sciences

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

A review on how the researchers prepare their nanofluids

Zoubida Haddad a, b, **, Chérifa Abid b, Hakan F. Oztop c, *, Amina Mataoui d
a
Department of Electronics and Electrical Engineering, University of Boumerdes, Algeria
b
Aix-Marseille University, CNRS, IUSTI UMR 7343, 13453 Marseille, France
c
Department of Mechanical Engineering, Technology Faculty, Firat University, 23119 Elazig, Turkey
d
Department of Fluid Mechanics, Faculty of Physics, University of Sciences and Technology e Houari Boumediene, Algiers, Algeria

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

Article history: The past decade has seen the rapid development of nanofluid science in different aspects, where the
Received 19 April 2013 researchers focused mainly on the enhancement of heat transfer. However nanofluids preparation also
Received in revised form deserves the same attention since the final properties of nanofluids are dependent on the stability of the
18 August 2013
dispersion. In this paper, we summarize the nanofluid preparation methods reported by different in-
Accepted 19 August 2013
Available online 17 October 2013
vestigators in an attempt to find a suitable method for preparing stable nanofluids. In this context,
nanofluids are classified according to material type as metallic and nonmetallic nanoparticles since
different nanoparticles need their own stability method. Various types of nanoparticles with different
Keywords:
Nanoparticles
base fluids are investigated. Also, the available data for the zeta potential as a function of pH is discussed.
Stability Ó 2013 Elsevier Masson SAS. All rights reserved.
Nanofluid preparation

1. Introduction Preparation of stable nanofluids is the key issue of nanofluid

Over the last several decades, researchers have attempted to
overcome the limited heat transfer capabilities of traditional heat
transfer fluids such as water, engine oil, and ethylene glycol (EG), by
developing a new class of fluids which offer better cooling or
heating performance for a variety of thermal systems. Applying
nanotechnology to thermal engineering, the novel concept of
“nanofluid” which was coined by Choi in 1995 [1] has been pro-
posed to meet these cooling challenges. Nanofluids, which are
solideliquid composite materials consisting of nanometer sized
solid particles suspended in different base fluids, provide a prom-
ising technical selection for enhancing heat transfer because of its
many advantages besides anomalously high thermal conductivity.
Nanofluids represent improved stability compared with conven-
tional fluids added with micrometer- or millimeter-sized solid
particles because of size effect and Brownian motion of the nano-
particles in liquids. With such ultrafine nanoparticles, nanofluids
can flow smoothly in a microchannel without clogging and the size
of the heat transfer system can be reduced for the use of nanofluids
with high heat transfer efficiency.
* Corresponding author. Tel.: þ90 424 237 0000x4248; fax: þ90 424 236 7064.
** Corresponding author. Department of Electronics and Electrical Engineering,
University of Boumerdes, Algeria.
E-mail addresses: zoubida.haddad@etu.univ-amu.fr (Z. Haddad), hfoztop1@
gmail.com, hfoztop1@yahoo.com (H.F. Oztop).
research. The stability of nanofluids refers to several aspects: 1)
Nanofluids are multi-phase dispersion system with high surface
energies and are, therefore, thermodynamic unstable. 2) Nano-
particles dispersed in the nanofluids have strong Brownian mo-
tions. The mobility of the nanoparticles can offset their
sedimentation caused by the gravity field. 3) Dispersion of nano-
particles in the fluids may deteriorate with time due to the aggre-
gation of nanoparticles, which is caused by van der Waals forces. 4)
No chemical reactions either between the suspended nanoparticles
or between the base fluid and nanoparticles are desired at working
conditions of the nanofluid. Therefore, there are two phenomena
that are critical to the stability of nanofluid, aggregation and
sedimentation.
It was found that only a few review papers have discussed on the
preparation methods for nanofluids [2e4]. In the present paper, we
attempt to review the preparation methods of nanofluids presented
in previously published data with much more details. The purpose
of this paper is to understand the lack stability of nanofluids, which
is a key issue that influenced the nanofluid properties for applica-
tion, and to propose suggestions that could lead to prepare stable
nanofluid over a long time, with negligible agglomeration and
without chemical change of the fluid properties. The review dis-
cussed different types of nanoparticles; nonmetals (Al2O3, ZnO,
CuO, TiO2, Fe3O4, CNTs, SiO2 and AlN) and metals (Al, Ag and Cu).
Also, we present the available data for the zeta potential as a
function of pH values.

1290-0729/$ e see front matter Ó 2013 Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.ijthermalsci.2013.08.010
 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
Fig. 1. Particle size distributions of AlN filtered nanofluid [7].
2. Preparation of nanofluids
Nanoparticles, the additives of nanofluids, play an important
role in changing the thermal transport properties of nanofluids. At
present, various types of nanoparticles, such as metallic nano-
particles and ceramic nanoparticles, have been used in the nano-
fluids preparation. In the following part, we will present the
nanofluid preparation methods for eleven different nanoparticles
reported in the literature.
2.1. Preparation of non-metallic nanofluids
2.1.1. Aluminum nitride -nanofluids
Aluminum nitride (AlN) is a nontoxic newer material in the
technical ceramics family. While its discovery occurred over 100
years ago, it has been developed into a commercially viable product
with controlled and reproducible properties within the last 20
years. AlN is one of the typical ceramics that have special properties
such as high thermal conductivity (8e10 times that of Al2O3), low
dielectric coefficient (about 8.15), high electrical resistance, corro-
sion & erosion resistance and low density. Because of these ad-
vantageous properties, it is used in various engineering
applications and has attracted the intense interest of researchers.
However, till date very few results concerning AlN nanofluids have
been reported in the literature. In this context, Hu et al. [5] were the
first to disperse AlN nanoparticle, produced by plasma arc in the gas
phase into ethanol with castor oil as a dispersant to improve sus-
pension stability. The suspension was then stirred with a high-
speed magnetic stirrer. The resulting suspension was placed in an
ultrasonic homogenizer for 10 min. It was observed that the pre-
pared sample can remain stable for more than 2 weeks without
settling. Choi et al. [6] mixed the agglomerated Al2O3 and AlN
nanoparticles with n-hexane and a proper amount of oleic acid. The
mixture was subjected to bead-milling with ZrO2 beads in a vertical
super-fine grinding mill. The powders were hydrophobic modified
by esterification reaction simultaneously with bead milling by
circulating the suspensions between bead mill and ultrasonic re-
action bath. A surface modified solution was then filtered using
ultra filtration (UF) membrane to remove excess oleic acid which
did not form stable chemical bonds with the particle surface. The
filtered solution was mixed with transformer oil, and then finally
dried off the n-hexane using a rotary vacuum evaporator. They
observed that for a period of one month, filtered and non-filtered
Al2O3 nanofluids are well dispersed at the beginning, while sedi-
mentation was very clear for non-filtered nanofluid after one
month. The settling phenomenon for non-filtered suspension was
interpreted as the formation of double chain of oleic acid (OA) on
the particle surface, making it hydrophilic again. Yu et al. [7]
169
Fig. 2. Sedimentation rate of AlNePPG 425/2000 diluted systems [8].
prepared AlNeethylene glycol and AlNepropylene glycol nano-
fluids by stirring and continuous sonication for 3 h, to ensure
uniform dispersion of nanoparticles in the base fluid. As shown in
Fig. 1, they found that the average particle sizes for AlNeEG and
AlNePG nanofluids are 165 and 169 nm, respectively. Wozniak et al.
[8] suspended AlN nanopowder in poly propylene glycol PPG 425
and PPG 2000, and then the suspensions were homogenized by
using a magnetic stirrer for 3 h. More concentrated AlN dispersions
were prepared using a laboratory dissolver, which had a mechan-
ically modulated dispersive disk. The powder was slowly and
incrementally added to PPGs. Each addition was followed by ho-
mogenization step. When all the powder was added, the disper-
sions were stirred for 40 min at 3000 rpm. It was reported that the
suspensions were of high flow-ability and noticeable homogeneity.
AlNePPG 425/2000 were of much higher sedimentation in PPG of
lower average molecular mass, i.e. 425. In addition, the particles
settled quite rapidly in PPG 425; after 30 h the sedimentation rate
was >90% and afterward it remained at the same level. However,
AlNePPG 2000 suspension demonstrated its sedimentation
behavior only slightly, which was confirmed by its low sedimen-
tation rate (max. w10% in 72 h), as shown in Fig. 2. The zeta po-
tential measurements in PPG media showed that zeta potential is
negative for both liquids; it averaged (30) mV for AlNePPG 425
dispersion and below (10) mV in case of AlNePPG 2000 system.
Although different surfactants and physical treatments were
used for the preparation of AlNenanofluids, only more than two
weeks stable time of nanofluids was reported [5]. Thus, other
preparation methods are highly desired to prepare stable AlNe
nanofluids.
2.1.2. Zinc oxide-nanofluids
Zinc oxide is emerging as a material of interest for a variety of
electronic applications such as semiconductor for making inex-
pensive transistors and thin film batteries. It can be used in a large
number of areas, and unlike many of the materials with which
competes, is inexpensive, relatively abundant, chemically stable,
easy to prepare, antibacterial and nontoxic. One of the first in-
vestigations dealt with this type of nanofluids was presented by Yu
et al. [9]. They prepared ZnO nanofluids by dispersing ZnO nano-
particles in ethylene glycol. The mixture was stirred and sonicated
(40 kHz and 150 W) continuously for 3 h to ensure uniform
dispersion of nanoparticles in the base fluid. Based on the influ-
ence of ultrasonification on the particle size, it was reported that
the average size decreases rapidly in the first 3 h, after 3 h the
average size was about 210 nm (w10e20 times the primary size). It
was concluded that ultrasonification was not effective in avoiding
particle aggregation and producing uniformly distributed and
well-controlled size of ZnO nanoparticles. Moosavi et al. [10] first
170 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
Fig. 3. The ZnO cluster size in suspension as a function of sonication time [12].
synthesized the ZnO nanoparticles, which were then mixed with
ethylene glycol and glycerol as base fluids with the aid of magnetic
stirrer. Ammonium citrate was added as dispersant to enhance the
stability of the suspension. The weight ratio of dispersant to
nanoparticle was 1:1. As a result, the samples were stable for
several months and no sedimentation and agglomeration of the
particles in the samples was observed. Raykar and Singh [11]
synthesized water soluble ZnO nanoparticles. The solutions were
sonicated for 1 h and a proper amount of acetylacetone (acac) was
added as a dispersant to the solutions, which were sonicated again
for 10 min. They showed that the nanofluids were stable over 9
months to 1 year, and the size of ZnO nanoparticles was reduced
from 150 nm to 80 nm due to the reaction with acac, and. Kole and
Dey [12] dispersed fairly agglomerated ZnO nanoparticles in
ethylene glycol by intense ultrasonication (200 W). The cluster size
of ZnO nanoparticles in suspension was plotted against sonication
time to ascertain the optimum time of sonication. As shown in
Fig. 3, it was observed that ZnO clusters size rapidly decreases from
w459 nm to w91 nm between 4 and 60 h. However, beyond 60 h
of sonication, cluster size increased and for 100 h of sonication ZnO
clusters increased to w220 nm. Therefore, an optimum duration
for sonication was chosen to be 60 h. As a result, the suspension
was stable for 30 days without any trace of visible sedimentation.
Chung et al. [13] dispersed two types of zinc oxide powders, pro-
duced by solegel and physical vapor synthesis in deionized water
containing ammonium polymethacrylate as a dispersant. The
mixture was stirred at 25  C for 30 min, and sonicated using
several ultrasonic agitation systems, including a single piezoac-
tuated bath, a solenoid-actuated bath and a static bath with
immersed horn. They found that dispersion by ultrasonic horn was
more effective in terms of the size reduction rate, the minimum
achievable size, and sedimentation rates. Suganthi and Rajan [14]
synthesized zinc oxide nanoparticles by chemical precipitation
method using zinc nitrate hexahydrate as precursor. The ZnOe
water nanofluid was prepared with the aid of ultrasonication for
3 h and stabilization using sodium hexametaphosphate (SHMP) as
a dispersant. A predetermined quantity of ZnO was added to the
surfactant solution under high shear homogenization and ho-
mogenized for 20 min at 7000 rpm, followed by ultrasonication for
180 min (750 W and 20 kHz). Surfactant: nanoparticle ratio was
fixed at 1:5. The obtained higher values of absolute value of zeta
potential ensured higher colloidal stability of dispersions, which
was confirmed also through visual observation as well. Zafarani-
Moattar and Majdan-Cegincara [15] dried ZnO nanoparticles in
an electrical oven at about 110  C for 24 h prior to use for removing
adsorbed water moisture on the surface. The nanoparticles were
dispersed in poly ethylene glycol and its aqueous solutions using
sonication. It was found that the average particle size measured for
the nanofluids investigated was much larger than the size of pri-
mary particles. It was also found that ZnOePEG nanofluid was
stable at least for 140 min. Saleh et al. [16] synthesized ZnO
powders using chemical precipitation method. The nanoparticles
were dispersed in ethylene glycol using a magnetic stirrer and
ultrasonic processor under continuous pulse for 2 h. Lee et al. [17]
prepared EG-based ZnO nanofluids using a one step method
known as pulsed-wire evaporation (PWE). The synthesized nano-
particles came into direct contact with EG inside the chamber wall
and the ZnO nanoparticles were obtained without any surface
contamination.
From the above ZnO-nanofluid preparation methods, it can be
seen that long-term stability was obtained when using acac and
sonication for 10 min [11]. This clearly indicates that acac can be a
suitable surfactant to stabilize ZnOewater nanofluids.
2.1.3. Titanium dioxide-nanofluids
Titanium dioxide has three types of crystal habits which are
brookite, anatase and rutile. Brookite is one kind of unstable
crystal, with no industrial value, while anatase and rutile all have
stable properties, which are very important white pigment.
Compared with other white pigments, it is well accepted for its
super whiteness, tinting strength, covering power, durability, heat
resistance, chemical stability, and especially without any toxicity.
Titanium dioxide is widely applied in many fields, including
nanofluids preparation. Kayhani et al. [18] functionalized TiO2
nanoparticles by a chemical treatment. The TiO2 nanoparticles
were mixed with 1,1,1,3,3,3 hexamethyldisilazane (C6H19NSi2) in a
mass fraction of 2:1. The resulting mixture was sonicated at 30  C
for 1 h using ultrasonic vibration (40 kHz). Then, the soaked
nanoparticles were dried with a rotary evaporation apparatus. The
nanoparticles were mixed with distilled water and subjected to
ultrasonic vibration (400 W and 24 kHz) for 3e5 h. The obtained
nanofluids were found to be stable for several days without any
visible sedimentation. He et al. [19] mixed TiO2 nanoparticles in
the form of large agglomerates with distilled water using ultra-
sonication for 30 min. Then, the suspension was processed in a
medium-mill to reduce the agglomerated nanoparticles. The pH
value was adjusted to 11 (corresponding to zeta potential of
w40 mV) to prevent re-agglomeration of the milled samples.
Therefore, the obtained nanofluids were found to be very stable for
months. Murshed et al. [20] used ultrasonic dismembrator for 8e
10 h to ensure proper dispersion of TiO2 nanoparticles with
deionized water. The size of the nanoparticles in the base fluid was
found to be increased. Therefore, oleic acid and cetyltrimethyl
ammonium bromide (CTAB) surfactants (0.01e0.02%) were added
to ensure better stability and proper dispersion. Duangthongsuk
and Wongwises [21] used CTAB with very low concentrations
(about 0.01%) to ensure better stability and proper dispersion of
the TiO2 nanoparticles in water, without affecting the thermo-
physical properties of the nanofluid. The surfactant was first
mixed with water, and the nanofluids were sonicated continuously
for 3e4 h using an ultrasonic vibrator. They observed little
agglomeration after 3 h of sonication. Kim et al. [22] synthesized
nanofluids containing Al2O3, TiO2 and ZnO in water and ethylene
glycol. The suspensions were sonicated in an ultrasonic bath for
1 h, and then agitated for 10 h by a magnetic stirrer to make the
nanofluids homogenous. Sodium dodecyl sulfate (SDS) of 0.05 M
(above the critical micelle concentration 0.01 M) was added as a
surfactant. They observed that all nanofluids were stable except
the 10 nm ZnO/EG nanofluid, where no trial was successful to
stabilize the fluid, including addition of different surfactants and
adjusting of the pH level. They attributed this to an increase in
 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
surface area of the ZnO nanoparticles. Abbasian Arani and Amani
[23] dispersed TiO2 nanoparticles in distilled water. They used
ultrasonic vibrator with magnetic stirrer for approximately 3 h in
order to break down agglomeration of the nanoparticles. CTAB
surfactant was added with very low concentration (around 0.01%)
to not affect nanofluids’ thermophysical properties even though it
was reported that sedimentation of nanoparticles is less important
for turbulent flow regime. Moreover, the pH values were between
5.62 and 7 (IEP of TiO2 is 2.9). A minimum of 2.7 l of each con-
centrations were prepared and it was observed that the suspen-
sions were stable for several hours (days). Utomo et al. [24] diluted
30e40 wt.% of alumina and titania suspensions by addition of
distilled water whilst keeping pH constant, and ultrasonicating the
suspension for 3 min to obtain homogenous mixtures. It was re-
ported that according to the manufacturer the alumina and titania
suspensions were stabilized by using octyl silane and ammonium
polyacrylate (molecular weight ¼ 3000 g/mol), respectively. It was
observed that even after sonication, nanoparticles formed rela-
tively large aggregates with the size of the order of 200 nm and
140 nm for alumina and titania, respectively. Longo and Zilio [25]
verified the dispersion efficiency of Al2O3ewater (15 wt.%) and
TiO2ewater (25 wt.%) nanofluids, that were prepared and mixed by
the supplier. Each nanofluid was subdivided into two parts: the
first was subjected to mechanical stirring, and the second was
sonicated at 25 kHz for 48 h. It was found that Al2O3ewater simply
stirred showed a distribution with two peaks corresponding to an
average size of 47 nm and 285 nm. Also, the Al2O3ewater soni-
cated nanofluid exhibited two peaks distributions corresponding
to an average size of 28 nm and 165 nm. The first peak of both
distributions was close to the declared average diameter of the
nanoparticles (30 nm), whereas the second peak indicates the
tendency of the nanoparticles to agglomerate into clusters. It was
also found that TiO2ewater simply stirred nano-fluid shows a
single peak distribution with an average size of 220 nm, whereas
the TiO2ewater sonicated nanofluid presents a single peak distri-
bution with an average size of 155 nm. It was concluded that the
ultrasound treatment shows better dispersion efficiency than
simple mechanical stirring, and that both nanofluids showed sta-
bility for more than one month. Chen et al. [26] formulated EGe
TNT nanofluids by using dry titanate nanotubes, synthesized based
on the alkali hydrothermal transformation. The nanofluid was
prepared by mixing nanoparticles with ethylene glycol under
gentle stirring, followed by sonication for 48 h using ultrasonic
bath. It was found that the average size was w260 nm for all
nanofluids. The nanofluids produced were stable over the period of
two months. Mo et al. [27] dispersed rutile and anatase TiO2
nanoparticles in deionized water. The pH value of the deionized
water was adjusted to eight by using ammonia, and sodium
dodecyl sulfate (SDS, C12H25SO4Na) was used as a surfactant to
ensure better stability and proper dispersion. The suspension was
whisked using magnetic stirrer for 10 min and sonicated for
40 min. They estimated the stability of the TiO2ewater nanofluids
by the changes in the weight concentrations of the TiO2 nano-
particles, which were measured using a spectrophotometer. It was
observed that the 0.30 wt.% and 0.70 wt.% TiO2ewater nanofluids
were kept stable for 286 h (about 12 days). However, the stability
of the 0.05 wt.% nanofluids was not so good. Bobbo et al. [28] used
different dispersants and various physical treatment techniques
including ultrasonic agitation, ball milling and homogenization.
They found that homogenization method was the best process to
improve the suspension stability. Also, SDS and PEG were identi-
fied as the best dispersants for the nanofluids based on single wall
carbon nanohorns (SWCNH) and TiO2, respectively. Hence, the
nanoparticles were mechanically dispersed in water. Then, a high
pressure homogenizer (up to 1000 bar) was employed to optimize
171
the dispersion. For the nanofluids based on SWCNH at concen-
trations of 0.1% and 1% by mass, the ratio between nanoparticles
and dispersant mass was 1:1. For the lowest concentration (0.01%
by mass), the ratio was 1:3. For watereTiO2 nanofluid, the ratio
between nanoparticles and dispersant mass was 1:2 for each
concentration. It was found that the nanofluids formed by water,
SDS and SWCNH were very stable even after several days. The
measured nanoparticle average diameter was around 140 nm,
188 nm and 120 nm for the 0.01%, 0.1% and 1% mass concentra-
tions, respectively. However, solutions of water, PEG and TiO2 were
less stable. It was found that all the measurements provide much
higher values than the 21 nm correspondent to the nominal
diameter of the nanoparticles: at 0.01%, 0.1% and 1% mass con-
centrations the measured average diameter was around 180 nm,
121 nm and 132 nm, respectively. The diameter increase indicates
a tendency of titania particles to rearrange in liquid media forming
aggregates. Hojjat et al. [29] subjected the suspensions of g-Al2O3,
TiO2, and CuO nanoparticles in deionized water to ultrasonic vi-
bration for about 1 h. Then, appropriate amounts of carboxy
methyl cellulose (05 wt.% of CMC in DIewater) were added to the
suspensions and thoroughly mixed to achieve the desired
composition of nanofluids. They observed no sedimentation after
several days following the nanofluid preparation. In addition, the
preparation of stable Al2O3 nanofluids was more difficult and, as a
result, Al2O3 nanoparticle dispersions were limited to 1.5 vol.%.
Fedele et al. [30] sonicated TiO2 nanofluid at 35 wt.%, then adding
bidistilled water in a weighed amount. They analyzed the average
dimension of the nanoparticles in suspensions using dynamic light
scattering method. The TiO2 mean diameter was 76 nm at 1 wt.%,
72 nm at 10 wt.% and 73 nm at 20 wt.%. They found that at these
compositions, the nanofluids were stable with absence of particles
aggregates. To determine the tendency of the particles to settle
down along time, they put two samples at 1 wt.% in two different
measurement cuvettes. The first sample was measured almost
every day for thirty-five days, without shaking the fluid. The sec-
ond sample was also measured almost every day for thirty-five
days after sonication of the fluid. In the case of static solutions, it
was observed that the nanoparticle mean size slightly decreased to
around 51 nm after 35 days, indicating a partial precipitation.
However, after 1 h of sonication, a mean particle size of 76 nm was
always recorded, suggesting the absence of further aggregation
phenomena. TiO2ewater nanofluid zeta potential was around
55 mV, which is higher than the empirical limit of 30 mV over
which a colloidal solution should be stable. The pH values were
1.86 for the 35 wt.% solution, 2.24 for 20 wt.%, 2.37 for 10 wt.%, and
3.07 for the 1 wt.%. Tajik et al. [31] and Chakraborty et al. [32]
produced Al2O3 and TiO2 nanofluids by dispersing nanoparticles
in distilled water, using continuous ultrasonication for 30 min and
ultrasonic stirring for 20 min, respectively. The prepared disper-
sion remains stable for the duration of experiment [28] and no
appreciable sedimentation was observed after 24 h [32]. Mitra
et al. [33] dispersed TiO2 and MWCNT nanoparticles in water fol-
lowed by 30 min of ultra-sonication. Sajadi and Kazemi [34] mixed
the proper amount of TiO2 nanoparticles with distilled water by a
mixer for 10 min. Then, ultrasonic cleaner was used to disperse
nanoparticles for 30 min. Suriyawong and Wongwises [35] diluted
40 wt.% of TiO2 nanofluid by adding water. After that, the nano-
fluids were treated with ultrasonic vibration for 2 h to distribute
the nanoparticles evenly. Other researchers have also prepared
TiO2 nanofluids by using only physical methods. However, they
didn’t indicate the time used for nanofluid preparation [36e39].
In this section we mainly discussed the TiO2enanofluids
preparation methods. It can be seen that stable nanofluid was ob-
tained using either sonication for 48 h [25,26] or adjusting the pH
value [19].
172 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
Fig. 4. Summary of DLS analysis of diluted SiO2 dispersions in TH66 24 h after ultra-
sonication; (a) no surfactant, (b) benzalkonium chloride, (c) benzethonium chloride,
(d) cetyltrimethyl ammonium bromide. (Inset, middle) Visual appearance of 1 vol.%
SiO2/TH66 with various surfactants. (Inset, right) SEM image of SiO2 powder used in
preparation of nanofluids [40].
2.1.4. Silicon dioxide-nanofluids
Silica is a widely used ceramic material both as a precursor to
the fabrication of other ceramic products and as a material on its
own. Silica has good abrasion resistance, electrical insulation and
high thermal stability. It is insoluble in all acids with the exception
of hydrogen fluoride (HF). Timofeeva et al. [40] dispersed silicon
dioxide nanopowders in non-polarorganic fluid (TH66). Benzalko-
nium chloride (BAC), benzethonium chloride (BZC), and cetyl-
trimethyl ammonium bromide (CTAB) were tested as surfactants
for dispersing silica. Surfactants were dispersed into the base fluid
first, followed by introduction of the nanopowder. The mixture was
homogenized by continuous stirring and sonicated 10 times
(w80 W) for 5 min each time. Suspensions with 1 vol.% of SiO2
nanoparticles with no surfactant and excess of each surfactant
(5 wt.% or w0.12e0.14 M) were prepared using the adsorption
model with ‘laying flat’ and compacted ‘standing up layers of the
surfactant molecules. The visual appearance of suspensions 24 h
after the last sonication indicated that BAC surfactant was the best
stabilizer for SiO2/TH66, as shown in Fig. 4. Both DLS and SEM re-
sults confirmed that the average particle size was the smallest in
suspension with BAC, followed by BZC. The suspension with no
surfactant had the largest agglomerates, while CTAB provided just
some reduction in the average agglomerate size. Nanofluids
appeared to be stable without any visual phase separation for at
least a week. Silica nanoparticles were functionalized using grafting
silanes directly to the surface of silica nanoparticles by Yang and Liu
[41]. A silane of (3-glycidoxylproyl) trimethyoxysilane was used for
the functionalizing process. The mass ratio of the reacting silane
and silica nanoparticles was taken as 0.115. The nanoparticles were
dispersed into water and the solution was kept at the environ-
mental temperature of 50  C for 12 h. It was found that function-
alized nanoparticles can still keep dispersing well after the
nanofluid has been standing for 12 months even at the mass con-
centration of 10%. Moreover, no sedimentation was observed. They
also prepared traditional nanofluid by dispersing and oscillating
nanoparticles into water. Silica nanoparticle powders were firstly
dispersed into deionized water and the suspension was then
oscillated in an ultrasonic bath for 12 h. It was observed that
sedimentation occurred after several days. Anoop et al. [42]
dispersed an appropriate amount of SiO2 nanoparticles in
Fig. 5. Photos of visualization and Tyndall effect of methanol-based SiO2 nanofluids
just right after preparation [45].
deionized water using an ultrasonic bath for 30 min. Further, this
colloidal suspension was subjected to intensified ultrasonication by
immersing a probe type sonicator in the nanofluids. Cyclic ultra-
sonic pulses for about 15 min were given to the suspension to
achieve maximum possible de-agglomeration of particles. The pH
value of the nanofluid suspension was kept away from the iso-
electric pH value, at a magnitude of 4.5 by adding reagent grade
nitric acid. It was observed that nanofluids exhibited good stability
over time. Qu and Wu [43] prepared Al2O3 and SiO2ewater nano-
fluids. They first adjusted the pH value of the nanofluids to a certain
value (with pH ¼ 9.7 and 4.9 for the silica and alumina nanofluids,
respectively), which was far away from the corresponding iso-
electric point (IEP) of silica (with pH w 3) or alumina (with
pH w 9), and then nanoparticles were added into water. The
dispersion solution was subsequently vibrated for about 4 h in an
ultrasonic bath. It was found that alumina nanoparticles were
better dispersed. Fazeli et al. [44] dispersed SiO2 nanoparticles in
distilled water, and then the suspension was sonicated by an ul-
trasonic bath for at least 90 min. They found that silica nanofluids
stayed stable for a period of 72 h without any visible settlement.
Pang et al. [45] mixed nanoparticles in pure methanol by using
ultrasonic vibration (750 W, 20 kHz) for 2 h to break down the
agglomeration. They studied the effect of nanoparticle concentra-
tion on the zeta potential and pH of methanol-based nanofluids.
They showed that zeta potential is highly related to the pH of the
suspension. The measured zeta potential of Al2O3 nanofluids was
over 60 mV, and the zeta potential of SiO2 nanofluids was over
30 mV, which indicates the good stability of both nanofluids.
However, it was observed that the nanoparticles in nanofluids
contact each other and form some clusters, and the cluster size of
SiO2 particle was larger than that of Al2O3 particle (clustering size of
SiO2: 280e401 nm; clustering size of Al2O3: 120e148 nm). The
photos of visualization and Tyndall effect showed that methanol-
based nanofluids were well dispersed, as shown in Fig. 5. Boluk-
basi and Ciloglu [46] prepared SiO2 nanofluids by using magnetic
stirrer. Then, the suspensions were transferred into an ultrasonic
vibrator and sonicated continuously for 2 h (600 W and 40 kHz).
They reported that no sedimentation was observed during the
period of experiment. Darzi et al. [47] added distilled water to a
specified amount of SiO2 nanoparticles and mixed together by
magnetic stirrer for 2 h. Kulkarni et al. [48] synthesized nanofluids
containing Al2O3, CuO and SiO2 nanoparticles. The nanoparticles
were obtained as colloidal dispersion in 50% water by weight. The
nanofluids were prepared in 60:40 ethylene glycol and water so-
lution (binary fluid). The samples were placed in a sonicator bath
for approximately 2 h to ensure proper dispersion and prevent
agglomeration. They confirmed from the DLS results that the
nanoparticles were dispersed uniformly in the suspension. Hwang
 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189 173

et al. [49] used an ultrasonic disruptor to produce CuO, MWCNTs Table 1

and SiO2 nanofluids. They obtained stable suspensions for the case The pH value and zeta potential of the nanofluids with various solid contents in this
experiment.
of SiO2 and CuO nanoparticles. However, sodium dodecyl sulfate
(SDS) was used as a surfactant when producing MWCNT nanofluids CuO NaHMP Wt ratio pH value Zeta
since MWCNTs are entangled and agglomerated in aqueous concentration concentration NaHMP/CuO (e) potential
(vol.%) (g/100 ml nanofluid) (mV)
suspension.
From the aforementioned preparation methods of nanofluids 0.01 0.2 3.12 6.66 59.8
0.02 0.4 3.12 6.66 51.3
containing mainly silica nanoparticles, it can be noticed that SiO2e
0.07 1.4 3.12 6.64 37.5
water nanofluid can be kept stable for 12 months even at 10% mass 0.10 2.0 3.12 6.68 *
concentration [41], which indicates that Surface-functionalized 0.20 2.0 1.56 6.70 *
silica nanoparticles can be competitive in the preparation of silica 0.40 2.0 0.78 6.67 *
nanofluids. *The high solid content turned the sample solution opaque so that the zeta potential
could not be measured using the dynamic light scattering analyzer [54].
2.1.5. Copper oxide-nanofluids
Nano-copper oxide is a widely used material. It has been applied
to the catalyst, superconducting materials, thermoelectric mate- potential and pH. It was found that dispersion stability of CuO/DIe
rials, sensing materials, glass, ceramics and other fields. Rohini water nanofluid fabricated by one-step method (zeta
Priya et al. [50] prepared CuO nanoparticles by a sol gel route using potential ¼ 30 mV) of the PLAL is much better than that prepared
cupric nitrate and sodium hydroxide. The synthesized particles by two-step method (zeta potential ¼ 15.8 mV). They attributed
were dispersed in water with aid of ultrasonic treatment for about this to the ions dissociated from water molecules during the laser
6 h, followed by addition of tiron (4,5-dihydroxyl-1,3- ablation process. Yang and Liu [53] dispersed CuO nanoparticles
benzenedisulfonic acid disodium salt) as dispersant. The opti- which were commercial products of gas condensation into deion-
mum ratio of CuO to tiron was determined by studying the colloidal ized water, then oscillated in an ultrasonic bath for 12 h. They found
stability of dispersions with different concentrations of surfactant. that the particle diameter distribution in suspension is almost three
The minimum concentration of surfactant required to ensure times larger than the nominal diameter. Chang et al. [54] synthe-
colloidal stability corresponded to CuO:Tiron ratio of 2.5:1. The sized copper oxide nanoparticles using spinning disk reactor (SDR).
prepared nanofluids were found to possess a maximum absolute The nanoparticles were agitated in jacketed vessel containing
zeta potential of 30 mV, which was considered sufficient to ensure NaHMP as dispersant, using sonication with a power intensity of
colloidal stability. In addition, the stability was also confirmed 165 W. The weight ratio of NaHMP to CuO was first kept at 3.12:1
through visual observation. Suresh et al. [51] also synthesized while the CuO content increased from 0.01 to 0.10 vol.%. Then, to
copper oxide powder by solegel method. The nanoparticles were reduce the extent of CuO dissolution caused by adding NaHMP, the
dispersed in water by using an ultrasonic vibrator (100 W and concentrations of NaHMP were fixed at 2 g/100 ml, but the CuO
36  3 kHz) for 6 h. The pH of the prepared nanofluid was measured content was varied from 0.10 to 0.40 vol.%. They observed that
and found to be around 4.83. Lee et al. [52] used in-house prepared when the CuO content was higher than 0.40 vol.%, the suspension
CuO nanofluids in two ways such as one step method and two step was very unstable and the CuO nanoparticles tended to settle
method. For the two step method, CuO/DIewater nanofluid was within several minutes, which rendered the experiment impos-
sonicated continuously for 6 h while the process of preparation of sible. It was reported that the high solid content turned the sample
CuO nanofluids in one step method was carried out by pulsed laser solution opaque so that the zeta potential could not be measured
ablation in liquids (PLAL) using a single-pulsed laser beam using the dynamic light scattering analyzer, as shown in Table 1.
(k ¼ 532 nm) as follows: first A Cu pellet was put at the bottom of a Harikrishnan and Kalaiselvam [55] synthesized CuO nanoparticles
beaker filled with DIW, and then a Nd:YAG laser was used to pro- by precipitation method. The preparation process of CuOeoleic acid
duce CuO/DIW nanofluid for 8 h. As shown in Fig. 6, the size of nanofluids were performed using an ultrasonic vibrator at a fre-
spherical CuO nanoparticle of nanofluid fabricated by one-step quency of 40 kHz and the residing times of nanofluids in the
method is much smaller than that used in two-step method. They vibrator were varied for different mass fractions and they were
checked the dispersion stability of nanofluids by measuring zeta 30, 35, 40 and 45 min for 0.5, 1.0, 1.5 and 2.0 wt.%, respectively.

Fig. 6. TEM images of CuO nanoparticles according to manufacturing methods: (a) one-step method and (b) two-step method [52].
174 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
They found that nanoparticles were stably dispersed and uniformly
distributed in base fluid. It was reported that CuO nanoparticles
were not dissolved in oleic acid, but dissociative adsorption might
exist between oleic acid and CuO nanoparticles. Saeedinia et al. [56]
dispersed CuO nanoparticles in oil by using an ultrasonic processor
(400 W and 24 kHz) to break large agglomerates of nanoparticles in
the fluid and make stable suspension. It was observed with naked
eyes that the nanofluids were uniformly dispersed for 24 h and the
complete sedimentation occurred after a week. Selvakumar and
Suresh [57] dispersed specified amount of nanoparticles in deion-
ized water by using an ultrasonic vibrator for 6 h. They measured
the pH of prepared nanofluids and the values were found to be
around 4.8, which is far away from the isoelectric point. It was
observed that the prepared nanofluids were stable even after a
week except very little sedimentation. Kannadasan et al. [58] pro-
duced CuO nanoparticles by chemical precipitation method, they
prepared CuOewater nanofluids using an ultrasonic bath (100 W,
36  3 kHz) for 4 h to get stable suspension. It was observed that
there was a very little settlement of nanoparticles even after 25
days. Byrne et al. [59] prepared CuOewater nanofluids with and
without surfactant. The amount of surfactant (CTAB) used was
equal to the volumetric amount of nanoparticles added to the base
fluid. Once the components were mixed, the batch was sonicated
using a high intensity ultrasonic processor (100 W) for 7e8 h to
ensure an adequate dispersion of particles. From the DLS results
with concentration of 0.1% and no surfactant, it was observed that
the average particle size in the quiescent fluid decreases steadily
from roughly 3000 nm at time zero to approximately 300 nm after
nearly 4 h, indicating the presence of agglomerates in the sample
since no surfactant was used. Also, it was observed that the 0.1%
nanofluid with surfactant had an average particle size of about
200 nm with almost no variation over 7 days. In addition, the rapid
initial settling of large agglomerates seen in the sample without
surfactant was not observed. They indicated that the use of a sur-
factant reduces the average particle size, improves the dispersion of
the particles and makes a suspension much more stable. Liu et al.
[60] dispersed CuO nanoparticles made by the gas-condensation
method into deionized water. The suspension was then oscillated
for about 10 h in an ultrasonic water bath with a working frequency
of 25e40 kHz to ensure full dispersion. They reported that the pH
value of the nanofluid relied weakly on the concentration and it
was fixed at about 7. Fotukian and Esfahany [61] prepared CuO
nanofluids by gradually adding nanoparticles to distilled water
while agitated in flask. The suspension was then vibrated for 10 h in
ultrasonic mixer. As a result, no precipitation was observed after
5 h. Liu et al. [62] produced CuO/ethylene glycolewater nanofluids.
They put the nanoparticles and water into a super-sonic water bath
and surged for about 12 h to form stable suspension. The results
showed that the stability and uniformity of nanoparticle suspen-
sions were poor after several days. Zeinali Heris [63] first used
mechanical agitator for 6 h to disperse the nanoparticles, then the
suspension was subjected to ultrasonication for about 2 h. No
precipitation of nanoparticles was observed after 22 h. Namburu
et al. [64] stirred and agitated the CuOenanofluid mixture thor-
oughly for 30 min using an ultrasonic agitator. Wongcharee and
Eiamsa-ard [65] dispersed CuO nanoparticles in water using an
ultrasonic vibrator for 5 h.
It can be clearly seen that NaHMP can be used for the prepara-
tion of copper oxide nanofluids at low volume fraction that is less
than 0.4 vol.%. In addition, CuO nanofluids showed short time
stability.
2.1.6. Aluminum oxide-nanofluids
Alumina is the most cost effective and widely used material in
the family of engineering ceramics. The raw materials from which
this high performance technical grade ceramic is made are readily
available and reasonably priced, resulting in good value for the cost
in fabricated alumina shapes. With an excellent combination of
properties and an attractive price, it is no surprise that fine grain
technical grade alumina has a very wide range of applications.
Sonawane et al. [66] performed a series of trials to determine
the exact proportion of surfactants to be added to the aviation
turbine fuel (ATF) to make a stable Al2O3 nanofluid. Initially, they
mixed 1 L of ATF with 1 vol.% of Al2O3 and ultrasonication was
carried out for 1 h, 2 h and 12 h, in three different experiments.
However, irrespective of the sonication time, the nanoparticles
were found to settle within an hour of completion of sonication. In
the next set of trials, six samples with ATF (10 ml) and Al2O3 (1% by
volume) were prepared along with Oleic acid as a surfactant to
prevent the nanoparticles from settling. A syringe was used to
carefully measure the addition of surfactants in the samples. Each
of the six samples has a different concentration of surfactant to find
the most appropriate combination for stability. The mixture was
continuously stirred while adding the nanoparticles and surfactant.
However, Al2O3 particles settle at the bottom in each case. The same
trial was repeated with a different surfactant, Polyoxyethylene
Sorbitan Monolaurate (known as ‘Tween’ 20 LR) known to be used
with organic fluids. Numerous trials were performed using
different concentrations of ‘Tween’ 20 LR. However, in these trials
too, the Al2O3 particles settle at the bottom. Subsequently, trials
were carried out using different concentrations of Tween 20 and
Oleic acid in combination, and the appropriate concentration of
surfactants to be mixed in ATF (10 ml) with 1% Al2O3 (by volume) is
found to be 3 drops (0.026 ml) each of Oleic Acid and ‘Tween’ 20 LR.
Trials are further extended for 1000 ml of ATF and 1 vol.% of Al2O3
and proportionately 300 drops (2.6 ml) of each surfactant were
used. The nanofluid was sonicated for 1 h, 2 h and 12 h. It was
observed that the solution was stable even after 24 h, and it was
independent of ultrasonication time. With this appropriate con-
centration of surfactants, nanofluids were prepared by suspending
Al2O3 nanoparticles in ATF. For higher nanoparticle volume con-
centration, the surfactant amount was proportionately higher.
Suresh et al. [67] synthesized Al2O3 nanoparticles by using chem-
ical precipitation method. They prepared nanofluids by dispersing a
specified amount of Al2O3 nanoparticles in water using an ultra-
sonic vibrator generating ultrasonic pulses of 100 W and
36  3 kHz. The nanofluids were kept under ultrasonic vibrator
continuously for 6 h. The pH of the prepared nanofluid was found to
be 4.8, which is far from the isoelectric point. In addition, the zeta
potential was expected to be around 45 mV which is an indicative
of good colloidal stability. They found that the Al2O3/water nano-
fluid was very stable for several weeks without visually observable
sedimentation. Beck et al. [68] subjected a mixture of Al2O3 nano-
particles and ethylene glycol to ultrasonic mixing for several mi-
nutes to obtain uniform dispersion. They reported that the
resulting dispersions were remained uniform for the duration of
the experiments because of surface charges on the particles.
Sharma et al. [69] used SDBS, measuring one tenth of nanoparticles
as a dispersant. The dispersant was mixed with water and the
calculated amount of nanoparticles was added. The mixture was
stirred continuously for 12 h. They observed that a nanofluid having
less than 3% volume concentration was stable for over a week.
However, some sedimentation was observed at higher concentra-
tion. Sundar and Sharma [70] used the same technique, the only
difference is the time of stirring which was 10 h. Gharagozloo and
Goodson [71] diluted 20% weight concentration Al2O3ewater
nanofluid with less than 1% nitric acid with deionized water to the
desired volume concentrations. The measured pH for each of the
nanofluid concentration was 5.5. The nanofluid was sonicated
continuously for 4 h at 60 Hz and 130 W. They observed that the
 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
nanofluid was stable with only minor settling after a week. Jung
et al. [72] produced two types of water-based alumina nanofluids
with/without polyvinyl alcohol (PVA), using a horn-type ultrasonic
disrupter for 2 h. The PVA concentration was set to be the same as
the nanoparticle concentration. They found that the particles in the
prepared nanofluids with/without PVA were below 300 nm, and
the aggregated particles were stably suspended for more than 1
month. Soltani et al. [73] first prepared the base liquid by mixing
Carboxy methyl cellulose (CMC) aqueous solutions with a concen-
tration of 0.5 wt.% with distilled water, using mechanical mixer.
Then, the nanoparticles were added thoroughly mixing for 6 h. The
prepared nanofluids were sonicated for 1 h just before the exper-
iment to increase the stability of solutions. Ho et al. [74] dispersed
nanoparticles into the bottle of ultra-pure Milli-Q water while
stirring with a magnetic stirrer for 2 h. They adjusted the pH value
of the nanofluid to pH ¼ 3. It was observed that the suspensions
were stable for at least two weeks. However, poor suspension
stability was observed for particle fraction greater than 4 vol.%.
Addition of a suitable amount of Triton X-100 (about 0.021 wt.%) as
dispersant to double distilled water to reach a homogenously
dispersed solution after sonication for about 30 min was done by
Yousefi et al. [75]. It was found that the obtained nanofluid was
stable about three days after sonication. Raveshi et al. [76] added
SDBS dispersant with a mass proportion of one tenth of the
nanoparticles to WEG50 as a base fluid, and then the mixture was
sonicated in ultrasonic bath for 2 h. Then, the nanoparticles were
dispersed in the mixture which was stirred for 5 h. No obvious
sedimentation was observed after 3 days. Hung et al. [77] produced
Al2O3/water nanofluid using a homogenizer operating at 8000 rpm
for 30 min, an electromagnetic agitator running at 600 rpm for
90 min, and an ultrasonic vibrator operating at 400 W for 60 min.
The base liquid was prepared by adding 0.2 wt.% of water-soluble
chitosan as a cationic dispersant to distilled water. They
confirmed that the difference between initial and final concentra-
tions (after 2 weeks) of Al2O3/water nanofluid was less than 5%,
indicating the stability of the prepared nanofluids. Heyhat et al. [78]
put Al2O3 nanoparticles into the weighed distilled water gradually
and sonicate the mixture continuously for 1 h at 400 W and 24 kHz.
The measured zeta potential was about 30 mV, which confirmed
the physical stability of the nanofluids. Singh et al. [79] dispersed
two sizes Al2O3 nanoparticles produced by vapor condensation
techniques in ethylene glycol and water. The aluminaewater
nanofluids were stabilized through electro-static method; a few
drops of hydrochloric acid were mixed to maintain the pH value
and hence the zeta potential. The pH value was fixed at 4 and the
zeta potential for these nanofluids was 58.7 mV. They concluded
that a pH of 3.5e5.0 was able to keep the nanofluids stable for a
long times. For Ethylene Glycol based nanofluids, nothing was
added and it was found that only sonication is enough to get a
stable suspension. Pandey and Nema [80] dispersed nanoparticles
in distilled water using ultrasonic processor for 8e16 h. No sedi-
mentation was observed in the produced nanofluids after 24 h.
Chandrasekar et al. [81] synthesized Al2O3 nanoparticles using
microwave assisted chemical precipitation method. The nanofluids
were kept under ultrasonic vibration for 6 h at 363 kHz and
100 W. The pH value was found to be around 5 which is far from the
isoelectric point for alumina nanoparticles. Qu et al. [82] regulated
the pH value of the base water by adding small amount of HCl
solution, and then the nanoparticles were added. The dispersion
was ultrasonic vibrated continuously for 4 h in an ultrasonic bath. It
was observed that nanoparticles could be stably suspended in
water at least for 3 days when the pH value is 4.9. Anoop et al. [83]
used two Al2O3 nanoparticle sizes produced by laser evaporated
physical methods to make alumina nanofluids. The particles were
dispersed using ultrasonication and by keeping the pH value away
175
Fig. 7. Effect of sonication time (h) on zeta potential of the Al2O3 nanoparticles
dispersed in water [84].
from the iso-electric point. The pH values used for 1 wt.%, 2 wt.%,
4 wt.% and 6 wt.% were 6.5, 6, 5.5 and 5, respectively. It was
observed that the suspensions were stable for several weeks. Lee
et al. [84] sonicated four dilute Al2O3-nanofluids with pH of 6.04 at
a fixed concentration of 0.1 vol.% for 0 h, 5 h, 20 h and 30 h at 30e
40 kHz, respectively. It was observed that sonication is needed for
long (w5) h to improve the particle dispersion, as shown in Fig. 7. It
was also observed that 5 h sonication provides good dispersion
with little aggregates. Kim et al. [85] synthesized spherical/fibrous
alumina nanoparticles. The spherical nanoparticles were prepared
by pulsed wire evaporation (PWE) while the fibrous nanoparticles
were prepared, using a hydrolysis reaction of spherical Al nano-
particles produced by PWE method. The fabricated alumina nano-
fibers were mixed with EG by sonication for 1 h. They found that
the dispersion stability for fibrous alumina nanofluid decreased
with time due to the aggregation of nanofibers. Hegde et al. [86]
stirred Al2O3ewater nanofluids in a sonicator for 3 h. The particle
size range was found to be between 10 nm and 120 nm, and the
nanofluid showed no agglomeration of the nanoparticles 2 h after
sonication. Esmaeilzadeh et al. [87] stabilized alumina water
nanofluids through a 4 h process of ultrasonication with 170 W and
50 Hz and electromagnetic stirring. No sedimentation was
observed throughout the testing period. Ali et al. [88] diluted
20 wt.% of alumina nanofluid using distilled water. The new diluted
solutions were ultrasonically vibrated. No precipitation was
observed two days after the ultrasonic vibration. Jacob et al. [89]
suspended alumina nanoparticles and adjusted the pH value of
the suspensions. The nanofluid was sonicated for 5e6 h. Teng et al.
[90] dispersed Al2O3/water nanofluid for several time by ultrasonic
vibration and electromagnetic agitation. The nanofluid formed was
added with cationic dispersant (0.3 wt.% of chitosan). They reported
that all the completed experimental samples have to be statically
placed for 1 month until good suspension effect was achieved.
From the above discussion, it can be seen that regardless the
base fluid, a stability of several weeks was obtained using only
sonication [67] or sonication with adjusting the pH value [83],
while a stability of a month was found using sonication and PVA
surfactant [72]. In addition, methanol nanofluids showed an
excellent stability (zeta potential over 60 mV) even though the
mixture was sonicated only for 2 h [45]. It should be mentioned
that some researchers didn’t give details about how the Al2O3
nanofluids were prepared for their experiments.
176 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
Fig. 8. Stability comparison of nanofluids containing PCNTs or TCNTs [91].
2.1.7. Carbon nanotube-nanofluids
Carbon nanotubes have strength and stiffness properties
several 1000 times better than that of steel and conductivity better
than copper, carbon nanotubes have extraordinary intrinsic elec-
trical, thermal and mechanical properties making them potentially
attractive materials for use in different fields. CNTs have attracted
many researchers due to their higher thermal conductivity and
very high aspect ratio, for preparing nanofluids. Chen et al. [91]
used commercial multi-walled CNTs, produced by chemical vapor
deposition method to prepare their nanofluids. It was revealed that
the as received pristine CNTs (PCNTs) were not only aggregated,
but also entangled. Therefore, they introduced hydrophilic func-
tional groups on the surface of the nanotubes by mechanochemical
reactor, and then dispersed the chemically treated CNTs (TCNTs)
into a base fluid. Potassium hydroxide was used to modify the
surfaces of CNTs. It was shown that the aggregates and entangle-
ments of PCNTs were broken after chemical treatment. The CNTs
were cut short by the intensive mechanical forces during the ball
milling process. It was also shown that PCNTs were precipitated to
the bottom when dispersed in most of the fluids even after long-
time intensive sonication if surfactant was not added and even
with surfactant like oleylamine. Almost all the nanotubes were
sedimented after 5 min for the suspension with 0.1 vol.% PCNTs
dispersed in DW, leaving upper fluid transparent, while the TCNTs/
fluid suspensions remained stable for many months with no visible
precipitation at the bottom, as shown in Fig. 8. Su et al. [92]
modified the surface of CNTs with nitric acid; One gram of CNTs
was suspended in 40 ml of concentrated nitric acid (z68%) and
refluxed for an hour at 120  C. After washing with deionized water
until the supernatant attained a pH value of around 7, the CNTs
were dried at 55  C. And then, the chemically treated CNTs were
added directly into the base fluid. The suspension was agitated for
2 h by ultrasonic applicator, with the frequency of 100 kHz. It was
found that almost all of PCNTs with 0.2 wt.% deposited, having
upper fluid transparent. In sharp contrast to PCNTs, TCNTs were
well dispersed in aqueous ammonia. Meng et al. [93] kept 1 g of
CNTs into 60 ml HNO3 at 120  C for 6 h. The mixture was cooled,
filtered and washed to neutral pH with distilled water. Then the
washed product was freeze-dried. Finally, the dried particles were
added to an appropriate amount of glycol under ultrasonic vibra-
tion to get the CNTs glycol nanofluid. They found that an untreated
CNTs tend to aggregate resulting in poor stability. However, the as-
prepared nanofluids could remain stable for more than two
months without sedimentation. Liu et al. [94] added the CNTs in an
alkali/deionized water mixture. Then, the CNTs alkali/deionized
water mixture was oscillated continuously for about 10 h in an
ultrasonic deionized water bath to break up the self-winding
structure of the CNTs and make the steady CNT suspension.
Later, the nitric acid was added into the CNT suspension and the PH
value was adjusted to a constant of 6.5. Finally, the CNT suspension
was again oscillated continuously for about 2 h and was then hold
in a tank. Before the boiling experiment, the suspension was
oscillated again for about 2 h. Wang et al. [95] used DI water and
the Carboxyl MWNTs to produce nanofluids. A binary mixture of
Triton X-100 and sodium dodecyl benzene sulfonate was used to
accomplish better stability. The mass ratios of Triton X-100/SDBS
and mixture/MWNT were about 20:1 and 3:20, respectively. Then,
the MWNT and surfactant mixtures were dispersed into a preset
amount of DI water, and the agglomerated MWNTs were separated
by a high-shear mixer. Meibodi et al. [96] synthesized carbon
nanotubes by catalytic decomposition of 20% methane in hydrogen
over CoeMo/MgO catalysts at 800e1000  C. They reported that a
typical process to make nanofluid stable for months involves
sonicating a functional SWNT (FSWNTs) sample in ultrasonic bath
for over 2 h, or disruptor 30 min and dispersing the sonicated
SWNTs into a preset amount of distilled water and adjusting the
suspension to a preset pH level. Liu et al. [97] mixed MWCNTs,
produced by a catalytic chemical vapor deposition method with
ethylene glycol or synthetic engine oil base fluids. The suspensions
were then homogenized by intensive ultrasonics. On the other
hand, N-hydroxysuccinimide (NHS) in the solid particle form was
employed as the dispersant in carbon nanotubeesynthetic engine
oil suspensions. NHS was added into CNTs directly. The mixture
was blended by a magnetic stirrer. Synthetic engine oil was then
filled into the CNTseNHS mixture. The mixture was mixed up by
an ultrasonic homogenizer. They reported that the CNTs were well
dispersed and the sedimentation of the suspensions was not
visible. Babu and Prasanna Kumar [98] synthesized MWCNTs using
an arc discharge method. Then the nanoparticles were chemically
treated; soaking the CNTs in an acid mixture containing HNO3 and
H2SO4 in the volumetric ratio of 1:3 for 5 h. To study the stability of
treated CNTs and pristine CNTs, the samples were sonicated at
20 kHz for 5 min. It was found that nanofluid containing TCNTs
exhibited a comparatively better stability over nanofluid contain-
ing PCNTs. Therefore, it was decided to sonicate the TCNT nano-
fluids for 1 h to disentangle and disperse the TCNTs well.
Kumaresan and Velraj [99] used MWCNTs produced by the
chemical vapor deposition method (VCD) to prepare nanofluids. To
disentangle the MWCNTs, a ball milling was carried out using
10 mm Tungsten Carbide balls for 45 min, followed by ultra-
sonication for 60 min under dry condition. The surfactant
(0.1 vol.% of SDBS) was dissolved in the base fluid mixture using
magnetic stirrer, followed by the addition of MWCNT. The mixture
was continuously stirred for 30 min, followed by ultra-sonication
for 90 min to ensure the proper dispersion of the MWCNT in wa-
tereethylene glycol mixture. It was observed that the prepared
nanofluid was stable for more than 3 months without any visible
sedimentation. Lamas et al. [100] functionalized the MWCNTs
produced by the chemical vapor deposition method. The pristine
MWCNTs were refluxed at 413 K in nitric and sulfuric acid at 1:3
volume ratio for 30 min, followed by exhausting wash with DW
until no signs of acidity and dried in an oven at 373 K, for at least
72 h, to evaporate the humidity. The functionalized MWCNTs were
dispersed in 50 ml of base fluid with a magnetic stirrer combined
with ultrasonication for 60 min. It was observed that after 24 h, the
sedimentation rate was slow and constant. Yousefi et al. [101]
added MWCNTs and 1:350 of Triton X-100 to CNT ratio to double
distilled water. Also, the pH value of MWCNTs suspensions was
adjusted. The mixture was sonicated for 30 min (time chosen after
several test). It was observed that the prepared nanofluid was
stable up to 10 days. Indhuja et al. [102] added pristine MWCNTs to
the base fluid during probe sonication, which was carried out for
4 h. 0.25 wt.% of gum Arabic was added and stirred in a magnetic
 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
Fig. 9. Sample nanofluid prepared by dispersing MWCNTs in deionized water: without
chitosan; (b) with 0.2 wt.% chitosan [106].
stirrer, followed by probe sonication for 1 h. The zeta potential of
gum arabic stabilized MWCNTewater nanofluids was found to
be 29.1 mV. It was reported that this method could be prepared
with a maximum MWCNTs concentration of 0.5 wt.% only. Garg
et al. [103] dissolved gum Arabic in DI water using a magnetic
stirrer, followed by the addition of MWCNT to the solution. The
resulting composition was ultrasonicated for 5 min at 100%
amplitude using a 130 W, 20 kHz ultrasonication probe, with
varying ultrasonication times including 20, 40, 60, and 80 min. The
sonication was followed by 5 min of magnetic stirring. The ultra-
sonication and magnetic stirring process were alternated every
5 min until the sample had been sonicated for the desired amount
of time. It was found that the samples prepared by this technique
were stable for over 1 month with no visible sedimentation or
settling. Ashtiani et al. [104] dispersed MWCNTs in heat transfer oil
(HT-B oil) by an electrical mixer for 10 min and then an ultrasonic
cleaner for 30 min. No settlement was observed with naked eyes
within 5 days for 0.4 wt.% nanofluid. Fakoor Pakdaman et al. [105]
used the same technique as Ashtiani et al. [104] to prepare
MWCNTs/HT-B oil. However, the time of dispersion using an ul-
trasonic processor and electrical mixer was 6 h and 1 h, respec-
tively. It was observed with naked eyes that the sedimentation
started after about 24 h of the time that the applied nanofluid was
made uniform by the ultrasonic device. Therefore, each day before
starting the experiments, the working fluid was made uniform by
the mentioned ultrasonic device. Phuoc et al. [106] first prepared
the base fluid by mixing an appropriate amount of chitosan into
deionized water having 0.5 vol.% acetic acid then was stirred for
24 h using a magnetic stirrer. The nanofluids were prepared by
dispersing an appropriate amount of MWCNTs into the prepared
base fluid. The mixture was then ultrasonicated for 10 min at 100%
amplitude using a 130 W, 20 kHz ultrasonic processor, and it was
followed by 20 min stirring using a magnetic stirrer. The process
was repeated until the total mixing time was 1 h. It was observed
that the nanofluid prepared without chitosan was not stable at all,
the solid precipitated quickly and settled down at the bottom of
the vial about 30 min after preparation, As shown in Fig. 9. How-
ever, the nanofluid stabilized by 0.2 wt.% chitosan was stable for
months. Ding et al. [107] dispersed the sonicated CNTs into a preset
amount of distilled water containing 0.25 wt.%. Gum Arabic
dispersant, adjusted the suspension to a preset pH level, and
treated the mixture with the high shear homogenizer for 30 min. It
was found that the CNT nanofluids made in this way were very
stable for months without visually observable sedimentation.
177
It can be noticed that CNTs nanofluids may be kept stable for
months if the nanoparticles are functionalized or dispersed with
surfactant.
2.1.8. Iron oxide-nanofluids
Iron oxides exist in many forms in nature, with magnetite (Fe3O4),
maghemite (g-Fe2O3), and hematite (a-Fe2O3) being probably the
most common. Magnetic fluid is a colloidal suspension consisting of
magnetic nanoparticles and carrier liquid. Due to its unique char-
acteristics, the magnetic fluid behaves as a smart or functional fluid
and has been finding more and more applications in a variety of
fields such as electronic packing, mechanical engineering, aerospace,
and bioengineering. Li et al. [108] prepared two types of nanofluids.
One was Fe3O4ewater magnetic fluid prepared by the chemical
precipitation method in which the oleic acid was added as a
dispersant. The samples with different particle volume fractions
were obtained by diluting the original sample of the magnetic fluid.
Also, Feewater magnetic fluid was prepared by the direct mixing
method. Fe nanoparticle were mixed with deionized water and
stabilized with sodium dodecylbenzenesulfonate. In addition, the
magnetic fluid sample was vibrated for several hours in an ultrasonic
vibrator. They found that if the suitable percentage of sodium
dodecylbenzenesulfonate is added, the stabilization of the suspen-
sion can last about from several hours to one week in the stationary
state. Sundar et al. [109] adjusted the pH value of Fe3O4-water
nanofluid at 3, using a small amount of sulfuric acid (H2SO4). Then,
the mixture was sonicated for approximately 2 h. They reported that
a uniform dispersion was established by measuring the densities of
nanofluid at different locations in the container. Sundar et al. [110]
synthesized the magnetic nanoparticles by chemical coprecipita-
tion of FeCl3$6H2O, FeCl2$4H2O, sodium hydroxide (NaOH). They
considered three different concentrations of base fluid like 60:40%,
40:60% and 20:80% of ethylene glycolewater mixture. The solution
was kept in ultrasonic bath up to 2 h. They found that all the
measured Zeta potential values were higher than 30 mV; the zeta
potential of 1.0% volume concentration of 60:40% EG/W was 54 mV,
40:60% EG/W was 45 mV and 20:80% EG/W was 49 mV at the so-
lution pH ¼ 5. In addition, no particle sedimentation was observed
up to 80 days. Asadzadeh et al. [111] added the nanoparticles to the
base fluid in the presence of vigorous mechanical agitation. Then, the
suspension was sonicated for an hour in the ultrasonic bath. No
sedimentation was observed in the 12 h subsequent to the nanofluid
preparation. Abareshi et al. [112] synthesized Fe3O4 nanoparticles by
a co-precipitation method at different pH values. The nanoparticles
were dispersed in deionized water, and tetramethyl ammonium
hydroxide was used as a dispersant. It was shown that changing the
final pH of the product (from 10.5 to 9.5) and increasing the initial pH
of the iron salts solution (from 1 to 1.5) improves remarkably the
crystallinity of Fe3O4 nanoparticles. Also, the measured zeta poten-
tial for f ¼ 2% was 41.7 mV at pH ¼ 12.8, indicating that Fe3O4
nanofluids have good dispersion and stability. Abareshi et al. [113]
synthesized magnetic nanoparticles of hematite, a-Fe2O3 by sol-
vothermal method using Fe(NO3)3 as a starting material. The nano-
particles were dispersed in glycerol using an ultrasonic processor at
20 kHz and 700 W for 30 min. Yu et al. [114] synthesized Fe3O4
nanoparticles by coprecipitation. Oleic acid was added to modify the
nanoparticles. After 1 h, kerosene was added to the mixture with
slow stirring. The phase-transfer process occurred spontaneously,
and there was a distinct phase interface between the aqueous and
kerosene. After removing the aqueous phase using a pipette, the
kerosene-based Fe3O4 nanofluid with volume concentration 1% was
obtained. It was shown that there is no clear relation between the
particle size and ultrasonication time, as shown in Fig. 10, indicating
that the phase-transfer method avoids the long time ultrasonication
and oxidation of Fe3O4 in the disperse process. Also, the Fe3O4
178 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
Fig. 10. Average particle size as a function of ultrasonification processing time for
1.0 vol.% Fe3O4 nanofluid [114].
nanoparticles modified by oleic acid have good compatibility with
kerosene, and the nanofluids were stable. Phuoc and Massoudi [115]
mixed the Fe2O3 nanoparticles with deionized water containing 0.2%
by weight of Polyvinyl pyrrolidone (PVP) or Poly (ethylene oxide)
(PEO) as a dispersant. The mixing was carried out using a magnetic
mixer and sonicated for 30 min using a 130 W ultrasonic processor. It
was found that using these polymers, the prepared nanofluids were
stable for about two weeks when the particle concentration was less
than 2% and less than a week when the concentration was higher.
Guo et al. [116] added sodium oleate as a dispersant to the mixture of
ethylene glycol and deionized water with volume ratio of 45:55, and
then the nanoparticles were gradually added into the base mixture
fluid with violent stirring. Afterward, the suspensions were stirred
using disperse mill (7200 r/min) for 40 min. Nanofluids with
different volume fractions were obtained by intensive ultra-
sonication for 45 min. It was shown that the average size is about
1200 nm without surfactant and about 150 nm with surfactant.
Sheikhbahai et al. [117] dispersed Fe3O4 nanoparticles in ethylene
glycol under ultrasonic mixing for an hour. Sonication was continued
for another hour to get stable nanofluid. Required amount of DI water
was gradually added to nanofluid under vigorous agitation in 30 min
period just before each experiment. No sedimentation was observed
at the bottom or clear layer at the top after 8 h.
It can be seen that the nanoparticles synthesized by chemical
precipitation method can be well dispersed by using only sonicat-
ion for 2 h [110].
2.2. Preparation of metallic nanofluids
2.2.1. Gold & silver-nanofluids
Metal nanoparticles such as gold (Au) and silver (Ag) have
recognized importance in chemistry, physics, and biology because
of their unique optical, electrical, and photothermal properties.
Such nanoparticles have potential applications in analytical
chemistry and have been used as probes in mass spectroscopy, as
well as in the colorimetric detection for proteins and DNA mole-
cules. Furthermore, Au nanoparticles have photothermal properties
that can be exploited for localized heating resulting in drug release.
Thus, increasing their potential for therapeutic applications. The
ease of synthesizing Au and Ag nanoparticles and their affinity for
binding many biological molecules, makes them attractive candi-
dates for study.
Fig. 11. Typical samples of Ag-deionized nanofluids generated by multi beam ablation
in liquid technique [119].
Patel et al. [118] used gold and silver for the first time to prepare
nanofluids. The gold and silver nanoparticles were prepared by the
citrate reduction route. Also, the gold nanoparticles with thiolate
covering were prepared using two-phase (wateretoluene) reduc-
tion of AuC14- by sodium borohydride in the presence of an alka-
nethiol. The samples were stable over a period of several months
and no degradation was observed during storage or in the course of
the experiment. Phuoc et al. [119] prepared different samples of
Agedeionized water using multi-pulse laser ablation in liquid
approach. The first sample (sample I, brownish yellow) was pre-
pared by ablating the silver target in deionized water for 30 min.
The second sample was prepared by ablating the silver target in the
previously produced sample that was aged for 2 weeks. The abla-
tion durations for the last three samples were 3 h. All the samples
were more than 7 months old and they were stable without using
any dispersants or surfactants, as shown in Fig. 11. Para-
metthanuwat et al. [120] prepared silver nanofluids using an ul-
trasonic bath at 43 kHz for 3 h. It was found that the stability was up
to 48 h. Hajian et al. [121] produced Silver in DIewater nanofluid by
a chemical method which consists of reduction of Ag ions. The
nanofluids were put in an ultrasonic bath for about 15 min before
injection into the heat pipe. Tamjid and Guenther [122] used a
colloid of silver nanoparticles produced by the Sputtering on
Running Liquid technique (VERL) at volumetric solids concentra-
tion of 4.37%. The colloid was stirred and agitated thoroughly for
5 min by an ultrasonic agitator in continuous mode to ensure
uniform dispersion of the nanoparticles in diethylene glycol.
Asirvatham et al. [123] mixed silver nanoparticles with deionized
water under ultrasonic vibration with power density of 750 W at
frequency of 20 kHz for 12 h. The measured pH values were 7.4, 7.1
and 6.8 for volume concentrations of 0.3%, 0.6% and 0.9%, respec-
tively. They reported that the nanofluids were essentially uniform,
but not without some agglomeration of the particles. Sharma et al.
[124] synthesized silver nanofluids using silver nitrate (precursor),
ethylene glycol (reducing agent), and poly (acrylamide-co-acryl-
icacid) (dispersion stabilizer). They found that the size of nano-
particles and dispersion stability are controlled by the
concentration of PAAeco-AA and the reaction conditions. Hari et al.
[125] produced spherical and rod silver nanoparticles. The silver
nanorods were prepared by seed mediated chemical synthesis and
stabilized with CTAB surfactant micelle, while the spherical nano-
particles were stabilized with trisodium citrate. It was found that
the nanofluids were stable for a maximum period of one week. Paul
et al. [126,127] synthesized nano-gold and silver dispersed water
based nanofluids by wet chemical bottom up approach. It was
revealed that uniform distribution, chemical nature (metallic) or
purity of the gold nanoparticles and color of the nanofluid
 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
Fig. 12. Effect of ultrasonic time on the effective thermal conductivity of nanofluid
(299.08 K) [132].
remained unchanged without sedimentation or agglomeration
even after 48 h. Kim et al. [128] dispersed Au-powders in water by
6-h ultrasonic-wave irradiation. Also, they produced gold nano-
particles suspended in water by pulsed laser ablation in liquids.
They reported that in spite of 6 h ultrasonic-wave irradiation,
almost all of the Au-powder was precipitated in water. The AueNPs
were still suspended in water after 1 month without any surfac-
tants. Lo et al. [129] prepared silver nanofluid by the submerged arc
nanoparticles synthesis system (SANSS). They observed that the
nanoparticles were well dispersed in deionized after using ultra-
sonic vibration for 15 min. Kang et al. [130] added silver nano-
particles produced by a catalytic chemical vapor deposition
method, using an ultrasonic homogenizer.
It should be noted that gold and silver-citrate or Auethiolate
nanofluids can be kept stable for a period of several months [118].
Moreover, Agedeionized water nanofluids prepared using multi-
pulse laser ablation in liquid approach were stable for several
months without using dispersant [119].
2.2.2. Copper-nanofluids
Intrinsically high resistance to corrosion makes copper as an
ideal metal for heat exchangers of all kinds, including solar water
heating systems. Nano copper can be used in the manufacture of
printing inks allowing conductive patterns that have to pass
through a thin film, creating a path of electrical conductivity for use
in scientific experiments, and also to create printable circuits for
electronic applications. Also in water, nano copper has been used at
least since 1931, as a fungicide in the cultivation of vines and fruit
trees, and as an algaecide in swimming pool water treatment.
Xuan and Li [131] prepared transformer oileCu suspensions and
watereCu suspensions. The first suspension was stabilized using
22 wt.% of oleic acid as dispersant (Several percentages of oleic acid
was tested). Then, the suspension was vibrated for 10 h in an ul-
trasonic vibrator. It was found that the stabilization of the sus-
pension can last about one week in the stationary state without
sedimentation. The second suspension was stabilized using 9 wt.%
laurate salt (Several percentages of laurate salt was tested), and
then vibrated in an ultrasonic vibrator. It was observed that the
suspension can be stable more than 30 h with some clusters. Yang
et al. [132] used an aqueous solution of cetyltrimethyl ammonium
chloride (CTAC)/sodium salicylate (NaSl) to prepare copper nano-
fluids. NaSl was added to the solution with the same weight con-
centration of that of CTAC, and distilled water was used as solvent.
The CTAC/NaSl solution was stirred about 8 h. Then the
179
nanoparticles were added into the base fluid by introducing an
intensive sonication of ultrasonic disruptor. Furthermore, an opti-
mum time of sonication was determined by measuring the thermal
conductivity of 0.6 vol.% Cu nanoparticles suspended in 50 ppm
CTAC/NaSl aqueous solution for different ultrasonic time, as shown
in Fig. 12. It was observed that when the ultrasonic time is over 3 h,
the thermal conductivity of Cu nanofluids tends to be a constant
value, meaning that 3-h ultrasonic time is enough to disperse the
Cu nanofluid. Also, it was reported that the prepared nanofluids by
introducing 3-h intensive sonication show a stable property. Peng
et al. [133] dispersed copper nanoparticles, produced by hydrogen
direct current arc plasma evaporation method in a refrigerant R113.
They used three types of surfactants which are miscible with R113;
Sodium Dodecyl Sulfate (SDS), Cetyltrimethyl Ammonium Bromide
(CTAB) and Sorbitan Monooleate (Span-80). The mixture of Cu-
R113 with surfactants was vibrated for 1 h. It was found that the
mixture can be kept stable for 24 h, and the duration of the
experiment for each sample of Cu-R113 nanofluid with surfactant
was less than 4 h which is shorter than 24 h. Kole and Dey [134]
prepared surfactant free copperewater nanofluids by addition of
an appropriate amount of Cu nanoparticles in distilled water. The
dispersion was done by intense ultrasonication for 10 h at 200 W
and subsequent homogenization for another 10 h using a magnetic
stirrer. The suspension stability of Cu nanoparticles in the prepared
nanofluids was tested for more than15 days without any visible
trace of sedimentation, but with the presence of clusters with an
average diameter between around 122 and 164 nm. Li et al.
[135,136] mixed copper nanoparticles and water with (SDBS or
CTAB) surfactant. The pH was controlled using HCl and NaOH. It
was shown that the average particle sizes obtained in the absence
of SDBS surfactant was 6770 nm and in the presence of SDBS sur-
factant was 207 nm, indicating better stability of CueH2O sus-
pension when using SDBS surfactant. In addition, pH ¼ 8.5e9.5 can
be selected as an operating pH for the suspensions with SDBS
surfactant. It was observed that the stabilization of the suspension
with CTAB dispersant can last about 1 week in the stationary state
without sedimentation, while the suspension without dispersant
exhibits weaker dispersion and quickly occurs aggregation.
Kathiravan et al. [137] prepared copper nanoparticles by the sput-
tering method. Then the nanoparticles were dispersed in water and
water with 9.0% SDS anionic surfactant using an ultrasonic bath for
about 10 h. It was found that the nanoparticles were dispersed in
water evenly even after 10 h of ultrasonic vibration with some
agglomerates. Robertis et al. [138] prepared copper nanofluids us-
ing a one-step technique. They used ethylene glycol as base fluid,
copper (II) nitrate hydrate as copper source; sodium hypophosphite
monohydrate as reducing agent and polyvinyl pyrrolidone (PVP) as
stabilizer. The nanofluids were synthesized using a microwave oven
without further dispersion. The particles settlement was about
28.5% in 50 days. They claimed that smallest particles tend to
remain suspended for longer periods. However, larger particles can
drag down these small particles and therefore reduce the stability
period of the suspension. Riehl and Santos [139] stated that an
agitation of copper nanofluids using an ultrasonic bath for 1.5 h was
enough to achieve a homogeneous solution, as no sedimentation
was observed after 4 h of observation. Senthilkumar et al. [140]
used an ultrasonic homogenizer for 6 h. Li et al. [141] vibrated
the suspension for 4 h in an ultrasonic vibrator, and they found that
the sample suspensions were kept stable in the stationary state
with little apparent sediment during the whole experiment pro-
cess. Lu et al. [142] dispersed copper nanoparticles using an ultra-
sonic box with a working frequency of 25e40 kHz for 10 h.
All the mentioned copper preparation methods showed that
copper nanofluids cannot be stable more than one month. The
preparation of nanofluids containing different concentrations,
180 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189

Table 2
Summary of nanofluids preparation.

Authors Particle Base fluid Parameters Characterization Surfactant/pH control Nanofluid stability
material

Hu et al. [5] AlN Ethanol f ¼ 0.5e4 vol.% TEM Castor oil Stable for more than 2
Approximately D ¼ 20 nm weeks.
spherical
Choi et al. [6] AlN Transformer oil f  4 vol.% e Oleic acid Sedimentation was
Spherical D ¼ 50 nm very clear for non-
Al2O3 D ¼ 2nm  20e200 nm filtered Al2O3 nanofluid
Rod-shape D ¼ 13 nm after one month
Spherical
Yu et al. [7] AlN EG f ¼ 1.0e10 vol.% SEM e e
PG D ¼ 50 nm Malvern nanosizer
Wozniak et al. [8] AlN PPG 425 f ¼ 10e25 vol.% SEM e AlNePPG 2000
PPG 2000 D ¼ 0.800e1.80 mm Zetasizer nano-ZS suspension
demonstrated slightly
sedimentation
Yu et al. [9] ZnO EG f ¼ 0.2e5 vol.% SEM e e
D ¼ 10e20 nm Malvern nano-sizer
Moosavi et al. [10] ZnO EG f  3 vol.% XRD Ammonium citrate Stable for several
Approximately G e TEM months
spherical SEM
Malvern nano-sizer
Raykar and Singh [11] ZnO Deionized f ¼ 0.075%, 0.25% and SEM acac Stable over 9 months to
Non-spherical water 0.5 wt.% DLS 1 year
D w 80 nm
Kole and Dey [12] ZnO EG f ¼ 0.5e3.75 vol.% TEM e Stable for 30 days
Nearly D < 50 nm Malvern nano-sizer without any trace of
spherical DLS visible sedimentation
Chung et al. [13] ZnO Deionized f ¼ 0.4e2 vol.% TEM Ammonium e
Off-white & water D ¼ 40e100 nm & PCS polymethacrylate
white D ¼ 20 nm
Suganthi and Rajan ZnO Water f ¼ 0.25e2 vol.% SEM SHMP Stability was confirmed
[14] Spherical D ¼ 30e45 nm Zetasizer through visual
XRD observation
Zafarani-Moattar and ZnO PEG f  8 wt.% DLS e Stable at least for
Majdan-Cegincara D ¼ 20 nm TEM 140 min
[15] UVeVis spectroscopy
Saleh et al. [16] ZnO PEG F ¼ 0.025e0.5 vol.% XRD e e
D ¼ 18 or 23 nm UVeVis spectroscopy
Lee et al. [17] ZnO EG F ¼ 0.5e5.5 vol.% XRD e e
Spherical and D < 100 nm TEM
rectangular
Kayhani et al. [18] TiO2 DIewater f ¼ 0.1e2 vol.% SEM Hexamethyldisilazane Stable for several days
Spherical D ¼ 15 nm without any visible
sedimentation.
He et al. [19] TiO2 DIewater f ¼ 1.0%, 2.5% and SEM PH ¼ 11 Stable for months
Spherical 4.9 wt.% Malvern nano-sizer
D ¼ 20 nm
Murshed et al. [20] TiO2 Deionized f  5 vol.% TEM Oleic acid & CTAB No sedimentation was
Spherical water D ¼ 15 nm Particle size analyzer observed after 24 h.
rod-shape D ¼ 10 nm  40 nm
Duangthongsuk and TiO2 Water f ¼ 0.2e2 vol.% TEM CTAB A little agglomeration
Wongwises [21] Spherical D ¼ 21 nm was observed 3 h after
sonication
Kim et al. [22] TiO2 (nearly Water D ¼ 10, 34, 70 nm TEM SDS No trial to stabilize the
spherical) EG D ¼ 38 nm fluid was successful for
Al2O3 D ¼ 10, 30, 60 nm the 10 nm ZnO/EG
(spherical) nanofluid
ZnO
(elongated)
Abbasian Arani and TiO2 DIewater f ¼ 0.2%e2.0 vol.% TEM CTAB Suspensions were
Amani [23] Approximately D ¼ 30 nm stable for several hours
Spherical (days)
Utomo et al. [24] TiO2 DIewater f ¼ 0.1%e9 vol.% TEM Octyl silane e
Al2O3 D ¼ 20e30 nm ammonium polyacrylate
Spherical f ¼ 0.1%e15 vol.%
D ¼ 50e60 nm
Longo and Zilio [25] TiO2 DIewater f ¼ 1%, 2%, 4% and Malvern nano-sizer e Stability for more than
Al2O3 6 vol.% one month
Spherical D ¼ 30e50  10 nm
f ¼ 1%, 2% and 4 vol.%
D ¼ 30  10 nm
Chen et al. [26] TiO2 EGeTNT f ¼ 0.1%e1.8 vol.% Malvern nano-sizer e Stability over the
Rod-like D ¼ w10 nm SEM period of two months
L ¼ w100 nm
 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189 181

Table 2 (continued )

Authors Particle Base fluid Parameters Characterization Surfactant/pH control Nanofluid stability
material

Mo et al. [27] Rutile TiO2 Deionized F ¼ 0.05, 0.3, 0.7 wt.% TEM SDS Nanofluids kept stable
(rod-shape) water D ¼ 15 nm Spectrophotometer for 286 h
Anatase TiO2 D ¼ 20 nm  50 nm
(spherical)
Bobbo et al. [28] TiO2 Deionized F ¼ 0.15, 013, 1 vol.% SEM SDS SWCNH-nanofluids
SWCNH water D ¼ 20e30 nm DLS PEG were very stable even
Spherical D ¼ 60 nm Malvern nano-sizer after several days.
However, TiO2-
nanofluids were less
stable
Hojjat et al. [29] TiO2 0.5 wt.% CMC F ¼ 0.1e4.0 vol.% e e No sedimentation after
CuO solution in D ¼ 10 nm several days
g-Al2O3 deionized D ¼ 30e50 nm Preparation of stable
water D ¼ 25 nm Al2O3 nanofluids was
more difficult for
f > 1.5%
Fedele et al. [30] TiO2 Bidistilled f ¼ 1%, 10%, 20% and DLS Acetic acid Stable suspension for
water 35 wt.% Malvern nano-sizer 35 days using
D ¼ 30 nm DLS sonication
Tajik et al. [31] TiO2 DIewater f ¼ 0.005, 0.15 and SEM e e
a-Al2O3 0.2 vol.%
D ¼ 27e43 nm
D ¼ 30e40 nm
Chakraborty et al. [32] TiO2 DIewater F ¼ 0.1e2 vol.% SEM e Stable for the duration
Cylindrical D ¼ 25e70 nm of experiment
Al2O3 D ¼ 20 nm  40 nm
Spherical D ¼ 20e50 nm
Mitra et al. [33] TiO2 Water F ¼ 0.1 wt.% e e e
Random shape D ¼ 20e70 nm
MWCNT F ¼ 0.01 wt.%
D ¼ 20e70 nm  100
e500 nm
Sajadi and Kazemi [34] TiO2 Deionized f ¼ 0.05e0.25 vol.% e e e
water D ¼ 30 nm
Suriyawong and TiO2 Water F ¼ 0.00005e0.01 vol.% TEM e e
Wongwises [35] Circular shape D ¼ 21 nm
Timofeeva et al. [40] SiO2 TH66 f1.2%e7 vol.% SEM BZC Nanofluids appeared
D ¼ 15 nm DLS CTAB stable without any
BAC visual phase separation
for at least a week.
Yang and Liu [41] SiO2 Water F ¼ 0.5e2.5 wt.% SEM Trimethyoxysilane Functionalized
D ¼ 30 nm nanofluid can still keep
dispersing well for 12
months even at 10 wt.%.
Traditional nanofluid:
sedimentation occurred
after several days
Anoop et al. [42] SiO2 Deionized f ¼ 0.2%, 0.5% and e pH ¼ 4.5 Nanofluids exhibited
water 1 wt.% good stability over time
D w 20 nm
Qu and Wu [43] SiO2 Pure water f ¼ 0.1e0.6 wt.% TEM pH ¼ 9.7 Alumina nanoparticles
Al2O3 D ¼ 30 nm pH ¼ 4.9 were better dispersed
Spherical f ¼ 0.1e1.2 wt.%
D ¼ 56 nm
Fazeli et al. [44] SiO2 DIewater f ¼ 3.5e5 vol.% e e Stable for a period of
Spherical D ¼ 18 nm 72 h without any visible
settlement.
Pang et al. [45] SiO2 Pure f ¼ 0.005e0.5 vol.% SEM e The dispersion stability
Al2O3 methanol D ¼ 10e20 nm DLS of the methanol-based
D ¼ 40e50 nm Al2O3 nanofluids was
stated to be good
Bolukbasi and Ciloglu SiO2 Deionized f ¼ 0.05e0.1 vol.% TEM e Stable during the
[46] water D ¼ 34 nm XRD period of experiment
Darzi et al. [47] SiO2 DIewater f ¼ 0.5 and 0.1% e e e
D ¼ 30 nm
Kulkarni et al. [48] SiO2 60:40 EG/W f  6 vol.% DLS e e
Al2O3 D ¼ 50 nm
CuO D ¼ 45 nm
D ¼ 30 nm
Hwang et al. [49] SiO2 DIewater f  6 vol.% TEM or SEM e e
MWCNT D ¼ 7 nm
CuO D ¼ 10e50mm  10
e30 nm
D ¼ 35.4 nm
(continued on next page)
182 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189

Table 2 (continued )

Authors Particle Base fluid Parameters Characterization Surfactant/pH control Nanofluid stability
material

Rohini Priya et al. [50] CuO Water F  0.016 vol.% SEM Tiron Stability was confirmed
Nonspherical Length to thickness XRD through visual
ratio w10 observation
Suresh et al. [51] CuO Water F ¼ 0.1%, 0.2% and XRD e e
0.3 vol.%
D ¼ 15.7 nm
Lee et al. [52] CuO DIewater F ¼ 0.001 vol.% TEM e Dispersion stability of
Spherical D ¼ 15 nm XRD CuO/DIW nanofluid
D ¼ 55 nm fabricated by one-step
method is much better
than that prepared by
two-step method
Yang and Liu [53] CuO Deionized F ¼ 0.1%e1.5 wt.% TEM e e
water D ¼ 50 nm DLS
Chang et al. [54] CuO Water F ¼ 0.01%e0.4 vol.% TEM NaHMP When the CuO content
D ¼ 20e300 nm DLS was higher than
XRD 0.40 vol.%, the
suspension was very
unstable and the CuO
nanoparticles tended to
settle within several
minutes
Harikrishnan and CuO Oleic acid F ¼ 0.5%e2.0 wt.% TEM e Based on the zeta
Kalaiselvam [55] D ¼ 1e80 nm XRD result, CuO
Malvern zeta sizer nanoparticles were
stably dispersed and
uniformly distributed
in base fluid
Saeedinia et al. [56] CuO Oil F ¼ 0.2e2 wt.% SEM e The complete
D ¼ 50 nm XRD sedimentation occurred
after a week
Selvakumar and Suresh CuO DIewater F ¼ 0.1% and 0.2 vol.% e e Nanofluids were stable
[57] D ¼ 27e37 nm after a week except
very little
sedimentation.
Kannadasan et al. [58] CuO DIewater F ¼ 0.1% and 0.2 vol.% XRD e Very little settlement of
D ¼ 10e15 nm nanoparticles even
after 25 days
Byrne et al. [59] CuO DIewater F ¼ 0.005%, 0.01% and SEM CTAB Suspension was much
0.1 vol.% DLS more stable when using
D ¼ 30e50 nm surfactant
Liu et al. [60] CuO Deionized F ¼ 0.5e2 vol.% e pH ¼ 7 e
water D ¼ 50 nm
Fotukian and Esfahany CuO DIewater F  3 vol.% e e No precipitation was
[61] D ¼ 30e50 nm observed after 5 h
Liu et al. [62] CuO Water F ¼ 0.5% and 1.0 wt.% TEM e The stability and
D ¼ 30e50 nm uniformity of
nanoparticle
suspensions were poor
after several days
Zeinali Heris [63] CuO 40% water F ¼ 0.1%, 0.2% and e e No precipitation of
60% EG 0.5 wt.% nanoparticles was
D ¼ 40 nm observed after 22 h.
Sonawane et al. [66] Al2O3 ATF F ¼ 0.1e1 vol.% TEM Oleic acid The solution was found
D ¼ 50 nm Tween-20 LR to be stable even after
24 h
Suresh et al. [67] Al2O3 DIewater F ¼ 0.3, 0.4 and XRD e The nanofluid was very
Nearly 0.5 vol.% TEM stable for several weeks
spherical D ¼ 40.3 nm without visually
observable
sedimentation
Beck et al. [68] Al2O3 EG F ¼ 1, 3 and 4 wt.% e e Dispersions were
D ¼ 20 nm remained uniform for
the duration of the
experiments
Sharma et al. [69] Al2O3 DIewater F < 3 vol.% e SDBS Nanofluid was
D ¼ 47 nm observed to be stable
for over a week
Gharagozloo and Al2O3 Deionized F ¼ 1, 3 and 5 vol.% DLS Nitric acid Nanofluid was stable
Goodson [71] water D ¼ 40.2 nm with only minor
(0.05% vol.) settling after a week
Jung et al. [72] Al2O3 DIewater F ¼ 105e101 vol.% DLS PVA The aggregated
D ¼ 45 nm particles were stably
suspended for more
than 1 month
 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189 183

Table 2 (continued )

Authors Particle Base fluid Parameters Characterization Surfactant/pH control Nanofluid stability
material

Soltani et al. [73] g-Al2O3 CMC F ¼ 0.8e1.4 wt.% e e e

Nearly D ¼ 20e30 nm
spherical
Ho et al. [74] Al2O3 Ultra-pure F ¼ 0.1e4 vol.% e pH Suspensions were
Milli-Q water D ¼ 33 nm stable for at least two
weeks
Yousefi et al. [75] Al2O3 Double DI F ¼ 0.2 and 0.4 wt.% e Triton X-100 The nanofluid stability
Spherical ewater D ¼ 15 nm was about three days
after sonication
Raveshi et al. [76] Al2O3 WEG50 F ¼ 0.05e1 vol.% TEM SDBS No obvious
Spherical D ¼ 20e30 nm sedimentation before
starting the experiment
Hung et al. [77] Al2O3 DIewater F ¼ 0.5, 1 and 3 wt.% UV/VIS spectrometer Chitosan The difference between
D ¼ 20 nm XRD initial and final
TEM concentrations (after 2
weeks) of Al2O3/water
nanofluid was less than
5%
Heyhat et al. [78] g-Al2O3 DIewater F ¼ 0.1e2 vol.% SEM e Nanofluids are
Spherical D ¼ 40 nm physically stable
Singh et al. [79] Al2O3 Deionized F ¼ 0.25, 0.5 and 1 vol.% TEM pH e
water D ¼ 45 and 150 nm
EG
Pandey and Nema [80] Al2O3 DIewater F ¼ 2, 3 and 4 vol.% e e No sedimentation was
D ¼ 40e50 nm observed in the
produced nanofluids
after 24 h
Chandrasekar et al. [81] Al2O3 DIewater F ¼ 0.33e5 vol.% SEM e e
D ¼ 43 nm
Qu et al. [82] Al2O3 Pure water F ¼ 0.1e1.2 wt.% SEM pH Nanoparticles could be
Spherical D ¼ 56 nm stably suspended in
water at least for 3 days
Anoop et al. [83] Al2O3 Water F ¼ 1e6 wt.% TEM pH The suspensions were
D ¼ 45 and 150 nm stable for several weeks
Lee et al. [84] Al2O3 DIewater F ¼ 0.01e0.3 vol.% TEM e Good dispersion with
D ¼ 30  5 nm little aggregates
Kim et al. [85] Al2O3 Deionized F ¼ 5.5 vol.% TEM e Aggregation of alumina
Spherical water D ¼ 80 nm (spherical) XRD nanofibers has a bad
Fibrous influence on the long-
term dispersion
stability
Hegde et al. [86] Al2O3 DIewater F ¼ 0.1e0.5 g/l TEM e No agglomeration
Spherical D ¼ 80 nm formed 2 h after
sonication
Esmaeilzadeh et al. [87] g- Al2O3 DIewater F ¼ 0.5 and 1.0 vol.% TEM e No sedimentation
D ¼ 15 nm XRD throughout the testing
period
Ali et al. [88] Al2O3 DIewater F ¼ 0.21, 0.51 and SEM e No precipitation was
0.75 wt.% observed two days after
D ¼ 10 nm the ultrasonic vibration
Jacob et al. [89] Al2O3 Deionized F ¼ 0.25, 0.5 and 1 vol.% e pH e
water D ¼ 50 nm
Teng et al. [90] Al2O3 Water F ¼ 0.5, 1 and 3 wt.% TEM Chitosan e
D ¼ 20e30 nm
Chen et al. [91] CNTs DIewater f ¼ 0.2%e1 vol.% TEM e TCNTs suspensions
EG D  H ¼ 15 nm  30 mm remained stable for
many months with no
visible precipitation
Su et al. [92] CNTs Ammonia f ¼ 12.05%e25 vol.% TEM e
e
Meng et al. [93] CNTs Glycol f ¼ 0.5%e4 wt.% TEM e Nanofluids could
Spectrophotometer remain stable for more
than two months
without sedimentation
Liu et al. [94] CNTs Deionized f ¼ 0.5%e4 wt.% TEM e e
water D  H ¼ 15 nm  5
e15 mm
Wang et al. [95] CNTs DIewater f ¼ 0.052%e1.27 vol.% TEM e e
D  H ¼ 20e30 nm  5
e30 mm
Meibodi et al. [96] CNTs DIewater f ¼ 1e5 vol.% TEM e e
ID/OD ¼ 0.8e1.1 nm/1
e4 nm
(continued on next page)
184 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189

Table 2 (continued )

Authors Particle Base fluid Parameters Characterization Surfactant/pH control Nanofluid stability
material

Liu et al. [97] CNTs EG f ¼ 0.2e1.0 vol.% TEM NHS The sedimentation of
Engine oil f ¼ 1e2.0 vol.% SEM the suspensions was
XRD not visible
Babu and Prasanna CNTs DIewater f ¼ 0.25e1.0 wt.% TEM e e
Kumar [98] D ¼ 9e15 nm SEM
XRD
Kumaresan and Velraj CNTs Deionized f ¼ 0.25e1.0 vol.% SEM SDBS Nanofluid was stable
[99] water-EG D  H ¼ 30e50 nm  10 for more than 3 months
e20 mm
Lamas et al. [100] CNTs DIewatereEG f ¼ 0.25e1.5 vol.% e e e
A ¼ 333 and 667
Yousefi et al. [101] CNTs Double DI f ¼ 0.2 wt.% TEM Triton X-100 Nanofluid was stable up
ewater D ¼ 10e30 nm to 10 days
Indhuja et al. [102] CNTs Water f ¼ 0.14e0.24 vol.% SEM Gum arabic e
D  H ¼ 10 nm  5 Zetasizer
e15 mm
Garg et al. [103] CNTs DIewater f ¼ 1 wt.% TEM Gum arabic Nanofluid stable for
D  H ¼ 10 over 1 month with no
e20 nm  0.5e40 mm visible sedimentation
or settling
Ashtiani et al. [104] CNTs HT-B oil f ¼ 0.1e0.4 vol.% SEM e e
D ¼ 10e30 nm
Phuoc et al. [106] CNTs Deionized f ¼ 0.1e0.4 vol.% e Chitosan Nanofluid was stable
water D ¼ 5e10 nm  10 for months
e30 mm
Ding et al. [107] CNTs DIewater f ¼ 0e1.0 vol.% SEM pH Nanofluids made in this
D ¼ 5e10 nm  10 TEM way were very stable
e30 mm for months
Li et al. [108] Fe3O4 f ¼ 1.0e5.0 vol.% e Sodium The suspension can last
Fe D ¼ 20 nm dodecylbenzenesulfonate about from several
D ¼ 26 nm hours to one week in
the stationary sate
Sundar et al. [109] Fe3O4 DIewater f ¼ 0e0.6 vol.% e pH ¼ 3 e
D ¼ 36 nm
Sundar et al. [110] Fe3O4 EGewater f ¼ 0e1.0 vol.% XRD e No particle
Cubical D ¼ 5e70 nm SEM sedimentation was
TEM observed up to 80 days
Asadzadeh et al. [111] Fe3O4 EG f ¼ 0.015e0.1 vol.% e e No sedimentation was
D ¼ 50 nm observed in the 12 h
subsequent to the
nanofluid preparation
Abareshi et al. [112] Fe3O4 DIewater f ¼ 0.025e3.0 vol.% XRD Tetramethyl ammonium Nanofluids have good
e TEM hydroxide dispersion and stability.
FTIR
VSM
Yu et al. [114] Fe3O4 Kerosene f ¼ 0e1.0 vol.% SPM Oleic acid Nanofluids were stable
D ¼ 15 nm XRD
DLS
Phuoc and Massoudi Fe2O3 Deionized f ¼ 1e4 vol.% e PVP Nanofluids were stable
[115] water D ¼ 20e40 nm for about two weeks
Guo et al. [116] G-Fe2O3 EGedeionized f ¼ 0.005e0.02 vol.% TEM e e
water D ¼ 20 nm
Sheikhbahai et al. [117] Fe3O4 EGedeionized f ¼ 0.01e0.1 vol.% SEM e No sedimentation was
water D < 50 nm observed after 8 h
Patel et al. [118] Au Water F ¼ 0.00013e0.005 TEM Thiolate The samples were
Ag Toluene D ¼ 10e20 nm stable over a period of
D ¼ 3e4 nm several months
Phuoc et al. [119] Ag Deionized F ¼ 0.01 vol.% TEM e The samples were
water D ¼ 20e30 nm stable for several
months
Parametthanuwat et al. Ag DIewater F ¼ 0.5% w/v e e The stability is up to
[120] D < 100 nm 48 h
Hajian et al. [121] Ag DIewater F ¼ 50, 200 and TEM e e
600 wt.%
e
Tamjid and Guenther Ag DEG F ¼ 0.11e4.37 vol.% TEM e e
[122] D w 40 nm
Asirvatham et al. [123] Ag Deionized F ¼ 0.3%, 0.6% and SEM e e
Nearly water 0.9 vol.%
spherical D w 80 nm
Sharma et al. [124] Ag EG F ¼ 1000e10,000 wt.% TEM PAAeco-AA e
EDX
XRD
UVevis spectroscopy
Zeta potential analyzer
 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189 185

Table 2 (continued )

Authors Particle Base fluid Parameters Characterization Surfactant/pH control Nanofluid stability
material

Hari et al. [125] Ag Deionized e SEM CTAB Nanofluids were stable

water TEM for a maximum period
UVevis spectroscopy of one week
Paul et al. [126] Au Water F ¼ 0.6  104 to XRD e No sedimentation or
Spherical 2.6  104 vol.% SEM agglomeration even
D ¼ 21 nm TEM after 48 h.
Paul et al. [127] Ag Water F ¼ 105 to 2.6  10 XRD e e
3
Spherical M SEM
D ¼ 55e95 nm TEM
DLS
Kim et al. [128] Au Water F ¼ 0.6  104 to XRD????? e AueNPs were still
Spherical 2.6  104 vol.% SEM suspended in water
D ¼ 45e130 nm TEM after 1 month
(commercial) Zeta potential analyzer
D ¼ 7.1e12.1 nm (18 h-
PLAL)
Lo et al. [129] Ag Deionized F ¼ 0.5 vol.% TEM e e
Spherical water D ¼ 6e25 nm XRD
SEM
Kang et al. [130] Ag Pure water F ¼ 1e100 mg/l TEM e e
D ¼ 35 nm
Xuan and Q. Li [131] Cu Transformer oil f ¼ 2 and 5 vol.% TEM Oleic acid Transformer oil-Cu
Water f ¼ 5 vol.% Laurate salt suspension can last
D w 50 nm about one week in the
stationary state
WatereCu suspension
can be stable more than
30 h
Yang et al. [132] Cu CTAC/NaSl f ¼ 0.05e2.5 vol.% SEM e e
Spherical D ¼ 50 nm
Peng et al. [133] Cu R113 f ¼ 0.1, 0.5 and 1.0 wt.% TEM SDS, CTAB and Span-80 Nanofluids were kept
D ¼ 20 nm Spectrophotometer stable for 24 h
Kole and T.K. Dey [134] Cu DIewater f ¼ 0.0005e0.5 wt.% TEM e No visible trace of
D ¼ 40 nm Malvern ZS Nano S sedimentation for >15
analyser days
Li et al. [135,136] Cu Pure water f ¼ 0.0005e0.5 wt.% TEM SDBS, CTAB Suspension with CTAB
Spherical or D ¼ 25 nm Malvern ZS Nano S dispersant can last
nearly spherical analyser about 1 week without
sedimentation
Kathiravan et al. [137] Cu DIewater f ¼ 0.25, 0.5 and TEM SDS Nanoparticles were
1.0 wt.% XRD dispersed in water
D ¼ 10 nm AFM evenly even after 10 h
Robertis et al. [138] Cu EG e TEM PVP The particles
Nearly D ¼ 50 nm XRD settlement was about
spherical 28.5% in 50 days

metallic and nonmetallic material and sizes of nanoparticles
dispersed in different base fluids are summarized in Table 2.
It should be noted that is difficult to compare the stability of
nanofluids reported by different researchers. This is due to the
fact that, the stability was found to be dependent on pH (i.e., zeta
potential), sonication time, volume fraction, nanoparticle size
and type, base fluids, surfactants and nanofluid production
methods.
3. Zeta potential
The stability of the dispersed particles is influenced by their
surface charge or zeta potential. The significance of zeta potential
(negative or positive) is that its value can be related to the stability
of colloidal dispersions. It is well known that suspensions with zeta
potential above 30 mV are physically stable and above 60 mV show
excellent stability while a suspension below 20 mV has limited
stability, and below 5 mV undergoes pronounced aggregation
[143]. The density value and isoelectric point (IEP) of different
nanoparticles are presented in Table 3.
There are few studies that discuss the change of zeta potential
with pH values. Fig. 13 shows the zeta potential of various types of
nanoparticles dispersed in water without any surfactant. Kim et al.
[128] found that any AueNPs suspended in water, have an almost
same zeta potential value of about 30 mV regardless of pH (6.8e4)
and vol.%, though no surfactants were used. It was reported that the

Table 3
Isoelectric point in water and density of different nanoparticles.

Nanoparticles CNTs SiO2 AlN Al2O3 TiO2 Fe3O4 ZnO CuO Cu Ag Au

IEP 7.5 2 e 9.2 6.5 e e 9.5 e e 3

Density (g/cm3) 2.1 2.2 3.26 3S.9 4.2 5.24 5.6 6.315 8.94 10.5 19.32
186 Z. Haddad et al. / International Journal of Thermal Sciences 76 (2014) 168e189
Fig. 13. Zeta potential of various nanoparticles dispersed in water as a function of pH
[144].
independence of zeta potential value on pH and volume fraction
may be due to the fact that the size of AueNPs was almost un-
changed; the zeta potential value of the AueNPs/water nanofluids
prepared by18-h PLAL was 21.2  1.10 mV even after 3 months.
TiO2, Al2O3 and SiO2 nanofluids show a maximum zeta potential
of 46 mV, 50 mV at lower pH values and 49 mV at higher pH values,
respectively. Pastoriza-Gallego et al. [145] stated that Al2O3ewa-
terenanofluids with pH values above 8 would clearly produce
sample flocculation. Mondragon et al. [146] showed that particle
volume fraction also affects the zeta potential of silicaewater
nanofluids. Moreover, it was observed that an increase of solid mass
load from 0.10 to 0.20 w/w leads to a decrease in the zeta potential
and surface charge.
CNTs and CuO nanofluids show a maximum zeta potential
around 25.5 mV, and this indicates that the force of electrostatic
repulsion between nanoparticles is not enough to overcome the
attraction force between particles. For CuO nanofluids, results
showed that when NaHMP was present in the CuO-suspension,
the zeta potential was lower than 40 mV for every pH. Also,
the nanofluid was found to be stable without adding additive at
pH value higher than 12 [54]. For CNT nanofluids, it was reported
that addition of gemini surfactant at pH of about 7 increases the
zeta potential to 50 mV, making CNTs disperse well in base fluid
[147].
4. Conclusion
The present paper presents an inclusive review on the nano-
fluids preparation methods. Although many preparation methods
were proposed, it is still a challenge to make a nanofluid homo-
geneous and long-term stable with negligible agglomeration, and
without affecting the thermophysical properties.
Three methods have been used to prepare nanofluids: 1) Soni-
cation: it was shown that sonication time has an effect on the zeta
potential and nanoparticles sizes. Therefore, an optimum time of
sonication should be taken into account. In addition, some nano-
fluids were sonicated just to be kept stable for the duration of the
experiment, which limits the commercialization of nanofluids. 2)
pH control: the value of zeta potential is generally obtained by
adjusting the pH value according to just one small volume fraction
value even though the particle volume fraction affects the zeta
potential, i.e., pH value. 3) Surfactants: a critical miscell concen-
tration should be respected to avoid speedly sedimentation of
nanoparticles.
Some researchers prepared their nanofluids without using sur-
factants or adjusting pH since they aim at changing the thermo-
physical properties of nanofluid. For such case, only TiO2 in EGe
TNT that showed a maximum stability of over the period of two
months. Therefore, it is unavoidable to prevent particle sedimen-
tation without using dispersants or pH control. However, an opti-
mum amount of surfactant and pH value can be found to keep the
physical properties constant.
The most attractive property of nanofluids is the enhancement
of the thermal conductivity. Therefore, further research in-
vestigations are needed to comprehensively understand the sta-
bility of nanofluids before evolving new energy efficient heat
transfer fluids specific to applications.
Acknowledgments
Authors would like to thank to reviewers due to their appro-
priate and constructive suggestions as well as their proposed cor-
rections, which have been utilized in improving the quality of the
paper.
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