20

Chapter 2
LITERATURE REVIEW
2.1 Review on Making Of Nanofluids
Several studies, including the earliest investigations of
nanofluids, used a two-step method in which nanoparticles or
nanotubes are first produced as a dry powder and then
dispersed into a fluid in a second processing step. In contrast,
the one-step method entails the synthesis of nanoparticles
directly in the heat transfer fluid. The two-step and one-step
methods are discussed in more detail in sections 2.1.1 and
2.1.2 respectively.
2.1.1 Two Step Process
The preparation of nanofluids begins by direct mixing of the
base fluid with the nanomaterials. In the first step,
nanomaterials are synthesized and obtained as powders, which
are then introduced to the base fluid in a second step.
Nanoparticles can be produced from several processes [11,12 ]
which can be categorized into one of five general synthetic
methods. These five methods are: (i) transition metal salt
reduction [13,14], (ii) thermal decomposition and photochemical
methods [15], (iii) ligand reduction and displacement from
organometallics [16] (iv) metal vapor synthesis, and (v)
electrochemical synthesis [17]. Transition-metal nanoclusters
are only kinetically stable because the formation of the bulk
metal is its thermodynamic minimum. Therefore, nanoclusters
21
that are freely dissolved in solution must be stabilized in a way
that prevents the nanoclusters from coalescing, because such
agglomeration would eventually lead to the formation of the
thermodynamically favored bulk metal [18].
Bonnemann et al [16] developed a method for the production of
very small (< 2 nm) and stable nanoparticles via chemical
reduction pathways, which might be suitable for application in
nanofluid synthesis. Organoaluminum compounds have been
used for the reductive stabilization of mono and bi-metallic
nanoparticles. Triorganoaluminum compounds were employed
as both the reducing agent and colloid stabilizer, which lead to
the formation of an organo-metallic colloidal protecting shell
around the particles [19,20 ]. This modification of the Al-
organic protecting shell leaves the particle size stable.
Silver nanoparticles are one of the most widely studied
nanomaterials because they exhibit unusual optical, electronic
and chemical properties, which depend on their size and shape
[21,22,23]. Silver is also one of the most thermally conductive
metals and its use in cooling applications would be interesting.
Besides silver nanoparticles, Xuan et al. [24] have used
commercially obtained Cu nanoparticles to prepare nanofluids
in both water and transformer oil by sonication in the presence
of stabilizers. Similarly, Kim et al. [25] prepared nanofluids
consisting of commercially obtained CuO nanoparticles in
ethylene glycol by sonication without stabilizers. The optimum
22
duration of sonication was found to be 9 hours and the average
nanoparticle size was 60 nm.
The two-step process is commonly used for the synthesis of
carbon nanotube based nanofluids. Single-wall carbon
nanotubes (SWCNTs) and Multi-walled carbon nanotubes
(MWCNTs) are cylindrical allotropes of carbon. SWCNTs consist
of a single cylinder of graphene, while MWCNTs contain multiple
graphene cylinders nesting within each other [26]. The carbon
nanotubes are usually produced by a pyrolysis method and then
suspended in a base fluid with or without the use of a
surfactant.
Some authors suggested that the two-step process works well
only for nanofluids containing oxide nanoparticles dispersed in
de-ionized water as opposed to those containing heavier metallic
nanoparticles [27,28,29]. Since nanopowders can be obtained
commercially in large quantities, some economic advantage
exists in using two-step synthesis methods that rely on the use
of such powders.
2.1.2 One step process
Few methods exist for the preparation of nanofluids through a
one step process. These methods include the thermal
decomposition of an organometallic precursor in the presence of
a stabilizer [30], chemical reduction [31], and polyol synthesis
[32, 33].
23
The polyol method is one of the most well known pathways to
noble metal nanoparticles [34, 35, 36]. In the polyol process, a
metal precursor is dissolved in a liquid polyol (usually ethylene
glycol), after which the experimental conditions are adjusted to
achieve the reduction of the metallic precursor by the polyol,
followed by atomic metal nucleation and metal particle growth
[37].
The direct-evaporation technique was developed by Choi et al
[28]. It consists of a cylinder containing a fluid which is rotated.
In the middle of the cylinder, a source material is vaporized. The
vapour condenses once it comes into contact with the cooled
liquid (Figure 2.1). The drawbacks of this technique however,
are that the use of low vapour pressure liquids are essential and
only limited quantities can be produced.
Various single-step chemical synthesis techniques can also be
employed to produce nanofluids. For example, Brust and co-
workers [36] developed a technique for producing metallic
nanoparticles in various solvents by the reduction of metal salts
to produce colloidal suspensions for a wide range of applications,
including studies of thermal transport. Excellent control of size
and very narrow size distributions can be obtained by using
such methods [2].
A submerged arc nanoparticle synthesis system (SANSS) was
developed to prepare CuO nanoparticles dispersed uniformly in
a dielectric liquid (deionized water). The method successfully
24
produced a stable nanofluid [37]. In principle, a pure copper rod
is submerged in a dielectric liquid in a vacuum chamber. A
suitable electric power source is used to produce an arc between
6000 - 12000 C which melts and vaporizes the metal rod in the
region where the arc is generated. At the same time, the
deionized water is also vaporized by the arc. The vaporized
metal undergoes nucleation, growth and condensation resulting
in nanoparticles dispersed in deionized water. Nanofluids
containing CuO particles of size 49.1 38.9 nm were obtained
[37].

Cooling System
Liquid
Resistively Heated
Crucible

Figure 2.1 One-step nanofluid production system (Choi
et.al. [28])

2.2 Review on Thermophysical Properties of Nanofluids
The thermal conductivity measurement of nanofluids was the
main focus in the early stages of nanofluid research.
Considering the application of heat transfer fluids, heat transfer
coefficients of nanofluids in flow condition is also very
25
important. The important properties other than thermal
conductivity that affect the heat transfer coefficients are density,
heat capacity and viscosity of dispersions (see Fig.2.2 to Fig.
2.5). Since the nanoparticle concentration in nanofluids usually
are very low (<1 vol%), the particle effect on the density and heat
capacity of the dispersions is not significant. However, due to
the small particle size, the nanoparticle effect on the viscosity of
the dispersions might be remarkable, especially for nanotube or
other high or low aspect ratio nanoparticle dispersions. Some of
the properties of nanoparticles & base fluids are listed in Table
2.1 useful for assessing the nanofluid properties.
Table.2.1 Thermophysical properties of Nanoparticle & base
fluids
Property Water Ethylene
glycol
Cu Al2O3 CuO Ti O2

C ( J/kg K
( kg/m
3
)
k (W/m

K)
(m
2
/s)

4179
997.1
0.605
1.47

2415
1111
0.252
93

385
8933
400
1163

765
3970
40
1317

535.6
6500
20
57.45

686.2
4250
8.9538
30.7

2.3 Density
The density of a nanofluid can be calculated by using mass
balance as

p f nf
) (1 | | + =
(2.1)
For typical nanofluids with nanoparticles at a value of volume
fraction less than 1%, a change of less than 5% in the fluid
density is expected (see Fig.2.2)
26
2.4 Specific Heat
The specific heat of a nanofluid can be calculated by using
energy balance as

nf
p p f
nf
C C

| + |
=
f
) - 1 (
C
(2.2)
Using these equations, one can predict that small decreases in
specific heat will typically result when solid particles are
dispersed in liquids. For example, adding 3 vol% Al2O3 to water
would be predicted to decrease the specific heat by
approximately 8% compared with that of water alone (see
Fig.2.3). The simple equations above may need to be modified if
nanoparticles are found to exhibit a size dependent specific heat.
2.5 Viscosity
The rheological and aggregation behaviors of spherical
nanoparticles in liquid suspensions have been studied quite
extensively (Meitz, Yen et al. [38]). They suggested at very low
volume fraction (| <=0.03), the shear viscosity of a hard sphere
suspension can be predicted by Einstein formula
) 5 . 2 1 (
f nf
| + = (2.3)
This equation was extended by Brinkman [39] as

5 . 2
f nf
) 1 (
1
|

=
(2.4)

The experimental results for the viscosity of copper nanofluids
from Xuans group [24] showed good agreement with this model.
27
Batchelor [40] gave another formula to calculate the viscosity of
particle suspensions (| <=0.01)

2
f
nf
2 . 6 5 . 2 1 | |

+ + =
(2.5)

However, most of the work was focused on concentrated
nanoparticle dispersions. Das sk et al. [41] conducted
experiments on 1~4 vol% Al2O3 nanoparticles (38nm) in water
dispersions. They reported nanofluids showed Newtonian
behavior and viscosities were higher than water. They also
suggested for many of the spherical nanoparticles dispersions,
the volume fractions of nanoparticle seems low enough to apply
Einstein or Batchelors equations to predict the increase of the
viscosity in dispersions.
The data reported by Chang et al.[42] in CuO nanofluids also
indicted that the viscosity of nanofluids increased with decrease
of particle size due to large specific area and electrostatic forces.
Wang et al [43] measured the viscosities of Al2O3 in water
nanoparticle dispersions which were created by different
dispersing methods. An increase between 20% and 30% was
reported to 3vol%. They indicated that the particle concentration,
size and particle shape, the aggregation structure of

28



Figure 2.2 Effect Nanofluids density with volume fraction


29

Figure 2.3 Effect of Nanofluids specific heat with volume fraction


30



Figure 2.4 Effect of Nanofluids Prandtl number with volume fraction


31



Figure. 2.5 Effect of Nanofluids thermal diffusivity with volume fraction
32

nanoparticles will also affect the rheological behaviors of particle
dispersions. They also gave a correlations as follows for Al2O3 +
water & EG and found to be nearer to experimental data as
shown in Fig.2.6.
For Al2O3 + water

1 3 . 7 123
2
+ + = | |
nf
(2.6)

For Al2O3 + Ethylene Glycol

1 0.19 - 306
2
+ = | |
nf
(2.7)
However, Pak & Cho [44] reported a three times higher viscosity
for Al2O3 (13nm) + water nanofluids that of water. The authors
suggested different dispersing techniques which can lead to
different particle or agglomerate size may be the reasons for this
large discrepancy. They also gave correlations for
For Al2O3 + water
) 9 . 533 11 . 39 1 (
2
f nf
| | + + = (2.8)
For TiO2 + water
) 2 . 108 45 . 5 1 (
2
f nf
| | + + = (2.9)
Chen et.al.[45] also gave correlation for the viscosity of TiO2 +
Ethylene glycol as follows
For TiO2 + Ethylene glycol
( )
2
) 6 . 10 6 . 10 1 ( | | + + =
f nf
(2.10)
33
For Cu + water
) 72 . 468 645 . 3 995 . 0 (
2
| | + + =
f nf
(2.11)

Tseng and Li [46] correlation for viscosity of TiO2 + water as
follows

|

98 . 35
f nf
e 47 . 13 =
(2.12)

Kulkarni et.al.[ 47] presented the correlation for the viscosity of
CuO + water as follows
B
T
A
nf

|
.
|

\
|
=
1
ln (2.13)
3 . 1078 15857 20587
2
+ + = | | A
8715 . 2 548 . 53 12 . 107
2
+ + = | | B
In the present work the above equations are used wherever
necessary and found to be nearer to experimental data available
in the literature.
2.6 Thermal Conductivity of Nanofluids
In this section the measurement of thermal conductivity of the
nanofluids is reviewed and important factors are discussed. The
possible mechanisms are explained for the high thermal
conductivity of nanofluids is presented in the following sections.
34



Figure 2.6 Effect of Nanofluids viscosity with volume fraction
35
2.6.1 Metallic nanoparticle dispersions
Choi et.al [48] pioneered the work in the nanofluids by dispersing
nanometer sized particles into liquids. They suggested that
compared with the suspension of larger particles, nanoparticles
can be kept in dispersions for much longer time. Because
nanoparticles are so small, they may act like macromolecules in
solution, dramatically reducing erosion and clogging and their
larger surface areas improve heat transfer. After that, numerous
experimental results have been reported and this concept has been
proved.
Enhanced thermal conductivities have been reported for metal
nanoparticle dispersions by different research groups. The metals
applied in dispersion are gold, sliver, copper, iron and aluminum.
Eastman et.al [49] reported that copper nanoparticles dramatically
increased the thermal conductivity of base fluid, ethylene glycol
(EG). The effective thermal conductivity of nanofluids with 0.3vol%
of copper nanoparticle (~10 nm) was 40% higher than that of pure
EG when thioglycolic acid was used as dispersing agent. The
nanoparticle dispersion without dispersant in it had a much lower
increase ratio (~ 5%) compared to an acid containing dispersion
with same particle loading (0.3 vol%). They also suggested Aging of
the dispersion can decrease the effective thermal conductivity of
36
the nanofluids. The authors suggested that particle size is an
important factor for the effective thermal conductivity of nanofluids.
Another work on copper nanoparticle in EG dispersions was done
by Asseal et.al [50]. The nanoparticle applied in their work had a
mean diameter of 10 nm, but containing agglomerates with sizes
greater than 50 nm. With 0.5 vol% of copper nanoparticles, the
effective thermal conductivity of EG increased 3.5%. They
suggested result is much lower than the one in Eastmans work
which may be caused by the agglomerates in the dispersions.
Li and Xuan [51] studied the particle size effect on copper
nanoparticle in water dispersions. They found that the dispersion
containing smaller particles (20 nm) had a higher thermal
conductivity than that containing bigger particle (100 nm). For
example, by adding 2 vol% of 20 nm copper nanoparticles, the
effective thermal conductivity of the base fluid increased 23% while
the increase was around 15% for the case when 100 nm particle
were used. They suggested that larger surface area of smaller
particles may help for heat transfer occurring at the interface. They
also measured the thermal conductivity of Al2O3 nanoparticle
dispersion and compared it with that of copper nanofluids. They
found the thermal conductivity of 2 vol% Al2O3 nanofluids only had
a 6.3% increase compared with water while copper nanofluid
showed a 23% increase. It indicated that the thermal property of
37
the particle is one of the essential factors for the properties of
nanofluids.
Naked gold nanoparticle in the 10~20 nm range and monolayer
protected gold nanoparticle were prepared and dispersed in water
and toluene by Patel et.al [52]. The naked nanoparticle dispersion
showed thermal conductivity enhancement of 5%~21% in the
temperature range from 30~60
0
C at very low loading (0.00026
vol%) while the dispersion containing nanoparticle with a thiolate
covering showed 7% ~ 14% for a loading of 0.011 vol%. It is
surprising that the particle volume fraction of particle in this work
is one or more order magnitude lower than other cases mentioned
above, and the differences of the thermal conductivities of two
nanofluids at different temperatures may suggested surface action
can have a significant effect on the behavior of the nanofluids.
They also measured thermal conductivity of sliver nanoparticle in
the 60~80 nm range and compared with those of small gold
nanoparticle dispersions. It showed that even with higher particle
loading, the thermal conductivity of the larger particle dispersion
was still comparatively lower than small particle dispersions. This
result was consisted with other studies of the particle size effect.
Hong et.al [53] studied the thermal conductivity of iron
nanoparticle in EG dispersions. The mean diameter of the
nanoparticles was 10 nm, however, they existed in the dispersion
38
as clusters due to the absent of dispersing agent. The authors
observed that the thermal conductivity of Fe nanofluids was
increased nonlinearly up to 18% as volume fraction of the
nanoparticle was increased up to 0.55 vol%. Compared with copper
nanofluids reported by Eastman et.al [49], higher increase ratios of
thermal conductivities for Fe nanofluids indicated the dispersion of
high thermal conductivity materials is not always effective for
improving the thermal properties of nanofluids. The authors
suggested that the size of nanoparticle clusters or the
microstructure in the dispersion is an important factor for
improving the thermal conductivity of fluids.
2.6.2 Nonmetallic nanoparticle dispersions
Compared with metal nanoparticle dispersions, experimental work
started earlier for oxide nanoparticle dispersions. Al2O3 and CuO
are most common candidates being applied for nanofluids research.
Masuda et.al [27] reported a 30% thermal conductivity increase of
water by adding 4.3 vol% of Al2O3 (average diameter ~13 nm)
nanoparticles. However, in the research done by Lee et.al [54] the
same amount (4.3 vol%) of Al2O3 (average diameter ~ 38 nm)
nanoparticles only lead to 10% thermal conductivity increase of
water. It is another example to show the importance of particle size
on thermal conductivity of nanofluids. In addition to the smaller
size of particle, the nanofluids prepared by the Masuda [27] group
39
contained chemical dispersant which was supposed to modify the
surface of nanoparticles while there was no such chemical added
in Lees work. This result is consisting with the one observed in
Eastmans [49] work on the metallic nanoparticle dispersions.
Lee et.al [54] also studied another three systems, Al2O3 in EG, CuO
in water, CuO in EG. The Cuo particles they used in their work
were smaller than Al2O3 nanoparticles, which had an average
diameter of 24 nm. They found that in low volume fraction range
(upto 5 vol%), the thermal conductivity increase ratios moved
almost linearly with particle loading, but with different rates for
each system. It indicates thermal conductivity depends on both
dispersed particle and base fluids. For the systems using the same
base fluid, knf /kf in CuO nanoparticle was always higher than that
of Al2O3 nanofluids which may be caused by the smaller size of
CuO particles. The thermal conductivity increase ratios of EG
nanofluids were always higher than those of water based
nanofluids. It suggested that the increase ratio was dependent on
the thermal conductivity of the base fluids. There is another very
interesting study of thermal conductivities of Al2O3 nanoparticle
dispersions. Xie et.al [55] used a series of different alumina
nanoparticles with different particle size, specific area and
crystalline phase and dispersion them into distilled water, EG and
pump oil. The experimental results showed that adding
40
nanoparticles into base fluids led to increased thermal
conductivities much higher than calculated from conventional
models. The enhanced ratio of thermal conductivity increased with
particle loading. They found that the increase ratio of thermal
conductivity decreased with increase of pH value of aqueous
dispersions. For the dispersions containing the same nanoparticle,
the enhancement ratio of the thermal conductivity was reduced
with the thermal conductivity of the base fluid. This result was
consistent with Lees results [54]. For the dispersions based on the
same base fluid, the thermal conductivity increase ratio was
dependent on specific surface area or particle size of the
nanoparticles. There was an optimal specific surface area 25 m
2
g
-1

(corresponding particle size 60 nm) which gave highest increase
ratio for the thermal conductivity of nanofluids. The particle
smaller or larger than 60 nm gave lower thermal conductivities.
The authors explained this maximum by two factors: interface area
at which heat transfer happened, and reduced intrinsic thermal
conductivity due to the scattering of phonons at particle-particle
boundaries. When the particle size is much larger than mean free
path of phonon (35 nm), the first factor dominated. The thermal
conductivity of the nanofluid increases with decrease of the
particle size. When the particle size is close to mean free path of
phonon, the thermal conductivity of nanofluid may decreases with
41
decrease of particle size. In another work from the same group, the
thermal conductivity of Al2O3 nanoparticle in water dispersion was
reduced adding dispersing agents. This result was contrary to the
work done by Eastman et.al [49] on copper nanofluid.
Wang et.al [43] dispersed Al2O3 and CuO nanoparticles into four
base fluids: distilled water, engine oil, EG and pump oil. They
suggested for both nanoparticles, the thermal conductivities of
water based nanofluids were always lower than those of EG based
nanofluids which proved the results from other groups. However,
compared to Al2O3 nanoparticle dispersions, EG and engine oil
based nanofluids gave the higher increase ratios of thermal
conductivity than water and pump oil based nanofluids. It
indicated that when same particles were dispersed into base fluid,
thermal conductivity of the base fluid was not the only factor to
affect the increase ratio of thermal conductivity of nanofluid.
The temperature effect of thermal conductivity enhancement in
nanofluids has been presented by SK Das et.al [41].They studied
thermal properties of Al2O3 and CuO nanoparticles at different
temperatures. The particle sizes in their work were 38.4 nm for
Al2O3 nanoparticle and 29 nm for CuO nanoparticles. Their
measurement results confirmed that the level of thermal
conductivity increase at room temperature as observed by Lee et.al
[54]. A dramatically increase of thermal conductivity ratios has
42
been observed at high temperatures. A two or four fold increase in
thermal conductivity enhancement was reported over a small
temperature range 20 ~50
0
C. They suggested this makes
nanofluids more attractive as cooling fluids which were likely to
work at higher temperature than room temperature.
Li and Perterson [56] conducted an experimental investigation to
examine the effects of variations in the temperature and volume
fraction on the effective thermal conductivity of CuO and Al2O3
water suspensions. Results demonstrated that nanoparticle
material, diameter, volume fraction and bulk temperature have
significant effects on the thermal conductivity of the nanofluids.
They observed three times enhancement in Al2O3/water
suspension, increase in mean temperature from 27 to 34.7
o
C. They
presented correlations for Al2O3/ water and CuO/ water nanofluids
( )
462 . 0 ) 15 . 273 T ( 0187 . 0 764 . 0
k
k k
f
f nf
+ =

| ( Al2O3 + water) (2.14)

( )
307 . 0 ) 15 . 273 T ( 0179 . 0 761 . 3
k
k k
f
f nf
+ =

| (CuO + water) (2.15)

Thermal conductivity of SiC nanoparticle dispersions have been
studied by Xie et.al [57], 26 nm spherical SiC particle and 600 nm
cylindrical particles were dispersed in distilled water and EG. They
found the thermal conductivities of nanofluids are higher than
corresponding base fluids and increase ratio of thermal
conductivity increased linearly with particle volume fraction.
43
Surprisingly, the increase ratio for 26 nm particles in water
dispersions was lower than that of 600nm particle dispersions. The
thermal conductivity increase ratio for same particle dispersions
seemed independent of base fluids.
Beck, M.P et al.[58] conducted experiments on alumina
nanoparticles dispersed in ethylene glycol in temperature range of
298
0
K to 411
0
K. They also compared theoretically by taking shape
factor of n=3.4 in Hamilton and Crosser model and found to be in
good agreement with experimental results.
Kim et al.[59] conducted experiments on water and ethylene glycol
based nanofluids containing Al2O3, ZnO,TiO2 nanoparticles and
found variation with volume fraction and size dependence. They
also observed the effect of particle size change by laser ablation for
ZnO nanofluids and reported thermal conductivity is inversely
proportional to the particle size and dependence appears to be
linear.
Hong et al.[60] proposed TiO2, Al2O3, WO3 nanoparticles dispersed
in water and ethylene glycol and found large enhancement than
basefluids. They reported surface to volume ratio of nanoparticle is
a primary factor in determining the thermal conductivity of
nanofluids.
Murshed et al. [61] conducted both experimental and theoretical
study on thermal conductivity and viscosity of nanofluids. They
44
reported both thermal conductivity and viscosity of nanofluids
increase with volume fraction and also found strong dependent on
temperature. They proposed two static mechanisms based models
to predict thermal conductivity of nanofluids having spherical and
cylindrical nanoparticles considering particle size, interfacial layer
and volume fraction showed reasonably good agreement with
experimental data.
2.6.3 Carbon nanotube dispersions
The large intrinsic thermal conductivity of carbon based
nanostructures combined with their low densities compared with
metals, makes them attractive for use in nanofluids. Moreover,
high aspect ratio particle are more effective than low aspect ratio
ones and much more attractive than spherical particles [62]. All of
the reasons above lead to extensive studies on carbon nanotube
dispersions to improve heat transport recently.
The first article on thermal conductivity of nanofluids containing
carbon nanotubes was published by Choi et.al [62]. Multiwalled
carbon nanotubes were dispersed into oil with loading up to 1 vol%
nanotubes. The thermal conductivity of nanofluids containing
nanotubes (MWNTs) was measured at room temperature and
results were compared to the predictions calculated from several
theoretical models. Nanotubes lead to an anomalously large
increase in the thermal conductivity of base fluid (up to a 160%
45
increase with 1 vol% nanotubes), which is by far the highest
thermal conductivity enhancement ever achieved in a liquid. They
suggested the nature of heat conduction in nanotubes dispersion
and an organized structure at the solid-liquid interface might be
responsible for the high thermal conductivity of nanotubes
dispersion. Moreover, the thermal conductivities of all spherical
nanoparticle dispersions showed linear dependence on the solid
loading in the range investigated (1-5 vol%), while thermal
conductivities of MWNT nanofluids showed nonlinear increase with
nanotubes volume fractions at low solid loadings (<1 vol%). Choi et
al [62] suggested it may be caused by the existence of interaction
among nanotubes even at low volume fractions. However, carbon
nanotubes have hydrophobic surface and can not be dispersed into
most of common heat transfer fluids like distill water and EG
without surface treatment and/or existence of dispersants. A
concentrated nitric acid treatment was applied by Xie at.al [63] to
disentangle MWNT aggregates and produce uniform nanotubes
dispersions. The acid treatment introduced oxygen containing
functional groups onto nanotube surfaces, so they could be
dispersed into polar liquids like distilled water and EG without
additional dispersants or surfactants and into non-polar liquids
like decene with oleylamine as surfactant. All the nanotube
dispersions showed substantial increase of thermal conductivity
46
and the thermal conductivity enhancement were much higher than
those calculated from conventional models. For 1 vol% particle
fraction, the thermal conductivity enhancements are 19.6%, 12.7%
and 7% for decene, EG and water. This trend was consistent with
the one showed in alumina dispersions (Lee,choi et.al [54]) that
thermal conductivity enhancement decreased with increase of
thermal conductivity of base fluids. However, thermal conductivity
increase in this work were just moderate by compared with the
results in Chois[62] work which reported 160% increase for 1 vol%
particles. Moreover, the thermal conductivity enhancements
seemed to increase linearly with particle loading at low volume
fraction (upto 1 vol%) while Choi [62] et.al reported a nonlinear
change. The authors suggested those discrepancies would be
attributed to different base fluids and preparation methods of
nanofluids.
Assael et.al [50] dispersed carbon MWNTs into water with the help
of the surfactant, sodium dodecyl sulfate (SDS).The maximum
thermal conductivity enhancement for 0.6 vol% nanotubes
dispersion was 38% compared with pure water. Another attempt to
disperse carbon nanotube into water has been done by Wen et.al
[64]. Instead of SDS they used sodium dodecylbenzene sulfonate
(SDBS) as dispersant in their work. Effects of particle
concentration and temperature on the thermal conductivity of
47
nanofluids were studied. Their results showed that the thermal
conductivity of nanofluids increased with increase of particle
loading, however, the dependence was nonlinear. The
enhancement ratio increased almost linearly when particle fraction
was lower than 0.2 vol% but the dependence tended to level off
above that loading. The increase ratio of 0.46 vol% nanofluid was
around 22% at room temperature which was much lower than that
of nanotube in oil dispersion (50%) with the same particle loading
reported by Choi et.al [62] but much higher than that of nanotube
in water dispersion (4%) made by Xie et.al [63]. The authors
suggested the possible reason may be the different thermal
conductivities of carbon nanotubes and different thermal
resistances at the interface. Thermal conductivity ratios in carbon
MWNT dispersion increased with temperature linearly on 20~30
0
C
range but the dependence leveled off when temperature was higher
than 30
0
C. This tendency was quite different from that in Al2O3 or
CuO nanoparticles dispersions which showed a linear increase
with temperature in 20~50
0
C range. Dispersant failure happened
in MWNT in water dispersions when temperature was higher than
60
0
C and nanofluids became unstable.
The dispersions of carbon nanotube in EG have been prepared by
Cho et.al [65]. Three different methods to make the nanofluids
were applied: 1) Sonication 2) Sonication plus dispersant
48
(ployacrylamide-co-acrylic acid) and 3) Sonication plus acid
treatment. The thermal conductivity ratios were 16%, 14% and
15% for those three cases respectively at same particle volume
fraction (1 vol%). The thermal conductivity ratios for sonication
nanofluids were 16%, 19% and 23% for 1,2,3 vol% nanofluids
which showed a nonlinear tendency similar to the one reported by
Wen et.al [64] in aqueous dispersions.
An enhancement ratio of 12.4% for nanotube in EG dispersion
without the help of dispersant has been reported by Liu et.al [66].
This result is quite close to the results of Chois [62] work. They
also measured the thermal conductivity of nanotube in engine oil
dispersions with N-hydrosuccinimide as dispersant. An increase
ratio of 30% has been claimed for 2 vol% dispersion system which
was much lower than the result reported by Choi et.al [62].
Biercuk et al. [67] measured the effective thermal conductivity of
suspensions of single wall carbon nanotubes (SWNTs) and vapor
grown carbon fibers (VGCF) in epoxy using a comparative method.
Results showed 125% and 45% improvements for 1 vol% SWNTs
and VGCF, respectively. They found choi et al. [62] on thermal
properties of SWNTs epoxy composites showed similar
improvement of the thermal conductivity. They pointed out that
the bonding of nanotubes could be an important factor for thermal
transport characteristics.
49
Jana et al [68] conducted experiments on nanofluids containing
SWNT, Cu, Au, separately and hybrids of them in water.
Enhancement in thermal conductivity of CNT, Cu, Au was
observed whereas hybrid CNT-Au and CNT-Cu did not improve the
thermal conductivity. They also reported Cu nanofluids showed
best results of 74% increase with base fluids and nonlinear
enhancement in CNT nanofluids. However, both Cu and CNT
nanofluids showed drastic decrease of their thermal conductivity
with time due to sedimentation and agglomeration
Based on the above exhaustive review a thermal conductivity of
nanofluids, the inferences drawn and the experimental
enhancement found by different researchers is presented in
Appendix I. It is observed from the table that most of the
experimental work is carried out for water and Ethylene glycol as
basefluids with either Al2O3 or CuO as nanoparticles. The appendix
I can be used as an immediate reference for finding out
enhancement of thermal conductivity for different nanofluids at
different concentrations and different particle sizes. The
observations recorded by earlier researchers in finding
enhancement are also presented for ready reference. The next
section is denoted to review the work carried out by several
researchers in the past to find out the thermal conductivity of
nanofluids theoretically.
50
2.7 Models for Thermal Conductivity of Nanofluids
The thermal conductivity enhancement of nanofluids was higher
than those predicted from conventional models (in Table 2.2) for
larger size particle dispersions as in Fig.2.7. Therefore, different
researchers (Li and Xuan [83]). Keblinski et.al [84]; Xie etal [85])
explored the mechanisms of heat transfer in nanofluids, and
proposed four possible reasons for the contribution of the system:
1. Brownian motion of the particle
2. Molecular-level layering of the liquid at the liquid/solid
interface
3. The nature of the heat transport in nanoparticles
4. The effects of nanoparticles clustering

Figure 2.7 Comparison of the Conventional Models with the
Experimental Data [41].
51
Table 2.2 Convectional models for effective thermal
conductivity of solid-liquid suspensions.
Models Expression
Maxwell (1873)
[76]
| o + o
| o
+ =
) 1 ( ) 2 (
) 1 ( 3
1
f
nf
k
k

Hamilton & Crosser
[77]
| |
| | ) ( ) 1 (
) ( ) 1 ( ) 1 (
p f f p
p f f p
f
nf
k k k n k
k k n k n k
k
k
| + +
| +
=
Bruggerman
[78]
( ) ( ) | | A + | + | =
f p nf
k 1 1 3 k 1 3 k
( ) ( ) | | ( ) | |
f p f
2 2
p
2
k k 1 9 2 2 k 1 1 3 k 1 3 | | + + | + | = A

Jeffrey
[79]
2
2 2
2
...)
) 3 2 ( 16
) 2 ( 9
4
3
3 ( 3 1 | +
+ o
+ o |
+
|
+ | + || + =
f
nf
k
k

Where
2
1
+ o
o
= | ; o= Kp/Kf
Davis
[80]
| |
2
) (
) 1 ( ) 2 (
) 1 ( 3
1 | o + |
| o + o
o
+ = f
k
k
f
nf

Where f(o)=2.5 for o= 10, and f(o)=0.5 for o=

Lu & Lin
[81]
2
1 || + o| + =
f
nf
k
k
; Where
2
1
+ o
o
= | ; o= Kp/Kf
Landau
Lifshitz/Looyenga
[82]
( ) | |
3
1/3
f
3 / 1
f
3 / 1
p
f
nf
k k k
k
k
+ | =
For better investigation of these mechanisms some of the authors
have even used computational methods. In the following sections
each possible mechanism will be discussed and theoretical work
on thermal conductivity of nanofluids will be reviewed.
2.7.1 Brownian motion of the particles
In 1827, Robert Brown[86] examined the form of Clarkia pulchella
pollen particles immersed in water and observed that many of
these particles were in continual motion that arose from neither
currents in the fluid, nor from its gradual evaporation, but rather
52
that appeared to belong to the particles themselves. This constant
and irregular motion increased as the size of the particle decreased
and continued for the entire time that the particle remained in
suspension. Further observation of this Brownian motion
illustrated the irregular energy and momentum exchanges of
molecules caused by the collision between particles and molecules,
and indicated a strong, temperature dependence.
Jang and Choi [87] derived a theoretical model that involves four
modes are shown in Fig. 2.8 such as

Figure 2.8 Modes of Energy transport in Nanofluids
(Jang and Choi [87])
1. Collision between base fluid molecules(kf (1 |)),
2. Thermal diffusion in nanoparticles in fluids(kp| ),
3. Collision between nanoparticles due to Brownian
motion(neglected),
4. Thermal interaction of dynamic or dancing nanoparticles
with the base fluid molecules (f h T).
53
Where h ~ kb / dpRe
2
Pr
2
and ~3dp presents the heat transfer
coefficient for the flow past nanoparticles and the thickness of the
thermal boundary layer, respectively. The advantage of the model
is to include the effects of concentration, temperature, and particle
size. The resulting expression for the effective thermal conductivity
of nanofluids is
. ( ) | + | + | = Pr Re 3 1
1 p f
p
f
p f nf
k
d
d
C k k k (2.16)
in which subscript f and p represents base fluid and nanoparticles.
D is diameter of particle or molecule. C1 is proportional constant
and Pr is Prandtl number of nanofluids.
Rep is defined as

v
d C
p
p
= Re (2.17)
in which C and v are the random motion velocity of nanoparticles
and dynamic viscosity of the base fluid. This model has been
compared with experimental results from several research groups
(Masuda, Ebata et al.[27]; Lee, Choi et al.[28]; Eastman, Choi et
al.[29] ; Das, Putra et al. [41]). Most of the data fell onto the
predicted curves calculated from model and it seems this model
not only includes the particle volume fraction and temperature
effect on the thermal conductivity of nanofluids, but also predicts
the strong size dependent conductivity. If the hypothesis in this
54
paper is correct, the increased thermal conductivity enhancement
with decrease of the nanoparticles size which happened in most
reports can be related to Brownian motion of the nanoparticles.
Kumar et al. [88] pointed out that since heat transfer is a surface
phenomenon, higher surface area to volume ratio of nanoparticles
can explain the enhancement of thermal conductivity of nanofluids.
A stationary model has been developed based on this theory,
showing that the enhancement in effective thermal conductivity
increased with the reciprocal of nanoparticles diameter. Moreover,
they developed a moving particle model based on Brownian motion
of the nanoparticles at different temperatures was combined with
stationary model to indicate temperate effect on the thermal
conductivity of nanofluids.
Chon et.al [89] developed an empirical correlation for the thermal
conductivity of Al2O3 nanofluids with different particle size (11nm ~
150nm) and temperature (21 ~ 71
0
C) based on Brownian motion of
the nanoparticles.
Bhattacharya et.al [90] developed a technique to compute the
thermal conductivity of nanofluids using Brownian dynamics
simulation in which they omitted the motion of liquid molecules
and their effects on nanoparticles and represented them as
random force and friction terms. In this simulation, the Langevin
equation of motion was used to describe the particle movement
55
and the effect of solvent molecules and was represented by a
combination of random forces and frictional terms. The potential
energy between the two particles was described by an exponential
model as:
(
(

= u
d
d r
B exp A
ij
ij
(2.18)
Where d is the particle diameter, A and B are the parameters for
the system, and is the distance between particles j and i. Their
simulation based on interparticle potential predicted the effective
thermal conductivity of nanofluids to a good level of accuracy in
comparison with some experimental data (Eastman, Choi et.al [28];
Wang et.al [43]).
Koo et.al [91] compared the relative effects of nanoparticle motion
mechanisms on the effective thermal conductivity of dilute
nanoparticle dispersions. They found the effect of Brownian motion
was more significant by factor of 10
6
and 10
8
than those of
thermophoresis and osmophoresis.
After reviewing the models mentioned above and performing an
order of magnitude analysis, Prasher et al [92] draw a conclusion
that local convention caused by Brownian motion of the
nanoparticle was the mechanism which can be used to explain
thermal conductivity enhancement of nanofluids. Based on a
traditional model (Nan, et al.[93]) for k of solid liquid composite
56
which considers interface resistance, they developed a semi-
empirical model to predict thermal conductivity of nanofluids. By
fitting the experimental data for aqueous Al2O3 and CuO
nanoparticle dispersions ( Masuda, Ebata et al.[27]; Lee, Choi et
al.[28] ; Xie, wang et al. [43]; Das, Putra et al. [41]) with various dp,
and T. They found most of data can be fit by this model, when
A=400000 and m=2.5+ 15% can be applied for water based
nanofluids.
Prasher et al.[94] in their recent experimental investigation, a drop
of dye in pure water diffuses much more slowly than the same
drop of dye in Al2O3/Water nanofluids. It was also determined that
the optimal volume fraction for the diffusion is around 0.5%. These
results would appear to provide significant evidence of the effect of
the Brownian motion on the enhanced thermal conductivity of
nanofluids.
Therefore, Brownian motion seems to be one of the possible
mechanisms to be applied for predicting thermal conductivity
enhancement in nanoparticle dispersions, especially in spherical
nanoparticle dispersions. Most of the important factors affecting
the enhancement of thermal conductivity in nanofluids can be
included in models base on this mechanism, such as particle size,
temperature, thermal conductivity of particle and base fluid and
viscosity of base fluid.
57
2.7.2 Interfacial layering of liquid molecules
Some literature (Nan, Birringer et al.[95]) addressed the effect of
interfacial resistance (Kapitza resistance) on thermal conductivity
of particulate composites due to weak interfacial contact. They set
up a theoretical model to predict thermal conductivity of
composites by including interfacial resistance. According to this
model, the effective thermal conductivity should decrease with
decrease of the nanoparticle size which is contrary to most of the
experiment results for nanofluids.
Yu et al [96] reported that molecules of normal liquids close to a
solid surface can organize into layered solid like structure. This
kind of structure at interface is a governing factor in heat
conduction from solid surface to liquid. Choi et al [28] pointed out
that this mechanism contributed to anomalous thermal
conductivity enhancement in nanotube dispersions. However,
Keblinski et al [84] indicated that the thickness of the interfacial
solid-like layer is too small to dramatically increase of the thermal
conductivity of nanofluids because a typical interfacial width is
only on the order of a atomic distance (1nm). So this mechanism
only can be applied to very small nanoparticles (<10nm).
In order to find the connection between nanolayer at interface and
the thermal conductivity of nanofluids, Yu et al. (Yu, Richter et al.
[96]; Yu and Choi [97]) modified the Maxwell equation for spherical
58
particles and Hamilton-Crosser equation for non-spherical
particles to predict the thermal conductivity of nanofluid by
including the effect of this ordered nanolayer. They applied this
model to fit some experimental data in which smallest
nanoparticles were dispersed (Lee, Choi et al[28]; Eastman, Choi et
al [29] ) and found the model predicted the experimental data well.
However, the model failed to predict the results for Cu nanofluids
with surfactant.
The simulation work done by Xue et al[98] indicated that the
strength of the bonding between liquid and solid is very important
in determining interfacial thermal resistance. Nanofluids with weak
atomic bonding at interface exhibit high thermal resistance and
wetting systems have small interfacial thermal resistance. Adding
dispersant into dispersion systems or surface treatment will
certainly change the atomic bonding at interface and lead to varied
interfacial resistance.
Xue [99,100] developed a novel model which was based on Maxwell
theory and average polarization theory for effective thermal
conductivity of nanofluids by including interface effect between
solid particle and base liquid. He considered solid nanoparticle and
interfacial shell (nanolayer of liquid molecules) as a complex
nanoparticle and set up the model based on this concept. The
theoretical results obtained form this model were in good
59
agreement with the experimental data for alumina nanoparticle
dispersions (Xue, Wu et al. [101] )and showed nonlinear volume
fraction dependence for thermal conductivity enhancement in
nanotube dispersions (Choi, Zhang et al. [62]).
Xie et al. (Ren, Xie et al.[102]; Xie, Fujii et al.[103]) investigated
the effect of interfacial layer on the effective thermal conductivity of
nanofluids. A model has been derived from general solution of heat
conduction equation and the equivalent hard sphere fluid model
representing microstructure of particle suspensions. Their
simulation work showed that the thermal conductivity of
nanofluids increased with decrease of the particle size and increase
of nanolayer thickness. The calculating values were in agreement
with some experimental data (Masuda, Ebata et al.[27];Lee, Choi et
al. [28]; Eastman, Choi et al. [29]).
Recently, a new thermal conductivity model for nanofluids was
developed by Yu et al.[104]. This model was based on the
assumption that monosized spherical nanoparticle are uniformly
dispersed in the liquid and are located at the vertexes of a simple
cubic lattice, with each particle surrounded by an organized liquid
layer. A nonlinear dependence of thermal conductivity on particle
concentration was showed by this model and the relationship
changed from convex upward to concave upward. A comparison of
theoretical prediction and experimental data showed that
60
calculation value were much higher than experimental results
which indicate that there is a potential to improve the effective
thermal conductivity of nanofluids.
Generally, the solid like nanolayer at liquid-solid interface can not
be used to explain most of experimental data in which
nanoparticles larger than 10nm were dispersed. However,
interfacial thermal resistance which had been noticed in particle
dispersion, both composites and larger particle in liquid
suspensions, will be a critical factor to affect the thermal
conductivity of nanofluids because of the huge interface area for
those nanosized particles. Inclusion of dispersant or surface
treatment of nanoparticles will dramatically affect the thermal
conductivity of nanofluids by changing the interactions between
solid and liquid surface
2.7.3 Nature of heat transfer in nanoparticles
Keblinski (Keblinski, Phillpot et al. [84) estimated the mean free
path of a phonon in Al2O3 crystal is ~35nm. Phonons can diffuse in
the 10nm particles but have to move ballistically. In order to make
the ballistic phonons initiated in one nanoparticle to persist in the
liquid and reach another nanoparticle, high packing fractions,
soot-like particle assemblies, and Brownian motion of the particles
will be necessary to keep the separation among nanoparticles to be
small enough.
61
However, Xie et al. (Xie, Wang et al. [55]) found in their research
about alumina nanofluids that when the particle size close to the
mean free paths of phonons, the thermal conductivity of nanofluid
may decrease with particle size because the intrinsic thermal
conductivity of nanoparticle was reduced by the scattering of
phonon at particle boundary. However, this result was not in
agreement with most of the experimental results from other groups.
Choi et al.[28] indicated that sudden transition from ballistic heat
conduction in nanotubes to diffusion heat conduction in liquid
would severely limit the contribution of ballistic heat conduction to
overall thermal conductivity of nanotube dispersions. They
suggested that both ballistic heat conduction and layering of liquid
molecules at interface contributed to the high thermal conductivity
of nanotube dispersions.
The nature of heat transfer in nanoparticles or the fast ballistic
heat conduction can not be the mechanism works alone to explain
thermal conductivity enhancement of nanofluids due to the barrier
caused by slow heat diffusion in liquid. Other mechanisms need to
be combined with it to fully understand the enhancement of the
thermal conductivity in nanofluids.
2.7.4 Nanoparticle clusters
Local nanoparticle clustering is another possible mechanism
offered by Keblinski, Phillpot et al [84]. They suggested that the
62
effective volume of a cluster can be much larger than the volume of
the particles which will lead to higher overall thermal conductivity
of nanofluids. Clusters with very low packing factor which is
defined as ratio of the volume of the solid particles in the cluster to
the total volume of cluster, and very larger effective volume might
be one of the reasons for the unexpected thermal conductivity
enhancement of nanofluids. However, the author also pointed out
that the clusters existing in the dispersion may cause the
settlement of particles or creating particle-free regions with high
thermal resistance.
Except for local clusters, the nanoparticles with aspect ratio much
higher or lower than one can reach the percolation threshold at
very low loading. Eq.2.19 shows an empirical formula (Garboczi,
Snyder et al.[105]) developed to predict the percolation threshold,
Pc as function of the particle aspect ratio, Af.

3
f
2
f
5 . 1
f f
2
f f
c
A 658 . 1 A 763 . 1 A 33 . 12 A 61 . 14 742 . 7
A A 875 . 9
p
+ + + +
+
= (2.19)
The calculation results from this equation were plotted in Fig 2.9.
When the particles reach the percolation threshold, they can build
up three dimensional network structures in the nanofluids and
change the properties of the base fluids substantially.
63


Figure 2.9 Percolation threshold for particles with different
aspect ratios (Garboczi, Snyder et al.[ [105])
A theoretical model which included Brownian motion and diffusion
limited aggregation was developed by Xuan et al.[83]. The
calculation values of enhancement of thermal conductivity of
nanofluids containing 10nm copper nanoparticles agreed with their
experimental data (Li and Xuan[51]). However, according to this
model, the thermal conductivities enhancement of nanofluids
should decrease with cluster size.
Wang et al.[106] developed another theoretical model to predict the
thermal conductivity of nanofluids with cluster in it. The specific
size effect on thermal conductivity and liquid monolayer adsorbed
on to solid surface were also included in the model.
64
Recently, Gao et.al [107] presented differential effective medium
theory by taking into account both physical and geometrical
anisotropy of the nanofluids to predict the enhanced thermal
conductivity of nanofluids. Interestingly, their simulation results
showed a nonlinear dependence of thermal conductivity
enhancement on volume fraction of nanoparticles which agreed
with the experimental results from Choi et al [28].
Based on the above review on theoretical thermal conductivity
models of nanofluids a summary of different models and equations
by different researchers is presented in Appendix II.
2.8 Convection heat transfer properties of Nanofluids
Increasing the heat transfer coefficient of the heat transfer fluids is
very important for Nanofluids applications. Compared with the
experimental work on thermal conductivity of Nanofluids, there
were fewer papers that discuss the heat transfer coefficients of
Nanofluids in convective flows. Choi [108] pointed out that heat
transfer coefficient should increase with flow rates or with the
thermal conductivities of the fluid, while other properties of the
nanofluid system, such as heat capacity, density and viscosity are
kept same as the base fluid. If a nanofluid can have high thermal
conductivity at low volume fractions, a high heat transfer
coefficient might be obtained without increasing the pumping
power. In heat exchanger design, the length of the exchanger
65
surface affects the local heat transfer coefficient via entrance
effects and other factors. In some cases, using Nanofluids can help
achieve higher exchanger efficiency without increasing its size.
2.8.1 Forced convection heat transfer coefficients for
Nanofluids
Forced convection heat transfer tests and theoretical simulations
have been done for different kinds of Nanofluids including metallic,
metal oxide nanoparticles and carbon nanotubes dispersions in
both laminar and turbulent flow conditions.
Ahuja [109] conducted an experimental investigation of the
effective thermal conductivity of suspensions in laminar flow. In
his investigation, the experimental system was calibrated using tap
water, and the over all accuracy was estimated to be within 10%.
The suspension samples were 88 to 105 micrometers in diameter
and 44 to 53 micrometer diameter polystyrene spherical particles
with a weight fraction of 1.2%, 1.9%, 3.1%, 4.6%, and 8.8% were
placed in a base liquid of aqueous sodium chloride (5.2 wt%) and
aqueous glycerine (20wt%). In this experiment, the effective
thermal conductivity of the suspension in flow was two times
higher than that of the non-flow nanoparticle suspension and
varied with different shear rates, particle concentrations, particle
sizes, tube sizes, and base liquids. The results indicated that the
angular Reynolds number and Peclet number both played an
66
important role in the enhancement of the effective thermal
conductivity of the suspension in a flow situation.
Xuan and Li[110] studied convective heat transfer and flow
charterstics of Cu-water Nanofluids in both laminar and turbulent
flow in circular tube. The heat transfer coefficients of their
nanoparticles suspensions are much higher than that of the base
fluid at the same Reynolds number and increase of the heat
transfer coefficients increased with particle volume fraction. For
example, they reported a 60% heat transfer coefficient increase
compared with that of base fluid by adding 2 vol% nanoparticles.
Increased thermal conductivity and chaotic movement of
nanoparticles were offered as two mechanisms for increased heat
transfer. When the volume fraction of nanoparticles is low, the
friction factor of the fluid is not changed compared with base fluid.
In one of their early reports, they pointed out that same factors
affected convective heat transfer behaviors of Nanofluids like heat
capacity, thermal conductivity of base fluid and nanoparticles, flow
velocity, volume fraction of nanoparticles, viscosity of Nanofluids
and the shape of the nanoparticle [111]. They proposed general
form for the Nusselt number of Nanofluids as

|
|
.
|

\
|
= n
c
c
k
k
f Nu
f p
p p
f
p
, ,
) (
) (
, Pr, Re, |

(2.20)
67
Based on the general form, they proposed a formula to correlate
the heat transfer coefficients of Nanofluids as

4 . 0
f
9238 . 0
f
001 . 0
p
f f
6886 . 0
f
Pr Re
D
d
Pr Re 6286 . 7 1 0059 . 0 Nu
(
(

|
|
.
|

\
|
+ = |
(2.21)
The calculated results from these model in turbulent flow showed
good agreement with experimental data they obtained for Cu
nanoparticle.
Lee et al. [112] studied the forced convection heat transfer behavior
of sliver Nanofluids with water; water-EG mixture and water-
ammonia mixtures as base fluids. The tests were done in double
pipe heat exchanger system and heat transfer coefficient of
Nanofluids were 5~13% higher than that of water at same
Reynolds number (laminar region).
Heat transfer behavior of aqueous Al2O3 (13nm) and Ti2O (27nm)
Nanofluids were studied experimentally in turbulent flow in a
circular tibe by Pak and Cho [44]. The viscosities of the Nanofluids
were much higher than that of water, especially for alumina
nanoparticles. The authors found that the Nusselt number of
nanofluid for fully developed turbulent flow increased with increase
of Reynolds number and volume fraction of nanoparticles. However,
when the heat transfer coefficients of Nanofluids and water were
compared at the same average velocity, they found that the heat
transfer coefficient value of 3 vol% Nanofluids was 12% lower than
68
that of water. Suppressed flow turbulence by higher viscosity of
Nanofluids may be the reason for this phenomenon. These results
suggested a proper choice of particle size and volume fraction. A
new correlation for turbulent convection heat transfer of
Nanofluids was established as

5 . 0
f
8 . 0
f
) (Pr ) (Re 021 . 0 Nu = (2.22)
Wen and Ding [113] reported experimental results for force
convection heat transfer of Al2O3 nanofluids in laminar flow regime.
It showed that addition of nanoparticles increased heat transfer
coefficients of base fluids and the enhancement increased with
Reynolds number and particle loading. Moreover, the enhancement
was significant at the entrance region and decreased with axial
distance. Since the classical model failed to predict the heat
transfer behavior of Nanofluids. The author suggested that
increased thermal conductivity was not the only reason to explain
the enhancement of convective heat transfer. Migration of
nanoparticles [114] was proposed to be another critical mechanism.
Experimental were conducted to study the convective heat transfer
of CuO (50nm) nanofluids in a mini tube by Chen et al. [115]. The
tests were taken in both laminar (Re=200~1500) and transition
(2000~4000) regimes. They found the inclusion of nanoparticle
increase heat transfer. In laminar flow, the enhancement always
increased with increase of Reynolds number. Surprisingly, for
69
transition regime, the enhancement of heat transfer coefficient
decreased with Re in mini tubes with smallest diameter.
A study on the heat transfer of nanotube dispersion was done by
Ding et al[71]. They studied the laminar heat transfer behavior of
aqueous carbon nanotube dispersions in horizontal tube. The
effective thermal conductivity, viscosity and heat transfer
coefficient were collected experimentally. They found that
nanotubes increased the heat transfer of base fluid and the
enhancement increased with Re, particle loading, and axial
distance. A maximum heat transfer enhancement happened in the
position between entrance and outlet. For given particle
concentration, a critical Re number existed above which dramatic
increase of the heat transfer coefficient occurred due to strong
shear thinning of nanofluids at certain shear rate. A maximum
heat transfer coefficient enhancement of 350% was claimed for 0.5
wt% nanotube dispersion when Re was 800. Particle
rearrangement, shear induced enhancement of thermal
conductivity, reduction of thermal boundary due to nanotubes
were suggested as possible mechanisms other than increased
thermal conductivity for increased heat transfer properties.
Heris et al. [116] investigated laminar flow of CuO/water and
Al2O3/water nanofluids through a 1 m annular copper tube with 6
mm inner diameter and with 0.5 mm thickness and 32 mm
70
diameter outer stainless steel tube, where saturated steam was
circulated to create constant wall temperature boundary condition
rather than constant heat flux condition by other researchers.
Comparison of experimental results showed that the heat transfer
coefficient enhanced with increasing volume fraction of
nanoparticles as well as Peclet number while Al2O3/water showed
more enhancement.
Tsai et al. [117] also employed aqueous solutions of various-sized
(235 nm and 1575 nm) gold nanoparticles, which were prepared
by the reduction of HAuCl4 with trisodium citrate and tannic acid.
They found a large decrease of thermal resistance of the heat pipe
with nanofluids as compared with de-ionized water. The thermal
resistance of the circular heat pipe ranged from 0.17 to 0.215 K/W
with different nanoparticle solutions. The reason is that the
included nanoparticles can bombard the vapor during the bubble
formation. Hence, the reduction of thermal resistance was obtained
due to the resulted smaller bubble size. Results indicated the high
potential of nanofluids as working medium to replace the
conventional fluids in heat pipes.
Maiga et al.[118-120] done a series of simulations on convective
heat transfer of Al2O3 in water and EG nanofluids in both laminar
and turbulent regimes. The inclusion of nanoparticles increased
heat transfer in a uniformly heated tube and the enhancement of
71
heat transfer increased with particle volume fraction and Reynolds
number. However, the presence of the nanoparticles caused a
negative effect on the friction which also increased with particle
loading. EG-based nanofluids showed higher enhancement of heat
transfer and stronger adverse effects on wall shear stress than
water based nanofluids. According to the simulation results,
correlations were provided by the authors to compute average
Nusselt number in laminar flow in circular tube.

5 . 0 55 . 0
Pr Re 086 . 0 = Nu for constant wall heat flux (2.23)

36 . 0 35 . 0
Pr Re 28 . 0 = Nu
for constant wall temperature (2.24)
S B Maiga et.al [120] considered the turbulent convection and
obtained the Nusselt number by using CFD based K-c model
applying genetic algorithm as

35 . 0
71 . 0
Pr Re 085 . 0
nf
Nu = (2.25)
In their simulation work, they applied classical formulas to
evaluate the physical properties of nanofluids including thermal
conductivity.
Roy et al. [121] considered the hydrodynamic and thermal fields of
aqueous Al2O3 nanofluids in a radial laminar flow cooling system.
The simulation results indicated that considerable heat transfer
enhancement (two fold increases for 10 vol% nanofluid). However,
wall shear also increased with nanoparticle loading.
72
By taking Brownian motion of nanoparticles into account, Koo and
Kleinstreuer [122] analyzed the laminar flow in microchannels for
CuO in water and EG nanofluids. New formula were developed and
applied to calculate the effective thermal conductivity and viscosity
of nanofluids. The effects of nanoparticle concentration on
microchannel pressure gradient, temperature profile and Nusselt
number were computed. High Pr number base fluid and
nanoparticle with similar dielectric constant with base fluid were
recommended by authors for maximizing the heat transfer property
of nanofluids.
The convective heat transfer coefficient were also calculated from a
thermal lattice Boltzmann model [123] proposed for simulating flow
and energy transport process of nanofluids. The external and
internal forces acting on nanoparticles were considered in the
model.
2.8.2 Natural convection heat transfer for nanofluids
Compared with research effort in forced convection, relatively few
results have been reported for natural convention. Khanafer et al.
[124] developed a natural convection heat transfer model to predict
heat transfer behaviors of nanofluids in a two dimensional
enclosure. The chaotic motion of nanoparticles was considered
through a thermal dispersion model. The simulation results
illustrated that the nanoparticle substantially increased the heat
73
transfer rate of base fluid at any Grashof number and rate
increased with nanoparticle volume fraction.
Putra et al. [125] and wen et al. [126] conducted an experimental
study of the steady state natural convection of two Al2O3 and CuO
nanoparticle suspensions, in distilled water, under different
conditions. However, in the experimental results (for Rayleigh
number 10
6
~10
9
) in horizontal cylinder showed significant
decrease with increase of nanoparticle volume fraction.
2.8.3 Two-Phase Change Heat Transfer Of Nanofluids
Another aspect of the heat transfer performance of nanoparticle
suspensions is the effect of these suspensions on boiling heat
transfer. You and Kim [127] experimentally investigated the
enhancement of the critical heat flux in pool boiling for Al2O3
nanoparticle suspensions. The results indicted that in the nucleate
boiling regime, the boiling heat transfer coefficient was not
influenced by the addition of the Al2O3 nanoparticles. However,
there was a dramatic increase in the critical heat flux (CHF), for
different concentrations of the nanoparticle suspension that
ranged as high as 300% of that for measured for pure water.
In the experimental investigation of Das et al. [128], the boiling
performance of the water was found to deteriorate with the
addition of the nanoparticles, and that a higher wall superheat
existed for the same heat flux. With the increase of the
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nanoparticle concentration in the suspension, the deterioration
was more apparent. It was observed that the nanoparticles with a
diameter of 20 to 50 nm filled the cavities of an uneven heating
surface and changed the surface characteristics by effectively
making it smoother. They suggested with the increase of
nanoparticle concentration, a layer of sedimentation of the
nanoparticles developed, which deteriorated the boiling
performance even further.
Vassallo et al. [129] and Zhou [130] studied the boiling
characteristic of silica nanoparticles and microparticle suspensions
with diameters of 15 nm, 50 nm, and 3000 nm in boiling
situations, ranging from nucleate boiling to film boiling under
atmospheric pressure. The heat flux was generated in a
horizontally fixed, NiCr wire and the water level was observed to
decrease approximately 6 mm during the experiment. All of the
suspensions expressed no difference in the boiling performance of
water, below the CHF point, but increased the CHF point
dramatically.
Based on the above review on convective heat transfer of
nanofluids, the inferences drawn and the experimental
enhancement found by different researchers is presented in
Appendix III.

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2.9 Review on Compact Heat Exchanger
2.9.1 Direct Test data
Direct test data for each compact heat exchanger surface is the
relation between Colburn factor (j) and mean friction factor (f)
obtained by Kays and Londan [8], their 24-year project sponsored
by the Naval Research, which cover experimental data of 132
compact heat transfer surfaces including the plate fin surfaces and
tube fin surfaces.
2.9.2 Surface selection
A general method for comparison of compact heat transfer surfaces
has been recently proposed by Cowell [133]. The method provides
compact statement of the relative merits of different heat transfer
surfaces by comparing relative pumping powers and relative
hydraulic diameters. Also, the relation between several factors of
the performance parameters was clarified.
Nunez [134] developed a thermo hydraulic model that represent
the relationship between pressure drop, heat transfer coefficient
and exchanger volume. A simple approach to surface selection was
based on the concept of volume performance index (VPI): the
higher the VPI, the lower the core volume required. Surfaces were
compared on the basis of VPI and envelopes for best utilization
could be achieved by using envelopes for best surface performance
together with the thermo-hydraulic model.
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Taylor [135] and Shah [136] used the traditional approach to
design the plate fin heat exchangers, and traced the pressure drop
as a constraint to see the acceptable pressure drop values for the
specified heat duty.
Hesselgreaves [6] has attempted to provide a treatment that goes
beyond dimensionless design data information. In addition to the
basic design theory, he includes descriptions of industrial CHEs,
specification of a CHE as a part of system using thermodynamic
analysis and broader design considerations for surface size, shape
and weight. Heat transfer and flow friction single phase design
correlations are given for the most commonly used modern heat
transfer surfaces in CHEs, with the emphasis on those surfaces
that are likely to be used in the process industries, and some of
the operational considerations including installation,
commissioning, operation, and maintenance, including fouling and
corrosion.
2.9.3 Entropy Generation
Tagliafico [137] provided a comparative study of entropy generation
of many surface scaled by that of reference configuration (a
parallel-plate channel), considering the irreversibility analyses an
important factor in determining the operating costs of the heat
exchanger. A possibility to combine hydraulic and heat transfer
characteristics is offered by the thermodynamic (second law)
77
analysis developed by Bejan [138], from this point of view, the
entropy generation (irreversibility) in the heat exchanger can be
assumed to measure the quality of the performance ( London,
[139]; Sekulic, [140];, Schenone, [141]).
2.9.4 Vortex Generators
Fiebig [142] provided a comprehensive study on the use of vortex
generators in either tube fin or plate fin compact heat exchanger
and showed the recent results from the Vortices & Heat transfer
group. He compared the performance of transverse vortex
generators and longitudinal vortex generators, described the
mechanism if heat transfer enhancement due to using vortex
generators and compared the performance of high performance
surfaces (louvered, strip) used in plate type compact heat
exchangers with two types of vortex generators surfaces. The first
vortex characteristic was obtained from Brockmeier [143] and
second is the ISB configuration.
Jacobi and Shah [144] discussed the recent progress of vortex-
induced heat transfer enhancement, the theoretical basis for
passive and active implementation. They also identified the
research needs in the area of vortex-induced heat exchanger
enhancement. Also they provided a full coverage for the application
of vortex generators in compact heat exchangers. They also studied
the behavior of air flow in complex heat exchangers passages with
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a focus of boundary layer development, turbulence, span wise and
stream wise, and wake management. Each of these flow features is
discussed for the plain, wavy, and interrupted passages found in
contemporary heat exchanger design.
2.9.5 Minimum Weight of Compact heat exchanger
Hesselgreaves [145] presented a dimensionless analytical method
of calculating the size and weight parameters of simplified plate fin
heat exchanger core for given thermal duty. The thickness of fin
material and separating plates which constitute the bulk of the
core weight, have lower limits set by pressure containment
capability, but it does not necessarily follow that the minimum fin
thickness gives the minimum core weight. This optimum fin
thickness is shown to be a function of several geometric, material
and performance parameters.
2.10 Thermal Design Procedures
The problem of heat exchanger design is complex and
multidisciplinary (Shah, [9]). The major design considerations for a
new heat exchanger include process/design specifications, thermal
and hydraulic design, mechanical design, manufacturing and cost
considerations, and trade-offs and system-based optimization, as
shown in Fig. 2.10. The thermal and hydraulic design methods are
mainly analytical, and the structural design is analytical to some
extent. Most of the other major design considerations involve
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qualitative and experience based judgments, trade-offs, and
compromises. Therefore, there is no unique solution to designing a
heat exchanger for given process specifications.
Two broad categories of design problem specifications as follows:
- Rating
- sizing.
The rating problem, also called to as the performance problem, is
analyzed for predicting the performance of an already built
exchanger. The objective here is either to verify vendors
specifications or to determine the performance at off-design
conditions. In this problem, the following quantities are specified:
the exchanger construction type, flow arrangement, overall core
dimensions, and complete details on the material and surface
geometries on both sides including their heat transfer and
pressure drop characteristics, fluid flow rates, inlet temperatures,
and fouling factors. The output is to predict the fluid outlet
temperatures, heat transfer rate, and pressure drop on each side.
The sizing problem, also called as design problem, involves a
design of new heat exchanger for specified performance within
known constraints and minimum objective function. In this
problem, the fluid inlet and outlet temperatures and flow rates are
generally specified as well as the pressure drop on each side. The
output is to select construction type, flow arrangement, materials
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and surfaces on each side, and to determine the core dimensions
to meet the specified heat transfer and pressure drop.
Many theories were developed to describe the design and
performance of compact heat exchangers starting with Bergeles
and Taborek [146], Bergeles [147] Bejan [148], Sparrow and Liu
[149], Shah and Bergeles [150] , kays and London[8], Sekulic [151],
Campell and Rohsenow [152], Smith [153]. More recent texts such
as those of Webb [154] Andrews and Fletcher[155], Kakac and Liu
[156] have also been referred to extensively in the CHE research.
Shah and Sekulic[9] presented the procedures of rating and sizing
using the mean temperature difference of the fluid on each side of
the heat exchanger in order to calculate the fluid on each side of
the heat exchanger in order to calculate the fluid properties
assuming the uniformity of thermo physical properties.
Sekulic [157] offered a very clear methodology for calculating core
dimensions of a compact heat exchanger. Considering the
analytical complexity of implemented calculations, the most
intricate basic flow arrangement situation in a single pass
configuration would be a crossflow in which fluids do not mix
orthogonal to the respective flow directions. Calculations are
executed using an explicit step-by-step routine based on set of
known input data is provided in the problem formulation. The
procedure follows a somewhat modified thermal design (sizing)
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procedure derived from the routine advocated in Shah and Sekulic
[9]. The main purpose of the calculation sequence is to illustrate
the iteration procedures used in commercial software.
Automobile industry is continuously straining to bring out the best
design of automotive vehicle in terms of improving its thermal
performance, optimizing the fuel consumption in addition to better
safety. In this process the cooling incorporated for the engine and
other related systems are found to be vital factors in improving the
thermal performance of the automobile. The heat exchanging
system adopted in
radiators, air conditioning system need to be optimized in terms of
weight, volume, which has a strong impact on the vehicle
aerodynamic characteristics. Normal practice to improve the heat
transfer from a surface is promoting heat transfer from a surface is
promoting turbulence and applying roughness to the surface etc.
However these two methods will create additional problem in terms
of pressure drop, increased drag etc.
In automobile applications use of compact tube fin heat exchanger
is ideal to reach high levels of temperature and pressure with in
severe constraints of dimensions. Different verities of
configurations are adopted to increase the heat transfer area such
as plain, wavy, perforated and louvered fins (Kays et al., [8]).
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Taler [158] proposed two numerical methods for determining
correlations for heat transfer coefficients in cross-flow
compact heat exchangers. In the first method, only the
correlation for the air-side heat transfer coefficient is
determined. The heat transfer coefficient on the tube-side is
calculated using the Gnielinski or Dittus-Boelter correlations.
In the second method, the heat transfer correlations both on
the tube and air-side are determined simultaneously in order
to predict the air-side heat transfer more accurately.
Charyulu et al. [159] developed a numerical model based on
NTU method and analyzed the characteristics of radiator in diesel
engine model TBD 2323 V-12 for different fin configurations and
tube materials. Carluccio et al. [160] presented numerical analysis
of air-oil radiator made of aluminum alloy using CFD and
compared with experimental data. Witry et al. [161] carried the
thermal performance using CFD for a radiator with aluminum
plate and established there dominates in terms of high heat
transfer rates, low pressure drop and smaller size. They have also
established that the coolant flow velocities decreases due to
impingement and erosion/corrosion of the plate. Mahmoudi [162]
conducted experimental and developed theoretical analysis using
2D CFD model for copper based automobile radiator. A detailed
83
Figure 2.10 Methodology of Compact Heat Exchanger Design
(Shah,[9])
84
knowledge base of parametric study of automobile radiators using
CFD based NTU method is proposed by Oliet et al.[163]. In
radiators which are vital in the control of engine temperature in an
automobile, the common liquid used is water + glycol mixture. This
hot liquid coming from the engine flows in flat tubes while the
atmosphere air drawn in flows in the channels setup by fin
configuration and cools the liquid.
Saripella et.al [164] conducted numerical simulation on Class 8
Truck engine cooling system using Nanofluids. They replaced
standard coolant 50/50 mixture of Ethylene glycol and water with
Nanofluids comprised of CuO nanoparticles suspended in base
fluid of 50/50 mixture of Ethylene glycol and water. They reported
that due to high heat transfer coefficients of nanofluids mainly an
improvement in engine heat rejection was observed.
Bang et al.[165] presented an axiomatic design approach for
innovative nanofluids as coolants by using Colloid science. They
suggested at parametric level the design of nanofluids is inherently
coupled with heat performance and flow performance and
developed a design matrix as a standard communication protocol
in the nanofluids research to practical use.
2.11 Conclusion
The transportation industry as well as many other industries has
specific needs to increase heat transfer rates under a variety of
85
constraints. Literature review shows that suspensions containing
nanometer-sized particles (nanofluids) show potential for use as
cooling fluids due to enhanced heat transfer properties. The two-
step method is the most widely used method to prepare nanofluids,
however, agglomeration during drying, storage and redispersion of
the nanoparticles in the base fluid are some of the drawbacks
which makes the one-step method a more attractive route to
nanofluids. A surfactant is generally used to prevent particle
agglomeration during nanoparticle formation and also to ensure
very small nanoparticles are formed. It is also known that
structural differences and defects present in most nanostructures
have a noticeable effect on their physico-chemical properties. The
rheological properties of the nanofluids are rarely investigated.
Nanofluids containing metal nanoparticles were found to be
Newtonian, whereas nanofluids containing metal oxides as well as
carbon nanotubes showed non-Newtonian, shear thinning
behavior. Since the interaction forces between particles usually
decrease during flow conditions, the flow resistance is also
decreased. With no significant interaction forces between the
particles, separation of the particles in the form of sedimentation
may occur and therefore, rheological studies could possibly provide
more information about the stability of the nanofluids and also the
interactions between the particles and fluid molecules.
86
The literature review also has shown that the research on
nanofluids thermal conductivity is far enough along to be able to
identify reproducible trends from multiple researchers in many
areas. Some parametric trends, such as particle size, still require
substantiation, and the use of additives has barely been addressed.
However, general trends were identified in thermal conductivity
and heat transfer enhancement in the range of 15-40% with oxide
and metallic nanoparticles in a variety of base fluids. But
comparing results among research groups involve in- accuracies
due to the poor characterization of the nanofluids studied. It is
difficult to measure the nanoparticle size, shape, and distribution
in fluids by laser scattering technique. A more advanced technique
for these measurements is X-ray small angle scattering, which can
potentially yield accurate measurements.
While many theoretical models have been proposed and
simulations have been developed for nanofluid thermal properties,
it is still not possible to specify a nanofluid for a particular
application based on general verified theory. Current theories
generally fail to predict thermal conductivity enhancement and its
temperature dependence from the properties of materials.
To solve these problems a semi empirical approach of experiments
and correlations should be developed for thermal conductivity of
nanofluids and also for both laminar and turbulent heat transfer
87
flows so that these correlations can be used in industrial
applications like vehicular transportation industry, power plants
etc.