Indian Journal of Pure & Applied Physics

Vol. 49, February 2011, pp. 117-125

Experimental study of supercooling and pH behaviour of a typical phase change
material for thermal energy storage

V V Tyagi
1
*, S C Kaushik
1
,
A K Pandey
2
& S K Tyagi
2

1
Centre for Energy Studies, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110 016, India
2
School of Infrastructure Technology & Resource Management, Shri Mata Vaishno Devi University, Katra 182 320 (J&K), India
*E-mail: vtyagi16@gmail.com; sudhirtyagi@yahoo.com
Received 4 February 2010; revised 6 October 2010; accepted 3 January 2011
Thermal energy storage plays an important role in the storage of available energy and hence, improves its utilization
during odd hours especially, in the presence of an intermittent heat source. Phase change materials (PCMs) also play very
important role in thermal energy storage due to their qualities to store more heat in small volume. But there are some
disadvantages in most of the inorganic PCMs, such as fluctuation in their normal freezing point, known as supercooling
behaviour. There are certain additives that play an important role in minimizing and/or removing the supercooling behaviour
of different PCMs. In the present study, the supercooling behaviour of a typical PCM and the effect of pH value have been
studied. The results obtained through experimental study have been compared with those obtained through differential
scanning calorimeter (DSC) and found to be in good agreement with each other.
Keywords: Thermal energy storage, Phase change materials, Supercooling, Differential scanning calorimeter
1 Introduction
Phase change materials play a very important role
in the thermal energy storage and heating and cooling
applications. Nowadays, a number of phase change
materials (PCMs) both organic and inorganic are
available in the market depending on the requirement
of melting and freezing points. As some of the energy
sources are intermittent in nature, both the short and
long term thermal energy storage are essential for
most of the applications. Both long and short term
thermal energy storage are equally important for
useful applications such as heating and cooling of
buildings, space air-conditioning, power generation
and so on. There are various thermal energy storage
methods, but the latent heat storage is the most
attractive due to the high storage density and a small
temperature variation for its retrieval. The application
of thermal energy storage includes solar energy,
greenhouse agricultural, temperature regulating in
textile, heat management of electronic and
telecommunication equipments, heating and cooling,
and space air-conditioning applications
1
.
The use of PCMs for construction of thermal
energy storage has been a subject of considerable
interest for the last few decades, due to their
interesting feature to store both the latent heat and the
sensible heat. As a PCM absorbs heat, its phase
change from solid to liquid and/or liquid to gas while
its temperature almost remains constant. On the other
hand when PCMs releases heat the temperature again
remains constant but its phase changes from liquid to
solid and/or gas to liquid. The heat absorbed or
released during these processes is a physical
phenomenon and since the temperature is nearly
constant during these processes, it is also known as
isothermal (heating and cooling) energy storage. The
materials to be used for thermal energy storage must
exhibit some physical, chemical and thermal
properties such as a large latent heat and high thermal
conductivity.
A PCM should have a melting temperature lying in
the practical range of operations depending on the
requirement of a particular application. For example,
it should melt congruently with minimum
supercooling and it must be chemically stable,
cheaper, and easily available besides, it must be non
toxic and non corrosive. The materials that have been
studied during the last four decades are hydrated salts,
paraffin waxes, fatty acids and eutectics of organic
and inorganic compounds. Latent heat storage
medium such as inorganic salts and organic materials
are more attractive than those of the sensible heat
storage medium due to the fact that the former has
higher heat storage density and a narrower
temperature range for the heat storage and recovery
cycles, while it is reverse in the case of later
2
. The
INDIAN J PURE & APPL PHYS, VOL 49, FEBRUARY 2011


118
inorganic salt hydrates as latent heat storage materials
have certain advantages over the organic materials in
the same melting temperature range. The salt hydrates
among the PCMs usually have high latent storage
densities, and they are non flammable because of
lower vapour pressure. However, practical difficulties
usually arise in the use of PCMs due to the low
thermal conductivity, density variations, instability of
properties under extended cycling and sometimes
phase segregation, especially, in salt hydrates and
supercooling
3
.
Among the above mentioned materials, hydrated
salts in general, are the most attractive materials for
thermal energy storage due to their high volumetric
storage density, relatively high thermal conductivity,
and moderate costs as compared to paraffin waxes,
with few exceptions. Besides, the temperature
remains nearly constant during the phase change,
which is beneficial for both the supply and demand,
especially, for active and passive heating/cooling and
space air-conditioning applications
4
. The previously
researched (PCM) salt hydrates are made of calcium
chloride hexahydrate (CaCl
2
.6H
2
O) and possess a
very high storage capacity due to a comparatively
high density but there are some crucial disadvantages
such as supercooling and phase instability
5
. A number
of researchers
6-9
have used the hydrated salts in direct
contact heat transfer between the immiscible heat
transfer fluid and the hydrated salt solution. Some of
the hydrated salts studied so far include
Na
2
SO
4
.10H
2
O, Na
2
HPO
4
.12H
2
O, NaCO
3
.10H
2
O, and
Na
2
S
2
O
4
.5H
2
O. These salts are generally, either
acidic or alkaline in nature besides; they react with
certain types of containers, so it is very important to
neutralize them before being used in thermal energy
storage.
In spite of the problems associated with hydrated
salts, non-agitated thermal energy storage materials
have been preferred. Nagano et al.
10
investigated the
phase change materials in the temperature range of
60-90C. They studied a particular PCM viz.
magnesium nitrate hexahydrate using a suitable
additive to regulate the melting point. The addition of
5-10 weight percentage of the additive resulted in a
regulated melting point of around 80C and the heat
of fusion of about 150 kJ/kg. Nagano et al.
10
also
found that the increasing mix ratio has a little effect
on the heat of fusion, while it has a significant effect
on the melting point. The repeated melting and
solidification tests showed that the heat of fusion and
melting point retained their original values after 1000
cycles. Ryu et al.
11
have performed extensive study on
suitable thickening and nucleating agents, which can
be used for a number of hydrated salts. Sari and
Karaipekli
12
studied the thermal conductivity and
latent heat storage characteristics of paraffin/
expended graphite composite as PCM through
differential scanning calorimeter (DSC) analysis.
They observed that by increasing the thermal
conductivity, the melting time decreases. They also
found that the variation in melting temperature is
negligible and the latent heat was observed
approximately equal to the original value of the
mixture.
In the present study, the degree of super heating
and the variation of pH value on the thermo-physical
properties of calcium chloride hexahydrate
(CaCl
2
.6H
2
O) has been carried out because it is easily
available in the market and has low cost than those of
the other PCMs salts. The latent heat of CaCl
2
.6H
2
O
is very high and the normal freezing temperature is
24C, which make it suitable for the use in building
heating/cooling and space air-conditioning
applications. But it has a disadvantage of super-
cooling, besides, it is acidic in nature.
2 Experimental Details
In the present study, commercial grade CaCl
2
.6H
2
O
salt was chosen and the necessary pH balance was
done using laboratory grade NaOH. The experiment
for the repeated hundred melt-freeze cycles has been
conducted in the laboratory to study the supercooling
behaviour at different pH values and the latent heat of
fusion was studied through DSC. The experimental
setup consists of a constant temperature unit,
thermocouples and data acquisition unit attached with
a PC for analysis. The constant temperature set-up
with cold and hot water unit has a temperature range
of 0 to 35C with resolution of 0.1C (Fig. 1).
Calibrated J-type thermocouples were used to
measure the temperature. In one side of the setup
there was a transparent glass window to check the
physical state (phase) of the PCM. The experimental
study was divided into two parts (i) to balance the pH
and (ii) to remove/minimize the supercooling. The
latent heat of fusion and the melting temperature were
also measured by DSC (Q-100) TA Instrument USA,
using an additive after 1
st
, 25
th
, 50
th
and 100
th
cycles.
The properties of the present chemical and the
specifications of the instrument are given in Table 1
and the results for different melt-freeze cycles by
DSC are given in Table 2, while the photographic
view of the instrument is shown in Fig. 2.
TYAGI et al.: SUPERCOOLING AND PH BEHAVIOUR OF PHASE CHANGE MATERIAL


119


Fig. 1 Experimental set-up with cold and hot water
temperature units

Table 1 Feature of the calcium chloride hexahydrate salt
and the specifications of Differential Scanning Calorimeter

Properties of the PCM Value

Freezing point of the calcium chloride
hexahydrate
24.0C *
Specific heat of Calcium chloride
hexahydrate
(I) Solid


1.4 kJ/kgC
(II) Liquid 2.1 kJ/kgC
Latent heat of calcium chloride hexahydrate 135 kJ/kg *
Density of calcium chloride hexahydrate (35
C)
1470 kg/m
3 **

Thermal conductivity of calcium chloride
hexahydrate
(I) Solid

1.09 (W/m C)
(II) Liquid 0.54 (W/m C)
Specifications of the DSC used in the present study
Temperature range -180 to 725 C

Temperature accuracy 0.1 C
Temperature precision 0.05 C
Sensitivity 0.2 W

*Measured by Differential Scanning Calorimeter (DSC)
**Measured by Hydrometer


Table 2 DSC test results on 1
st
, 25
th
, 50
th
, 100
th
Cycle

Sample with pH 5.3 Sample with pH 6.0
M
e
l
t
-
f
r
e
e
z
e

c
y
c
l
e
s

Latent Heat
(kJ/kg)
Freezing
Temp.
(C)
Latent Heat
(kJ/kg)
Freezing
Temp.
(C)

1
st
131 24.58 123.4 24.0
25
th
135.6 24.58 132.2 24.59
50
th
130.3 24.82 130.1 24.95
100
th
129.4 24.80 130.0 24.75

Sample with pH 6.5 Sample with pH 7.0

1
st
135.2 24.47 133.3 24.15
25
th
130.3 24.68 134.4 24.21
50
th
129.5 24.63 128.1 24.97
100
th
131.8 24.54 133.1 24.50



Fig. 2 Camera snaps of differential scanning calorimeter (DSC)

2.1 Balancing of pH
A 25 ml sample of CaCl
2
.6H
2
O at room
temperature was taken and NaOH solution was used
to attain a pH of 7.0 in steps for four different samples
as below:

i) pH 5.3 (initial),
ii) pH adjusted to 6.0,
iii) pH adjusted to 6.5, and
iv) pH adjusted to 7.0.

All four samples, mentioned above, have been
categorized as pH 5.3, pH 6.0, pH 6.5, and pH 7.0,
respectively. After adjusting the pH value, all the
samples were used for cycle testing from 1 to 100
cycles and the supercooling behaviour was analyzed
and the results of 1
st
, 25
th
, 50
th
, 100
th
cycle are shown
on the respective graphs in Figs 3-10. In order to
remove and/or minimize the supercooling of
CaCl
2
.6H
2
O, the experiment was repeated for total
two hundred heating and cooling cycles into two steps
viz. one hundred cycles with additive and another
hundred cycles without additive. The study of all the
four samples without additive for one hundred cycles
and with a variable weight percentage of the additive
for another hundred cycles have been carried out
thoroughly and the results were compared with those
obtained through DSC analysis.

3 Results and Discussion
3.1 Without additive
The pH value of CaCl
2
.6H
2
O was balanced using
NaOH solution in all four samples taking initial pH
value of 5.3 and has been analyzed up to 100 cycles.
Each sample exhibits different behaviour after each
cycle and the results of four different melting and
freezing (1
st
, 25
th
, 50
th
and 100
th
) cycles are shown in
their respective figures.
INDIAN J PURE & APPL PHYS, VOL 49, FEBRUARY 2011


120



Fig. 3 Variation in freezing temperature of Cacl
2
.6H
2
O without additive at different pH values after 1
st
melt-freeze cycle



Fig. 4 Variation in freezing temperature of Cacl
2
.6H
2
O without additive at different pH values after 25
th
melt-freeze cycle
TYAGI et al.: SUPERCOOLING AND PH BEHAVIOUR OF PHASE CHANGE MATERIAL


121


Fig. 5 Variation in freezing temperature of Cacl
2
.6H
2
O without additive at different pH values after 50
th
melt-freeze cycle



Fig. 6 Variation in freezing temperature of Cacl
2
.6H
2
O without additive at different pH values after 100
th
melt-freeze cycle
INDIAN J PURE & APPL PHYS, VOL 49, FEBRUARY 2011


122


Fig. 7 Variation in freezing temperature of Cacl
2
.6H
2
O with additive at different pH values after 1
st
melt-freeze cycle



Fig. 8 Variation in freezing temperature of Cacl
2
.6H
2
O with additive at different pH values after 25
th
melt-freeze cycle
TYAGI et al.: SUPERCOOLING AND PH BEHAVIOUR OF PHASE CHANGE MATERIAL


123


Fig. 9 Variation in freezing temperature of Cacl
2
.6H
2
O with additive at different pH values after 50
th
melt-freeze cycle



Fig. 10 Variation in freezing temperature of Cacl
2
.6H
2
O with additive at different pH values after 100
th
melt-freeze cycle
INDIAN J PURE & APPL PHYS, VOL 49, FEBRUARY 2011


124

To study the melting-freezing behaviour of
different samples, the temperature of the experimental
unit was set at 20C for the first cycle. As can be seen
from Fig. 3 that sample with pH 5.3 freezes at 24.4C
while sample with pH 6.0, pH 6.5 and pH 7.0 could
not be freezed. The temperature of the setup was
further decreased up to 15, 10 and 0C to solidify
other samples with pH 6.0, pH 6.5 and pH 7.0. These
samples were in the liquid phase up to temperature of
7.8, 5.2 and 6.2C, respectively but as their
temperatures further decrease all the samples solidify
simultaneously. The result of all samples with pH 5.3,
6.0, 6.5 and 7.0 after 25
th
cycle shows different
behaviour in comparison to that of 1
st
cycle, which
means the supercooling still exists in all the samples.
As a result, sample with pH 5.3 freezes at 24.6C and
hence, there is no supercooling in this particular
sample up to 25
th
cycle as can be seen clearly from
Fig. 4.
As the testing continued further up to 100
th
cycle
with an interval of 25 cycles, the supercooling was
observed after 50
th
and 100
th
cycles (Figs 5-6). As a
result sample with pH 5.3 was found to be in the solid
state at 9.9C and 13.1 C at 50
th
and 100
th
cycle,
respectively. Similar results were observed in other
samples with pH 6.0, 6.5, and 7.0. Sample with
pH 6.0 was found to be in the solid state at 7.2 C, 1.9
C, and 7.5 C, respectively, after 25
th
, 50
th
, and 100
th

cycles. On the other hand, samples with pH 6.5 and
pH 7.0 were solidify at 24.6C and 7.6C after 25
th

cycle, at 1.1C, and 1.4C after 50
th
cycle, and at
10.1 C and 1.2C after 100
th
cycle, respectively. The
above results exhibit that the supercooling exists in all
the samples mentioned above without any additive as
can be seen clearly from Figs 3-6.
3.2 With additive
In order to remove and/or minimize the
supercooling, the second part of the experiment was
conducted with a variable weight percentage of an
additive in all the four samples with pH 5.3, 6.0 6.5
and 7.0 as mentioned above. The experiment was
repeated up to 100 cycles in the same way as it has
been done without additive in the previous section.
After 1
st
test cycle, it was observed that sample with
pH 5.3 freezes at temperature of 23C, while samples
with pH 6.0 and pH 6.5 freeze at 24C. On the other
hand, sample with pH 7.0 solidify at 23.5C as can be
seen from Fig. 7. Figure 7 shows that all the samples
with pH values of 5.3, 6.0, 6.5 and 7.0, have very
small degree of supercooling after a selective weight
percentage of the additive was mixed in all the four
samples. These results show that the weight of the
additive mixed in these samples has not reached the
optimum value to remove the supercooling
completely. Thus there is a need to further increase
the weight percentage of the additive in all the
samples, in order to completely remove the
supercooling of CaCl
2
.6H
2
O.
Again, the weight percentage of the additive has
been increased slightly and all the samples were
tested up to 25 cycles. It was observed that the
freezing point of sample with pH 5.3 was found to be
23C, for sample of pH 6.0 was found to be 24.5C,
for sample with pH 6.5 was found to be 23.5C and
for sample with pH 7.0 was found to be 24C,
respectively, as can be seen from Fig. 8. The results
shown in Fig. 8, exhibit that the supercooling still
exists in all the four samples and hence, the weight
percentage of additive has not yet reached the
optimum value of the total weight of PCM. That is
why all the four samples have fluctuation in the
freezing point, i.e. these samples solidify at different
temperatures. However, this fluctuation in the
freezing points of different samples is not very high
and hence, can be minimized further by using the
suitable weight percentage of the additive in all the
four samples.
In the last two experiments, the weight percentage
of the additive was increased by a significant amount
in two parts and has been tested for 50 and 100
cycles. The samples tested for 50 cycles have less
weight percentage of the additive while it was more in
all samples used for 100 cycles. The results for 50
cycles are shown in Fig. 9, while the results for 100
cycles are shown in Fig. 10. It can be seen that the
freezing point of four samples with pH values of 5.3,
6.0, 6.5 and 7.0, respectively, were found to be 23.8,
24, 24.2 and 24.5C after 50
th
cycle as can be seen
from Fig. 9. On the other hand, the freezing point of
all the four samples were found to be 23.9, 24, 24.1
and 24.2C, respectively, after 100
th
cycle, as can be
seen from Fig. 10. Thus the freezing point of all four
samples after 50
th
and 100
th
cycles are very closed to
each other, besides, all the samples after 100
th
cycles
solidify at a temperature very closed to one another
irrespective of their pH values, as can be seen from
Figs 9-10. In other words, the supercooling in all the
samples with pH 5.3, pH 6.0, pH 6.5 and pH 7.0 is all
most negligible. It means the supercooling from
CaCl
2
.6H
2
O after mixing a suitable weight percentage
of the additive has been minimized in this particular
study.
TYAGI et al.: SUPERCOOLING AND PH BEHAVIOUR OF PHASE CHANGE MATERIAL


125
All the samples after certain (1
st
, 25
th
, 50
th
and
100
th
) cycles were tested for measuring the latent heat
and freezing points using DSC. The results obtained
through DSC tests were found to be very close to
those of the experimental results, which is a strong
point to verify that the experimental analysis has been
conducted with the best possible precautions. The
latent heat and melting temperatures of all the
samples obtained through DSC are given in Table 2.
It is observed that the experimental results are in good
agreement with those obtained through DSC tests.
The experimental study carried out in the present
work has been very useful in the removal and/or
minimizing the supercooling of CaCl
2
.6H
2
O with the
mixing of an additive in the optimum weight
percentage for applications in the thermal energy
storage.

4 Conclusions
The supercooling behaviour of a typical PCM and
the comparative effect of different pH values with and
without additive has been presented. The results of all
samples after melting freezing testing cycle show
different behaviour, it means the supercooling exist in
all the samples without additive. It can be seen that
the freezing of all four samples after hundred cycles is
found to be stable with certain weight percentage of
the additive. This particular result exhibits that there
is almost no supercooling as all the samples freezed at
almost the same temperature. Hence, it can be
concluded that the optimum percentage weight of the
additive plays a very important role in removal and/or
minimizing the supercooling of any phase change
material to be used in the application of the thermal
energy storage. All the samples after certain cycles
were tested through DSC and the latent heat and
freezing point were measured. The results obtained
through DSC tests were found to be very close to
those of the experimental results, thus the
experimental results are in good agreement with
analytical results. It can be concluded that a PCM
without supercooling can be used as a latent heat
storage material for heating and cooling and space air-
conditioning applications in the thermal comfort
range of suitable temperature.

Acknowledgement
One of the authors (VVT) highly acknowledges the
financial assistance in the form of Research
Associateship due to CSIR, New Delhi, India. Sincere
thanks are also due to the referees for their valuable
and encouraging suggestions.
References
1 Meng Q H & Hu J L, Sol Energy Mater Sol Cells, 92 (2008)
1260.
2 Frederic K, Joseph V & Jean N, Appl Thermal Eng, 28
(2008) 1291.
3 Tyagi V V & Buddi D, Sol Energy Mater Sol Cells, 92
(2008) 891.
4 Garg H P, Mullick S C & Bhargava A K, Solar thermal
energy storage (Reidel Publishing Company, Holland), 1985,
pp 78-80.
5 Conrad V, Oliver K & Milan O, Energy Build, 40 (2008)
937.
6 Costello Y A, Melsheimer S S & Edie D D, ASME Meeting,
San Francisco, USA, 1978, p 10.
7 Edie D D & Melsheimer S S, Proceedings of Sharing the
Sun: Solar Technology in the Seventies, The American
Section of the International Solar Energy Society, 1976, p
227.
8 Fouda A E, Despault G J, Taylor J B & Capes C E, Sol
Energy, 32 (1984) 57.
9 Farid M M &Yacoub K, Sol Energy, 43 (1989) 237.
10 Nagano K, Ogawa K, Mochida T, Hayashi K & Ogoshi H,
Appl Thermal Eng, 24 (2004) 221.
11 Ryu H W, Woo S W, Shin B C & Kim S D, Sol Energy
Mater and Sol Cells, 27 (1992) 161.
12 Sar A & Karaipekli A, Appl Thermal Eng, 27 (2007) 1271.