Fullerenes, Nanotubes and Carbon Nanostructures

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Expedited energy charging of water using natural

graphite flake for cool thermal storage

V. Kumaresan, K. S. Raghavan, M. P. Vikram & J. Iyyappan

To cite this article: V. Kumaresan, K. S. Raghavan, M. P. Vikram & J. Iyyappan (2021): Expedited
energy charging of water using natural graphite flake for cool thermal storage, Fullerenes,
Nanotubes and Carbon Nanostructures, DOI: 10.1080/1536383X.2021.1879056

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FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES
https://doi.org/10.1080/1536383X.2021.1879056

Expedited energy charging of water using natural graphite flake for cool
thermal storage
V. Kumaresan, K. S. Raghavan, M. P. Vikram, and J. Iyyappan
Department of Mechanical Engineering, College of Engineering Guindy Campus, Anna University, Chennai, India

ABSTRACT ARTICLE HISTORY

This study investigates the solidification characteristics of deionized water dispersed with natural Received 9 December 2020
graphite flakes (NGF), called micro-particle enhanced phase change material (MePCM), in two Accepted 18 January 2021
spherical capsules of ‘64 mm’ and ‘52 mm’ diameter. Heterogeneous nucleation factor of deionized
KEYWORDS
water reduces from 0.0531 to 0.0001 due to reduction in contact angle with addition of NGF.
Phase change material;
Thermal conductivity results show an enhancement of 25% in the MePCMs with 5 wt. % over the natural graphite flake;
base PCM and the enhancement is not proportional to increase in mass fraction of NGF. The pres- heterogeneous nucleation
ence of NGF in deionized water eliminates the subcooling and expedites the solidification rate. factor; subcooling; cool
The MePCM stores almost 94% of cool energy in a shortened duration compared to the base PCM thermal energy storage
in both capsules. In summary, the NGF can be a promising thermal enhancer to prepare the
MePCMs in large scale at an affordable cost for the cool thermal energy storage applications.

Nomenclature: d: Equivalent molecular diameter (m); D: Minimum value of experimental parame-

ters; f (h): Heterogeneous nucleation factor; k: Thermal conductivity (W m
1 K
1); m: Mass (kg); M:
Molecular mass (kg mol
1); NA: Avogadro constant (mol
1); r: Critical nucleation radius (m); r:
Radius (m); Rth: Thermal resistance (K W
1); T: Temperature (K); t: Time (s); uD: Experimental
uncertainty
Abbreviations: CTES: Cool thermal energy storage; MePCM: Micro-particle enhanced phase
change material; NGF: Natural graphite flake; PCM: Phase change material; RTD: Resistance tem-
perature detector
Greek characters: DD: Deviation range of experimental parameters; DGv: Volumetric surface free
energy (kJ m
3); Dh: Latent heat (kJ kg
1); DT: Subcooling degree (K); h: Contact angle; c: Surface
energy (kJ m
2); q: Density (kg m
3)

1. Introduction reduce the mismatch between energy demand and supply.

Global energy demand has been increasing exponentially
due to growth in population, rapid urbanization and indus-
trialization, resulting in a multifold increase in the con-
sumption of fossil fuels. This causes severe environmental
deterioration, raising concerns on ozone layer depletion, glo-
bal warming and climatic change. Strategic energy saving
measures are to be developed and implemented in energy
intensive sectors such as transportation, electronic industry,
chemical industry and buildings. Among these, buildings
sector accounts 40% of the world’s total energy consumption
for different applications,[1] consuming nearly 45% of total
building energy by the HVAC system. A large portion of
this energy is consumed by the chiller unit in the HVAC
system, designed to meet the peak cooling load that lasts
few hours in a day. Different methods have been imple-
mented to minimize the energy consumption by downsizing
the chiller capacity, without compromising the thermal com-
fort conditions in the building envelope. The integration of
cool thermal energy storage (CTES) system with the chiller
unit is the most promising energy management method to
Cool thermal energy can be stored either in a sensible or
latent form; first one with a lower energy storage density,
storing and retrieving the energy in a non-isothermal man-
ner.[2] These limitations can be overcome in the latent heat
thermal energy storage systems using phase change materials
(PCM). Water is being utilized as a potential PCM in the
CTES applications, owing to its high solid to liquid thermal
conductivity ratio, latent heat and ease of handling.
However, subcooling in water necessitates the working tem-
perature of the evaporator in the chiller unit well below the
phase change temperature of water. This increases the spe-
cific energy consumption by 3%–4% per unit temperature
drop in the evaporator.[3] Numerous studies on subcooling
behavior and solidification characteristics of water have been
reported with the dispersion of different nanometric par-
ticles such as aluminum oxide,[4] titanium oxide,[5] copper
oxide,[6] carbon black,[7] graphene oxide nanosheets,[8] gra-
phene nanoplatelets[3] and multiwall carbon nanotubes.[9]
The results showed a significant improvement in thermal
conductivity and cooling rates, but the concerns regarding

CONTACT V. Kumaresan kumaresanvm1973@gmail.com Department of Mechanical Engineering, College of Engineering Guindy Campus, Anna University,
Chennai 600025, India.
ß 2021 Taylor & Francis Group, LLC
2 V. KUMARESAN ET AL.
energy consumption during nanoparticles synthesis, thermal
stability, material cost and availability are yet to
be addressed.
Natural graphite flake (NGF) is an allotrope of carbon,
containing the stacked sheets of carbon atoms with a hex-
agonal crystal structure.[10–13] Fascinating features of NGF
such as inherent high thermal conductivity, high specific
surface area, self-lubrication and low density have received
much attention as a suitable thermal conductivity enhancer
in thermal energy storage applications.[14] Liu et al.[15]
reported an improvement in the thermal conductivity of
paraffin by 58.6% and 41.4% with 2 wt. % of graphene and
exfoliated graphite sheet respectively, as a result of a larger
lamellar structure of graphene compared to exfoliated graph-
ite sheet. Results of Wang et al.[16] showed a subcooling
elimination in OP10E/water emulsion with nano-graphite at
a concentration greater than 2 wt. %. Thermal conductivity
of the emulsion was augmented by 111.8% and exhibited a
higher cooling rate with the addition of nano-graphite. Kim
et al.[17] analyzed the thermal conductivity of basalt fiber/
reinforced epoxy with NGF and reported an enhancement
of 252% with 40 wt. %. The phonon transfer between the
matrix provided the efficient heat transfer paths for improv-
ing the thermal conductivity. According to Zhou et al.,[18]
dispersion of modified expanded graphite in magnesium
chloride hexahydrate resulted in an abrupt reduction of sub-
cooling and an increase in thermal conductivity of 7.7 folds
than the base PCM. Al-shannaq et al.[19] performed experi-
mental studies on the phase change behavior of water and
organic PCM (PureTemp4) in a spherical capsule coated
with graphite. A remarkable reduction in both freezing and
melting times was observed through the accelerated nucle-
ation of PCM. However, the PCM entrapped inside the
graphite pores suppressed the free convective currents dur-
ing the melting process. Cheng et al.[20] developed a theoret-
ical model with inclusion micromixing process of
heterogeneous constituents for attaining the optimal thermal
conductivity of the composite. Based on their results,
expanded graphite was considered as a suitable additive
because of its favorable microstuture paramentes such as
aspect ratio, specific surface area and equivalent thickness.
Thermal conductivity enhancement of 16 times was reported
by Li et al.[21] in n—eicosane/expanded graphite composite
with 30 wt. %. This enhancement resulted from the loading
of base PCM in the pores of expanded graphite, which pro-
vided the interconnected pathways for continuous ther-
mal transport.
As inferred from the literature review, the carbonaceous
particles have been utilized as a promising thermal conduct-
ivity enhancer in many PCMs, but no studies have been
reported on the phase change characteristics of water dis-
persed with NGF. In this study, the main focus is to prepare
water based composite with NGF, called micro-particle
enhanced phase change material (MePCM) and investigate
its solidification characteristics in two different sizes of
spherical capsule. Effects of NGF addition on thermal con-
ductivity, nucleation and solidification characteristics of
water are studied and the advantages of partial energy
Table 1. Specification of NGF and PVP.
Parameter NGF PVP
Formula C (C6H9NO)n
Molecular weight 12.01 g mol
1 111.14 g mol
1
Density 1800 kg m
3 1200 kg m
3
Diameter 50–800 lm –
Thickness 1–150 lm –
Melting temperature 3654–3697  C 150  C
charging in the MePCM are explored for the CTES
applications.
2. Experimental methods
2.1. Preparation of MePCM
A new kind of MePCM is prepared with de-ionized (DI)
water as the PCM and NGF as the additive via the two-step
method. The hydrophilic properties of NGF are advanta-
geous for interfacial adhesion with any base material, but
the adsorption of airborne hydrocarbon contaminations with
exposure to ambient transforms the NGF into hydrophobic.
Considering this, a polymer surfactant, polyvinyl pyrrolidone
(PVP) is taken as the surfactant for increasing the stability
of the suspension. The NGF with 99% purity (Sigma
Aldrich, India) and PVP (SRL Scientific, India) are used as
received and their specifications are given in Table 1.
Initially, the required mass of NGF and PVP (20 wt. % of
NGF) is weighed in a precision electronic balance (Wenser,
PGB 200) and it is then mixed with a known volume of
base PCM. This mixture is subjected to magnetic stirring for
15 min, followed by probe sonication for 30 min at 20 kHz.
The heat generated during the sonication is dissipated by
placing the mixture in a water bath at 20  C. Following the
above steps, MePCMs are prepared with the different NGF
mass concentrations of 1%, 2%, 3%, 4% and 5% and kept
idle for 72 h to study their stability. The NGF settles at the
bottom of the container after 2 h and therefore the MePCMs
are prepared afresh under two different sonication times of
‘60 min’ and ‘90 min’. The stability of MePCM has not
improved for the sonication time ‘60 min’, while no visible
precipitations are noticed in the MePCM sonicated for
‘90 min’, as illustrated in Figure 1. After ensuring the stabil-
ity, the size of dispersed NGF is measured using a scanning
electron microscope (Hitachi S3400N). The random overlap-
ping of NGF results with an increase in size, as the concen-
tration varying from 1 wt. % to 5 wt.% as shown in Figure
2(a) and 2(b).
2.2. Contact angle measurement
In this study, the contact angle of MePCM is measured
using a goniometer (Kyowa Interface Science, DMe 211)
that works based on the sessile drop method. Firstly, a
known volume of MePCM (2 lL) is taken in a syringe and
injected out at a controlled flow rate on a borosilicate glass
substrate. The droplet is captured by a camera system, after
its spreading from initial to equilibrium position on the sub-
strate. The images are processed for obtaining the contact

Figure 1. Preparation process of MePCM.
Figure 2. SEM images of dispersed NGF (a) 1 wt. %, (b) 5 wt. %.
angle according to the equation, tan h2 ¼ HR , where, H—
height of the droplet and R—radius of the droplet on the
substrate. The aforesaid procedure is repeated thrice for
each sample to ascertain the repeatability of the data and
their average is considered for evaluating the heterogeneous
nucleation factor.
2.3. Thermal conductivity measurement
It is essential to explore the effects of NGF addition on the
thermal conductivity of the MePCM, as it mainly influences
the rate of energy stored and retrieved during the phase
change process. Thermal conductivities of the MePCMs are
measured at 10  C, 20  C and 30  C, using a KD2 pro ther-
mal analyzer (Decan Devices Inc., USA) The analyzer has a
needle probe sensor with an inbuilt heating element that
works based on the transient inline source method. A
known volume of MePCM (25 ml) is poured into a cylin-
drical glass container and the sensor is inserted at the cen-
ter. This container is placed in a thermally insulated
rectangular chamber of 7 l capacity, filled with an aqueous
mixture of ethylene glycol (60:40 by volume) as the coolant.
The coolant mixture is circulated through a refrigerated–cir-
culator (Poly Science, AD7R 20), bringing the temperature
of MePCM to the required test condition. The thermal con-
ductivity measurement is subsequently carried out for 90 s
(30 s each for equilibrium, heating and cooling time). For
every MePCM sample, three experimental trials are
FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES 3
performed at each temperature condition to ensure the
repeatability of the measured data.
2.4. Description of experimental system
Figure 3 illustrates the schematic arrangement of the test
facility for studying the solidification behavior of MePCM,
consisting of a chiller unit (Siskin Instruments, RCC 700,),
temperature bath, heating element and data logger (Agilent,
34972 A). An aqueous mixture of ethylene glycol (60:40 by
volume) is filled in the temperature bath and brought to

7  C using the chiller unit. The output of heating element
is regulated through a proportionate temperature differential
controller (PTDC) according to bath temperature and a
mechanical stirrer is used for maintaining the temperature
uniformity. The prepared MePCM is poured into a spherical
borosilicate glass capsule of ‘64 mm’ diameter (Case 1) with
a wall thickness of 1 mm. To accommodate the volume
expansion of MePCM during the solidification, the capsule
is filled up to 80% of its volume and three resistance tem-
perature detectors (RTD) are located at different locations in
each capsule; from the center at 12 mm, 24 mm and 32 mm
for ‘Case 1’ while 9 mm, 19 mm and 26 mm for ‘Case 2’ as
shown in Figure 3. The capsule with MePCM is placed in
the temperature bath at
7  C. Transient temperature varia-
tions of the MePCM are continuously measured every ‘10 s’
from the initial condition of 30  C till the solidified MePCM
attains
4  C. Similar experiments are performed in a
4 V. KUMARESAN ET AL.

Figure 3. Schematic arrangement of the test facility.

spherical borosilicate glass capsule of 52 mm size (Case 2) Table 2. Uncertainty results.

with a wall thickness of 1 mm, positioned with three RTD as Parameter Uncertainty (%)
shown in Figure 3. For every MePCM sample, the experi- Temperature ±1.50
mental trials are repeated twice in each capsule to ascertain Contact angle
Volumetric surface free energy
±3.26
±2.16
the repeatability of the data. Critical nucleation radius ±9.34
An uncertainty analysis associated with temperature, con- Thermal conductivity ±5.22
tact angle, volumetric surface free energy, critical radius of
nucleation and thermal conductivity is carried out by calcu- Table 3. Nucleation parameters of MePCMs.
lating the deviation in the measurements using Eq. (1), NGF (wt. %) Contact angle f (h)
s ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2  2  2  2 0 43 540 0.053114
DD1 DD2 DD3 DDn 1 21 120 0.003360
uD ¼ þ þ þ ::::::::::::: þ 2 17 180 0.001516
D1 D2 D3 Dn  0
3 14 48 0.000817
(1) 4 10 180 0.000194
5 9 120 0.000124
where ‘D’ and ‘DD’ denote the minimum value and devi-
ation range of experimental parameters, respectively. The
evaluated uncertainty values are presented in Table 2.
Table 4. Solidification duration of the MePCMs.
rs–r1 (min) rs–rc (min)
rs –r2 (min)
3. Results and discussion Mass fraction (wt. %) Case 1/Case 2
3.1. Nucleation analysis of MePCMs 0 23/11.5 58/30 73/53
1 20.5/9.5 52/27.6 63.5/46.5
Dispersion of solid particles or other impurities in the base 2 17.5/8.3 48.3/25.5 62/41.8
3 14.8/7.1 41/22 55.8/40.5
PCM can effectively reduce the nucleation barriers, provid- 4 12.3/6.4 35.3/19 49.6/35.5
ing the favored interfacial sites for the heterogeneous nucle- 5 9.5/5.2 32.5/17 48/33
ation. The following major parameters are evaluated as
follows;
a high temperature driving force for the onset of solidifica-

2ciw
Critical nucleation radiusðrÞ ¼ (2) tion. The critical nucleation radius of the base PCM is calcu-
DGv lated as 8.6 nm, which is in accordance with the results of
Surface free energy per unit volume ðDGv Þ Zhang et al.[23] and the ice embryos grow steadily, when
r  r. Looking at Table 3, the lower contact angle of

qs  Dh  DT
¼ (3) MePCM compared to base PCM indicates a high surface
Ts wettability due to decrease in the surface tension. The
Heterogeneous nucleation factor, f ðhÞ equivalent molecular diameter of the base PCM is calculated
2 as 0.38 nm from dPCM ¼ 0:1ðNA pq 6M
Þ1=3 , given by
ð2 þ cos hÞð1
cos hÞ Corcione, [24] l
where ‘M’ ¼ molecular mass of water (kg
¼ (4)
4 mol
1), ‘NA’¼ Avogadro number (mol
1) and ‘ql’ ¼ liquid
where ‘qs’—solid density (kg m
3), ‘Dh’—latent heat (kJ density (kg m
3). The NGF which is several fold larger in
kg
1), DT—degree of subcooling (K), Ts—solidus tempera- size than the base PCM molecules, attracts a large number
ture (K), ciw—interface free energy of ice-water ¼ 0.023 J of PCM molecules toward itself, thereby decreasing the sur-
m
2.[22] The volumetric surface free energy of base PCM is face tension of MePCM. This effect is predominant with
7640.2 kJ m
3, as a result of high degree of subcooling. This increase in concentration of NGF consequently lowering the
contributes to thermodynamic and kinetic barriers, requiring heterogeneous nucleation factor of the MePCM compared to
 FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES 5

Figure 4. Thermal conductivity of MePCMs.

the base PCM. For instance, the heterogeneous nucleation

factor of MePCM with 5 wt. % NGF is 0.00014 against the
base line case of 0.053114 that shows a substantial reduction
in the excess free energy. Therefore, the presence of NGF
accelerates the nucleation rate and eliminates the subcooling
of MePCM even at a minimal concentration. The nucleation
rate of MePCM depends on size, surface area and the num-
ber of particles that influence the formation of ice embryos
on the NGF surface. Nucleation of base PCM on the surface
of NGF is quite difficult to evaluate experimentally, as it
involves complexity in the measurement of contact angle
between the base PCM molecules and NGF surface.
Fortunately, this contact angle can be determined from the
studies of Zhang[25] based on measured contact angle data
as given below; Figure 5. Transient temperature variation of the MePCMs (a) Case 1, (b) Case 2.
qffiffiffiffiffi qffiffiffiffiffi  
ci d cw d
cw cw d
þ cw d

1 cos hw
NGF
ci
cos hi
NGF ¼ (5)
ci w
NGF and filling the gap between the flakes by the base PCM
where hi
NGF —contact angle between ice and NGF, ci d ¼ molecules result in thermal conductivity enhancement.
0.033237 J m
2, ci ¼ 0.081972 J m
2, cw d ¼ 0.022261 J m
2, Evidently as shown in Figure 2(a) and 2(b), the size of
cw ¼ 0.074289 J m
2.[26] The contact angle between ice and agglomerates becomes larger with an increase in concentra-
NGF is evaluated as 65 for hw
NGF ¼ 86 .[27] This wettabil- tion, which provides the high surface area for heat conduc-
ity behavior of water increases the probability of forming tion in the MePCM. At the same time, this enhancement is
more nucleation sites on the NGF surface, accelerating the not proportional to the increase of NGF concentration due
heterogeneous nucleation process. to directional variation in thermal conductivity and random
orientation of the NGF flakes. Looking at Figure 4, thermal
conductivities of the MePCM show a temperature independ-
3.2. Thermal conductivity of MePCM
ency similar to other carbonaceous particles, indicating the
Figure 4 shows the enhanced thermal conductivity of absence of ‘Brownian motion’. Generally, the presence of

kPCM
MePCMs, defined as kMePCM kPCM , at the tested temperature PVP weakens the effective thermal conductivity of the
conditions. As observed, the MePCM exhibits a thermal MePCM, as a result of narrowing the surface area for heat
conductivity augmentation of 11% (0.63 W m
1 K
1) and transfer by adsorption of PVP molecules on the NGF sur-
25.3% (0.7 W m
1 K
1) over the base PCM (0.56 W m
1 face. This decrement is predominant at a higher mass frac-
K
1) with NGF loading of 1 wt. % and 5 wt. %, respectively, tion of PVP, which lowers the efficacy of high conductive
at 30  C. This enhancement is attributed to the formation of NGF in the MePCM. In view of the above, a suitable
NGF agglomerates, forming the chain structures to provide method is to be developed for the preparation of the
the additional heat conductive paths. High thermal conduct- MePCMs without the surfactant for achieving the maximum
ivity and aspect ratio, self-lubrication characteristics of the thermal conductivity enhancement.
6 V. KUMARESAN ET AL.

3.3 Time–temperature curves of MePCM

Solidification characteristics of the MePCMs for ‘Case 1’ and
‘Case 2’ are discussed from the results of temperature pro-
files to explore its potential application. Figure 5(a) depicts
the transient temperature variation of the base PCM at the
center of the capsule in ‘Case 1’at Tsurr ¼
7  C. As seen
from the figure, the base PCM undergoes a subcooling of

5.4  C in a metastable liquid region and subsequently, the
nucleation gets initiated instantaneously. The latent heat
released during phase change from liquid to solid raises the
temperature of subcooled PCM for attaining its solidus tem-
perature. The onset of solidification occurs at 1.4  C in the
base PCM, taking a solidification duration of 73 min
between ‘rs–rc’. The PCM near the surface is solidified at a
faster rate due to its negligible thermal resistance, but the
heat transfer is hindered as a result of increase in thermal
resistance offered by the growing ice thickness. As could be
noticed from the figure, adding NGF to the base PCM does
not have a significant effect in the liquid sensible cooling
region, owing to the suppression of natural convection
effects. Astonishingly, the complete elimination of subcool-
ing is observed in the MePCM with 1 wt. %. NGF through
the creation of more nucleation sites. The solidification dur-
ation between ‘rs–rc’ is 48 min for the MePCM with 5 wt. %,
exhibiting a reduced duration of 34% compared to base
PCM. The major factors contributing to the above men-
tioned reduction are thermal conductivity enhancement and
sub cooling elimination with the presence of NGF. In the
solid sensible cooling region, the MePCM with the max-
imum mass fraction of NGF attains
4  C in 2.5 min against
the baseline case of 6.8 min.
Results of the solidification experiment for ‘Case 2’ are
plotted in Figure 5(b) to compare the effects of capsule size Figure 6. Solidification time at different locations in (a) Case 1, (b) Case 2.
on solidification characteristics of the MePCM. As perceived,
the base PCM undergoes to a lower subcooling by 2  C
compared to ‘Case 1’, due to the reduction in the capsule in Figure 6(a) for ‘Case 1’, the time taken to solidify 53.5%
size. However, the base PCM remains in a meta-stable liquid of the base PCM volume between ‘rs–r2’ is 33.5% of total
state for a prolonged duration, delaying the onset of solidifi- solidification duration, as a result of accelerated mode of
cation by 27% in comparison with ‘Case 1’. It can be energy charging with a meager thermal resistance. The grad-
ascribed to a relatively smaller surface area, inhibiting the ual increase in thermal resistance of the solidified mass as
heat transfer at a given temperature driving potential. given in Eq. (6), diminishes the accelerated mode of energy
Realizing this undesirable delay, attempts are being made for charging between ‘r2–r1’, solidifying 40.5% of volume in
minimizing the duration by improving thermal conductivity 43.5% of total duration.
of the capsule material through the passive methods, which
rc
r1
are under progress. The base PCM shows a faster charging Rth ¼ (6)
rate than ‘Case 1’, possibly due to lower conductive resist- 4pkice rc r1
ance offered by the PCM in the smaller capsule. For the where kice—thermal conductivity of solid ice in W m
1 K
1.
MePCM with 5 wt. %, the solidification duration is short- As the inward solidification proceeds further from ‘r1’, the
ened by 38% compared to base PCM with synergistic effects conductive thermal resistance attains 1.84  C W
1, hindering
of NGF and short heat conduction path in a smaller size the heat transfer significantly. On analyzing the data, only
capsule. As shown in Figure 5(b), subcooling elimination is 6% of the base PCM volume is solidified in the remaining
observed in all the MePCMs similar to ‘Case 1’. 23% of the total solidification duration in a decelerated
mode. It is observed that the MePCMs exhibit a similar
mode of charging as that of base PCM, but with an appre-
3.4. Mode of energy charging
ciable reduction in the solidification duration. For the
Temperature profiles of the MePCMs at three different loca- MePCM with 5 wt. %, the charging prevails for 9.5 min
tions in the spherical capsules are used for analyzing the between ‘rs–r2’ in a shortened duration of 61.5%, compared
mode of energy charging during the solidification. As shown to the base PCM. This reduction can be attributed to the
 FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES 7

Table 5. Cost comparison of additives.

Additive Particle size Mass fraction (%) Subcooling reduction (%) Cost per grama (USD)
[4]
Aluminum oxide 433 nm 0.2 70 4.0
Multi wall carbon nanotube[9] 25–82 nm 1.2 21 2.0
Copper oxide[6] 37–59 nm 0.1 100 6.5
Graphene oxide nanosheets[20] 60 nm 0.05 69 140
Graphene nanoplatelets[3] 8 nm 1.2 64 15
Graphene oxide nanosheets[22] 132 nm 0.1 74 140
Graphene oxide nanosheets[8] 52 nm 0..03 20 140
Natural graphite flake (Present work) 1–2 lm 1 100 0.05
a
Source: Sigma Aldrich, USA and Cheap Tube, USA.

presence of high conductive ice molecules between the flakes
and on the surface of NGF, providing the efficient heat per-
colation path. Further, charging of the MePCM bound
between ‘r2–r1’ takes 23.1 min, storing a cumulative cool
thermal energy of 94% in a shorter duration of 32.5 min,
against the baseline case of 58 min. Considering the above, it
is suggested to turn off operate the chiller unit during the
decelerated mode of charging, storing only 6% of cool ther-
mal energy. From the volume solidified results for ‘Case 2’
as illustrated in Figure 6(b), the MePCM smaller capsule
size provides a higher energy storage rate, owing to shorter
heat conduction path. Perceiving the data in Table 4, the
solidification of base PCM between ‘rS–r1’ takes 30 min for
storing 96% of cool thermal energy, while it is 17 min is by
the MePCM with 5 wt. %. It is construed that, the energy
storage per unit volume is at a faster rate in the smaller
spherical capsule than the larger one, accelerating it further
in the MePCM with the presence of NGF.
An attempt has been made to compare the cost of com-
monly used additives in the PCM based applications, par-
ticularly water as the base PCM. For that, the present results
are compared with the published data, in terms of subcool-
ing reduction and the price of the additives, as presented in
Table 5. It can be seen that the low price of NGF and its
abundant availability can primarily reduce the synthesis and
operational costs, affording the utilization of the proposed
MePCM in the real-time CTES system in the most econom-
ical way.
4. Conclusions
Solidification characteristics of de-ionized water with differ-
ent mass fractions of natural graphite flake have been
experimentally studied in two different spherical capsules.
Thermal conductivities of the MePCM exhibit a stronger
dependency on mass fraction of NGF, attaining an enhance-
ment of 25.3% over the base PCM. The presence of NGF
reduces the nucleation energy barrier in the base PCM, con-
sequently intensifying the nucleation rate with the elimin-
ation of subcooling. Augmentation in thermal conductivity
of MePCM contributes to the maximum reduction in solidi-
fication duration of 34% (Case 1) and 38% (Case 2), com-
pared to the base PCM. Evidently, the MePCM stores 94%
of cool energy in a shorter duration under the accelerated
mode, enabling in practice to turn-off the refrigeration sys-
tem during the remaining charging process. In conclusion,
the low nucleation energy barrier, subcooling elimination,
enhanced thermal conductivity, partial charging in an accel-
erated mode and low cost of NGF will make MePCM as the
potential energy storage material in the CTES applications.
Acknowledgments
The authors acknowledge the financial support from the Technology
Mission Division (Grant No. DST/TMD/MES/2K16/98), Department of
Science and Technology, New Delhi, Government of India.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
Department of Science and Technology, Ministry of Science
and Technology.
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