Sustainable Cities and Society 51 (2019) 101767

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Experimental charging and discharging performance of alumina enhanced T

pentaerythritol using a shell and tube TES system
⁎
K.P. Venkitaraja,b, S. Suresha, , B. Praveena
a
Department of Mechanical Engineering, NIT Tiruchirappalli, Tiruchirappalli 620015, India
b
Department of Mechanical Engineering, College of Engineering, Adoor 691551, India

A R T I C LE I N FO A B S T R A C T

Keywords: The work presented in this paper is the results of an experimental study conducted on the thermal energy storage
Pentaerythritol (TES) performance of pentaerythritol (PE) added with alumina (Al2O3) nanoparticles. The charging and dis-
Solid–solid PCM charging experiments are performed using PE added with 0.5 and 1.0 wt.% of Al2O3 in a shell and tube type
Al2O3 nanoparticles thermal energy storage system. The experimental data are analyzed to obtain the charging/discharging effi-
Charging and discharging
ciencies and the overall efficiency of the TES system at different flow rates 2, 4, 6 LPM of the heat transfer fluid
Energy efficiency
Exergy efficiency
(HTF, Therminol-55). Exergy analysis based on the 2nd law of thermodynamics is also carried out in this ex-
perimental work. The results indicated that charging and discharging time is reduced due to the addition of
Al2O3 with PE at all volume flow rates of HTF. The maximum charging and discharging powers of 289.3 W and
230.8 W respectively are observed in the case of PE + 1.0% Al2O3 corresponding to the flow rate of 6 LPM. The
efficiencies of charging and discharging showed maximum values of 86.8% and 75.0% respectively at 6 LPM.
The overall energy efficiency of the thermal energy storage system found increased from 38.3% obtained in the
case of PE to 50.5% and 58.5% obtained for PE added with 0.5 wt.% and 1.0 wt.% of Al2O3 nanoparticles
respectively.

1. Introduction transformation involves latent heats comparable to the most effective

The latent heat storage method using phase change materials (PCM)
have been employed for various applications such as solar, medical,
textile, electronic, energy efficient buildings, air conditioning, in-
dustrial and aerospace, etc. (Nkwetta & Haghighat, 2014). Extensive
work is going on the application of PCM for thermal energy storage in
heat exchangers (Anish, Mariappan, & Suresh, 2019; Seddegh, Joybari,
Wang, & Haghighat, 2017) and energy efficient buildings (Arcuri,
Spataru, & Barrett, 2017; Mourid, El Alami, & Kuznik, 2018). So-
lid–liquid PCM which are mostly used in the field of thermal energy
storage and heat transfer applications suffer from serious limitations
like expansion and leakage in their liquid phase. An easy way to avoid
these limitations is to use a PCM that undergoes a solid–solid phase
transition. Solid–solid PCM undergo a solid to solid phase transition
which is associated with absorption and release of a large amount of
heat. They change their crystalline structure from one lattice type to
another at a definite temperature (Cao, Ye, & Yang, 2013) and this
solid/liquid PCM. Several materials show the solid–solid reversible
phase transition behavior, but only a handful has sufficient latent heat
to be a possible latent heat storage material. These solid–solid PCM are
categorized into two types, namely, organic solid–solid PCM and in-
organic solid–solid PCM (Busico, Carfagna, Salerno, Vacatello, &
Fittipaldi, 1980; Gu, Xi, Cheng, & Niu, 2010; Jiang, Ding, & Li, 2002;
Landi & Vacatello, 1975; Li et al., 1999; Li & Ding, 2007; Pielichowska
& Pielichowski, 2010; Qi & Liu, 2006; Ruan, Li, & Hu, 1995; Ruiyun,
Dejun, Xian, & Jing, 1990; Xi, Gu, Cheng, & Wang, 2009).
Organic solid–solid PCM mainly comprises a particular group of
hydrocarbon compounds, polyhydric alcohols, and polymers.
Polyalcohols or polyols are hydrocarbon compounds that have body-
centered tetrahedral molecular structure at low temperatures. These
polyalcohols and their amine derivatives show a solid-state crystalline
transition because of the presence of metastable, vibrant hydrogen
bonds between molecules in their crystal lattice. When the temperature
rises, these bonds break and the crystal structure changes from an

Abbreviations: PCM, phase change material; HTF, heat transfer fluid; PE, pentaerythritol; DSC, Differential Scanning Calorimetry; LPM, liter per minute; TES,
thermal energy storage; SSPCM, solid–solid PCM; TEM, transmission electron microscope; SEM, scanning electron microscope; XRD, X-ray diffraction; EDX, Energy
Dispersive X-ray; FESEM, field emission scanning electron microscope
⁎
Corresponding author at: Department of Mechanical Engineering, National Institute of Technology Tiruchirappalli, India.
E-mail addresses: venkitaraj@cea.ac.in (K.P. Venkitaraj), ssuresh@nitt.edu (S. Suresh), praveennitt15@gmail.com (B. Praveen).

https://doi.org/10.1016/j.scs.2019.101767
Received 6 April 2019; Received in revised form 7 July 2019; Accepted 5 August 2019
Available online 12 August 2019
2210-6707/ © 2019 Elsevier Ltd. All rights reserved.
K.P. Venkitaraj, et al.
Notations and symbols
T temperature (°C)
cp,p specific heat of the PCM (kJ/kg K)
mp mass of the PCM (kg)
Qsp heat supplied (kJ)
Qst heat stored (kJ)
Qre heat rejected (kJ)
Qsen sensible heat (kJ)
Qtrs solid–solid transition heat (kJ)
ṁh mass flow rate hot fluid (kg/s)
ṁc mass flow rate of cold fluid (kg/s)
cp,h specific heat of hot fluid (kJ/kg K)
cp,c specific heat of cold fluid (kJ/kg K)
ordered tetrahedral phase to a disordered cubic phase accompanied
with the absorption of a significant amount of energy, more significant
the disorder, more substantial is the amount of energy absorbed. Now,
when the temperature is lowered, at the transition temperature, the
hydrogen bonds reform and the materials regain its original tetrahedral
structure which causes the stored thermal energy to get released (Singh
et al., 2015). Polyalcohols also called as “plastic crystals,” which dis-
play crystalline disorder at elevated temperatures accompanied by the
absorption of thermal energy (Timmermans, 1961). Among poly-
alcohols, the most exciting materials are pentaerythritol (PE), penta-
glycerine (PG), Neopentyl glycol (NPG) and Neopentyl alcohol (NPA).
Certain amine derivatives of polyalcohols such as Tris (hydroxymethyl)
aminomethane (TAM) and Aminoglycol (AMPL) were also very tested
and proved by various researchers as potential solid–solid PCM for
thermal energy storage applications (Benson, Burrows, & Webb, 1986;
Murrill & Breed, 1970).
Most organic and some inorganic PCM have an inherently low
thermal conductivity which leads to poor charging and discharging
performances. Improving the thermal conductivity of PCM by disper-
sing thermally conductive materials is more widely used for enhancing
the effectiveness of the PCM-based TES systems. The majority of PCM,
in general, has a very poor thermal conductivity which results in lower
charging and discharging rates. The literature reported the use of
thermally conductive particles like nanoparticles as additives to en-
hance the thermal energy storage performance of organic and inorganic
PCM. The research findings also indicated that the enhancement of
thermal conductivity accompanied by a slight decrease in the phase
change properties of PCM (Adorno & Silva, 2006). Siegel (1977) in-
vestigated the use of high conductivity particles to enhance the rate of
solidification molten salt. He conducted an analysis to determine how
the solidification rate is influenced by the introduction of high con-
ductivity particles into a solidifying low conductivity material. He
concluded that for reasonable concentrations such as 20% particles by
volume, the heat removal rate for a plane geometry can be increased by
10–20% depending on the ratio of particle to matrix conductivity.
Cabeza, Mehling, Hiebler, and Ziegler (2002) and Py, Olives, and
Mauran (2001) studied PCM/graphite enclosed in waterlogged metal
modules. They observed a heat barrier between the metal modules and
water. Yin, Gao, Ding, and Zhang (2008) experimented paraffin/ex-
panded graphite composite and reported that the thermal conductivity
enhanced about 17 fold compared to the thermal conductivity of pure
paraffin. Kim and Drzal (2009) reported that the presence of conductive
graphite affects the phase change properties of PCM. Elgafy and Lafdi
(2005) studied the performance enhancement of paraffin/carbon na-
nofibers (CNF) with the mass fraction of CNF varied between 1% and
4%. Teng and Yu (2012) prepared composite PCM comprising paraffin
and 1.0, 2.0, and 3.0 wt.% of Al2O3, TiO2, and SiO2 nanoparticles. Their
study revealed that TiO2 enhances the thermal performance of paraffin
more efficiently compared to other nanoparticles. Ge et al. (2014)
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Sustainable Cities and Society 51 (2019) 101767
Pc average charging power (W)
Pd average discharging power (W)
tc time for charging (min/s)
td time for discharging (min/s)
ηc charging efficiency (%)
ηd discharging efficiency (%)
η overall energy efficiency (%)
Th,i inlet temperature of hot HTF (°C)
Th,o outlet temperature of hot HTF
T̄p,i mean initial temperature of PCM (°C)
T̄p,f mean final temperature of PCM (°C)
Tc,o outlet temperature of cold HTF (°C)
Tc,i inlet temperature of cold HTF (°C)
tested composite PCM comprising carbonate-salt for medium and high-
temperature energy storage applications. Li et al. (2017) investigated
calcium chloride hexahydrate with aluminum oxide nanoparticles for
thermal energy storage. Singh et al. (2017) experimentally studied the
thermal energy storage performance of Myo-Inositol based nano PCM.
They used Myo-Inositol added with 1%, 2% and 3% mass fractions of
CuO and Al2O3 nanoparticles. Based on the results of Differential
Scanning Calorimetry (DSC), Thermogravimetric analysis (TGA), and
Fourier Infrared Transforms (FTIR) analysis, they commented that the
nano-enhanced myo-inositol is a potential PCM for thermal energy
storage.
Though there are numerous investigations reported on solid–liquid
PCM, the papers on thermal energy storage performance of SSPCM with
heat transfer enhancement additives are decidedly less in number. Hu,
Zhao, Jin, and Chen (2014) studied the solid-state phase transition of
PE added with nano-aluminum nitride. In our recent work (Venkitaraj
& Suresh, 2019) we studied the thermal and chemical stability of PE
added with 0.1 wt.% of metal oxide nanoparticles. We found that the
nanoparticles decreased the subcooling found during the cooling cycle.
We have earlier investigated the energy storage characteristics and
crystallization kinetics of PE added with indium (Venkitaraj & Suresh,
2018).
The experimental heat transfer analysis of PCM involves conducting
charging and discharging performances of the PCM for evaluating the
energy efficiency of the thermal energy storage system. Numerous ex-
perimental and numerical studies on the thermal performance of latent
heat storage (LHS) system have been reported in the literature. Among
the various works reported, a sizeable number of research works dis-
cusses the various improvements in the thermal performances of the
LHS system. This includes geometrical design (Khan, Khan, & Ghafoor,
2016; Khodadadi & Zhang, 2001; Medrano et al., 2009), using metal
fins (Liu, Sun, & Ma, 2005), dispersion of thermally conductive particles
(Liu, Su, Tang, & Fang, 2016), use of form stabled and encapsulated
PCM (Giro-Paloma, Martinez, Cabeza, & Fernandez, 2016; Liu, Rao,
Zhao, Huo, & Li, 2015). Researchers have been trying different geo-
metric configurations of the LHS system for performing the charging
and discharging processes. Khodadadi and Zhang (2001) numerically
investigated the effect of convection on the melting process using a
spherical container. They observed a higher rate of heat transfer at the
upper side of the sphere than at the lower side. Medrano et al. (2009)
conducted experimental heat transfer study of the PCM embedded in a
graphite matrix using five different types of heat exchangers and they
observed greater heat transfer in the case of pipe in pipe type heat
exchanger. Liu et al. (2005) studied the thermal energy storage analysis
of stearic acid using vertical annulus storage system. They investigated
the dependence of Reynolds number on the heat transfer performance
of stearic acid.
As mentioned in the discussion above, the geometric configuration
of the heat exchanger in TES is a very important matter. Among the
K.P. Venkitaraj, et al.
different types of heat exchangers, shell and tube type is very much
used by various researchers due to its simple installation requirements
and better heat transfer performance (Agyenim, Hewitt, Eames, &
Smyth, 2010). The numerical work reported by Wang, Zhang, Wang,
and He (2013) involved a shell and tube heat exchanger to study the
thermal energy storage performance of n-octadecane. Their results re-
vealed that the charging time reduces significantly with the increase in
the inlet temperature of the HTF. They also reported that the charging
time reduces with the increase in the mass flow rate of the fluid. The
experimental study conducted by Ezan, Ozdogan, and Erek (2011)
discussed the thermal storage performance of a shell and tube heat
exchanger using water as the HTF. They reported the effects varying the
inlet temperature, flow rate, shell diameter and shell material on the
thermal performance of the system. They observed that the charging
and discharging processes are dominated by free convection. The effect
varying the inlet temperature on the thermal performance is more
compared to the effect of varying the flow rate of the HTF. The nu-
merical study conducted by Seddegh, Wang, and Henderson (2016)
reported the thermal storage performance of paraffin using a shell and
tube system. They tested the storage performance of the LHS system
corresponding to the horizontal and vertical orientation of the shell and
tube heat exchanger and concluded that the geometrical orientation has
Fig. 1. (a) Molecular structure of PE molecule, (b) XRD pattern of PE, (c) SEM image of PE, and (d) photograph of PE.
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a very little effect on the thermal performance due to the conduction
dominant heat transfer during the charging and discharging process.
The result of varying the number and orientation of HTF tubes in using
a horizontal shell and tube heat exchanger on thermal performance was
numerically studied by Luo, Yao, Yi, and Tan (2015). They observed
better thermal performance in the case of multi-tube arranged sym-
metrically with respect to the center.
The results of the experimental investigations using shell and tube
heat exchangers can be further improved by the use of extended sur-
faces (fins) or by enhancing the thermal conductivity of PCM by adding
thermally conductive particles. Darzi, Jourabian, and Farhadi (2016)
performed a numerical study of thermal performance of n-eicosane
using a longitudinally finned horizontal shell and tube heat exchanger.
They reported an increase in the solidification when fins were em-
ployed. The results of the experimental and numerical study conducted
by Meng and Zhang (2017) for testing the thermal performance of
paraffin-copper foam composite using a rectangular shaped shell and
tube heat exchanger was used. They indicated the dependence of soli-
dification time on the temperature gradient between the HTF and PCM.
The experimental paper published by Pandiyarajan, Pandian,
Malan, Velraj, and Seenira (2011) discussed the thermal energy storage
performance of a finned shell and tube heat exchanger for IC engine
K.P. Venkitaraj, et al.
exhaust heat recovery. Their study indicated about 10–15% of waste
heat recovery using the finned shell and tube TES system. They sug-
gested a cascade LHS system using multiple PCM for increasing the %
heat recovery. Khan and Khan (2017) investigated the charging and
discharging of paraffin using a longitudinally finned shell and tube heat
exchanger for domestic and industrial applications. They investigated
the effect of inlet temperature and volume flow rate of HTF on phase
transition rate and mean power. by regulating the inlet temperature or
volume flow rate of HTF, the influence of overall thermal resistance was
minimized. Mean discharge power is enhanced by 36.05% as the inlet
temperature is reduced from 15 °C to 5 °C. Likewise, the mean discharge
power is improved by 49.75% as the volume flow rate was increased
from 1.5 LPM to 3 LPM. They also observed that with an increase in
volume flow rate, the discharge time of the equal amount of thermal
energy 12.09 MJ was reduced by 24%. It as, therefore, concluded that
by adjusting operating conditions, the required demand for output
temperature and mean discharge power can be attained. Agarwal and
Sarviya (2016) experimentally evaluated the thermal and heat transfer
characteristics of paraffin using a shell and tube type LHS system during
charging and discharging processes. They used air as heat transfer fluid
(HTF) and determined the effectiveness of the LHS for drying of food
products.
Majority of energy storage applications involve the use of solid–li-
quid phase change materials for thermal energy storage. However, the
solid–liquid PCM have disadvantages of volume expansion and leakage
issues in their liquid phase. These limitations do not exist in the case of
solid–solid PCM since these type of PCM exhibit structural changes
involving enthalpy change in their solid state. Polyalcohols are a class
of organic solid–solid PCM having very high enthalpy change of tran-
sition. But, being organic materials, the thermal conductivity of poly-
alcohols is low causing poor charging and discharging performances.
Therefore, to improve the heat transfer in organic PCM, thermally
conductive particles are employed. Nanoparticles are one type of heat
transfer enhancement additives that are widely used by various re-
searchers. Most of the experimental investigations reported in the lit-
erature discussed the charging and discharging performances of so-
lid–liquid PCM. Again, to improve the thermal performance of the
system, the researchers made use of finned type shell and tube based
TES. The papers published on the charging and discharging perfor-
mances of solid–solid PCM are limited. Some of the papers available in
literature reports study on the characterization, charging and dischar-
ging performances of pure solid–solid PCM. But, there is very little
research work that studied the effect of heat transfer enhancement
additives on charging and discharging performances of polyalcohols is
reported in the literature. The work presented in this thesis is aimed at
filling this gap found in the literature.
NKhonjera et al. (2016) experimentally studied the charging and
discharging performance of rectangular type TES provided with fins
Fig. 2. (a) XRD pattern and (b) SEM image of Al2O3.
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using pentaerythritol as the PCM. The objective of the work was to
determine the influence of the PCM to fins volume ratio on the per-
formance of the LHS unit for cooking. They concluded that the charging
and discharging performances decrease with PE to fin volume ratio. In
one of our recent work (Venkitaraj, Suresh, & Venugopal, 2018), we
experimentally investigated the thermal performance of pentaerythritol
added with Al2O3 nanoparticles for IC engine exhaust heat recovery
applications. The experimental results showed that the addition of 0.1%
and 0.5% weight fractions of Al2O3 results in 36.36% and 73.39% in-
crease in the amount of heat recovered compared to pure PE. The
present work reports the energy and exergy analysis of charging and
discharging processes using PE added with 0.5 and 1.0 wt.% of Al2O3
using Therminol-55 as the heat transfer fluid for charging and dis-
charging of PE. A shell and tube heat exchanger consisting of three
horizontal circular tubes was used as the TES for conducting the energy
storage and discharge experiments. As far as the knowledge of the au-
thors concerned, there is no research work that performed the energy
and exergy analysis of a solid–solid PCM based TES using therminol as
the HTF is reported in the literature.
2. Material preparation
Pentaerythritol [PE] is a polyalcohol having the chemical formula
C5H12O4. PE is an organic solid–solid PCM that exhibits a structural
transition from tetragonal to cubic at a fixed temperature in the range
187–189 °C. At ordinary temperature, PE has the body-centered tetra-
gonal (BCT) molecular structure consisting of four C–CH2–OH frag-
ments (Fig. 1(a)). In a PE molecule, the middle carbon atom is tetra-
gonally surrounded by four other carbon atoms. The PE molecules are
arranged flat in a sheet parallel to the crystallographic c-plane. The
transition to the face-centered cubic (FCC) crystalline structure is ac-
companied by the absorption of the energy required for the breaking of
hydrogen bonds. During the phase transition, the hydrogen bonds break
resulting in a change in the crystal structure. The separated molecules
are held in their lattice sites by dispersion forces. During the dischar-
ging period, the hydrogen bonds reform by rejecting the stored energy.
Fig. 1(b) shows the X-ray diffraction (XRD) pattern of PE obtained using
Bruker AXS D8 Advance X-ray diffractometer having Cu-kα1 radiation
in the range of 0–90°. The reflections in the XRD pattern obtained were
recognized as matching to the tetragonal phase of PE using JCPDS
(Joint Committee on Powder Diffraction Standards). The Scanning
Electron Microscope (SEM) analysis was performed using Jeol JSM
6390LV SEM to study the microstructure of PE. The obtained SEM
image showed that PE has a loose microstructure with a large number
of individual lamellae on the surface (Fig. 1(c)). Pentaerythritol (ana-
lytical reagent grade, purity 98.0%) in white crystalline powder form
was supplied by Alfa Aesar, USA (Fig. 1(d)).
The alumina nanoparticles supplied by Alfa Aesar, USA were used as
K.P. Venkitaraj, et al.
the additive to pentaerythritol in this experimental study. The specifi-
cations of the nanoparticles are as follows: alumina (Al2O3), NanoDur
99.5%, APS: 40–50 nm, SA: 32–40 m2/g, MW: 101.96. The XRD pattern
of Al2O3 nanoparticles confirmed its crystalline nature. The diffraction
peaks in the XRD pattern of Al2O3 nanoparticles (Fig. 2(a)) were
identified as those present in the case of hexagonal α-Al2O3. Fig. 2(b)
exhibits the microstructure of alumina obtained using Jeol JSM 6360
Scanning Electron Microscope.
The dimension, profile, growth, and distribution of the Al2O3 na-
noparticles were studied by transmission electron microscopic (TEM)
images. The images were obtained using Jeol/JEM 2100 having point
and lattice resolution of 0.23 nm, and 0.14 nm respectively, and mag-
nification ranging from 2000× to 1,500,000×. The TEM photographs
of the Al2O3 nanoparticles are shown in Fig. 3. The obtained images
indicated the spherically shaped alumina nanoparticles have particle
sizes ranging from 14 to 58 nm.
The alumina nanoparticles were added to pentaerythritol in 0.5%
and 1% weight fractions. The dispersion of nanoparticles in PCM was
ensured with the help of the low energy ball mill run at 200 rpm for
1.5 h. The dispersion stability of nanoparticles and particle aggregation
in the prepared PCM samples were analyzed by a field emission scan-
ning electron microscope (FESEM) system to obtain the topographical
and elemental information of the PE/Al2O3 composite PCM. Elemental
identification with mapping to study the dispersion of nanoparticles in
PE was carried out by Energy Dispersive X-ray (EDX) mapping.
Fig. 4(a) shows the FESEM image of PE added with Al2O3 nano-
particles. The image shows nanoparticle agglomeration at some places
with some areas without any presence of nanoparticles. The reason for
Fig. 3. TEM images of Al2O3 nanoparticles.
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the heterogeneous mixing of pentaerythritol and alumina was the fact
that the dispersion of Al2O3 nanoparticles was purely physical using a
ball-mill. The region circled in red color indicates the particle ag-
gregation and the area shown by blue arrow represent the region that is
deprived of nanoparticles. Fig. 4(b) and (c) shows the EDX spectra of
the PE added with Al2O3 nanoparticles before and after thermal cycling.
The elemental mapping is shown in Fig. 4(b) also indicated the het-
erogeneous mixing of Al2O3 nanoparticles with PE. The EDX spectrum
of the thermally cycled sample shown in Fig. 4(c) confirms that the
dispersion of alumina nanoparticles in PE was not much disturbed even
after several thermal cycles.
Fig. 5 shows the Fourier Transform Infrared (FTIR) spectrum of the
PE + 0.5 wt.% Al2O3 before and after thermal cycling. Since the spectra
of the uncycled and cycled samples are identical, it can be confirmed
that there involved no chemical reaction between the PCM and the
nanoparticles.
3. Thermal conductivity measurement
The thermal conductivity of the PCM samples was determined by T-
history method (Venkitaraj & Suresh, 2018). The T-history analysis is
based on lumped capacitance theory in which a uniform temperature
profile is maintained. In order to ensure that the lumped heat capacity
theory is applicable, the test conditions used in T-history analysis
should have of Biot number (Bi) value less than unity. In T-history
method, the variation of temperature of the test samples and the re-
ference sample with time during the cooling process is recorded. The
thermal conductivity values of the test samples are then determined by
K.P. Venkitaraj, et al.
Fig. 4. (a) FESEM image, (b) EDX spectrum of PE with Al2O3 before thermal cycling, and (c) EDX spectrum of PE with Al2O3 after thermal cycling.
Fig. 5. FTIR spectrum of PE added with Al2O3 nanoparticles.
comparing their cooling curves with the cooling curves of the reference
samples. The detailed experimental requirements and the procedure of
T-history method are given in our previously published article
(Venkitaraj & Suresh, 2018).
4. Determination of enthalpy of transition
Thermal property analysis in terms of latent heat capacity and phase
transition temperature for pure and nano-enhanced PE were de-
termined using DSC (Mettler Toledo DSC 822e, Hong Kong). The
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instrument had a temperature range from −130 °C to max. 450 °C and a
measurement range ± 350 mW at RT with a measurement resolution of
0.04 mW at room temperature, temperature accuracy of ± 0.2 °C and
temperature reproducibility of ± 0.1 °C. The PCM samples were sub-
jected to heating and cooling between the temperature range 30–280 °C
at 10 °C/min.
5. Charging and discharging performance
5.1. Experimental setup
The performance of pentaerythritol added with Al2O3 nanoparticles
in energy storage application was tested by conducting charging and
discharging experiments using a thermal energy storage system. A
schematic diagram of the experimental setup is shown in Fig. 6. The
experimental setup comprises a shell and tube type heat exchanger
filled with the PCM. The shell side of the heat exchanger filled the PCM.
The fluid flowing through the copper tubes exchanges heat with the
PCM during the charging and discharging process. The hot thermal
fluid from the hot fluid container is pumped through the heat exchanger
using a gear pump. The flow rate of the hot thermal fluid is controlled
using a bye pass valve provided in the delivery side of the gear pump. A
rotameter is provided to monitor the flow rate of hot therminol flowing
through the heat exchanger. The hot fluid after flowing through the
copper tubes flows back to the hot reservoir. During the flow through
the heat exchanger, the hot fluid loses its heat to the PCM surrounding
the copper tubes. This is the charging cycle of the experiment. The cold
line of the experimental setup consists of a cold fluid container cen-
trifugal pump; rotameter, and an air-cooled heat exchanger.
During the discharge cycle, the cold thermal fluid is pumped
K.P. Venkitaraj, et al.
Fig. 6. Schematic diagram of the experimental setup for heat transfer study.
through the heat exchanger using the centrifugal pump. The flow rate
of the cold fluid is monitored and controlled by using a rotameter and a
valve provided in the delivery side of the centrifugal pump. The cold
fluid flowing through the copper tube receives heat stored by the PCM.
The cold fluid leaving from the other end of the heat exchanger flows
back to the cold reservoir via an air-cooled heat exchanger. During the
flow through the radiator, it loses heat. The temperature of the PCM
inside the shell at six different locations is also monitored using the K-
type thermocouples. The temperature of the PCM inside the shell at the
leading end, middle and, trailing ends are also monitored using the K-
type thermocouples. A multi-channel data logger records the PCM and
the fluid temperatures during the charging and discharging process.
The photograph of the actual experimental setup fabricated in-
cluded as Fig. 7. Fig. 8 shows the photographs of the shell and tube heat
exchanger before and after insulating.
Fig. 9 shows the constructional features of the shell and tube heat
Fig. 7. The photograph of the actual experimental setup.
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exchanger. The heat exchanger comprises three tubes of 20 mm inner
diameter, 2 mm thickness, and 45 cm effective length enclosed within a
shell of 65 mm inner diameter, and 5 mm thickness. The tubes are made
of copper and the shell is made of mild steel. The shell insulated using
glass wool and asbestos in order to minimize the heat loss to the sur-
roundings. The quantity of PCM required for filling in space inside the
shell estimated to be 1.22 kg. The heat transfer fluid used in the hot and
cold circuits is Therminol-55. Some important properties of Therminol-
55 are shown in Table 1. The temperature of therminol oil maintained
at 200 °C by using two hand immersion heaters of 1500 W each. The
gear pump (Make: HMP pumps, power: 0.5 HP, size: ½″ × ½″, rpm:
1440, maximum discharge: 30 LPM) was used to pump the hot ther-
minol oil through the heat exchanger. The cold fluid pumped by using a
monoblock centrifugal pump (Make: Lakshmi pumps, power: 0.5 HP,
size: 1″ × 1″, rpm: 1400, max. discharge: 45 LPM). The flow rate of hot
therminol oil is measured using a metal tube magnetic rotameter
K.P. Venkitaraj, et al. Sustainable Cities and Society 51 (2019) 101767

Fig. 8. Shell and tube heat exchanger.

(Make: Eureka, model: SSVS-MTS-4, range: 1.1–11 LPM). The flow rate Table 1
in the cold side of the experimental setup measured by using an acrylic Properties of Therminol-55.
body rotameter (Make: flow point, range: 1–10 LPM). Two metal con- Property Value
tainers, each 20-l capacity, were used as hot and cold fluid reservoirs.
The entire hot circuit, part of the cold circuit between the heat ex- Appearance Clear, yellow liquid
changer exit and air-cooled heat exchanger inlet are well insulated to Composition Synthetic hydrocarbon
Average molecular weight 320
minimize the heat loss to the surroundings. Density 864 kg/m3 @33 °C
815 kg/m3 @220 °C
Kinematic viscosity 19 mm2/s @ 40 °C
5.2. Procedure
Specific gravity 0.876
Specific heat 1.95 kJ/kg K @33 °C
The experiments performed using pure PE and PE added with 0.5 2.21 kJ/kg K @220 °C
and 1.0 wt.% of Al2O3. The detailed experimental procedure is given Normal boiling point 351 °C
below. The heat exchanger filled with pure PE on the shell side Maximum use temperature 315 °C
mounted in the experimental setup. The heaters in the hot fluid re-
servoir are switched on to heat the therminol oil above 200 °C. The hot
the heat exchanger by starting the centrifugal pump. The flow rate of
therminol oil pumped through the heat exchanger by switching on the
the cold therminol adjusted to 2 LPM by operating the valve. The
gear pump. The flow rate of the oil set at 2 LPM by regulating the bye
temperature of the cold therminol entering and leaving the heat ex-
pass valve. The temperature of the hot therminol entering and leaving
changer and the PCM temperatures at different locations recorded.
the heat exchanger and the PCM temperatures at different locations
The centrifugal pump switched off when the PCM temperature re-
recorded. The gear pump switched off when the PCM temperature re-
stored to its ambient temperature. This completes the discharging
corded crosses the solid–solid transition temperature of the PCM. This
process. The experiment repeated for hot and cold therminol flow rates
completes the charging process. The cold therminol oil pumped through

Fig. 9. Constructional details of the heat exchanger.

8
K.P. Venkitaraj, et al.
of 4 LPM and 6 LPM. The experiment is repeated for PE/LMA composite
PCM of 0.5 and 1.0 wt.% Al2O3.
5.3. Data reduction
5.3.1. Energy analysis
The heat supplied to the PCM is given by,
Qsp = m˙ h c p,h (Th,i − Th,o) tc, kJ
where ṁh is the mass flow rate (kg/s) of hot HTF, cp,h is the specific heat
of hot HTF, Th,i and Th,oare the inlet and the exit temperature of the hot
HTF, and tc is the charging time.
The heat stored in the TES is calculated as Heat stored = sensible
heat + solid–solid transition heat.
Qst = Qsen + Qtrs = m p c p,p (T¯p,f − T¯p,i ) + m p htrs , kJ
mp – the mass of the PCM (pentaerythritol), T̄p,f – mean final PCM
temperature, T̄p,i – mean initial temperature of the PCM, htrs – enthalpy
of transition, cp,p is the specific heat of PCM.
The average charging power (Pc) is obtained as the ratio of the heat
stored (Qst) to the time for charging (tc).
Qst
i.e. Pc =
tc
Now, charging efficiency is found as the ratio of the heat stored (Qst) by
the PCM to the heat supplied (Qsp) by the HTF during the charging
cycle. i.e.,
Qst
Charging efficiency (%), ηc = × 100
Qsp
Heat rejected to the cold HTF,
Qre = m˙ c c p,c (Tc,o − Tc,i) td, kJ
where ṁc – mass flow rate (kg/s) of cold HTF, cp,c – specific heat of cold
HTF, Tc,i and Tc,o – the inlet and the outlet temperature of the cold HTF,
and td – time taken for the discharge.
The average discharging power (Pd) is calculated as the ratio of the
heat rejected (Qre) to the cold HTF to the discharging time (td).
Qre
i.e., Pd =
td
The discharging efficiency determined as the ratio of the amount of
heat rejected to the cold HTF (Qre) to the heat stored (Qst) by the PCM
during the discharging cycle, i.e.,
Qre
Discharging efficiency (%), ηd = × 100
Qst
The overall energy efficiency of the thermal energy storage (TES)
system used in this experimental study calculated by combining the
efficiencies computed separately for the charging and discharging
processes (Jagadheeswaran, Pohekar, & Kousksou, 2010; Rezaei et al.,
2013).
The overall energy efficiency of the TES system, η = ηc × ηd
5.3.2. Exergy analysis
The energy analysis explained in the previous section is based on the
first law of thermodynamics. Even though it provides an estimation of
the performance of the thermal energy storage system, it does not re-
flect the quality of energy stored/recovered. This shortfall can be
overcome by performing the exergy analysis based on the second law of
thermodynamics.
Exergy is the quality or usefulness of energy. It is the maximum
amount of work that can be generated by a system as it comes to
equilibrium with surrounding.
During charging mode, the HTF transfers the exergy to PCM and
Sustainable Cities and Society 51 (2019) 101767
part of the exergy is stored in the PCM. The rate of exergy supplied by
HTF during the charging period is computed using the following
equation.
T
˙ input = m˙ h cp,h ⎡ (Th,i − Th,o) − To ln ⎛⎜ h,i ⎞⎟ ⎤
Ex ⎢ ⎥
⎣ ⎝ Th,o ⎠ ⎦
where To is the ambient temperature.
(1) The rate of exergy stored in the PCM is obtained as
˙ stored = m p htrs ⎡1 − To ⎤ + m p c p,p ⎡ (Ttrs − T¯p,i ) − To ln ⎛⎜ Ttrs ⎞⎟ ⎤
Ex
⎢ Ttrs ⎥ ⎢ ¯ ⎥
⎣ ⎦ ⎣ ⎝ Tp,i ⎠ ⎦
¯
+ m p c p,p ⎡ ¯ ⎛ Tp,f ⎞ ⎤
⎢ (Tp,f − Ttrs) − To ln ⎜ Ttrs ⎟ ⎥
⎣ ⎝ ⎠⎦
(2)
where Tp,i and Tp,f are the initial and final PCM temperatures and Ttrs is
the PCM transition temperature.
The rate of exergy extracted from the PCM by the HTF during the
discharging period is computed using the equation,
T
˙ output = m˙ c cp,c ⎡ (Tc,o − Tc,i ) − To ln ⎛⎜ c,o ⎞⎟ ⎤
Ex ⎢ ⎥
⎣ ⎝ Tc,i ⎠ ⎦
(3) The charging exergy efficiency (ψchar) is computed as the ratio of rate of
exergy stored by the PCM to the exergy supplied by the HTF during the
charging period. Similarly, discharging exergy efficiency (ψdischar) is
estimated as the ratio of the rate of exergy extracted from the PCM to
the exergy stored by the PCM.
The overall exergy efficiency (ψ) of the thermal energy storage
(4) process is computed from the exergy efficiencies of charging and dis-
charging processes as ψ = ψchar × ψdischar.
(5)
6. Results and discussion
6.1. Thermal properties of nano-enhanced PE
The thermal conductivity of the PE with and without the addition of
Al2O3 nanoparticles calculated using the temperature data obtained
from the T-history plots. In T-history method, the thermal properties of
the PCM samples were estimated by comparing their temperature plot
(6)
with that of the glycerin which was taken as the reference medium. The
obtained thermal conductivity value of pure PE was 0.106 W/m K. The
values obtained for the PE samples added with Al2O3 nanoparticles
showed very significant changes in the thermal conductivity values.
The T-history results showed that the thermal conductivity of PE en-
hanced by 33.0% and 51.9% respectively corresponding to 0.5 and
(7)
1.0 wt.% of Al2O3 nanoparticles. The improved thermal conductivities
of PE + 0.5 wt.% Al2O3 and PE + 1.0 wt.% Al2O3 obtained as 0.141 W/
m K and 0.161 W/mK respectively.
The variation of thermal conductivity with temperature is also in-
vestigated using the T-history data recorded in the application range
40–205 °C of pentaerythritol. The whole range is divided into three
smaller temperature ranges: (i) from 40 to 95 °C with 77.5 °C as the
(8)
mean temperature, (ii) from 95 to 150 °C with 122.5 °C as the mean
temperature, and (iii) from 150 to 205 °C with 177.5 °C as the mean
temperature, the range in which the solid–solid transition occurs in PE
(Fig. 10). Table 2 shows the thermal conductivity measurements ob-
tained for pure PE and PE added with 0.5 and 1.0 wt.% of Al2O3 na-
noparticles in the above temperature ranges.
It can be understood from the tabulated results that the thermal
conductivity of all the tested samples decreases with temperature.
Table 3 displays the thermal conductivity values of the PCM samples
before and after thermal cycling. It can be seen from the table that the
thermal conductivity of the PE added with 0.5 and 1.0 wt.% of Al2O3
nanoparticles were significantly greater than that of pure PE even after
1000 thermal cycles. This meant that Al2O3 nanoparticles did not
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6.3. Charging performance analysis

6.3.1. Charging time

The charging performance experiments were conducted to study the
effect of heat transfer enhancement additive (Al2O3 nanoparticles) on
the thermal energy storage performance of PE. For this, experiments
were conducted using pure PE and PE added with 0.5 and 1.0 wt.% of
Al2O3 nanoparticles. During the charging process, the HTF (therminol
oil) heated to about 225 °C and circulated through the heat exchanger.
The PCM temperature variation from the inlet to the exit of the heat
exchanger in the axial direction is recorded for evaluating the charging
performance of the PCM. Fig. 12 shows the temperature variation in the
case of pure PE for HTF flow rates of 2, 4, and 6 LPM. The variation of
the PCM temperature at six locations in the heat exchanger is plotted in
this figure. During the charging process, the PCM in the shell side of the
heat exchanger absorbs the heat of the hot HTF. The charging process
continued until all the temperatures recorded by the thermocouples
exceeded the solid–solid transition temperature of pure PE. The char-
Fig. 10. Variation thermal conductivity of PE + Al2O3 with temperature. ging process ended in 152 min when the HTF flow rate of 2 LPM
maintained through the heat exchanger. The charging period found
decreased to 103 min and 68 min when the therminol flow rate changed
Table 2
Thermal conductivity variation with temperature. to 4 LPM and 6 LPM respectively. The increase in charging time ob-
served was because of the increased energy supplied at a higher flow
Temperature range Average Thermal conductivity (W/m K)
rate.
(°C) Temp (°C)
PE PE + 0.5% PE + 1.0% The charging experiments repeated for PE added with 0.5 and
Al2O3 Al2O3 1.0 wt.% of Al2O3 nanoparticles. Fig. 13 shows the temperature dis-
tribution in the PCM during the charging process of PE added with
40–95 67.5 0.112 0.148 0.165 0.5 wt.% of Al2O3 nanoparticles. The charging of PE + 0.5 wt.% Al2O3
95–150 122.5 0.108 0.139 0.157
150–205 177.5 0.104 0.132 0.149
ended in 127 min when the HTF flow rate of 2 LPM maintained through
the heat exchanger. The charging period decreased to 89 min and
56 min when the therminol flow rates changed to 4 LPM and 6 LPM
Table 3 respectively.
The thermal conductivity of PE with Al2O3 nanoparticles before and after Fig. 14 shows the charging process in the case of PE + 1.0 wt.%
thermal cycling. Al2O3 at different flow rates of the HTF. The charging of PE + 1.0 wt.%
PCM samples Thermal conductivity (k) (W/m K)
Al2O3 ended in 112 min when the HTF flow rate of 2 LPM maintained
through the heat exchanger. The charging period decreased to 78 min
Before thermal cycling After 1000 thermal cycles and 50 min when the flow rates changed to 4 LPM and 6 LPM respec-
tively.
PE 0.106 0.096
(−9.4%)
Fig. 15 shows the % reduction in the charging time of PE due to the
PE + 0.5 wt.% Al2O3 0.141 0.128 addition of Al2O3 nanoparticles at different flow rates of the HTF. It can
(+33.0%) (+20.8%) be understood from the graph that the charging time of PE decreases
PE + 1.0 wt.% Al2O3 0.161 0.140 due to the addition of 0.5 and 1.0 wt.% of Al2O3 nanoparticles at all
(+51.9%) (+32.1%)
volume flow rates of the heat transfer fluid.

undergo any deterioration in thermal property and caused very sig-

nificant enhancement thermal conductivity of PE even after several
thermal cycles.

6.2. Enthalpy of transition

The enthalpy of solid–solid transition is an important thermal

characteristic parameter of pentaerythritol. Differential Scanning
Calorimetry (DSC) analysis of the PCM samples was performed using
Mettler Toledo DSC 822e, Hong Kong. The heat capacity and enthalpy
of the solid–solid transition of the PCM samples obtained using the DSC
data. Fig. 11 illustrates the DSC plot obtained for pure PE sample.
The two peaks seen in the DSC curve represent the phase change
process in PE. The first peak corresponds to the solid to solid phase
change and the second peak corresponds to the solid–liquid phase
change. Table 4 summarizes the temperature and enthalpy of the so-
lid–solid transition of pure PE and PE added with 0.5 and 1.0 wt.% of
Al2O3 nanoparticles during the charging and discharging processes.

Fig. 11. DSC curve of pure PE.

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Table 4
Enthalpy of the transition of the PCM samples.
Samples Heating Cooling
Solid–solid transition Solid–solid transition

Onset Peak End set Enthalpy change Onset Peak End set Enthalpy change
(°C) (°C) (°C) (kJ/kg) (°C) (°C) (°C) (kJ/kg)

PE 181.3 187.8 193.6 263.9 165.6 163.5 163.0 238.9

PE + 0.5% Al2O3 180.8 188.4 190.0 255.0 169.5 168.9 162.9 229.5
PE + 1.0% Al2O3 180.9 188.4 200.6 251.7 169.8 169.6 162.6 226.5

Fig. 12. Charging process of pure PE at different flow rates of HTF.

6.3.2. Charging power and charging efficiency
The average energy stored in unit time is estimated as the charging
power. Fig. 16 shows the average charging power estimated in the case
of pure PE and PE added with 0.5 wt.% and 1.0 wt.% of Al2O3 nano-
particles.
It can be understood that the charging power of PE increases with
the addition of Al2O3 nanoparticles for all the heating rates considered
in this study. The average energy storage power of pure PE corre-
sponding to 2 LPM, 4 LPM, and 6 LPM flow rates estimated as 100.5 W,
149.0 W, and 222.5 W respectively. The average energy storage power
corresponding to 2 LPM, 4 LPM, and 6 LPM flow rates increased to
117.45 W, 165.7 W, and 261.5 W respectively when 0.5 wt.% of Al2O3
nanoparticles were added to PE. When the weight fraction of Al2O3
nanoparticles increased to 1.0%, the average energy storage power
corresponding to 2 LPM, 4 LPM, and 6 LPM flow rates estimated as
130.5 W, 186.3 W and 289.3 W respectively.
Fig. 17 shows the charging efficiency obtained in the case of pure PE
and PE added with 0.5 and 1.0 wt.% of Al2O3 nanoparticles at different
HTF flow rates. In the case of pure PE, an amount of 916.4 kJ energy
stored out of the 1418.2 kJ heat supplied at an HTF flow rate of 2 LPM,
indicating a charging efficiency of 64.6%. When the flow rate changed
to 4 LPM, 911.6 kJ of heat was stored out of 1322.8 kJ of heat supplied.
This accounts for a charging efficiency of 68.9%. When the flow rate
further increased to 6 LPM, the heat supplied and heat stored estimated
as 907.8 kJ and 1256.8 kJ showing a charging efficiency of 72.2%. The
charging efficiency estimated for PE + 0.5 wt.% Al2O3 and PE + 1.0 wt.
% Al2O3 is also shown in Fig. 17. The results of PE + 0.5 wt.% Al2O3
indicated charging efficiencies of 72.4%, 76.7% and 80.7% at HTF flow
rates of 2, 4 and 6 LPM respectively. The heat supplied and heat stored
at these flow rates obtained as 1235.2 kJ, 1154.2 kJ, 1089.3 kJ, and
894.4 kJ, 884.7 kJ, 878.7 kJ respectively. The results of PE + 1.0 wt.%
Al2O3 indicated charging efficiencies of 80.3%, 83.0% and 86.8% at
HTF flow rates of 2, 4 and 6 LPM respectively. The heat supplied and
heat stored at these flow rates obtained as 1093.4 kJ, 1050.2 kJ,
1089.3 kJ, and 877.5 kJ, 872.1 kJ, 868.0 kJ respectively.
6.4. Discharging performance analysis
6.4.1. Discharging time
To study the discharge performance of the PCM, the PCM is first
charged to a temperature above the solid–solid transition point and
then allowed to cool back to the ambient conditions. During the dis-
charging process, the HTF at room temperature circulated through the
heat exchanger. The PCM rejects the heat stored to the circulating HTF.

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K.P. Venkitaraj, et al. Sustainable Cities and Society 51 (2019) 101767

Fig. 13. Charging process of PE + 0.5 wt.% Al2O3 at different flow rates of HTF.

Fig. 14. Charging process of PE + 1.0 wt.% Al2O3 at different flow rates of HTF.

12
K.P. Venkitaraj, et al.
Fig. 15. Reduction in charging time of PE due to Al2O3.
Fig. 16. Average charging power at different HTF flow rates.
Fig. 17. Charging efficiency at different flow rates.
The PCM temperature variation from the inlet to the exit of the heat
exchanger in the axial direction is recorded for evaluating the dis-
charging performance of the PCM.
13
Sustainable Cities and Society 51 (2019) 101767
Fig. 18 shows the temperature variation in the case of pure PE for
HTF flow rates of 2, 4, and 6 LPM. The variation of the PCM tempera-
ture at six locations in the heat exchanger is plotted in this figure.
During the discharging, the PCM in the shell side of the heat exchanger
rejects the heat to the HTF. The discharging process continued until all
the temperatures recorded by the thermocouples recorded temperature
equal to the ambient condition. The charging process ended in 106 min
when a flow rate of 2 LPM maintained through the heat exchanger. The
charging period found decreased to 86 min and 65 min when the HTF
flow rate changed to 4 LPM and 6 LPM respectively. The decrease in
charging time observed was because of the increased heat absorption at
the higher flow rates.
The discharging performances of PE added with 0.5 and 1.0 wt.% of
heat transfer enhancement additives Al2O3 nanoparticles, LMA and
LMM are also analyzed in this section. Fig. 19 shows the temperature
distribution in the PCM during the discharging process of PE added
with 0.5 wt.% of Al2O3 nanoparticles. The results showed that the dis-
charging time corresponding to the HTF flow rate of 2 LPM decreased
from 106 min to 90 min. This indicated that the discharging time re-
duced by 15% due to the increased heat transfer rated resulted from the
addition of 0.5 wt.% of Al2O3 nanoparticles. The discharging time
found decreased from 86 min to 72 min when the flow rate changed to
4 LPM indicating a 16.3% decrease. The discharge time further de-
creased to 54 min indicating a 16.9% decrease when the flow rate ad-
justed to 6 LPM.
Fig. 20 shows the temperature distribution in the PCM during the
discharging process of PE added with 1.0 wt.% of Al2O3 nanoparticles.
The results showed that the discharging time corresponding to the HTF
rate of 2 LPM decreased from 106 min to 78 min. This indicated that the
discharging time reduced by 26.4% due to the increased heat transfer
rated resulted from the addition of 1.0 wt.% of Al2O3 nanoparticles. The
discharging time found decreased from 86 min to 65 min when the flow
rate changed to 4 LPM indicating a 24.4% decrease. The discharge time
further decreased to 57 min indicating a 26.2% decrease when the flow
rate adjusted to 6 LPM. Fig. 21 summarizes the % reduction in the
discharging time of PE due to the addition of 0.5 and 1.0 wt.% of Al2O3
nanoparticles.
6.4.2. Discharging power and efficiency
The average energy released per unit time to the circulating HTF is
estimated as the discharging power. Fig. 22 shows the average dis-
charging power estimated in the case of pure PE and PE added with
0.5 wt.% and 1.0 wt.% of Al2O3 nanoparticles at different flow rates of
the HTF.
The experimental results showed that the discharging power of PE
increases with the addition of additives for all the heating rates con-
sidered in this study. The average energy discharging power of pure PE
corresponding to 2 LPM, 4 LPM, and 6 LPM flow rates estimated as
75.8 W, 98.8 W, and 136.5 W respectively.
The average discharging power corresponding to 2 LPM, 4 LPM, and
6 LPM flow rates increased to 101.1 W, 134.8 W, and 187.0 W respec-
tively when 0.5 wt.% of Al2O3 nanoparticles were added to PE. When
the weight fraction of Al2O3 nanoparticles increased to 1.0%, the
average energy discharging power corresponding to 2 LPM, 4 LPM, and
6 LPM flow rates estimated as 124.1 W, 153.9 W, and 230.8 W respec-
tively.
Fig. 23 shows the discharging efficiency obtained in the case of pure
PE and PE added with 0.5 and 1.0 wt.% of Al2O3 nanoparticles at dif-
ferent HTF flow rates. In the case of pure PE, an amount of 482.2 kJ of
energy discharged, out of the 916.4 kJ heat stored, at an HTF flow rate
of 2 LPM. This indicated a discharging efficiency of 52.6%. When the
flow rate changed to 4 LPM, 510.0 kJ of heat was released to the HTF,
out of 911.6 kJ of heat available. This accounts for a discharging effi-
ciency of 55.9%. When the flow rate further increased to 6 LPM, the
heat rejected to the HTF estimated as 532.2 kJ, out of 907.8 kJ heat
stored by the PCM during the charging cycle. This gave a discharging
K.P. Venkitaraj, et al. Sustainable Cities and Society 51 (2019) 101767

Fig. 18. Discharging process of PE at different flow rates of HTF.

Fig. 19. Discharging process of PE + 0.5 wt.% Al2O3 at different flow rates of HTF.

14
K.P. Venkitaraj, et al.
Fig. 20. Discharging process of PE + 1.0 wt.% Al2O3 at different flow rates of HTF.
Fig. 21. % reduction in discharging time of PE due to Al2O3 nanoparticles at
different HTF flow rates.
efficiency of 58.6%.
The discharging efficiencies obtained for PE + 0.5 wt.% Al2O3 and
PE + 1.0 wt.% of Al2O3 are also displayed in Fig. 23. The results of
PE + 0.5 wt.% Al2O3 indicated discharging efficiencies of 61.0%,
65.8% and 70.2% at HTF flow rates of 2, 4 and 6 LPM respectively.
During the discharging cycle, 545.9 kJ of heat rejected, out of 894.4 kJ
of heat available, to the HTF circulated at 2 LPM. The heat released at
the flow rate of 4 LPM estimated to be 582.3 kJ, out of 884.7 kJ heat
stored by the PCM during the charging period. The heat discharged at
6 LPM flow rate estimated to be 617 kJ, out of 878.7 kJ heat that was
stored during the heating cycle. The discharging efficiency of
PE + 1.0 wt.% Al2O3 corresponding to the HTF flow rates of 2, 4 and
15
Sustainable Cities and Society 51 (2019) 101767
Fig. 22. Average discharging power at different HTF flow rates.
6 LPM calculated as 66.2%, 68.8%, and 75.0% respectively. The heat
rejected to the HTF at these flow rates obtained as 580.9 kJ, 600.1 kJ,
and 650.9 kJ respectively. The heat stored in the previous heating cycle
was 877.5 kJ, 872.1 kJ, and 868.0 kJ corresponding to the flow rates 2,
4, and 6 LPM respectively.
6.5. Overall energy efficiency
The overall energy efficiency of the thermal energy storage (TES)
system used in this experimental study is calculated by combining the
energy efficiencies computed separately for the charging and dischar-
ging processes. Fig. 24 displays the overall efficiencies obtained using
the different PCM samples for energy storage and release. The experi-
mental results showed that the TES system using pure PE gave overall
K.P. Venkitaraj, et al.
Fig. 23. Discharging efficiency of PE with additives at different flow rates.
Fig. 24. Overall energy efficiency of the thermal energy storage system.
energy efficiencies of 34%, 38.5% and 42.3% corresponding to HTF
flow rates of 2 LPM, 4 LPM, and 6 LPM respectively. The average effi-
ciency of the system in the flow rate range 2–6 LPM was estimated to be
38.3%. The addition of Al2O3 nanoparticles to PE resulted in an in-
crease in the overall efficiency of the system. The overall efficiency of
the TES system employing PE + 0.5 wt.% Al2O3 showed overall energy
efficiencies of 44.2%, 50.5%, and 56.7% respectively corresponding to
HTF flow rates of 2 LPM, 4 LPM, and 6 LPM. The average efficiency of
the system in the flow rate range 2–6 LPM found to be 50.5%. When the
Al2O3 wt.% increased to 1.0, the TES system exhibited overall effi-
ciencies of 53.2%, 59.1% and 65.1% when the HTF flow rates were
2 LPM, 4 LPM, and 6 LPM respectively. The average efficiency of
PE + 1.0 wt.% Al2O3 in the flow rate range 2–6 LPM found to be 58.5%.
Fig. 25 shows the % enhancement in the overall energy efficiency of
the TES system at different flow rates. The addition of 0.5 wt.% of Al2O3
nanoparticles to PE at HTF flow rates of 2, 4 and 6 LPM gave en-
hancement of 10.2%, 12%, and 14.4% respectively compared to pure
PE. When the weight fraction of Al2O3 nanoparticles was increased to
1.0%, the overall energy efficiency showed enhancement of 19.2, 20.6
and 22.8 at HTF flow rates of 2, 4 and 6 LPM respectively compared to
PE.
The results of the experimental investigation discussed in the pre-
ceding sections revealed that the incorporation of Al2O3 nanoparticles
enhanced the thermal energy storage performance of pentaerythritol.
The enhanced energy storage and release performance can be attributed
16
Sustainable Cities and Society 51 (2019) 101767
to the improved thermal conductivity of PE due to the presence of
conductive Al2O3 nanoparticles as reported in the section on thermal
property measurement. The maximum value of the overall efficiency
obtained corresponding to 1.0 wt.% of Al2O3 nanoparticles at HTF flow
rate of 6 LPM. This indicated that the charging and discharging occurs
more efficiently at higher weight % of the heat transfer enhancement
additives and at higher flow rates of the HTF. Higher the weight % of
Al2O3 nanoparticles, greater is the enhancement in the thermal con-
ductivity which resulted in the heat transfer at an enhanced rate.
During the charging process, the hot HTF transfers heat to the PCM
filled in the shell side of the heat exchanger. Initially, heat is transferred
from the circulating HTF to the inner surface of the tubes through
convection. The heat is then conducted through the tube material by
conduction. The PCM layer in contact with the outer surfaces of the
tube receives this heat by conduction and then flows outwards into the
bulk of the PCM. The continuous heating of the PCM due to the transfer
of the heat from the HTF causes the temperature to increase linearly.
When the temperature of PE reaches its solid–solid transition tem-
perature, the added heat causes the breaking of metastable hydrogen
bonds in the PE molecules. The breaking of hydrogen bonds is an en-
dothermic process involving a large enthalpy change. Thus, a con-
siderable amount of heat is absorbed by the PCM during the breaking of
bonds. At ordinary temperature, P PE has the body-centered tetragonal
(BCT) crystal structure. At the transition temperature, the crystal
structure changes to face-centered cubic (FCC). If the PCM is further
heated above this transition temperature, the PCM receives heat again
by sensible heating.
During the discharging process, the heat stored by the PCM is re-
jected to the circulating cold HTF. The heat from the outer layer of the
PCM in contact with the shell is conducted toward the center resulting
in the sensible cooling of the PCM. When the temperature of the PCM
reaches the solid–solid transition temperature, the hydrogen bonds
which were broken earlier get reforms and the PE molecule regains its
original BCT structure. This reformation process is accompanied by the
release of heat. When the temperature of the PCM reaches below the
transition temperature, further release of heat is because of the sensible
cooling of the PCM. The outside surface of the metal tube wall receives
heat by conduction from the PCM layer in contact with the tubes. Heat
is conducted through the material of the tubes and then transferred to
the cold HTF by convection from the inner surface of the tubes.
The addition of Al2O3 nanoparticles has resulted in increasing the
thermal conductivity of PE. This caused an enhanced rate of heat
transfer by conduction through the PCM. Subcooling in solid–solid PCM
refers to the cooling of material below its transition temperature but
without the solid to solid transition actually taking place. The large
Fig. 25. % enhancement in overall efficiency.
K.P. Venkitaraj, et al. Sustainable Cities and Society 51 (2019) 101767

degree of sub-cooling may affect the performance of phase change

materials and limit their application. During subcooling, the storage
material behaves similar to a sensible storage material, and the storage
capacity is reduced. This undesired subcooling in PE was currently re-
duced by using Al2O3 nanoparticles as nucleating agents, also called
nucleators. These additives remain solid at all times and act as centers
of crystal growth for the material that undergoes the phase change. The
reduction in subcooling was attributed to being heterogeneous nu-
cleation which occurred along with the Al2O3 particles in the crystal-
lization process.

6.6. Exergy analysis

The data obtained from the charging and discharging experiments

are used to carry out the exergy analysis of the TES system. Exergy-
based performance evaluation of TES system gives more perspective
measure than energy based one as it reveals the true potential of the
system and the economic assessment of the storage/discharge process.
The exergy input, exergy stored and the exergy output estimated in the
case of PE, PE + 0.5 wt.% Al2O3 PE + 1.0 wt.% Al2O3 for flow rates of
2, 4 and 6 LPM of the HTF are summarized in Table 5.
The energy efficiency of a TES under ideal condition will be 100% as
there is no energy loss in the system. But in the actual case, there are
always irreversibilities in the system which results in energy loss.
Therefore, energy efficiencies calculated do not reflect the useful en-
ergy since the lost energy is not. In the case of exergy evaluation, both
the useful and lost energies are taken into consideration. Due to this
reason, the exergy efficiency is much less than the energy efficiency for
all the test conditions mentioned above. The results show that addition
of the alumina nanoparticles has resulted in enhancing the exergy ef-
ficiency of the TES system. For each PCM tested, the exergy efficiency is
found increasing with the increase in the flow rate of the HTF. The
reason for the enhanced heat transfer occurred at a higher flow rate was
because of the increased turbulence in the flow. The increased turbu-
lence in the region near to the tube wall caused very efficient fluid
mixing and efficient redevelopment of the thermal/hydrodynamic
boundary layer leading to the improvement in the convective heat
transfer (Chandrasekar, Suresh, & Chandra Bose, 2010; Suresh,
Venkitaraj, Selvakumar, & Chandrasekar, 2012). The experimental re-
sults summarized in Table 3 indicate that the addition of Al2O3 nano-
particles to PE has resulted in an increase in the charging and dis-
charging exergy efficiency of the TES for all the flow rates of the HTF
tested. Table 5 also presents the overall exergy efficiency of the TES
using pure PE and PE added with 0.5 and 1.0 wt.% of Al2O3 nano-
particles. In the case of pure PE, overall exergy efficiencies of 21.5%,
25.2%, and 29.1% have obtained corresponding to the HTF flow rates
of 2, 4 and 6 LPM respectively. The addition of 0.5 wt.% of Al2O3 to PE
resulted in an increase in the exergy efficiency by 5.6%, 5.8% and 7.5%
corresponding to the HTF flow rates of 2, 4 and 6 LPM respectively.
When the weight fraction of Al2O3 was increased to 1.0%, the test
Fig. 26. Lost and useful exergy.
results showed 12.6%, 15.1% and 18% increase in the overall exergy
efficiency corresponding to the flow rates 2, 4 and 6 LPM respectively.
Amount of exergy lost at each test condition is estimated from the
input and output exergy values and are presented in Fig. 23. The
quantification of lost exergy is very important in the life cycle cost
evaluation of PCM.
It can be understood from Fig. 26 that the fraction of useful exergy
increases due to the incorporation of Al2O3 nanoparticles for all the
flow rates of HTF. In other words, the fraction of lost exergy decreases
due to the addition of Al2O3 nanoparticles.
6.7. Experimental uncertainties
The main parameter monitored during T-history, and thermal sto-
rage/release performance tests were the PCM and HTF temperatures. In
this experimental study, K type thermocouples connected to a multi-
channel data acquisition system (KEYSIGHT 34972A LXI) were used to
record the various temperatures. The uncertainties in the energy mea-
surements were calculated using the temperature and flow rate un-
certainties. The uncertainties in the flow meter reading are specified by
the manufacturer as ± 1% of full flow. The calibrated temperature
sensors showed an uncertainty of ± 0.1 °C. Now the uncertainty in the
heat supplied/recovered (δQ) was calculated using the know un-
certainty values of temperature (δT) and mass flow rate of the HTF (δṁ ).
Therefore,

Table 5
Input, stored and output exergy.
PCM Flow rate ˙ input
Ex ˙ stored
Ex ˙ output
Ex Charging exergy efficiency Discharging exergy efficiency Overall exergy efficiency
(LPM) (kJ/day) (kJ/day) (kJ/day) (%) (%) (%)
ψchar ψdischar ψ

PE 2 6655 3182 1440 47.8 45.2 21.6

4 9277 4693 2337 50.6 49.8 25.2
6 12,759 6979 3719 54.7 53.3 29.1

PE + 0.5 wt.% Al2O3 2 7086 3740 1930 52.8 51.6 27.2

4 9312 5223 2889 56.1 55.3 31
6 13,339 8191 4879 61.4 59.6 36.6

PE + 1.0 wt.% Al2O3 2 6897 4132 2356 59.9 57 34.2

4 9201 5903 3710 64.2 62.9 40.3
6 13,065 9059 6153 69.3 67.9 47.1

17
K.P. Venkitaraj, et al.
˙ ˙ T )2
δQ = tcp,htf (ΔT δm˙ )2 + 2(mδ
where ṁ – the mass flow rate of the HTF, cp,htf – specific heat of the
HTF, ΔT – the difference between the inlet and exit fluid temperatures, t
– time of charging/discharging.
The uncertainty in the heat stored was estimated as
δQstored = Mcp,pcm (ΔT × δT) + M(δh), where δh is the uncertainty in
the enthalpy change given by the DSC equipment and M is the mass of
the PCM and cp,pcm is the specific heat of the PCM.
Using the above relations, the average uncertainties in heat sup-
plied, the heat stored and heat recovered in the HTF flow rate range
considered in this work were estimated as 8.1%, 7.1%, and 8.5% re-
spectively.
7. Summary and conclusion
The effect of adding Al2O3 nanoparticles on the thermal energy
storage performance of PE was studied by conducting the experiments
using pure PE and PE added with 0.5 and 1.0 wt.% of Al2O3 nano-
particles. During the charging process, the hot HTF (therminol oil) at
about 225 °C, and circulated through the heat exchanger at different
flow rates of 2 LPM, 4 LPM, and 6 LPM. During the discharging process,
cold HTF (therminol oil) at about 30 °C, and circulated through the heat
exchanger at different flow rates of 2 LPM, 4 LPM, and 6 LPM. The main
findings of the experimental study are given below
• The results of the charging and discharging experiments indicated a
significant reduction in the charging and discharging time of PE due
to the addition of 0.5 and 1.0 wt.% of the additives Al2O3 nano-
particles.
• The charging and discharging power and efficiency of PE with Al2O3
nanoparticles found increased at all flow rates of the HTF. The
maximum enhancement in the efficiency of charging and dischar-
ging observed at the highest flow rate of 6 LPM.
•
The charging efficiency found increased to 72.4%, 76.7% and 80.7%
at HTF flow rates of 2, 4 and 6 LPM respectively when 0.5 wt.% of
Al2O3 nanoparticles was added to PE. The results of PE + 1.0 wt.%
Al2O3 indicated a further increase in the charging efficiencies to
80.3%, 83.0% and 86.8% corresponding to the HTF flow rates of 2,
4 and 6 LPM respectively.
• The discharging efficiency found increased to 61.0%, 65.8% and
70.2% at HTF flow rates of 2, 4 and 6 LPM respectively when 0.5 wt.
% of Al2O3 nanoparticles was added to PE. The results of
PE + 1.0 wt.% Al2O3 indicated a further increase in the discharging
efficiency to 66.2%, 68.8% and 75.0% corresponding to the HTF
flow rates of 2, 4 and 6 LPM respectively.
• The mean value of the overall energy efficiency of the thermal en-
ergy storage system using pure PE estimated to be 38.3%. The ad-
dition of 0.5 and 1.0 wt.% of Al2O3 nanoparticles caused the mean
value of overall efficiency to increase to 50.5% and 58.5% respec-
tively.
• The overall efficiency of a thermal energy storage system employing
0.5 and 1.0 wt.% of Al2O3 nanoparticles showed very significant
improvement at all flow rates of HTF considered in this study.
Therefore, it can be concluded that the use of 0.5 and 1.0 wt.%
Al2O3 nanoparticles for heat transfer enhancement results in very
significant improvement in the thermal performance of PE for long
term energy storage applications.
Acknowledgments
Authors express their sincere gratitude to the Centre for Engineering
Research and Development (KTU/RESEARCH 3/1199/2017 dated
19.04.2017) for the financial assistance given for the execution of the
work reported in this paper.
18
Sustainable Cities and Society 51 (2019) 101767
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