A Review of Nanofluid Stability Properties and Characterization in Stationary Conditions

A review of nanouid stability properties and characterization
in stationary conditions
A. Ghadimi
, R. Saidur, H.S.C. Metselaar

Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
a r t i c l e i n f o
Article history:
Received 3 December 2010
Received in revised form 1 April 2011
Accepted 1 April 2011
Keywords:
Stability
Nanouid
Characteristics
Thermal conductivity
Viscosity
Thermo-physical properties
a b s t r a c t
A new engineering medium, called nanouid attracted a wide range of researches on many cooling pro-
cesses in engineering applications, which are prepared by dispersing nanoparticles or nanotubes in a host
uid. In this paper, the stability of nanouids is discussed as it has a major role in heat transfer enhance-
ment for further possible applications. It also represents general stabilization methods as well as various
types of instruments for stability inspection. Characterization, analytical models and measurement tech-
niques of nanouids after preparation by a single step or two-step method are studied.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
One of the most signicant scientic challenges in the industrial
area is cooling, which applies to many diverse productions, includ-
ing microelectronics, transportation and manufacturing. Techno-
logical developments such as microelectronic devices operating
at high speeds, higher-power engines, and brighter optical devices
are driving increased thermal loads, requiring advances in cooling.
The conventional method for increasing heat dissipation is to in-
crease the area available for exchanging heat to use a better heat
conductive uid. However, this approach involves an undesirable
increase in the size of a thermal management system; therefore,
there is an urgent need for new and novel coolants with improved
performance. The innovative concept of nanouids heat transfer
uids consisting of suspended of nanoparticles has been
proposed as a prospect for these challenges [1].
Maxwell was the rst presenter of a theoretical basis to predict
a suspensions effective conductivity about 140 years ago (1873)
and his theory was applied from millimeter to micrometer sized
particles suspensions but Choi and Eastman [2] introduced the
novel concept of nanouids by applying the unique properties of
nanouids at the annual Mechanical Engineering meeting of
American Society at 1995. Goldstein et al. [3] added the condition
that the particles must be in colloidal suspension. Choi and his
colleagues have carried out experiments on heat transport in sys-
tems with CuO nanoparticles in water and Al
2
O
3
particles in ethyl-
ene glycol and water. They found that the particles improve the
heat transport by as much as 20%, and they interpreted their result
in terms of an improved thermal conductivity k/k
0
which they
named the effective thermal conductivity [3].
A nanouid is a uid produced by dispersion of metallic or non-
metallic nanoparticles or nanobers with a typical size of less than
100 nm in a liquid. Nanouids have attracted huge interest lately
because of their greatly enhanced thermal properties. For instance,
experiments showed an increase for thermal conductivity by dis-
persion of less than 1% volume fraction of Cu nanoparticles or car-
bon nanotubes in ethylene glycol or oil by 40% and 150%,
respectively [1]. There are also various potential advantages from
nanouid testing namely: better long-term stability and thermal
conductivity compared to millimeter or even micrometer sized
particle suspensions and less pressure drop and erosion particu-
larly in microchannels. Though, there are still major application
prospects in advanced thermal applications, they remain in the
early stages of development. About a decade ago, some researchers
reported the heat transfer and ow characteristics of the different
nanouids namely: Trisaksri and Wongwises [4], Beck [5], Wang
and Mujumdar [6], Duangthongsuk and Wongwises [7], Godson
et al. [8], Li et al. [9] and Wen et al. [10], Leong et al. [11]. However,
prior to use nanouids for heat transfer, signicant knowledge
about their thermophysical properties is required, especially their
thermal conductivity and viscosity. Many researchers have
measured the thermophysical properties of nanouids while many
0017-9310/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijheatmasstransfer.2011.04.014
Corresponding author. Tel.: +60 3 79674451; fax: +60 3 79675317.

E-mail addresses: Azadeh_ghadimi@yahoo.com, Azadeh_ghadimi@siswa.um.
edu.my (A. Ghadimi).
International Journal of Heat and Mass Transfer 54 (2011) 40514068
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others used well-known predictive correlations. Their works have
been both experimental and theoretical [12].
This review focuses on the stability of nanouids, which is crit-
ical to eventual utilization of nanouid in practice. The subject was
put into consideration recently since different investigators reach
different results with the same nanoparticles. Therefore, it was
concluded that stability measurement and investigation for each
nanouid preparation may be leading to a standard way of prepa-
ration and unied data. Hence, experimental studies on prepara-
tion and different stability methods of nanouids are reviewed.
Theoretical attempts made to explain the associated characteristic
mechanisms are also outlined. In addition to these, the measure-
ment methods proposed for the determination of stability are sum-
marized and thermophysical property predictions of the models
are compared with experimental ndings, and signicant discrep-
ancies are specied.
2. Nanouid preparation methods
Preparing a stable and durable nanouid is a prerequisite opti-
mizing its thermal properties. Therefore, many combinations of
material might be used for particular applications, namely: nano-
particles of metals, oxides, nitrides, metal carbides, and other non-
metals with or without surfactant molecules which can be
dispersed into uids such as water, ethylene glycol, or oils [1]. In
the stationary state, the sedimentation velocity of small spherical
particles in a liquid follows the Stokes law [13]
V
2R
2
9l
q
p
q
L
g 1
where V is the particles sedimentation velocity; R is the spherical
particles radius; l is the liquid medium viscosity; q
P
and q
L
are
the particle and the liquid medium density, respectively and g is
the acceleration of gravity. This equation reveals a balance of the
gravity, buoyancy force, and viscous drag that are acting on the sus-
pended nanoparticles. According to Eq. (1), the following measures
can be taken to decrease the speed of nanoparticles sedimentation
in nanouids, and henceforth to produce an improvement for the
stability of the nanouids: (1) reducing R, the nanoparticles size;
(2) increasing l, the base uid viscosity and (3) lessening the differ-
ence of density between the nanoparticles and the base uid
(q
P
q
L
). Clearly reducing the particle size should remarkably de-
crease the sedimentation speed of the nanoparticles and improve
the stability of nanouids, since V is proportional to the square of
R. According to the theory in colloid chemistry, when the size of
particle decreases to a critical size, R
c
, no sedimentation will take
place because of the Brownian motion of nanoparticles (diffusion).
However, smaller nanoparticles have a higher surface energy,
increasing the possibility of the nanoparticle aggregation. Thus,
the stable nanouids preparation strongly link up with applying
smaller nanoparticles to prevent the aggregation process concur-
rently [14].
Two different techniques apply to produce nanouids namely:
single-step and two-step method.
2.1. Two-step technique
In this method, dry nanoparticles/nanotubes are rst produced,
and then they are dispersed in a suitable liquid host, but as nano-
particles have a high surface energy, aggregation and clustering are
unavoidable and will appear easily. Afterward, the particles will
clog and sediment at the bottom of the container. Thus, making a
homogeneous dispersion by two step method remains a challenge.
However, there exist some techniques to minify this problem like
high shear and ultrasound. Therefore, we will discuss different
methods of making a stable nanouid in the next section. Nano-
uids containing oxide particles and carbon nanotubes are produced
by this method. This method works well for oxide nanoparticles
and is especially attractive for the industry due to its simple pre-
paring method. But its disadvantage due to quickly agglomerated
particles brings about many challenges nowadays. As nanoparti-
cles disperse partially, dispersion is poor and sedimentation hap-
pens so a high volume concentration is needed increasing the
heat transfer (10 times of single step) and accordingly the cost
would be as much as loading [15]. The two-step method is useful
for application with particle concentrations greater than 20 vol.%
but it is less successful with metal nanoparticles. However, some
surface treated nanoparticles showed excellent dispersion [16].
The rst materials tried for nanouids preparation were oxide par-
ticles, mainly because they are easy to make and chemically stable
in solution [17].
2.2. Single step technique
In this method nanoparticle manufacturing and nanouid prep-
aration are done concurrently. The single-step method is a process
combining the preparation of nanoparticles with the synthesis of
nanouids, for which the nanoparticles are directly prepared by
physical vapor deposition (PVD) technique or a liquid chemical
method (condensing nanophase powders from the vapor phase
directly into a owing low-vaporpressure uid is called VEROS).
Nomenclature
E energy
El electrostatic repulsion
x interparticle surface-to-surface distance
W weight/stability coefcient
M molecular weight
N Avogadros constant
K thermal conductivity
k constant rate of aggregation
T temperature
Greek symbols
a collision efciency
k mean free path
l dynamic viscosity
t viscosity
q density
U volume fraction
W surface potential
Subscripts
A van der Waals
d particle
IEP iezo electric point
M maximum
Nf nanouid
PZC point of zero charge
S nanoparticle
tot sum
4052 A. Ghadimi et al. / International Journal of Heat and Mass Transfer 54 (2011) 40514068
In this method drying, storage, transportation, and dispersion of
nanoparticles are avoided, so the agglomeration of nanoparticles is
minimized and the stability of the nanouids is increased. A disad-
vantage of this method is that it is impossible to scale it up for
great industrial functions and is applicable only for low vapor pres-
sure host uids. This limits the application of the method
[1,3,6,9,15]. Recently, Chang et al. [18] prepared nanouids of
TiO
2
nanoparticles dispersed in water by a one-step chemical
method using a high pressure homogenizer. This method is called
modied magnetron sputtering. The schematic of the apparatus
can be seen in Fig. 1.
3. Importance of the stability of nanouid
Preparing a homogeneous suspension is still a technical chal-
lenge due to strong van der Waals interactions between nanopar-
ticles always favoring the formation of aggregates. To obtain
stable nanouids, some methods are recommended, such as phys-
ical or chemical treatment. They are listed as the addition of surfac-
tant, surface modication of the suspended particles or applying
powerful forces on the clustered nanoparticles. Spreading sur-
face-active agents have been used to modify hydrophobic materi-
als to enable dispersion in an aqueous solution [2022].
Otherwise clogging, aggregation and sedimentation happen and
cause declining of suspension characteristics like thermal conduc-
tivity, viscosity and increasing specic heat.
There exists a theory that clustering and aggregation is one of
the main features in stability and extraordinary enhancement in
thermal conductivity of nanouids [23,140] although this theory
may be highly specic to the high aspect ratio nanoparticles,
including single wall nanotubes. Philip et al. [24] and Evans et al.
[23] claimed that the high aspect ratio structure of the fractal-like
aggregates is a key factor allowing rapid heat ow over large dis-
tances. They also stated that well dispersed composites show low
thermal conductivity enhancement but composites with fractal
aggregates show signicant enhancements, even with considerable
interfacial resistance. Gharagozloo and Goodson [25] also mea-
sured fractal dimensions for the 1%, 3% and 5% volume concentra-
tions of Al
2
O
3
in H
2
O and concluded that aggregation is a more
likely cause for the measured enhancements of nanouid. Con-
trarily, another theory shows that agglomeration and clustering re-
duce stability and thermal conductivity improvement. Hong et al.
[26,110] claimed that ultrasonicated Fe nanouids, due to their
broken clusters, got enhancement in thermal conductivity
although this enhancement reduced as a function of elapsed time
after production. Therefore, for classication of the stability theory
more experimental works are needed to clarify the role of aggrega-
tion in conductivity enhancement. But generally, to obtain a high-
quality suspension, small particles have to meet these two princi-
ples: (1) diffusion principle: particles are scattered by a liquid
medium and dispersed into the liquid medium. (2) Zeta potential
principle: the zeta potential absolute value among particles must
be as large as possible, making a common repulsive force between
the particles [27].
According to the literature, there are three effective tactics used
to manage stability of suspension against sedimentation of nano-
particles. Some of the researchers applied all of these methods to
gain better stability [2830] but others just applied one [31] or
two techniques [3234] with satisfaction. There is no standard to
recognize the superlative mix up of combining methods. This area
acquires more experiments to be claried. The techniques are sum-
marized below:
3.1. Surfactant or activator adding
This is one of the general methods to avoid sedimentation of
nanoparticles. Addition of surfactant can improve the stability of
nanoparticles in aqueous suspensions. The reason is that the
hydrophobic surfaces of nanoparticles/ nanotubes are modied to
become hydrophilic and vice versa for non-aqueous liquids. A
repulsion force between suspended particles is caused by the zeta
potential which will rise due to the surface charge of the particles
suspended in the base uid [35,36]. However, care should be taken
to apply enough surfactant as inadequate surfactant cannot make a
sufcient coating that will persuade electrostatic repulsion and
compensate the van der Waals attractions [37]. The effect of sur-
factant on aggregated particle size distribution can be demon-
strated as shown in Fig. 3.
Popular surfactants that have beenusedinliterature canbe listed
as sodium dodecylsulfate (SDS) [35,3741], SDBS [21,28,29,39],
salt and oleic acid [38,42,139], cetyltrimethylammoniumbr-
omide (CTAB) [32,138], dodecyl trimethylammonium bromide
(DTAB) and sodium octanoate (SOCT) [43], hexadecyltrimeth-
ylammoniumbromide (HCTAB), polyvinylpyrrolidone (PVP)
[22,44,45] and Gum Arabic [39]. Choosing the right surfactant is
the most important part of the procedure. It could be anionic,
cationic or nonionic [46].
Fig. 1. Ultrasonic-aided submerged arc nanoparticle synthesis system to produce
TiO
2
nanouid [18].
Fig. 2. Schematic diagram of the high-pressure homogenizer for producing
nanouids [18].
A. Ghadimi et al. / International Journal of Heat and Mass Transfer 54 (2011) 40514068 4053
The disadvantage of surfactant addition is for applications at the
high temperatures [10,14,47] as above than 60 C [32,48] the
bonding between surfactant and nanoparticles can be damaged.
Therefore, the nanouid will lose its stability and sedimentation
of nanoparticles will occur [6].
3.2. pH control (surface chemical effect)
The stability of an aqueous solution nanouid directly links to
its electrokinetic properties. Through a high surface charge density,
strong repulsive forces can stabilize a well-dispersed suspension
[2729,4953]. Xie et al. [54] showed that by simple acid treat-
ment a carbon nanotube suspension gained a good stability in
water. This was caused by a hydrophobic-to-hydrophilic conver-
sion of the surface nature due to the generation of a hydroxyl
group. The isoelectric point (IEP) is the concentration of potential
controlling ions at which the zeta potential is zero. Thus, at the
IEP, the surface charge density equals the charge density, which
is the start point of the diffuse layer. Therefore, the charge density
in this layer is zero. Critical to nanoparticle nucleation and stabil-
ization in solution is that the repulsive energy is smaller for small
particles, so a larger zeta potential is required for suspension sta-
bility [18]. As the pH of the solution departs from the IEP of parti-
cles the colloidal particles get more stable and ultimately modify
the thermal conductivity of the uid. The surface charge state is
a basic feature which is mainly responsible for increasing thermal
conductivity of the nanouids [52,53]. Also in some experiments
particles shape conversion was related to the pH variation [49,55].
In the liquid suspension, particles attract or repel each other.
This interaction depends on the distance between particles and
the total interface energy E
tot
that is the sum of the van der Waals
attraction E
A
and the electrostatic repulsion E
el
between them. The
E
el
between two charged particles with the surface potentials W
d1
and W
d2
is approximated by the DLVO theory:
E
el

0
1
r
1
r
2
r
1
r
2
2W
d1
W
d2
In
1 expkx
1 expkx
_ _
W
2
d1
W
2
d2
ln1 exp2kx
_ _
2
where r is the radius of particles, x is an interparticle surface-to-sur-
face distance, and the other symbols have their conventional
meanings.
It is notable that higher potentials (W
d
or f) lead to a bigger po-
tential barrier for agglomeration. In aqueous nanouid of CuO with
0.3 vol.% and PZC of about 8.59.5, the interparticle distance is
about 100 nm for mobility-equivalent spherical particles. At this
condition, the second term in the bracket of above equation is neg-
ligible compared to the rst. Thus, the repulsion energy of the
same-sized particles goes up approximately in proportion to f
2
.
The attraction energy between the same particles is given by
the Hamaker equation: E
A
= A
132
r/(12x). The Hamaker constant
A
132
of metal oxide is typically on the order of 10
20
J. Using the
above equation, the Hamaker equation, and the estimated W
d
, E
tot
is calculated as a function of x at different pHs as shown in Fig. 4. In
this condition, the repulsion barrier gets bigger than the attraction
as pH goes from the PZC, which makes the colloids more stable. At
pH 8 or 10 when W is small, however, the repulsion barrier disap-
pears, and particles are only subjected to the attractions. Strong
particle agglomeration is expected in that situation. Here, we need
to quantify the suspension stability in terms of collision efciency,
Fig. 3. Particle size distributions of nano-suspensions. (a) Al
2
O
3
H
2
O without SDBS, (b) Al
2
O
3
H
2
O with SDBS, (c) CuH
2
O without SDBS and (d) CuH
2
O with SDBS.
Concentration of nanoparticles and SDBS surfactant are 0.05% weight fraction, respectively [29].
Fig. 4. The interaction potentials at various pHs as a function of interparticle
distance [53].
a, which is responsible for colloidal particle growth. The a, a reci-
procal value of stability coefcient W, is related to the rate con-
stant of aggregation, k = ak
diff
= k
diff
/W.
The k
diff
represents the rate constant of the coagulation between
uncharged particles. Then a general relation of stability coefcient
W to total interaction energy E
tot
can be derived [53]
W 2r
_
1
0
exp
E
tot
k
b
T
_ _
dx
2r x
2
3
For example, as the pH of the nanouid goes far from the isoelectric
point, the surface charge increases by applying SDBS surfactant in
CuH
2
O nanouid. Since more frequent attacks occur to the surface
hydroxyl and phenyl sulfonic group by potential-determining ions
(H+, OH and phenyl sulfonic group), zeta potential and the colloi-
dal particles increase. So the suspension gets more stable and even-
tually changes the thermal conductivity of the uid [21].
Lee [56] also worked on different pH of nanouids with Al
2
O
3
.
The experiments indicated that when the nanouid had a pH of
1.7, the agglomerated particle size was reduced by 18% and when
the nanouid had a pH of 7.66, the agglomeration size was in-
creased by 51%. More particles aggregated in pH of 7.66 because
of reduction in electric repulsion force. When Al
2
O
3
particles are
immersed in water, hydroxyl groups (OH) are produced at the
surface of the Al
2
O
3
particle. The relevant reactions depend on
the solution pH. When the pH of the solution is lower than the
PZC, the hydroxyl groups react with H
+
from water which leads
to a positively charged surface. Alternatively, when the pH of the
solution is higher than the PZC, the hydroxyl groups react with
OH
from water and create a negatively charged surface [107]. In

addition, as it is demonstrated from Table 1, the particle sizes differ
when the pH of nano-suspensions change [39].The optimized pH is
different for different nanoparticles. For example, the proper pH for
alumina is around 8 meanwhile for copper and graphite nanopar-
ticles are 9.5 [57] and about 2.0 respectively. The pH for the point
of zero charge also changes by temperature variation as is shown
in Table 2 [50].
3.3. Ultrasonic vibration
All the mentioned techniques aim to change the surface proper-
ties of suspended nanoparticles and to suppress forming clusters of
particles, with the purpose of attaining stable suspensions. Ultra-
sonic bath, processor and homogenizer are powerful tools for
breaking down the agglomerations in comparison with the others
like magnetic and high shear stirrer as experienced by researchers
[38]. However occasionally after passing the optimized duration of
the process, it will cause more serious problems in agglomeration
and clogging resulting in fast sedimentation. Furthermore, there is
a new method to get stable suspensions proposed by Hwang et al.
[38] which consists of two micro-channels, dividing a liquid stream
into two streams. Both streams are then recombined in a reacting
chamber. Breaking the clusters of nanoparticles was studied using
the high-energy of cavitations [58]. This work was conducted for
Carbon Black with water and silver with silicon oil nanouids.
When the suspension contacted with the interior walls of the
interaction chamber, it will ow through the microchannel. There-
fore, the ow velocity of the suspension through the microchannel
should be increased according to Bernoullis theorem, and concur-
rently cavitations extensively occurred. In this fast ow region,
particle clusters must be broken by the combination of various
mechanisms, including (i) strong and irregular shock on the wall
inside the interaction chamber, (ii) microbubbles formed by cavita-
tion-induced exploding energy, and (iii) high shear rate of ow.
This leads to obtain homogeneous suspensions with fewer aggre-
gated particles at high-pressure. This procedure can be repeated
a number of three times to achieve the required homogeneous
nanoparticle distribution in the base uids. A schematic of this
method is presented in Fig. 2.
An ultrasonic disruptor is a more general accessible apparatus
than the one prepared by Hwang et al. [38]. Many researchers used
this technique to obtain a stable nanosuspension. In some cases,
they mixed different methods of stabilization to ne-tune the re-
sults. A summary of investigators who reached diverse duration
of stability using ultrasonic methods is given in Table 3. Although
it was noted that typically it is rare to maintain nanouids synthe-
sized by the traditional one-step and two-step methods in a homo-
geneous stable state for more than 24 h (Peterson & Li, 2006) [107]
we gathered.
4. Stability inspection instruments
There are some instruments and methods that can rank the rel-
ative stability of nanosuspension. The list includes UVVis spectro-
photometer, zeta potential, sediment photograph capturing, TEM
(Transmission Electron Microscopy) and SEM (Scanning Electron
Microscopy), light scattering, three omega and sedimentation bal-
ance method. Therefore, the rate or percentage of sedimentation
will be identied by analyzing gathered data.
4.1. UVVis spectrophotometer
Even though the stability of a nanouid is the key issue for its
application, there are limited studies on estimating the stability
of a suspension. Ultra VioletVisible spectrophotometer (UVVis)
measurements have been used to quantitatively characterize col-
loidal stability of the dispersions. One of the most striking features
of this apparatus is its applicability for all base uids, whereas zeta
potential analysis has restrictions for the viscosity of the host uid.
An UVVis spectrophotometer exploits the fact that the inten-
sity of the light becomes different by absorption and scattering
of light passing through a uid. At 200900 nm wavelength, the
UVVis spectrophotometer measures the absorption by liquid
and is used to analyze various dispersions in the uid [56]. Typi-
cally, suspension stability is resolved by measuring the sediment
volume versus the sediment time. However, this method is unsuit-
able for nanouid dispersions with a high concentration and espe-
cially for CNT solutions. These dispersions are too dark to
differentiate the sediment visibly. Jiang et al. [37] were the rst
investigators who proposed sedimentation estimation using UV
Vis spectrophotometer for nano suspensions. In this method, the
Table 1
Particle size change of Al
2
O
3
/distilled water nanouids with two pH values [39].
Nanouid Al
2
O
3
/DI Al
2
O
3
/DI/PBS
a
/HCl Al
2
O
3
/DI/PBS
pH 1.7 7.66
Mean particle size (nm) 170 139 1033
a
Phosphate buffered saline contains sodium chloride, sodium phosphate and
potassium phosphate and helps to keep a constant pH.
Table 2
Values of pH
pzc
of the TiO
2
between 5 and 55 C [50].
Temperature (C) PH
PZC
5 6.62
15 6.39
25 6.17
35 5.97
45 5.78
55 5.61
rst step is to nd the peak absorbance of the dispersed nanopar-
ticles at very dilute suspension by scanning. As the concentration
of suspension has a linear relation with absorbance, preparing a
standard to t a linear relation to at least three different dilute con-
centrations (0.010.03%) will be the next step in this method. Rel-
ative stability measurement will be followed by preparing the
desired concentration of nanouid and put aside for a couple of
days. Whenever it is needed to check the relative stability, the
supernatant concentration will be measured by UVVis spectro-
photometer and the concentration can be plotted against time. This
method was used by Refs. [35,56,65,66]. There also exist a sum-
mary from different nanouid peak absorptions by UVVis spec-
trophotometer in Table 4.
According to Mies theory [68], the surface plasmon absorption
and the plasmon bandwidth are dependent on the size of metallic
particles in the solution. Consequently, the peak value represents
the most populated nanoparticle size in the solution. Additionally,
by increasing the particle size especially smaller than 20 nm, the
bandwidth decreases. Contrarily, the bandwidth of the surface
Plasmon for the particles larger than 20 nm, increases with the par-
ticle size [69,70]. As the particle size increases, the local peak in the
UVVis spectra shifts towards longer wavelength [71]. Tsai et al.
[71] have conducted a series of tests on this theory. The sizes of
Au nanoparticles from different preparation methods measured
by TEM and peak wavelength are summarized in Table 5.
4.2. Zeta potential test
Zeta potential measurement is one of the most critical tests to
validate the quality of the nanouids stability via a study of its
electrophoretic behavior [53,72]. According to the stabilization
theory [7], the electrostatic repulsions between the particles in-
crease if zeta potential has a high absolute value which then leads
to a good stability of the suspensions [22].
Table 3
Summary of different ultrasonic processes.
Investigator Nanoparticle Base uid Concentration Stability process Duration Sedimentation
[59] Al
2
O
3
(45 nm) DW 15.5 vol.% Ultrasonic cleaner 15 h Minutes after preparation
EG 18 vol.%
[60] Al
2
O
3
(11 nm) DW 0.8 vol.% Ultrasonication 6 h N/A
[61] Al
2
O
3
(38.4 nm) DW 14 vol.% Ultrasonication 11 h After 12 hours
CuO (28.6 nm) 14 vol.%
[62] CuO (10 nm) DI 0.003 vol.% Ultrasonication 27 h N/A
[35] MWCNT DI + SDS 01.6 vol.% N/A N/A N/A
(10
50
10
30
nm) Oil + SDS
Fullerene (10 nm) DI + SDS 01.6 vol.% N/A N/A N/A
Oil + SDS
Mixed fullerene (10 nm) EG + SDS 01.6 vol.% N/A N/A N/A
C
70
and C
60
Oil + SDS
DI + SDS
CuO (33 nm) EG + SDS 01.6 vol.% N/A N/A N/A
DI + SDS
SiO
2
(12 nm) DI + SDS 01.6 vol.% N/A N/A N/A
[29] Al
2
O
3
(25 nm) DW + SDBS 00.08
(N.P) wt.%
Ultrasonication, pH control and Surfactant
adding
15 min N/A
DW 00.14 wt.%
(SDBS)
1 h
Cu (25 nm) DW + SDBS 15 min
DW 1 h
[12] TiO
2
(21 nm) DW 01.2 vol.% Ultrasonication 2 h N/A
[31] Al
2
O
3
(43 nm) DW (0.335) vol.% Ultrasonication 6 h N/A
[63] TNT (10 100 nm) EG (0.5-8) wt.% Ultrasonic bath 48 h More than 2 months stability
[26] Fe (10 nm) EG (0.2
0.55) vol.%
Ultrasonic 10
70 min
Optimized 30 min
cell disrupter
[53] CuO (25 nm) DW 0.3 vol.% N/A N/A
[21] CuO (25 nm) DW + SDBS 0.1 wt.% Ultrasonic vibrator, pH control and
surfactant addition
1 h N/A
[22] Graphite (nm) DW + PVP 0.5 wt.% Ultrasonic vibration 30 min N/A
[42] Fe
3
O
4
(15 nm) Kerosene + oleic
acid
01.2 vol.% Ultrasonication 0
80 min
Stable
[64] ZnO (20 nm) ammonium poly 0.02 vol.% Horn ultrasonic 0
60 min
Stable over 10,000 h
(40100 nm) methacrylate + DI
[39] Al
2
O
3
(4050 nm) DW 1 vol.% Horn ultrasonic 0
30 min
Particle size reduction
Ultrasonic bath 8 h
[40] MWCNT
(10
30
nm 10
50
lm)
DW + SDS 01 vol.% Ultrasonic disruptor 2 h Surfactant adding avoid
entanglement
SiO
2
(7 nm) DW Stable
CuO (35.4 nm) DW Stable
CuO (35.4 nm) EG Stable
Table 4
Summary of different nanouids peak absorption measured by UVVis
spectrophotometer.
Nanoparticle Base uid Peak wavelength Investigator
MWCNT and fullerene Oil 397 [35]
Aligned CNT DW 210 [67]
CNT DW 253 [37]
Tio
2
DW 280400 nm [18]
Cu DW 270 [27]
CuO DW 268 [27]
Ag DW 410 [44]
The experiments are conducted by using a 0.05% weight fraction
of nanosuspension to measure zeta potential and particle size [29].
The relationship between suspension stability and zeta-poten-
tial arises from the mutual repulsion that occurs between like-
charged particles. For this reason, particles with a high surface
charge tend not to agglomerate, since contact is opposed. Typically
accepted zeta-potential values are summarized below in Table 6.
Generally, a suspension with a measured zeta-potential above
30 mV (absolute value) is considered to have good stability
[73,74] this is one of the most common methods among the
researchers to determine the stability as mentioned above.
4.3. Sediment photograph capturing
A primary method to nd out about sedimentation of nanouids
is photo capturing. After preparation, some amounts of the suspen-
sion will put aside to capture photos after certain period of time. By
comparing these photos of nano suspensions, sedimentation of sus-
pension will be apparent. Different sets of nanouid preparation for
the photo capturing canbe seenat Figs. 57. Clearly variable pH, vis-
cosity and weight fractions for Al
2
O
3
and Cu and Cu
2
O were investi-
gated after seven days and 24 h by photo capturing.
4.4. TEM (Transmission Electron Microscopy) and Scanning Electron
Microscope (SEM)
TEM and SEM are very useful tools to distinguish the shape, size
and distribution of nanoparticles. Nevertheless, it cannot present
the real situation of nanoparticles in nanouids when dried sample
are needed. Cryogenic electron microscopy (Cryo-TEM, Cryo-SEM)
might provide a method to resolve this problem if the microstruc-
ture of nanouids is not changed during cryoation. Nanoparticles
Table 5
Volumes of gold nanouid in different synthesis conditions [71].
Condition Baseuid Na
3
citrate
(ml)
Tannic
acid
(ml)
HAuCl
4
(ml)
Particle
size
(nm)
Peak
wavelength
A DW 0.2 2.5 3 21.3 528
B DW 0.2 5 6 43.7 530.5
C DW 3 0.1 1 8 568.5
E DW 3 2.5 6 9.3 647
G DW 3 0.1 3 15.6 721.5
Table 6
Zeta potential and associated suspension stability [74].
Z potential (absolute value [mv]) Stability
0 Little or no stability
15 Some stability but settling lightly
30 Moderate stability
45 Good stability, possible settling
60 Very good stability, little settling likely
Fig. 5. Variation of the nanouids viscosity with pH and nanoparticles weight fraction at temperature 303 K: (a) the variation of the viscosity with pH, (b) the variation of the
viscosity with nanoparticles concentration, (c) the sediment photograph of Al
2
O
3
H
2
O suspensions after depositing for seven days, (d) the sediment photograph of CuH
2
O
suspensions after depositing for seven days [57].
Fig. 6. Octahedral-Cu
2
O nanouids 24 h after their preparation (CuSO
4
molar
concentration from 0.0025 mol/L to 0.002 mol/L) [49].
aggregation structure in nanouids could be directly monitored by
this instrument as well [14].
The following procedure is attributed to the standard SEM/TEM
micrographs of nanoparticles [75]:
(1) Obtain stable nanouid in solution form.
(2) Drop one drop of the solution on sticky tape of top surface of
the SEM specimen holder (carbon grid in the case of TEM).
(3) Heat in the vacuum oven to dry the liquid drop or dried in
the air naturally.
(4) Obtain solid particle.
(5) Bring into the vacuum chamber of SEM/TEM for picture after
coating with Au and Pd.
The stable nanouids have different shapes after preparation as
are shown in TEM and SEM images in Figs. 711.
4.5. Light scattering method
The single-particle analysis from which the light scattering
theory can be approached has been used to visualize polymer mol-
ecule structure in solutions or colloidal particles in suspension. The
intensity of scattered light for a single particle is related to the
particle volume. While the interaction of electromagnetic radiation
with a small particle is weak in light scattering, most of the inci-
dent light is transmitted and only a little amount of light is distrib-
uted. In one study, the average size of the clusters was obtained
every ve minutes after the sonication stopped [26].
4.6. Sedimentation balance method
The stability of the nano-suspension can be also measured by
another method named a sedimentation balance. The tray of a sed-
Fig. 7. TEM pictures of (left) Cu nanouids, (middle) CuO nanoparticles and (right) alkanethiol terminated AuPd colloidal particles [1].
Fig. 8. SEM of carbon nanotube (a) single-walled carbon nanotubes obtained by arc discharge and (b) multiwalled carbon nanotubes obtained by chemical vapor deposition
growth [1].
Fig. 9. TEM micrograph of nanoparticles (a) nano-alumina (b) nano-copper [29].
imentation balance is immersed in the fresh nano-suspension. The
weight of sediment nanoparticles during a certain period of time is
measured. The suspension fraction (F
s
) of nanoparticles at an ac-
cepted time is calculated by the formula F
s
= (W
0
W)/W
0
in which
W
0
is the total weight of all nanoparticles in the measured space,
and W is the weight of the sediment nanoparticles at a certain time
[22].
4.7. Three omega method
The colloidal stability of nanouid can also be determined by
the three omega method. It can be evaluated by detecting the ther-
mal conductivity growth caused by the nanoparticle sedimentation
in a wide nanoparticle volume fraction range. There are a few sta-
bility measurements attributed to this method in the literature
[59,76,111].
5. Characteristic measurement
There are four major thermophysical properties that change
their values due to nanoparticle addition to the host uid which
is thermal conductivity, viscosity, density and specic heat. Differ-
ent investigators have unlike ideas about the effect of nanoparticle
dispersion. Typically, these nanouid properties will increase ex-
cept for the specic heat which decreases. The percentage of incre-
Fig. 10. TEM photographs of Au, Al
2
O
3
, TiO
2
and CuO particles and carbon nanobers [41].
ment will vary as the function of dispersion, volume concentration,
temperature, base uid. There is not a standard for preparation of
nanouid since then it would be obvious if the data will vary from
time to time.
5.1. Thermal conductivity
Thermal conductivity is the most important factor that can be
investigated to prove the heat transfer enhancement of a prepared
nanouid. Reviewing available literature explains that the rise in
thermal conductivity of the nanouids is large. Addition of only a
small volume percent of solids produces a dramatic enhance of
thermal conductivity [4,6,77,78].
Several mechanisms for this strange enhancement of thermal
conductivity have been already discussed. Among them, Brownian
motion, interfacial layer and aggregation of particles have been
talked about comprehensively [7988]. Some researchers dis-
cussed a nanouid as a two-phase ow mixture and utilized theo-
ries of a two-phase mixture or properties of nanouid, such as
Maxwells theory [89] and the Hamilton and Crosser approach
[90]. These models are based on an effective medium theory that
presumes well dispersed particles in a uid medium. If aggregated
particles in the uid bring about particle chains or clusters, the pre-
dicted thermal conductivity would be signicantly higher as was
observed by many researchers [10,91] and might be of a strong
function of the aggregates dimension and the radius of gyration
of the aggregates. This result is based on the three-level homogeni-
zation theory, validated by MC (Monte Carlo) simulation of heat
conduction on model fractal aggregates [23,25,92]. As it can be
seen in Fig. 12, they related the enhancement of thermal conduc-
tivity to nanoparticle aggregation. It is seen that there should be
an optimized aggregation structure for achieving maximum ther-
mal conductivity, which is far beyond the prediction from homoge-
neous dispersions. Such an argument eliminates thermal
conductivity as an intrinsic physical characteristic. Possible inu-
ence of particle aggregation on conduction highlights the colloid
chemistrys signicant role in optimizing this property of nano-
uids. Meanwhile, there exists another theory of lowering thermal
conductivity of aggregation forming as found by Hong et al.
[26,110] from experiments by light scattering of Fe nanoparticles
aggregate.
The effective thermal conductivity increment may also depends
on the shape of nanoparticles as discussed by Zhou and Gao [93
95]. They proposed a differential effective medium theory based
on Bruggemans model [79] to approximate the effective thermal
conductivity of nano-dispersion with nonspherical solid nanoparti-
cles with consideration of the interfacial thermal resistance across
the solid particles and the host uids. They found that a high
enhancement of effective thermal conductivity can be gained if
the shape of nanoparticles deviates greatly from spherical.
Many of the researchers suggested altogether new mechanisms
for the transport of thermal energy [79]. There is another idea pro-
posed by Keblinski et al. [1] of an ordered liquid layer at particle
interfaces and tunneling of heat-carrying phonons from one par-
ticle to another. The subsequent simulation work from the same
group of investigators concludes that these mechanisms do not
contribute considerably to heat transfer. Koo and Kleinstreuer
[96] found that the role of Brownian motion is much more signif-
icant than the thermophoretic and osmo-phoretic motions. In con-
Fig. 11. Bright eld TEM micrographs of ZnO aggregates from (a) As-mixed suspension from powder A, (b) same suspension, ultrasonically agitated for 60 min with horn, (c)
as-mixed suspension from powder B and (d) same suspension, ultrasonically agitated for 60 min with horn [64].
Fig. 12. Aggregation effect on the effective thermal conductivity [10].
1
2
clusion, some investigators believe that nanoparticle aggregation
plays an important role in thermal transport due to their chain
shape [23,97] but some others believe that the time-dependent
thermal conductivity in the nanouids proves the reduction of
thermal conductivity by passing time due to clustering of nanopar-
ticles with time [98].
Vadasz [72] showed that heat transfer enhancement may be
caused by a transient heat conduction process in nanouids. Exper-
iments demonstrate that a nanouids thermal conductivity de-
pends on a great number of parameters, such as the chemical
composition of the solid particle and the base uid, surfactants,
particle shape, size, concentration, polydispersity, etc., though the
exact variation trend of the conductivity with these factors has
not yet been found. Additionally, the temperature inuences the
thermal conductivity of a nanouid as shown in several studies
that have been carried out to see that effect on CuO, Al
2
O
3
, TiO
2,
ZnO dispersed nanouids by Mintsa et al. [38], Duangthongsuk
and Wongwises [39], Vajjha and Das [40], Murshed et al. [41], Yu
et al. [42] and Karthikeyan et al. [98]. A temperature increase im-
proves the thermal conductivity of the nanouids. However, the
actual mechanism of this increment has not been revealed yet. A
deciency of reliable data for the conductivity of nanouid is the
major problem of non-commercialization for this product.
The other inuencing factor for the thermal conductivity in-
crease of nanosuspension is the volume fraction which has been di-
rectly proportional with this characteristic [31], although this
relationship is generally nonlinear for nanoparticles with a high as-
pect ratio [99]. Thermal conductivity increment data for DI (De-
Ionized) water based suspensions were investigated by Wang
et al. [80], which showed a high rise in comparison with the results
of Lee et al. [100] and Das et al. [101]. Moreover, experiments con-
ducted by Oh et al. [59] for EG based nanouids data showed rel-
atively low thermal conductivity values compared to those of Lee
et al. [100] and Wang et al. [80].
It has been found that the thermal conductivity of a base uid is
nearly constant at different doses of surfactant or base. Hence it
seems that this property improvement is related only to the parti-
cles when dispersing the nanoparticles into water. The general
behavior of the particle-water interaction depends on the proper-
ties of the particle surface. Addition of surfactant may cause high
or low pH value, which result in a lower surface charge and a
weaker repulsion between particles. Therefore, this action leads
to a stronger coagulation [29].
Yimin et al. [81] developed a classic theory of Brownian motion
and the Diffusion Limited Aggregation (DLA) model for random
movement of suspended nanoparticles. This theory does not
describe the experimentally determined thermal conductivity sat-
isfactorily, however, the dependence of this characteristic on tem-
perature is also mentioned in their work.
The effect of particle surface charge and IEP is also exposed in
varying thermal conductivity experiment sets conducted by Lee
et al. [53]. They proved that the colloidal particles get more stable
and enhance thermal conductivity of nanouid when the pH of
the solution goes far from the IEP of particles. Moreover, research,
demonstrated that there is a priority factor in controlling nano-
uid aggregation by surface charge. They proposed a new inter-
pretation of the charged sites and ion densities in the diffuse
layer as the number and efciency of channels for phonon trans-
port, respectively. The same theory was accepted by Wang et al.
[57,29,21].
In conclusion, understanding the mechanism and magnitude of
effective thermal conductivity (k
eff
) of nano-scale colloidal suspen-
sions still continues to be an active research area. A summary of
experiments and proposed theories is given in Table 7.
5.1.1. Analytical model
Even though many models have been developed to predict the
nanouid thermal conductivity, all presented models can be classi-
ed into two general groups, as follows:
i. static models such as those of Maxwell and Hamilton
Crosser, which presume immobile nanoparticles in the host
uid in which conduction-based models predict the thermal
transport properties, and
ii. dynamic models, which are based on the idea that nanopar-
ticles have sideways, arbitrary movement in the uid. The
particle motion is believed to be responsible for energy
transport directly through collision between nanoparticles
or indirectly through micro liquid convection that enhances
the thermal energy transfer.
A simple relationship suggested by Weber shows the thermal
conductivity of liquids with accuracy usually within 15% and the
equation is:
k 3:59 10
9
C
p
q
q
M
_ _1
3
4
This formula has been developed previously to calculate the ther-
mal conductivity of nanouids [28], as:
k
nf
3:59 10
9
C
p;nf
q
nf
q
nf
M
nf
_ _1
3
5
Table 7
Summary of different tests that conduct to a theory.
Investigator Nanouid type Concentration
(%)
Thermal conductivity
enhancement
Theory
Karthikeyan
et al. [98]
CuO
(8 nm) + DW + EG
1 vol.% 31.6%
54%
Nanoparticle size, polydispersity, particle clustering and the volume fraction of
particles
Kwak et al. [102] CuO (10
30 nm) + EG
<0.002 vol.% Thermal conductivity enhancement due to viscosity increase
Lee et al. [53] CuO
(25 nm) + DW
0.3 vol.% 3 times increasing Setting pH far from isoelectric point getting 3 times effective thermal
conductivity and better dispersion
pH from 8 to 3
Wang et al. [57] Al
2
O
3
(15
50 nm) + DW
0.4 wt.% 13% pH control and adding surfactant far from isoelectric point
Cu(25
60 nm) + DW
15%
Li et al. [21] Cu + DW 0.1 wt.% 10.7% pH control and adding surfactant far from isoelectric point
Zhu et al. [22] Graphite
(106 nm) + DW
2.0 vol.% 34% pH control and adding surfactant far from isoelectric point
Wei et al. [49] Cu
2
O
(200.5 nm) + DW
0.01
0.05 vol.%
24% Thermal conductivity can be controlled by either the synthesis parameters or
its temperature
3
4
5
By supposing well dispersed nanoparticles, the thermo-physical
properties of the particle uid mixture can be evaluated using
Eqs. (6)(8). Properties with subscript s are for nanoparticles
while without subscripts are for base uid
q
nf
1 Uq Uq
s
6
qC
p
nf
1 UqC
p
Uq
s
C
p;s
7
M
nf
1 UM UM
s
8
The effective thermal conductivity is dened as the ratio of the ther-
mal conductivity of nanouid to that of the base uid. Therefore,
from Eqs. (4) and (5), the generalized form of relative thermal con-
ductivity can be given as:
k
nf
k

C
p;nf
C
p
_ _
a
q
nf
q
_ _
b
M
M
nf
_ _
c
9
In which a, b and c should be dened from experiments and are
equal to 0.023, 1.358 and 0.126, respectively for Al
2
O
3
/water
nanouids. Yimin et al. [81,103] proposed a formula for the effec-
tive thermal conductivity in conjugate with Brownian motion and
DLA theory as follows:
k
eff
k
f
k
p
2k
f
2Uk
f
k
p
k
p
2k
f
Uk
f
k
p

q
p
UC
p
2k
f
k
B
T
3pr
c
g
10
where k
f
, k
p
, q, Cp, T, g, U and r
c
are the actual thermal conductivity
of the base liquid and the nanoparticle, density, specic heat, tem-
perature (K), viscosity, volume concentration and the radius of the
cluster, respectively.
Meibodi et al. [104] described the model of thermal barrier
resistance and claimed that the most important factor for thermal
conductivity enhancement of nanouids might be MFP (Mean Free
Path), the distance between particles that can be calculated by
Brownian approach for very low nanoparticle volume fractions
and by effective diameter for micro-particles and/or high particle
volume fractions [104]. The schematic of this model is presented
in Fig. 13. Likewise, Hadjov et al. [55] assumed a ux jump and a
discontinuity between the inclusion and the matrix as well which
is called the thermal conductive interface. This assumption con-
icts with the previous model. They stated that the thermal con-
ductivity depends strongly on the morphology via the kind of
particle packing.
5.1.2. Measurement apparatus
The measurement of thermal conductivity of liquids is a chal-
lenging task. In general, Fouriers law of heat conduction is
exploited for the measurement of thermal conductivity.
The thermal conductivity of nanouids can be measured by dif-
ferent methods, including transient hot-wire (THW, also called
transient line heat source method) which are further categorized
into a basic transient hot-wire method, insulated wire method
and liquid metal wire method [5,108,109]. A detailed explanation
of the transient hot wire method in measuring the thermal conduc-
tivity of nanouids is given by Lee et al. [100]. Also, a summary of
the apparatus utilized for thermophysical properties by different
investigators is given in Table 9.
Among the stated techniques, the steady state parallel plate
method used by Wang et al. [80] seems to be least affected by
the particle sedimentation for their thickness of the loaded sample
uid is less than one mm. The sedimentation of nanouids can af-
fect the THW method used by Lee et al. [100]. An increment of the
temperature gradient within the vertical hot wire may be caused
by non-homogeneous nanoparticle concentration which might be
a source of measurement errors. This is also true for the
temperature oscillation technique by Das et al. [101] where the
Fig. 13. Schematic modeling of a homogeneous suspension containing spherical mono-sized particle with resistance model [104].
Table 8
Most applicable models for viscosity of nanouids [31].
No. Model Equation Remarks
1 Einstein
model
l
r

l
nf
l
1 gU
Applicable when U< 1% and when there is no interaction between the particles
2 Batchelor
model
l
r

l
nf
l
1 gU gU
2
Brownian motion of the nanoparticles and the interaction between them was taken into account in this
model and it is an extension of the Einstein model
3 Ward model
l
r

l
nf
l
1 gU gU
2
gU
3
An exponential model for U up to 35%
4 Renewed
Ward model
l
r

l
nf
l
1 gUe gUe
2
gUe
3
The inuence of liquid layering is taken into account to calculate U, U is replaced by U
e
thermocouple that measures the uid temperature oscillation lies
in the upper half of the nanouid chamber [59].
The 3x method is exploited by the small number of investiga-
tors; a thin lm heater is powered by an AC power source so there
is an oscillating heat transfer rate through the material, whose
thermal conductivity is to be measured. The three omega wire
method may be suitable to measure temperature-dependent ther-
mal conductivity [112].
5.2. Viscosity
The viscosity is the other vital factor in designing dynamic
nanouid for heat transfer applications as the pressure drop and
the resulting pumping power depend on it. In comparison with
the works carried out on thermal conductivity of nanouids, only
a few studies have been reported on the rheological behavior of
nanouids. Kang et al. [113] measured the viscosities of UDD
(ultradispersed diamond)/ethylene glycol, silver/water, and silica/
water nanouids and found the viscosity increment of 50%, 30%
and 20% for UDD/EG, silver/water and silica/water nanouids at
volume concentrations of 1%, 2% and 3%, respectively. Prasher
et al. [114] showed the independence of the viscosity to shear rate
for alumina/propylene glycol (PG) nanouids. This proves the
Newtonian nature of nanouid and viscosity growth by increasing
nanoparticle volume concentration. They found a 30% increase in
viscosity at 3% volume concentration and related this phenomenon
to aggregation of the nanoparticles in the nanouid with the size of
the aggregates of around three times the size of the individual
nanoparticles. The effect due to temperature and particle volume
concentration on the dynamic viscosity for an Al
2
O
3
/water nano-
uid has been experimentally investigated by Nguyen et al.
[115]. They found a signicant increase in nanouid dynamic vis-
cosity with particle volume concentration and an obvious decline
with a temperature increase. In their experiments, another factor
emerged, which is known as a critical temperature. Beyond that
temperature, the properties of particle suspension seem to be var-
ied, which leads to a hysteresis phenomenon. This fact has raised
serious doubts about the reliability of using nanouids for heat
transfer enhancement purposes. Murshed et al. [48] measured rel-
ative viscosity data for TiO
2
and Al
2
O
3
/water-based nanouids, and
reported a maximum increase of 80% at 4% and 5% particle volume
fraction, respectively. Similar increments in viscosity were re-
ported earlier by Masuda et al. [116] and Wang et al. [80]. Xie
et al. [117] ran experiments for nanoparticles dispersed in organic
uids like EG and showed that the increase for the viscosity of
Al
2
O
3
/EG nanouids is smaller than those of water based suspen-
sions, indicating the important effect of the base uid on nanouid
viscosity. They also studied the dependence of the viscosity on the
pH values. But when the pH value is close to PZC, it causes coagu-
lation of nanoparticles and therefore a viscosity increment. Namb-
uru et al. [118] presented some experiments for rheological
behavior of CuO/EG and water based nanouid over temperatures
ranging from 35 C to 50 C. Kwak and Kim [102] demonstrated
that large thermal conductivity enhancements are accompanied
by sharp viscosity increases at low (<1%) nanoparticle volume frac-
tions, which is a logical consequence of aggregation effects.
There are theoretical models to calculate the ratio of effective
viscosity of nanouids to that of base uid. A few of the frequently
used models [119,120] which have their limitations and applica-
tions are listed in Table 8. Murshed et al. [48] showed that the
measured viscosities of Al
2
O
3
/water and TiO
2
/water nanouids
were under predicted by the KriegerDougherty (KD) model. In
contrast, Chen et al. [121] showed that the viscosity of nanouids
can be predicted by the KriegerDougherty model if the volume
concentration is replaced by the volume concentration of nanopar-
ticle aggregates. In relation to their experiments, for spherical
nanoparticles, an aggregate size of approximately three times the
primary nanoparticle size gives the best t with the experimental
data. Chen et al. [121] proposed a categorization for the rheological
behavior of nanouids into four groups as (i) dilute nanouids
(with volume concentration less than 0.1%) whose viscosity ts
the Einstein equation and there is no visible shear-thinning behav-
ior; (ii) semi-dilute nanouids (with 0.15% volume concentration)
with aggregation of nanoparticles, whose viscosity ts the modi-
ed KD equation and there is no obvious shear-thinning behavior;
(iii) semi-concentrated nanouids (with 510% volume concentra-
tion) with aggregation of nanoparticles whose viscosity ts the
modied KD equation and there is noticeable shear-thinning
behavior; and (iv) concentrated nanouids (with volume concen-
tration more than 10%) with interpenetration of aggregation
and this is out of the normal concentration range of nanouids
[31,63].
There is a concern about different experimental results for vis-
cosity as shown by Pak and Cho [122] for 13 nm particle-size data
are much higher than all other results while Wang et al. [80] data
are relatively low. Nguyen et al. [123] claimed that it is compli-
cated to sketch any certain clarication about such results, apart
from saying that this interesting behavior may be related to vari-
ous factors such as different nanouid preparation methods.
5.2.1. Analytical models
In the case of aqueous nanouid preparation, viscosity data col-
lection should be accompanied with distilled water in which mea-
sured data have to be compared by the following correlation [124]:
Table 9
Equipments used for characteristic measurements.
Investigator Nanouid Thermal conductivity Viscosity Specic heat Density Surface tension
[132] CuO + CT
AB
THW (Assael et al., 2004) Rheometer with coaxial cylinders
(HaakeRheostress RS600)
DSC (Setaram
C80D)
Weighting a known
volume of nanouid
Pendant drop (KSV
CAM 200)
Al
2
O
3
CNT
TiO
2
[31] Al
2
O
3
+ DW KD2 Pro (Decagon
Devices, Inc., USA)
Brookeld cone and plate viscometer
(LVDV-I PRIME C/P)

[12] TiO
2
+ DW THW Bohlin rotational rheometer
[57] Al
2
O
3
+ DW TPS Capillary viscometer
Cu + DW
[49] Cu
2
O + DW KD2 system
[133] KD2 system Bohlin CVO rheometer
[134] KD2 pro Ubbeholder capillary viscometer (Fisher
Scientic)
l
bf
10
4
exp
1:12646 0:039638 T
1 0:00729769 T
_ _
11
where T (K) is the uid temperature and l in cP [123,125].
There are a few theoretical formulas that can be used to approx-
imate nanouid viscosities. Almost all such formulas have been de-
rived from the original work of Einstein (1906) which is based on
the assumption of a linearly viscous uid containing a dilute, sus-
pension of spherical particles. The energy dissipated by the uid
ow around a single particle was calculated by Einstein in this arti-
cle, and associated with that the work required moving this parti-
cle relatively to the surrounding uid, he obtained:
l
r

l
nf
l
bf
1 2:5U 12
Einsteins formula was found to be applicable to relatively low par-
ticle volume fractions, U< 2%. Beyond this value, it underestimates
the effective viscosity of the resulting mixture as it ignores particle
particle interaction. Since the publication of Einsteins work, many
researchers have contributed to the correction of his formula.
Based on the assumption of a very slow ow, inertial effect in the
uid has been considered negligible by the authors in most of these
works, which technicality makes linearity for the equations of mo-
tion. Two factors were frequently employed to correct Einsteins
result: the rst is that the particles may not be small, and the sec-
ond is that the structure of the particles within the continuous
phase may also affect the viscosity of the mixture. A brief review
of the relevant works is given below. There exists an extended Ein-
steins formula for use with moderate particle concentrations pro-
posed by Brinkman [126], as follows:
l
nf
l
bf
1
1 U
2:5
13
Frankel and Acrivos [127] proposed the following formula:
l
nf
l
bf
9
8
U=U
m
1=3
1 U=U
m
1=3
_ _
14
where U
m
is the experimental value for the maximum particle vol-
ume fraction. Alternatively, Lundgren [128] has offered the subse-
quent equation as a Taylor series in U:
l
nf
l
bf
1 2:5U
25
4
U
2
0U
3
15
Clearly, if the terms O (U
2
) or higher are neglected, the above for-
mula reduces to that of Einstein. Batchelor [129], in his notional
analysis, considered the effect due to the Brownian motion of parti-
cles on the bulk stress of an approximately isotropic suspension of
rigid and spherical particles. He proposed the following formula:
l
nf
l
bf
1 2:5U6:5U
2
16
Graham [130] has proposed the following formula as a generalized
form of the Frankel and Acrivos [127] formula that agrees well with
Einsteins for small U:
l
nf
l
bf
1 2:5U4:5
1
h
d
P
_ _
2
h
d
P
_ _
1
h
d
P
_ _
2
_
_
_
_ 17
where d
p
is the particle radius and h is the inter-particle spacing.
In fact, practically none of the above mentioned models can de-
scribe the viscosity of nanouids exactly in a wide range of the
nanoparticle volume fractions. Nguyen et al. [115] found that the
conditional formula, including Einsteins formula and the ones pro-
posed by Brinkman[126], Lundgren [128] and Batchelor had all
underestimated the nanouids viscosity even for a relatively low
particle fraction. They also suggested two correlations for Al
2
O
3
aqueous nanouids consisting of 47 and 36 nm nanoparticles as
follows:
l
nf
l
bf
0:904e
0:483U
for 47 nm Al
2
O
3
18
l
nf
l
bf
1 0:025U0:015U
2
for 36 nm Al
2
O
3
19
Lee [73] synthesized aqueous nanouids containing low volume
concentrations of Al
2
O
3
nanoparticles in the 0.010.3 volume per-
centage. His viscosity measurements showed that there was a con-
siderable decline with temperature increase. In addition, the
measured viscosities of the mentioned nanouids showed a nonlin-
ear relation with the concentration even in the low volume concen-
tration (0.010.3%) range, in contrast with the Einstein model which
predicts a linear relation and therefore it severely underestimates
the viscosity.
The temperature as another important factor other than the vol-
ume fraction inuences the viscosity of nanouids. There are lim-
ited researches about the dependence of viscosity on temperature;
whereas it is interesting to observe that for particle concentrations
lower than 4%, all tested nanouids exhibit almost constant rela-
tive viscosities that are independent of temperature. Between the
two aluminawater nanouids, just a slight difference in the levels
of relative viscosity arises. Such differences, however, become
much more visible at higher particle fractions, e.g. for 7% and 9%,
where we can observe not only a temperature dependence, but a
particle-size-dependence as well. The effect of particle-size ap-
pears somewhat paradoxical: for a particle fraction of 7% for exam-
ple, viscosities for 36 nm are slightly higher than those of 47 nm;
while for a 9% volume fraction, the reverse behavior is found.
For Al
2
O
3
water and CuOwater nanouids, the following for-
mulas have been proposed to compute the dynamic viscosity for
all three nanouids and particle concentrations tested [123]:
l
nf
l
bf
1:1250 0:0007 T 20
l
nf
l
bf
2:1275 0:0215 T 0:0002 T
2
21
There are also other correlations proposed for dependence of viscos-
ity to temperature by investigators. The correlation of Kulkarni et al.
[131] related the viscosity of CuOwater nanouids with the tem-
perature in the range of 550 C:
lnl
s
A
1
T
_ _
B 22
Here A and B are the functions of volume percentage U. Since this
correlation is obtained for an aqueous solution, it is not valid for
subzero temperature range. Praveen [132] derived an exponential
model for CuOwater nanouids with base uid of 60:40 (by
weight) ethylene glycol and water mixture as follows:
logl
s
Ae
BT
23
where l
s
is the CuO-water nanouid viscosity in (cP), T is the tem-
perature in K and A, B are functions of particle volume percentage
U. It should be noted that some discrepancy appeared among a
few studies on the rheology of nanouids [114,133] which showed
the Newtonian behavior of nanouids while others observed
noticeable non-Newtonian behavior [134]. Prashers results [114]
depicted that the normalized shear viscosity has a linear relation-
ship with the nanoparticle volume fractions, whereas investigations
of Nguyen et al. [115] for particle volume fractions lower than 4%,
the viscosity of CuOwater is approximately the same as that of
the aluminawater nanouids considered earlier, though for higher
particle loading, the increase in viscosity with respect to particle
concentration is clearly much greater. Such great values of viscosity
may result from the intrinsic molecular structure of the mixture it-
self and the particular chemical dispersing agents used.
These discrepancies between investigations might be due to dif-
ferent volume concentration, type of nanoparticles, chemical prop-
erties of base uids and nanoparticle preparation method. As
shown by Ko et al. [135], nanouids prepared by the acid treat-
ment (TCNT) have much lower viscosity than the ones made with
surfactant (PCNT). Also, we can see that the use of the Batchelor
[129] and Brinkman [126] formulas for CuOwater nanouid is
inappropriate. Therefore, the following correlation was proposed
for computing CuOwater viscosity:
l
r
1:475 0:319U0:051U
2
0:009U
3
24
Fullman [136] and Noni et al. [137] derived a formula from the
model of the mean free path for relative viscosity of suspensions
of solid particles in a liquid medium as:
l
r
1 a
1
k
n
25
where the constants a and n depend on material characteristics
while the mean free path (k) is dened as:
k
2
3
d
1 U
U
26
Substituting Eq. (26) in Eq. (25) and for a given particle size,
l
r
1 b
U
1 U
_ _
n
27
This model (Eq. (27)) which considers the mean free path is used to
predict the effective viscosity of Al
2
O
3
/water nanouids [31].
5.3. Density
The key parameters for assessing the heat transfer merits of
nanouids are their thermo physical properties. The mixture prop-
erties of nanouids are normally expressed in volume percent U
while the loading analysis was obtained in weight percent (wt).
The conversion between the weight and volume fractions is done
through the bulk density q
p
U
wq
f
q
P
1 w wq
f
28
5.4. Specic heat
Thermal conductivity studies have been the main focus of nano-
uid investigations, and certain efforts have also been done on the
viscosity of nanouids. The density has been reported to be consis-
tent with the mixing theory. However, the specic heat Cp of nano-
uids has received very little attention [141].
The heat capacity of the nanouid is incorporated into the
energy equation, so it is important to be able to calculate it accu-
rately. Most researchers use one of two correlations, which are in
Eqs. (29) and (30), The rst model is based on the volume fraction
whereas the second model is based on heat capacity concept. Both
models are often cited by a number of researchers for calculating
the specic heat of nanouid.
Pak and Cho model [122]
c 1 Uc
bf
Uc
p
29
and Xuan and Roetzel model [142].
c
1 Uqc
bf
Uqc
p
q
30
Where c is the heat capacity, U is the volume fraction of nanopar-
ticles, and q is the density. The subscript bf refers to properties of
the base uid, and the subscript p refers to properties of the nano-
particles. Eq. (29) is simply the rule of mixtures applied to heat
capacity; while Eq. (30) is an altered form. It clearly shows that
the specic heat decreased with increasing nanoparticle concentra-
tions [10,141].
In some investigations, the inuence of nanoparticles on the
specic heat of nanouid seems too small to be considered due
to the low nanoparticle volume fraction.
6. Conclusion
The present outlook is the rst and inclusive review on the re-
search progress made in the stability of the nanouids. Nanouid
preparation with a single and two-step method would denitely
affect the stability as the two-step method needs a higher nanopar-
ticle concentration to equalize the heat transfer enhancement
reached by single step. A higher concentration causes more sedi-
mentation. However, unfortunately, the single step method is not
industrialized in a wide range so experiments are mostly con-
ducted by two-step method. Therefore, higher costs and lower sta-
bility are inevitable.
Major factors inuencing the extraordinary enhancement of
heat transfer are listed as chemical composition of the solid parti-
cle and the baseuid, particle source and concentration, particle
shape and size, surfactants, temperature, pH value (surface
charge), monodispersity, IEP and elapsed time.
Comparing several studies in the literature, some discrepancies
appear among the results. At this moment, it cannot be clearly ex-
plained why incongruities take place among the measurements of
the nanouid characteristics such as thermal conductivity and vis-
cosity. However, at least we are able to mention that different
sources of measurement uncertainties such as sedimentation and
aggregation of nanoparticle, lack of a standard for nanouid prep-
aration, different source of nanoparticle manufacturing, various
stabilization methods, and time duration between the nanouids
preparation and measurement in which cause the aggregate to
grow with time, could be the most important reasons for the dis-
persed data. Furthermore, the timing for the ultrasonic processes
such as horn processor or ultrasonic bath is not optimized properly
with respect to different nanoparticles and base uids.
There is also another important result regarding stability and
thermal conductivity that more stable nanouid does not necessar-
ily have more enhanced characteristics.
Three methods of homogenization are used by researchers and
bring about various results. It can be mentioned that different
nanoparticles need their own stability method. Sometimes, these
methods have to be combined together while in other cases just
one method would be adequate to obtain the preferred stability.
Surfactant selection in nanouid preparation has an important
role in improving heat transfer. Temperature is considered as a re-
stricted factor in case of nanouid application for exploiting at the
high temperatures. Likewise, the optimum percentage of surfac-
tant should be considered as a factor in stable nanouid prepara-
tion as well.
Ultrasonication method, particularly the more effective one
named horn ultrasonic, attracts much attention for its short timing
preparation among the other homogenization techniques. It has to
be considered that if a critical time is exceeded, it may have an in-
verse effect and cause agglomeration and speedy sedimentation of
nanoparticles.
The pH control, which has an important role in stability control,
places the IEP of the suspension, far from the PZC in order to avoid
coagulation and instability. It should be taking into account that
acidic or alkaline pH is corrosive to metals. Therefore, it can lead
to damage to the piping and instrumentation in long term
applications.
In support of stability measurement, it is better to examine at
least three different tests with the different stability measurement
apparatus to come out with a reasonable result regarding stability.
Furthermore, reproducibility is important in experiments so the
samples have to be run at least three times to meet the require-
ments of uncertainties.
Among the characteristics discussed in the literature, thermal
conductivity and viscosity have a major role in nanouid charac-
terization. To reach the best hypothesis for thermal conductivity
enhancement, different theories were discussed such as Brownian
motion, interfacial layer and aggregation of particles. Additionally,
some researchers discussed nanouid as a two-phase ow mixture
and utilized certain formulas of two-phase mixtures for properties
of nanouid. However, still none of the proposed theories can ex-
actly predict the improvement of thermal conductivity of nano-
uid. Although there are some results regarding the viscosity of
nanouids, none is usable across a wide range of volume fractions
of nano particles so further experiments are required.
Systematic experiments are needed that will show the effect of
the stability on heat transfer mechanism and characteristics
enhancement in stationary condition. Refer to other thermophysi-
cal properties, including, specic heat and density, a few research-
ers conducted tests as the correlations satised the result of
experiments.
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A Review of Nanofluid Stability Properties and Characterization in Stationary Conditions

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A Review of Nanofluid Stability Properties and Characterization in Stationary Conditions

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A review of nanouid stability properties and characterization

, R. Saidur, H.S.C. Metselaar

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from water and create a negatively charged surface [107]. In

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