Experimental study on thermophysical properties of nanouids

as phase-change material (PCM) in low temperature cool storage

Qinbo He
a,b
, Shuangfeng Wang
a,
, Mingwei Tong
c
, Yudong Liu
c
a
Key Lab of Enhanced Heat Transfer and Energy Conservation, The Ministry of Education, School of Chemistry and Chemical Engineering, South China University of Technology,
Guangzhou 510641, China
b
Shunde Polytechnic, Foshan, Guangdong 528300, China
c
College of Power Engineering, Chongqing University, Chongqing 400044, China
a r t i c l e i n f o
Article history:
Received 17 December 2011
Received in revised form 13 April 2012
Accepted 13 April 2012
Available online 26 September 2012
Keywords:
Nanouids
Phase change material (PCM)
Thermophysical properties
Cool storage
a b s t r a c t
In this article, a new sort of nanouid phase change materials (PCMs) is developed by suspending a small
amount of TiO
2
nanoparticles in saturated BaCl
2
aqueous solution. Its thermal conductivities, supercool-
ing degree, latent heat, specic heat, and rheological behaviors of the nanouids PCMs were investigated.
The experimental results show that with volume fraction is 1.130%, the thermal conductivities of nano-
uids PCMs is enhanced by 12.76% at 5 C, the supercooling degree is reduced by 84.92%. The latent heat
and specic heat are slightly decreased with suspending nanoparticles. The viscosity increased with the
increasing volume fraction, which will have no effect on the cool storage system. The higher thermal per-
formances of nanouids PCMs indicate that they are suitable for the industries low temperature energy
storage.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Energy conservation and environment protection are the very
important topics in the eld of energy. Cool thermal energy storage
has become one of the primary solutions to the electrical power
imbalance between daytime need and nighttime abundance [1,2].
Phase change materials (PCMs) is a kind of very important latent
heat energy storage materials. It has wide applications in many
elds. Such as refrigeration and air conditioning systems, solar en-
ergy systems, and heating and cooling of buildings. It has attracted
great interest in recent years [36].
Inorganic compounds are the one of major categories PCMs
used in building cool storage applications. Most inorganic PCMs
such as salt hydrates are chemically stable and non-ignitable.
However, the problems of bigger supercooling degree and poor
thermal conductivity exist. The big supercooling degree make the
evaporating temperature of refrigerator lower, and reduce the
refrigeration efciency. In addition, the low thermal conductivity
unable to enhance the performance of energy storage devices.
Numerous investigation have been made to solve these thermal
properties limitation. On the one hand, in order to eliminate the
supercooling degree, many researchers used ultrasonic vibration
[7] or add some chemistry nucleating agents. For instance, silver
iodide, lead iodide, Okawa et al. [8,9] using a sheet of membrane
to induce freezing of supercooled solution. But those methods un-
able to improve the thermal conductivity of salt hydrates PCMs. On
the other hand, diverse methods have been proposed to improve
the thermal conductivity of PCMs: (1) PCMs embedded in a high
conductivity metal matrix structure [10]; (2) llers such as carbon
bers scattered in PCMs [11]; (3) nanoparticles embedded in PCMs
[12].
With the development of nanotechnology, an innovative heat
transfer uid arise. Nanouids, a suspension of metal or metal-
oxide nanoparticles in base liquid through a certain method, have
been considered as a new-type heat transfer uid because of their
enhanced thermal conductivities [1316]. Many researchers have
carried out similar studies for the heat transfer performance of
nanouids. For example, Lee and Choi [17] have tried to use nano-
uids and miniature heat exchangers constitute efcient cooling
system. In order to solve some special occasions heat dissipation
problems, nanouids were used in a different heat pipe for enhanc-
ing its thermal performance [1821].
In recent years, nanouids has been employed to enhance the
heat transfer in PCMs for energy storage, due to its desirable prop-
erties of high thermal conductivity. Khodadadi and Hosseinizadeh
[22] studied the phase change process of CuH
2
O nanouids by
using numerical simulation method. The nanouids shows the
preferable thermal energy storage characteristic, the heat release
rate is higher than that of pure water. Li and Zhu [23] performed
the experiments of cool storage feature for CuH
2
O nanouids.
The supercooling degree of CuH
2
O nanouids is reduced by
0196-8904/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.enconman.2012.04.010

Corresponding author. Tel.: +86 20 22236929.

E-mail address: sfwang@scut.edu.cn (S. Wang).
Energy Conversion and Management 64 (2012) 199205
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78.3% with nanoparticle mass fraction 1.0%. Wu et al. [24] investi-
gated the thermal properties of Al
2
O
3
H
2
O nanouids, they con-
cluded that the supercooling degree was reduced by 70.9% with
suspending 0.2 wt.% Al
2
O
3
nanoparticles in water. Shin and Baner-
jee [25] studied the high-temperature silica-nanouids for solar
thermal storage applications, the specic heat capacity of the
nanouid was enhanced by 14.5%. Li [26] has provided a series of
experimental studies on thermal properties of PCMs used for air
conditioning.
The previous researchers primarily focused on the nanouid
PCMs used in the air conditioning cool storage, which the phase
change temperatures is above 0 C. However, some enterprises,
such as the brewhouse and chemical plant, need the cool storage
temperature below 0 C. Up to present, few of investigations and
applications for nanouid PCMs in low temperature cool storage
are reported.
In this paper, in allusion to the low temperature refrigerating
system of a brewery in which refrigerants temperature is 4 C.
While the phase-change temperature of BaCl
2
H
2
O solution
(22.5 wt.%) is about 8 C. In consideration of the heat loss, the
4 C temperature difference is appropriate. So it was screened
out as a candidate for PCM. The problem is that it possess higher
supercooling degree and lower thermal conductivity, which are
undesirable. With the development of the technology for preparing
nanopowder, TiO
2
BaCl
2
H
2
O nanouids are prepared by a super-
sonic oscillator through appending hydrophilic dispersants into
BaCl
2
solution.
The mass fraction of BaCl
2
solution is 22.5 wt.%. The TiO
2
nano-
particles have the function of sterilization and water purication.
While suspending in BaCl
2
solution, it can not only as nucleating
agent [27], but also can enhance the thermal conductivity of the
PCMs [2830].
The most important thermophysical properties such as thermal
conductivity, latent heat of phase change, specic heat, degree of
supercooling and viscosity were investigated by experiments. The
aim is to analyze the effects of volume fraction of the TiO
2
nano-
particles suspended into nanouids PCMs. The relevant parameters
were compared with the basic liquid BaCl
2
H
2
O solution. The main
purpose of this study is to discuss the feasibility for TiO
2
BaCl
2

H
2
O nanouids PCMs apply to low temperature phase change cool
storage.
2. Experimental setup
2.1. Preparation of nanouids
We adopted two-step method to prepare the nanouids (ana-
tase TiO
2
, supplied by Chongqing Chemical Industry Co. Ltd., China;
the water is deionized water). The nanoparticle has a bigger spe-
cic surface area and surface energy because of its small size. It
is apt to reunite in the process of preparation, reprocessing and
the application. So it is the critical step to obtain well-distributed
and stabilized nanouids. The particle size was measured by TEM
(PHILIPS, TECRAI 20), as shown in Fig. 1. There are a few larger par-
ticles, which are likely aggregates of the smaller ones, but the
whole distribution of the particles is relatively well-dispersed.
The particles are basically spherical or near spherical, the average
diameter is about 20 nm.
First, suspend nano-TiO
2
particles into saturated BaCl
2
aqueous
solution with PH 8 (The pH was controlled using HCl and NaOH in
analytical grade), and add some of the hydrophilic surfactants to
the suspensions, then ultrasonicated for about 40 min (KQ2200DE,
Kunshan of Jiangsu Equipment Company, China). Four samples
were prepared for measurement. The nanoparticle volume fraction
of the samples is 0.167%, 0.283%, 0.565% and 1.130%, respectively.
The dose of surfactants is 0.06 vol%, 0.10 vol%, 0.19 vol%, 0.38 vol%,
respectively, referring to Zhu and Li [31]. All the volume fraction
can be calculated by the following expression [32]. The mass frac-
tion associated with volume fraction of the samples is shown in
Table 1.
1
/
m
1
1
/
m
1

q
p
q
f
1
where /
v
is the volume fraction of TiO
2
nanoparticle; /
m
is the mass
fraction of TiO
2
nanoparticle; q
f
is the density of BaCl
2
H
2
O solu-
tion, kg/m
3
; q
p
is the density of TiO
2
nanoparticle, kg/m
3
.
2.2. Measurement of thermal conductivity
The thermal conductivities of the TiO
2
BaCl
2
H
2
O nanouids
PCMs were measured with transient hot wire method (Fig. 2),
which has been used most extensively (Richard and Shankland
[33], Yu and Choi [34], Hong et al. [35]). The hot wire method is
a standard transient dynamic technique based on the measure-
ment of the temperature rise in a dened distance from a linear
heat source (hot wire) embedded in the test material. The platinum
wire is used both as heat source and as the temperature sensor
(thermocouple). A constant current is supplied to the wire to raise
its temperature. The heat dissipated in the wire increases the tem-
perature of the wire as well as that of the nanouid. This temper-
ature rise depends on the thermal conductivity of the nanouid
sample, in which the wire is inserted [36].
2.3. Measurement of supercooling degree
The degree of supercooling is an important parameter for PCMs.
On the one hand, the evaporating temperature of the refrigerator is
lower with more large supercooling degree, which will reduce the
efciency of refrigeration. On the other hand, before the PCMs
freezing, the energy storage only depends on sensible heat at that
time, which cannot store a good deal of cool storage capacity. Fig. 3
is the schematic diagram of supercooling degree measuring sys-
tem. It consists of a thermostatic bath and data acquisition system.
Fig. 1. TEM micrograph of TiO
2
nanoparticles.
Table 1
The wt.% associated with vol% of the samples.
wt.% vol%
0.07 0.167
0.13 0.283
0.25 0.565
0.50 1.130
200 Q. He et al. / Energy Conversion and Management 64 (2012) 199205
The bath temperature can reach 15 C, ethylene glycol (40 vol%)
as the refrigerating medium. The test tubes are immersed in the
thermostatic bath. The temperatures inside test tubes were mea-
sured by thermocouples (Type T). The test precision of thermocou-
ples is 0.2 C, and they were calibrated by a precision
thermometer. All thermocouples were connected to the data
acquisition system ADAM4000.
2.4. Measurement of latent heat and specic heat
The latent heat and specic heat will affect the cool storage
density and the volume of cool storage bath, which is one of the
main parameter to choose PCMs. The latent heat and specic heat
were tested by Differential Scanning Calorimetry (DSC, made in
German NETZSCH company, DSC-200 PC Phox).
2.5. Measurement of viscosity
The viscosity was measured by cone-and-plate viscometer with
a type rotor system (NXE-1B, made in chengdu China). The appara-
tus can measure the viscosity of all kinds of newtonian uid and
the apparent viscosity of Non-newtonian uid, the temperature
of sample can be controlled by the thermostatic bath with a tem-
perature accuracy of 0.1 C.
3. Results and discussion
3.1. Thermal conductivity
In order to investigate the effect of temperature on the
enhancement of the thermal conductivity, the thermal conductiv-
ity data ranging from 5 to 25 C (Figs. 4 and 5) are measured.
Fig. 4 shows the enhanced thermal conductivity as a function of
volume fraction of TiO
2
suspended into nanouids PCMs. k and k
f
stand for the thermal conductivity of the nanouids PCMs and
BaCl
2
solution, respectively. The data indicates that the thermal
conductivity of nanouid increases nearly linearly with volume
fraction of the nanoparticles. The trends show a good agreement
with the previous research [37]. When the volume fraction is
1.130%, thermal conductivity is increased up to 16.74% at 25 C,
while at low temperature the thermal conductivity can also be en-
hanced obviously, the enhancement value is up to 12.76% at 5 C.
At low temperature, the Brownian motion is relative weak, the
main reason for enhancing thermal conductivity may be due to
the surface charge states of nanoparticle surface [38]. This feature
is important for nanouids PCMs used in low temperature cool
storage, because the thermal conductivity of BaCl
2
H
2
O solution
will decline with the temperature dropping, and affect the ef-
ciency of cool storage and cool discharge.
The increase in thermal conductivities illustrates that the con-
centration of nanoparticles is an important factor in improving
thermal transport properties of TiO
2
BaCl
2
H
2
O nanouids PCMs.
In addition, as can be seen from Fig. 5, a very similar trend of ther-
mal conductivity enhancement with changing the nanouids tem-
perature was observed in different volume fraction of
nanoparticles. For instance, the thermal conductivity with nano-
particles of 0.565 vol% increased 12.1% as temperature is increased
from 5 to 25 C, which indicates the strong temperature effects of
nanouids PCMs. This phenomenon may be due to the fact that as
temperature is increased, the dynamic viscosity of a base uid is
decreased. So the Brownian motion of the nanoparticles is in-
creased [39].
1-rubber ball, 2-red copper slider, 3-water bath, 4-nanofluid samples, 5-platinum wire,
6-rubber plug, 7- spring, 8-glass tube
To Wheatstone bridge
ethylene glycol outlet
ethylene glycol inlet
Fig. 2. Schematic diagram of transient hot wire instrument.
1-computer, 2-data transform module,3-data acquisition module,
4-thermocouple,5-tube, 6-nanofluids, 7- thermostatic bath
Fig. 3. Schematic diagram of supercooling degree measuring system.
1.00
1.02
1.04
1.06
1.08
1.10
1.12
1.14
1.16
0.000 0.167 0.283 0.565 1.130
Volume fraction (%)
T
h
e
r
m
a
l

c
o
n
d
u
c
t
i
v
i
t
y

r
a
t
i
o

(
k
/
k
f
)
-5
0
5
10
15
20
25
Fig. 4. Thermal conductivity ratio (k/k
f
) as a function of temperature at different
volume fraction of TiO
2
.
0.52
0.54
0.56
0.58
0.60
0.62
0.64
0.66
0.68
0.70
0.72
-10 -5 0 5 10 15 20 25 30
T
h
e
r
m
a
l

c
o
n
d
u
c
t
i
v
i
t
y

(
W
/
m

K
)
0% 0.167%
0.283% 0.565%
1.130%
Temperature (C)
Fig. 5. Thermal conductivity as a function of temperature at different volume
fraction of TiO
2
.
Q. He et al. / Energy Conversion and Management 64 (2012) 199205 201
3.2. Supercooling degree
Freezing experiments were performed for TiO
2
BaCl
2
H
2
O
nanouids and BaCl
2
H
2
O solution, the aim is to analyze the effect
of supercooling degree with suspended nanoparticles into BaCl
2

H
2
O solution. The four samples and BaCl
2
H
2
O solution were
transferred into ve test tubes, these tubes were immersed into
the thermostatic bath. In the test, the temperature of the bath
was kept at 15 C during the cooling period and at 15C during
the melting period. The interval time of data acquisition is 30 s,
each experiment was repeated six times to calculate the mean va-
lue of the experimental data.
The cooling curves of nanouids PCMs are shown in Fig. 6. The
results show that the nanoparticle volume fraction has an enor-
mous inuence on the nucleating supercooling degree and the
beginning nucleation time. The supercooling degree of nanouids
PCMs is reduced constantly with the nanoparticle volume fraction
increasing. Moreover, the total freezing time is lower than that of
BaCl
2
H
2
O solution. As can be seen from Fig. 6, the supercooling
degree of TiO
2
BaCl
2
H
2
O (0.167 vol%) is 2.93 C, which is reduced
by 22.49% than that of BaCl
2
H
2
O solution (3.78 C), and the begin-
ning nucleation time is ahead of 270 s. As the nanoparticle volume
fraction is increased up to 1.13%, the supercooling degree is re-
duced by 84.92%. The degree of supercooling was nearly elimi-
nated, the time of beginning nucleation is ahead of 1050s, and
the total freezing time is reduced by 64.5%. If the nanouids PCMs
are used into cool storage system, it can not only increase the evap-
orating temperature, but also reduce the running time of refriger-
ator, and enhance the efciency of refrigerators. The specic values
of phase change temperature, supercooling degree are listed in
Table 2.
The uncertainty of super cooling degree can express with the
formula recommended by Moffat [40], here the TiO
2
BaCl
2
H
2
O
(1.130 vol%) as the example, the data is shown in Table 3.
dDT
DT

dT
n
T
n

2

dT
m
T
m

2
" #
0:5
dT
n
T
n

0:13
9:29
1:40%
dT
m
T
m

0:05
8:72
0:57%; and
dDT
DT
1:51% 2
where T
n
is supercooling temperature; T
m
is phase change temper-
ature; DT is supercooling degree, DT = T
m
T
n
.
The supercooling degree of base uid is reduced obviously with
mixed nanoparticles, this phenomenon can be explained by the
mechanism of heterogeneous nucleation. The energy barrier for a
cluster to overcome before it grows irreversibly as a crystal can
be dened as [41]:
DG

C

16pc
3
SL
X
2
S
3Dg
2
f h 3
f h
2 cos h1 cos h
2
4
4
where X
S
is the volume per particle and c
SL
is the interface solidli-
quid free energy, Dg is the free energy difference of per particle be-
tween liquid and crystalloid. The factor 16/3 is related to the shape
of the nucleus, which is assumed to be spherical. h is the contact
angle.
From the Eq.(3), (4), only the h is reduced can the DG

C
lessen, if
the h is equal to zero degree, the effect of nucleation is the highest.
The relation between h and surface energy dened as:
cos h
r
LB
r
SB
r
LS
5
Here r
LB
is the specic surface free energy between nanoparti-
cle and uid; r
SB
is the specic surface free energy between crystal
nucleus and nanoparticle; r
LS
is the specic surface free energy be-
tween crystal nucleus and uid. So the r
SB
is more little, the cos h is
more equal to one, and the DG

C
is more equal to zero. The crystal
nucleus can be formed nearly without supercooling degree.
According to the principle of similar structure and corresponding
dimension is that the crystal face structure of nanoparticles and
base uid is more similar the surface free energy r
SB
will be more
less, in this paper, the size of TiO
2
nanoparticle is about 20 nm,
which is close to BaCl
2
H
2
O solution. Consequently, the r
SB
be-
tween crystal nucleus and nanoparticles is little, and the wetting
and contacting between nanoparticles and liquid can be very well.
The contact angle is close to zero degree, and the supercooling de-
gree of nanouids is also approach zero degree. Thus, it is feasible
to choose the nanoparticles for nucleating agent.
On the other hand, the development of crystalloid is depend on
its heat transfer, which will release abundant latent heat when it
crystallizing, if the heat cannot be moved, crystallization will be
hold-up. The nanouids has the higher thermal conductivity than
the base liquid, therefore, the speed of growth for crystalloid will
accelerate, and the rate of freezing enhanced greatly.
-20
-15
-10
-5
0
5
10
15
0 4000 8000 12000 16000 20000
Time (s)
0.565%
0%
0.167%
1.130%
0.283%
T
e
m
p
e
r
a
t
u
r
e

(

C
)
Fig. 6. Cooling curve of TiO
2
BaCl
2
H
2
O with different nanoparticle volume
fraction.
Table 2
Supercooling degree of BaCl
2
H
2
O and TiO
2
BaCl
2
H
2
O.
Volume fraction (%) T
n
(C) T
m
(C) DT (C) (DT
bf
DT
nf
)/DT
bf
(%)
0.000 11.94 8.16 3.78
0.167 11.54 8.61 2.93 22.49
0.283 11.12 8.61 2.51 33.60
0.565 10.49 8.61 1.88 50.26
1.130 9.29 8.72 0.57 84.92
Notes: T
n
, supercooling temperature; T
m
, phase change temperature; DT, superco-
oling degree, DT = T
m
T
n
; DT
bf
, the supercooling degree of BaCl
2
H
2
O; DT
nf
, the
supercooling degree of TiO
2
BaCl
2
H
2
O.
Table 3
Uncertainty analysis of super cooling degree (TiO
2
BaCl
2
H
2
O:1.130 vol%).
Times T
n
(C) T
m
(C)
1 9.23 8.75
2 9.42 8.69
3 9.26 8.77
4 9.21 8.74
5 9.25 8.69
6 9.37 8.68
Mean value 9.29 8.72
202 Q. He et al. / Energy Conversion and Management 64 (2012) 199205
3.3. Latent heat and phase change temperature
DSC melting curve of TiO
2
BaCl
2
H
2
O is shown in Fig. 7, the
area that composed by the tangent of phase change baseline and
endothermic peak is the melting latent heat. Figs. 8 and 9 show
the latent heat and phase change temperature at different volume
fraction of TiO
2
nanoparticle, respectively. As can be seen form the
data, the latent heat of the TiO
2
BaCl
2
H
2
O (0.167 vol%) dropped
very little, but when the nanoparticle volume fraction reach
0.283 vol%, the latent heat has a drastic drop. According to the the-
ory of mixtures, the latent heat of TiO
2
BaCl
2
H
2
O is equal to the
values calculated by multiplying the latent heat value of BaCl
2

H
2
O with its mass fraction in the nanouids PCM. May be above
phenomenon can be explained as follows: (1) the 0.283 vol% nano-
particles reduced the concentration of BaCl
2
H
2
O highly, while the
nanoparticles will not change its phase at 8 C. Hence, the latent
heat of the TiO
2
BaCl
2
H
2
O is offered completely by BaCl
2
H
2
O,
which result in the latent heat dropping; (2) after the nanoparticles
composite with BaCl
2
H
2
O, a fraction of liquid phase BaCl
2
H
2
O
coat in the surface of nanoparticles. when the composites phase
change, the molecular arrangement of liquid in the lm changed,
the state of its free energy also changed. Surface free energy occupy
big proportion in the system energy. Hence, the thermal property
of system is affected [42].
Although the latent heat of nanouids is reduced, but the extent
is slight. For example, the latent heat of TiO
2
BaCl
2
H
2
O
(1.130 vol%) is 254.2 kJ/kg, which is only reduced by 9.57%. In addi-
tion, the lower phase change temperature (as can be seen from Ta-
ble 2) make nanouids PCMs supply the more sensible heat than
that of the basic liquid, which can reduce the temperature of cool-
ants, and in favor of minishing the size of coolants running piping,
saving energy consumption.
The phase change temperature (Fig. 9) is affected very little for
different TiO
2
nanoparticle volume fractions. The maximum
change is 2.84%, which could be negligible. The above similar re-
sults were also found by Wu et al. [24].
The thermal reliability of PCMs is very important, otherwise it
will affect the performance of the thermal storage system. In this
experiment, the TiO
2
BaCl
2
H
2
O with nanoparticle volume frac-
tion 1.130 vol% was used to test its thermal stability. After
50 times melting/freezing cycling, the results show the thermal
performance is stable (see Figs. 10 and 11), the data indicates that
the change of latent heat and phase change temperature is very lit-
tle, the maximum change of latent heat only is 0.16%, and 1.55% is
the maximum change of phase change temperature. These changes
are negligible for latent heat thermal energy storage applications.
3.4. Specic heat
Fig. 12 shows the specic heat as a function of temperature at
different volume fraction of TiO
2
. It can be seen that the specic
heat is reduced on addition of nanoparticles. Along with the vol-
ume concentration increased, the value of specic heat decreases
more. For example, the specic heat value of nanouid is decreased
-25 -20 -15 -10 -5 0 5
Temperature /C
0
0.5
1.0
1.5
2.0
2.5
Onset: -9.4 C
End: -3.5 C
Peak: -5.9 C
Peak: -8.5 C
Area: 279.5 J/g

DSC /(mW/mg)
Fig. 7. DSC melting curve of TiO
2
BaCl
2
H
2
O (0.167 vol%).
240
250
260
270
280
290
300
0.000 0.200 0.400 0.600 0.800 1.000 1.200
Volume fraction (%)
L
a
t
e
n
t

h
e
a
t

(
k
J
/
k
g
)
Fig. 8. Latent heat of TiO
2
BaCl
2
H
2
O with different volume fractions.
-12
-11
-10
-9
-8
-7
-6
-5
-4
0.000 0.200 0.400 0.600 0.800 1.000 1.200
Volume fraction (%)
Fig. 9. Phase change temperature of TiO
2
BaCl
2
H
2
O with different volume
fractions.
240
250
260
270
0 10 20 30 40 50 60
Cycling times (times)
L
a
t
e
n
t

h
e
a
t

(
k
J
/
k
g
)
Fig. 10. Effect of thermal cycles on the latent heat (TiO
2
BaCl
2
H
2
O:1.130 vol%).
Q. He et al. / Energy Conversion and Management 64 (2012) 199205 203
by 2.9% and 12.4% with 0.167 vol% and 1.130 vol% at 10 C, respec-
tively. The corresponding value is 2.3% and 9.0% at 80 C. However,
the temperature has less affection on specic heat. The maximum
change is 3.1% for 1.13 vol% nanouid between 10 C and 80 C,
which could be negligible in small temperature range.
Wu [43] and Zhou and Ni [44] tested the specic heat on Cu-
parafn nanouid and Al
2
O
3
H
2
O nanouid, respectively. The re-
sults show that the specic heat of nanouids will reduced with
the increase of the volume fraction of nanoparticles. On the con-
trary, Shin and Banerjee [45] reported that the specic heat capac-
ity of alkali metal chloride salt eutectics doped with silica
nanoparticles enhanced by 14.5% at 1% mass concentration of
SiO
2
. There are two reasons to affect the specic heat of composite
material. On the one hand, the specic heat of nanoparticles affects
that of the composite material. If the nanoparticles specic heat is
less than the basic liquid, the specic heat of suspension will les-
sen. Otherwise it will rise, for instance, the specic heat of carbon
nano-tube (CNT) is higher than that of ethylene glycol, the specic
heat of CNT glycol nanouid is enhanced [46]. On the other hand,
the interfacial free energy of solidliquid is changed with sus-
pended nanoparticles. Because of the nanoparticles bigger specic
surface area, its surface free energy has a greater proportion in the
system capacity, which affect the specic heat of composite mate-
rials [47].
3.5. Viscosity
Fig. 13 shows the viscosity as a function of temperature at dif-
ferent volume fraction of TiO
2
. The viscosity of nanouids increases
with increasing the volume fraction in agreement with other stud-
ies [4850]. For example, the viscosity of 0.167 vol% TiO
2
BaCl
2

H
2
O is only increased up to 2.86% at zero temperature, while the
particle volume fraction of TiO
2
is 1.13 vol%, the viscosity can be in-
creased by 31.9%. May be it can be explained like this. As the par-
ticle volume fraction increases, the distance between particles
decreases. The frictional force among nanoparticles and between
nanoparticle and water molecule are enhanced quickly. It mani-
fests the increase of viscosity in macroscopic [51,52].
The viscosity of TiO
2
BaCl
2
H
2
O nanouids increases in accor-
dance with increasing particle concentration in the suspension,
which will increase the system ow resistance when used heat
transfer in pipe ow. However, when the nanouids used as the
PCMs, it is general storaged in the ice storage tank, which need
not consume the pump power. Therefore, the high viscosity has
no negative effect on cool storage system. On the contrary, the high
viscosity is in favor of the suspension stable for nanoparticles [53].
As can be easily observed from Fig. 13, the viscosity is reduced
with the increase of the temperature. When the temperature goes
up, the Brownian motion enhances. Consequently, the forces be-
tween particles decreases, which can cut down the ow resisting
force and heat resistance.
4. Conclusions
In order to improve the thermophysical property of BaCl
2
H
2
O
PCMs, the potential of TiO
2
BaCl
2
H
2
O nanouids as a new sort of
phase change material was investigated in this study. The thermal
conductivity of TiO
2
BaCl
2
H
2
O nanouids is enhanced obviously.
It is increased up to 16.74% as the volume fraction is 1.130%. The
supercooling degree of TiO
2
BaCl
2
H
2
O nanouids is improved
tremendously. Hence, using the nanopartilces as the nucleation
seed crystal is superior to other nucleating agents. The latent heat
of TiO
2
BaCl
2
H
2
O nanouids (257.4 J/g) is slight less than that of
BaCl
2
H
2
O solution, but greater than that of NaClH
2
O solution
(236.1 J/g) and CaClH
2
O solution (212.6 J/g). The specic heat is
slightly reduced on addition of nanoparticles. The viscosity of
TiO
2
BaCl
2
H
2
O nanouids increases in accordance with increas-
ing particle concentration in the suspension and with declining
temperature. From previous, it can be recommended that the low
temperature TiO
2
BaCl
2
H
2
O nanouids PCMs is suitable for the
industries low temperature energy storage.
1
1.5
2
2.5
3
3.5
4
0.000 0.500 1.000 1.500 2.000
Volume fraction (%)
V
i
s
c
o
s
i
t
y

(
m
P
a

s
)
-8
-5
0
5
10
15
20
Fig. 13. Viscosity as a function of temperature at different volume fraction of TiO
2
.
-10.0
-9.5
-9.0
-8.5
-8.0
-7.5
-7.0
0 10 20 30 40 50 60
Cycling times (times)
Fig. 11. Effect of thermal cycles on the phase-change temperature (TiO
2
BaCl
2

H
2
O:1.130 vol%).
2
2.5
3
3.5
4
4.5
5
0 10 20 30 40 50 60 70 80 90
0% 0.167%
0.283% 0.565%
1.130%
Fig. 12. Specic heat as a function of temperature at different volume fraction of
TiO
2
.
204 Q. He et al. / Energy Conversion and Management 64 (2012) 199205
Acknowledgments
This work was supported by Natural Science Foundation of Chi-
na (No. 51146009) and the International Cooperation and Ex-
change Program from the Ministry of Science and Technology of
China (Grant No. 2011DFA60290).
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