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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy
h i g h l i g h t s
High thermal conductivity and low-viscous ZnOethylene glycol nanouids prepared.
ZnOethylene glycolwater nanouids prepared by hierarchical method.
Liquid layering and Brownian motion contribute to thermal conductivity enhancement.
Improvement in nanouid cooling performance inline with thermal conductivity rise.
a r t i c l e
i n f o
Article history:
Received 20 May 2014
Received in revised form 14 August 2014
Accepted 5 September 2014
Available online 26 September 2014
Keywords:
ZnOethylene glycol
ZnOethylene glycolwater
Transient heat transfer
Nanouid
Liquid layering
Heat transfer rate ratio
a b s t r a c t
Experiments were carried out on preparation and characterization of ZnOethylene glycol (EG) and ZnO
ethylene glycolwater nanouids and analysis of their performance as coolants. Favorable interactions
between ZnO nanoparticles and ethylene glycol molecules ensured superior transport properties of
ZnOEG nanouids. These interactions were utilized during formulation of ZnOEGwater nanouids
with preservation of ethylene glycol molecules over ZnO nanoparticles surface rendering them with better transport properties. ZnOEG nanouids containing 4 vol.% nanoparticles showed thermal conductivity enhancement of 33.4% and viscosity reduction of 39.2% at 27 C. Similarly, 2 vol.% ZnOEGwater
nanouids showed thermal conductivity enhancement of 17.26% and viscosity reduction of 17.34% at
27 C. Disturbance of hydrogen bonding network of ethylene glycol by ZnO nanoparticles resulted in
reduced dispersion viscosity. Empirical models were developed to predict the thermal conductivity
enhancement and viscosity reduction of the nanouids apart from elucidating mechanisms for the same.
Transient heat transfer experiments showed that ZnOEG and ZnOEGwater nanouids had better heat
absorption characteristics compared to their respective base uids. The enhancements in heat transfer
were proportional to thermal conductivity enhancements, which showed that superior thermal conductivity of nanouids could be harnessed for cooling applications.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Thermal management and energy storage systems are thrust
areas of research in elds such as automobile/industrial cooling,
renewable energy utilization as evident from the recent literature
[111]. Maintenance of ideal working temperature by removing
the heat dissipated is essential for proper functioning of high speed
engines, microprocessors, etc. This has become a great challenge
due to increasing thermal loads driven by technological advancements. The strategies to improve efciency of heat transfer systems include active modes (increasing coolant velocity, use of
coolants with higher thermal conductivity) and passive modes
549
Nomenclature
Symbol
a, b, c
cp
k
m
Q
T
t
Uf
Uxj
x
y
Meaning
coefcients in Eq. (14)
specic heat (J/kg K)
thermal conductivity (W/mK)
mass (kg)
amount of heat transferred (W)
temperature (C)
time (s)
uncertainty associated with the measurement of parameter f
uncertainty in the measurement of variable Xj
function of nanoparticle concentration
function of nanoparticle concentration and temperature
A, B
N
Greek symbols
/
nanoparticle volume concentration
l
viscosity (mPa s)
q
density (kg/m3)
Subscripts
bf
base uid
nf
nanouid
r
relative/ratio
550
"
2 #0:5
N
X
@f
Uf
U xj
@xj
j1
Fig. 1. Schematic representation of the experimental setup used for heat transfer
experiments.
Fig. 2. (a) Scanning electron micrograph of synthesized ZnO nanoparticles and (b)
X-ray diffraction pattern of ZnO nanoparticles.
551
552
l AT B
Fig. 4. (a) Inuence of shear rate on viscosity of ZnOEG nanouids of different
concentrations and ethylene glycol and (b) inuence of nanoparticle volume
concentration on relative viscosity of ZnOEG nanouids.
the viscosities of ZnOEG nanouids might be due to the differences in nanouid formulation method (ultrasonication time/use
of surfactant), morphological characteristics of ZnO nanopowder
used, etc. which ultimately resulted in different aggregate size
distributions.
Intermolecular as well as intramolecular hydrogen bonding persists in ethylene glycol. Metal oxide nanoparticles are known to
have hydroxyl groups on their surface when dispersed in polar liquids [66]. Hydroxyl groups engaged in intramolecular and intermolecular hydrogen bonding between ethylene glycol molecules are
likely to form hydrogen bonds with hydroxyl groups on nanoparticles surface. Hence, the hydrogen bonding network of ethylene
glycol is reorganized.
At higher nanoparticle concentration, the number of ZnO nanoparticles interacting with ethylene glycol molecules was higher
and hence, perturbations to the hydrogen bonding network of ethylene glycol were enhanced leading to decrease in viscosity with
increasing nanoparticle concentration.
In our recent studies of propylene glycol based nanouids
[24,40,48,67], rheological behavior similar to that of ZnOEG
nanouids of the current study was observed. CuOPG,
ZnOPG, Fe2O3PG, sandPG, Mn0.43Fe2.57O4PG nanouids had
viscosities lesser than propylene glycol and perturbations in
hydrogen bonding network was identied as the rationale
behind the unusual rheological behavior of propylene glycol
based nanouids.
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nanoparticles to increased viscous dissipation is temperature-independent. Hence, viscosity of ZnOEG nanouid shows lower temperature dependence than pure ethylene glycol, with lowest
temperature dependence observed at the highest nanoparticle concentration (4 vol.%) investigated.
In order to further evaluate the effect of addition of nanoparticles on nanouid viscosity, the relative viscosity of nanouids was
calculated as follows:
Anf T Bnf
Abf T Bbf
3.1.2.2. Viscosity model. The abundance of suspensions and dispersions in practical applications puts forward the demand for development of models to predict viscosity. Einstein [71] derived an
expression to determine viscosity of dispersions of spherical,
non-interacting particles in a dilute suspension. Mooney [72] proposed a model for prediction of relative viscosity of concentrated
suspensions (/ > 0.05) in which empirical constants were used. A
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lr x y
lr 1 5:9765/ f T; /
Taking into account of the fact that the relative viscosity-nanoparticle concentration relationship is linear at all temperatures
(Fig. 8), the y in Eq. (4) is expected to vary linearly with nanoparticle concentration and non-linearly with temperature.
Using the relative viscosity data over a temperature range of
27140 C, the following empirical correlation was obtained using
Minitab 16 with a regression coefcient of 0.9135.
f T; / 5T 0:1802 /0:5455
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kr 1 7:926/
kr 1 3/
10
Comparing Eqs. (9) and (10), it can be observed that slope of the
Eq. (9) is about 2.64 times greater than that of HamiltonCrosser
equation (Eq. (10)). Anomalous enhancement in thermal conductivity of nanouids is due to nanoscale phenomena occurring in
the colloidal solidliquid dispersions. Microconvection induced
by Brownian motion of nanoparticles, ordered arrangement of
liquid molecules over solid nanoparticles (liquid layering), particle
clustering and ballistic heat transport [75] have been identied as
the major mechanisms responsible for anomalous enhancement of
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Liquid layering of propylene glycol molecules over ZnO nanoparticles was found to inuence thermal conductivity enhancement in ZnOPG nanouids and its unique temperature
dependence [57]. As propylene glycol and ethylene glycol have
similarity in chemical nature, the course of thermal conductivity
change with change in temperature can be explained by the liquid
layering of ethylene glycol molecules on ZnO nanoparticles
surface.
Fig. 12(c) shows the inuence of temperature on thermal conductivity of ZnOEG nanouids and ethylene glycol, the base uid.
Highest thermal conductivity enhancement was achieved at the
lowest temperature investigated, 10 C (Fig. 12c). The trend of variation of thermal conductivity of ZnOEG nanouids with temperature could be divided into two sections, (i) a temperature range
(1030 C), within which nanouid thermal conductivity
decreased with temperature and (ii) a temperature range (30
60 C), within which nanouid thermal conductivity was temperature-independent.
Ordered arrangement of liquid molecules over solid surfaces
have higher thermal conductivity compared to bulk liquid, since
the ordered liquid molecular structure mimics the atomic arrangement in crystalline solids with high thermal conductivity. The
thickness of such ordered layers greatly inuences thermal conductivity enhancement of nanouids and have been shown to
increase with decreasing temperature [57]. The thickness of ethylene glycol molecular layer increased with decreasing temperature
and the maximum thermal conductivity enhancement was
observed at the lowest temperature (10 C). It can also be observed
from Fig. 12c that the magnitude of the slope of the curve (10
30 C) increases with increasing concentration. Thermal conductivity increase at 10 C for 4 vol.%, 2 vol.% and 1 vol.% are 55%, 36% and
14% respectively. The amount of liquid layers contributing to thermal conductivity enhancement will be higher at higher concentrations owing to the presence of larger number of nanoparticles.
In our earlier work [57], a simplied form of Yu and Chois
model given below, was used to predict thermal conductivity
enhancement of ZnOPG nanouids at lower temperatures.
kr
knf
1 3/1 b3
kbf
11
kr 1 8:195/
12
From Eqs. (9) and (12), it is evident that the thermal conductivity enhancements of ZnOEG and ZnOEGwater nanouids are
comparable. This might be yet another testimony to the preservation of layers of ethylene glycol over ZnO nanoparticles.
The inuence of temperature on thermal conductivity of
ZnOEGwater nanouids (2 vol.%) is shown in Fig. 14b. Temperature-independent behavior of ZnOEGwater nanouids can be
attributed to the combined inuence of liquid layering and Brownian motion. As temperature increases, thickness of liquid layers
decreases and hence thermal conductivity decreases. This is offset
by Brownian motion due to lower dispersion viscosity. Hence,
these two phenomena counterbalanced each other resulting in
temperature-independent thermal conductivity of ZnOEGwater
nanouids.
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T at 2 bt c
15
Q ratio
Q nf
Q bf
16
Q mcp
dT
dT
V qcp
dt
dt
13
In Eq. (13), V is the volume of the test uid. The product of density and specic heat (qCp) was calculated as follows [79,80]:
14
The test uid temperaturetime data were tted using a polynomial equation for the entire duration of the experiment as
follows:
Table 1
Coefcients a and b and the intercept c for each of the test uid.
Nanoparticle volume concentration (%)
0
0.25
0.5
1
1.5
2
ZnOEG
ZnOEGwater
8.383E06
8.594E06
9.829E06
9.361E06
0.0292
0.0302
0.0332
0.0339
30.981
30.411
29.489
31.096
6.78E06
7.53E06
6.84E06
1.23E05
0.0286
0.0313
0.0321
0.0354
31.803
30.373
28.981
32.685
558
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