Thermochimica Acta 680 (2019) 178343

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Energy storage performance of pentaerythritol blended with indium in T

exhaust heat recovery application
KP Venkitaraja,b, S Suresha, , B Praveena
⁎

a
Department of Mechanical Engineering, National Institute of Technology, Tiruchirapalli, Tamilnadu, 620015, India
b
Department of Mechanical Engineering, College of Engineering Adoor, Kerala, 691551, India

ARTICLE INFO ABSTRACT

Keywords: This paper presents the effect of adding indium, a low melting metal on thermal energy storage performance of
Pentaerythritol pentaerythritol in IC engine exhaust gas heat recovery application. Charging and discharging experiments were
Low melting metal conducted using pentaerythritol added with 0.1, 0.5 and 1.0 wt. % of indium in a shell and tube heat recovery
Energy savings heat exchanger. The experimental results showed reduction in charging and discharging time due to the addition
Charging efficiency
of indium leading to improved thermal energy storage performance of pentaerythritol. The charging efficiency of
Exhaust heat
PE enhanced by 3.5, 6.8 and, 11.2% corresponding to 0.1, 0.5 and, 1.0 wt.% of indium under full load condition.
The energy stored by pentaerythritol increased by 6.9, 14.65 and, 25.8% with respect to 0.1, 0.5 and 1.0 wt. % of
indium. The energy recovered during the discharge period found increased by 5.4, 12.3 and, 18.6% corre-
sponding to 0.1, 0.5 and, 1.0 wt. % of indium.

1. Introduction phase transition temperatures below 15 °C, suitable in air conditioning

applications and the food industry; (ii) mid temperature PCM with
The increasing energy requirements and decreasing energy sources phase transition temperatures in the range 15–90 °C suitable for solar,
necessitate the use of renewable energy sources as well as efficient ways medical, textile, electronic and building cooling applications (iii) high
of energy conservation. The over-dependence of conventional fossil temperature PCM with a phase transition above 90 °C developed mainly
fuels has adverse impacts like acid precipitation, ozone depletion and for industrial and aerospace applications [2]. The PCM include various
greenhouse effect on the environment [1]. It is therefore essential to organic, inorganic and eutectic materials showing a phase transition
reduce the high-intensity pollution associated with conventional fossil within the required working temperature range. The energy storage
fuels to put control over global warming. Waste heat recovery is one of using PCM require very less space, and therefore the cost of storage
the energy conservation methods that is as important as developing a media is comparatively low [3–5]. The reliability of a PCM ensured by
new source of energy. The hot flue gases generated from boilers, fur- testing their thermal, chemical and physical stability [6]. The phase
naces and internal combustion engines carry a large quantity of waste transition in most of the PCM is from solid to liquid [7]. The solid-liquid
heat, and if some part of the heat is recovered, a considerable amount of PCM suffer from disadvantages like volume expansion and leakage in
primary fuel could be saved. Therefore, its thermal utilization requires their liquid phase. Microencapsulation of solid–liquid PCM is an im-
efficient storage so that the waste heat can be collected and stored for portant technology to protect them from leakage. Liu et al. [8] reviewed
later use. Thus, the development of an efficient energy storage system is the methodologies and technologies for the encapsulation of PCM with
a promising solution for the energy crisis and environmental dete- a variety of wall materials from traditional organic polymers to novel
rioration. inorganic materials to pursue high encapsulation efficiency, excellent
Phase change materials (PCM) are used for thermal energy storage thermal energy-storage performance and long-term operation dur-
since they can store large amount of heat at nearly constant tempera- ability.
ture. Based on the temperature range of phase transition, PCM can be The problems associated with solid-solid PCM can be eliminated by
classified into three main categories : (i) low-temperature PCM with using solid-solid PCM. The solid-solid PCM show a transition in their

Abbreviations: PCM, phase change material; LMM, low melting metal; PE, pentaerythritol; IC, internal combustion; TES, thermal energy storage; LHTES, latent heat
thermal energy storage; DSC, differential scanning calorimetry; WHR, waste heat recovery; HRHE, heat recovery heat exchanger; RT, room temperature; RSS, root
sum squares
⁎
Corresponding author.
E-mail addresses: venkitaraj@cea.ac.in (K. Venkitaraj), ssuresh@nitt.edu (S. Suresh), praveennitt15@gmail.com (B. Praveen).

https://doi.org/10.1016/j.tca.2019.178343
Received 9 February 2019; Received in revised form 18 July 2019; Accepted 22 July 2019
Available online 23 July 2019
0040-6031/ © 2019 Elsevier B.V. All rights reserved.
K. Venkitaraj, et al. Thermochimica Acta 680 (2019) 178343

crystal structure from one lattice type to another at a definite tem- et al. [37] investigated the effect of adding nano-AlN on the crystal-
perature, and this transition accompanied with significant enthalpy lization and the supercooling in pentaerythritol (PE). They found that
change [9]. Several materials show the solid-solid reversible phase the nano-AlN accelerate the crystallization of PE during the discharging
transition behavior, but only a handful has sufficient latent heat to be a process. In our previously published papers [38–40], we have reported
potential latent heat storage material. These solid -solid PCM are ca- thermal and chemical stability, thermal properties and non-isothermal
tegorized into two types, namely, organic solid-solid PCM, and in- crystallization characteristics of pentaerythritol added with thermally
organic solid–solid PCM [10–20]. conductive particles such as Al2O3 nanoparticles, low melt metal (LMM)
Organic solid-solid PCM mainly comprises a particular group of and a low melt alloy(LMA).
hydrocarbon compounds, polyhydric alcohols, and polymers. Some significant reviews on the use of different PCM for thermal
Polyalcohols or polyols are hydrocarbon compounds that have body- energy storage applications made by Zalba et al. [41], Sharma et al.
centered tetrahedral molecular structure at low temperatures. These [42] and Jagadheeswaran and Pohekar [43]. The utilization of the
polyalcohols and their amine derivatives show a solid-state crystalline waste heat of the hot exhaust gas from internal combustion engines is
transition because of the presence of metastable, vibrant hydrogen one of the central areas in which a few research works reported. Yang
bonds between molecules in their crystal lattice. When the temperature et al. [44] tested the practicality of the heat recuperation from hot IC
is raised, these bonds break and the crystal structure changes from an engine exhaust using a heat pipe. The experimental study reported by
ordered tetrahedral phase to a disordered cubic phase accompanied V. Pandiyarajan et al. [45] made use of common sensible and latent
with the absorption of a significant amount of energy, more significant heat storage system for heat recuperation from IC engine exhaust. They
the disorder, more substantial is the amount of energy absorbed. Now, reported that about 10–15% of the energy supplied by the fuel collected
when the temperature is lowered, at the transition temperature, the as heat in the combined system. Schatz [46] performed an experimental
hydrogen bonds reform and the materials regain its original tetrahedral study of using a heat battery for storing the heat recovered from the
structure which causes the stored thermal energy to get released [21]. engine coolant. M. Chinnapandian et al. [47] introduced a PCM based
Polyalcohols also called as “plastic crystals,” which display crystalline cascaded energy storage system for exhaust heat recuperation from an
disorder at elevated temperatures accompanied by the absorption of IC engine by incorporating a shell and tube heat exchanger in the IC
thermal energy [22]. Pentaerythritol, pentaglycerine, and neopentyl engine experimental set up. Jung Wook Shon et al. [48] studied the
glycol are polyalcohols which are having an enthalpy of solid-solid energy storage performance of Xylitol by recovering the heat from the
phase change comparable to the fusion enthalpy of paraffin [23]. The engine coolant using a fin and tube heat storage system. They observed
molecular structure of polyalcohols is body-centered tetrahedral type at that the time taken for warming up the engine decreased by 33.7% by
normal temperature and at higher temperaturs, the crystal structure installing the energy storage system. The experimental study of Dheeraj
changes to face-centered cubic. The change in the crystal structure as- Kishor et al. [49] using erythritol for the recovery of heat of the engine
sociated with the enthalpy change at a fixed temperature [24]. Nu- exhaust obtained the charging and discharging efficiencies of 69.5%,
merous experimental investigations using solid-solid PCM for energy 38.0% respectively at the full load condition. Venkitaraj et al. [50]
storage have been reported in the literature [25–28]. The energy re- previously experimented with the IC engine exhaust heat recovery
leased by the PCM during cooling is lower than the energy absorbed using pentaerythritol added with Al2O3 nanoparticles.
during the heating [29]. Pentaerythritol is a solid-solid PCM that has a very high heat of
The energy storage characteristics of the majority PCM is low be- transition associated with the breakage and reformation of hydrogen
cause of their poor thermal conductivity. Efficient PCM-based thermal bonds during the crystal structure change at a higher temperature.
energy storage (TES) systems obtained by dispersing heat transfer en- However, being an organic material, pentaerythritol has low thermal
hancement additives to enhance the thermal conductivity of PCM. The conductivity. The thermal conductivity of the metal caused by the
most commonly used method in the experimental research works uti- electron motion is much higher than that of the organic materials.
lized nanoparticles to enhance the energy transfer in organic and in- Therefore, metal (or its alloys) with a low melting point used as a PCM
organic PCM. However, the use of nanoparticles to enhance the thermal will exhibit a much stronger heat transfer capacity than that of tradi-
performance affects the thermal properties of PCM [30]. Elgafy and tional PCM. Based on this point, authors have attempted to study the
Lafdi [31] conducted an experimental and analytical study of the per- use of low melting metal (LMM) as a useful additive for improving the
formance of Paraffin added with carbon nanofibres in 1–4 wt.%. They thermal energy storage performance of organic PCM.
reported a linear relationship between the thermal conductivity and the Most of the experimental investigations reported in literature dis-
mass ratio of carbon nanofibres. Wang et al. [32] reported the experi- cussed the charging and discharging performances of solid-liquid PCM.
mental results of thermal conductivity enhancement of palmitic acid Again, to improve the thermal performance of the system, the re-
added with carbon nanotubes. Tun-Ping Teng and Chao-Chieh Yu [33] searchers made use of finned type shell and tube based TES. The papers
reported the thermal storage performance of paraffin mixed with 1.0, published on the charging and discharging performances of solid-solid
2.0, and 3.0 wt.% of alumina (Al2O3), titania (TiO2), silica (SiO2), and PCM are very limited. Some of the papers available in literature reports
zinc oxide (ZnO). They found that the energy storage performance of study on the characterization, charging and discharging performances
paraffin using TiO2 was more efficient among the additives used. of pure solid-solid PCM and soli-solid PCM added with different na-
Mettawee and Assassa [34] performed an experimental study using noparticles as heat transfer enhancement additives. But, there is no
paraffin added with 0.1, 0.3, 0.4 and 0.5 wt.% Al2O3 particles and re- research work that studied the effect of low melting metal, as heat
ported a reduction in charging time with compared to paraffin. The transfer enhancement additives, on charging and discharging perfor-
high-temperature thermal energy storage applications using composite mances of polyalcohols is reported in the literature. The work presented
PCM comprising carbonate-salts experimented by Zhiwei Ge et al. [35]. in this thesis is aimed at filling this gap found in the literature. In the
Xiang Li et al. [36] performed an experimental study of thermal energy present work, we studied the effect of adding indium, a low melting
storage performance of calcium chloride hexahydrate added with Al2O3 metal, on the heat transfer performance of pentaerythritol. For this,
nanoparticles. They found that the proposed composite PCM possesses experiments conducted with PE added with 0.1, 0.5 and, 1.0 wt. % of
excellent stability, and energy transfer performance suited for low- indium utilizing the heat released by the IC engine exhaust at different
temperature applications. load conditions. Thermal conductivity and specific heat values of pen-
Solid-solid organic PCM such as Polyalcohols have low thermal taerythritol blended with LMM before and after500 thermal cycles were
conductivity and hence comparatively poor energy storage character- estimated using T-history method [51,52]. The temperature and en-
istics. Therefore, to overcome the with low heat transfer characteristics, thalpy change corresponding to the solid transition of the different PCM
thermally conductive additives like nanoparticles are employed. P.Hu samples determined from the DSC analysis. The effect of cooling rate on

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K. Venkitaraj, et al. Thermochimica Acta 680 (2019) 178343

Fig. 1. Solid-solid phase transition of pentaerythritol (Legend: carbon, black; oxygen, red; hydrogen, green, Dashed lines mark the hydrogen bonds. Solid lines
represent the unit cell) (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article).

the enthalpy of solid-solid transition and degree of supercooling were temperature regulated by using an autotransformer (0–270 V, 0–20 A)
studied using DSC data. Finally thermal energy storage and discharge fitted with a voltmeter and ammeter. The hot plate surface temperature
performance of PE added with indium for IC engine exhaust gas heat and sample temperatures measured using K-type thermocouples (ac-
recovery application was tested. There is no work is reported in lit- curacy of ± 0.25 °C), calibrated using a handheld dry-well calibrator
erature which investigated the effect of adding a low melting metal like (Fluke 9100S). The sample temperature continuously monitored using a
indium as a heat transfer enhancement additives on thermal storage multi-channel data acquisition system (KEYSIGHT 34972A LXI). In the
performance of a solid-solid organic PCM. thermal cycling test, the samples are repeatedly heated and cooled at
10 °C/min in the temperature range 30–210 °C with a 10 min dwell
2. Materials and methods period in between. Each thermal cycle completed in 50 min. In this
experimental work, the samples of PE, PE + 0.1 wt. % In, PE + 0.5 wt.
2.1. Material preparation % In and PE + 1.0 wt% In were subjected to 500 thermal cycles.

Pentaerythritol (PE), an organic material, is used as the solid-solid 2.2. Thermal property analysis
PCM for storing the heat released by the hot exhaust gas. It has a body-
centered tetragonal crystal structure (α) at ordinary temperature, and The thermal properties such as thermal conductivity and specific
at an elevated temperature (187–189 °C) it attains a face-centered cubic heat of the PCM samples determined from the Temperature -history
crystal structural (γ). The indium is a metal that has a lower melting analysis based on the lumped capacitance theory suggested by Zhang
point (156.6 °C) than that of pentaerythritol. The solid-solid phase Yinping et al. [43]. The experimental setup, procedure and relevant
transition of pentaerythritol is shown in the Fig. 1. Both the pentaery- equations required to determine the thermal conductivity and specific
thritol and indium purchased from Alfa Easer, USA. The supplied heat explained in detail in our previous published work [23]. The
pentaerythritol is of analytical grade, 98.0% pure and in white powder temperature and enthalpy of solid-solid phase transition of the prepared
form. The indium is 99% pure, 100 mesh in size, and in silver-grey PCM samples obtained from the Differential scanning calorimetry
powder form. The indium added to PE in 0.1, 0.5 and 1.0 wt.% by using (DSC), Mettler Toledo DSC 822e, Hong Kong. The device had an op-
a low energy ball mill (0.5 HP/230 V/50 Hz/300 rpm, Make: VB Cera- erating range from −130 °C to max. 450 °C and a measurement
mics)) operated at 200 rpm for about 90 min. The dispersion of indium range ± 350 mW at RT with a measurement resolution of 0.04 mW at
particles in PE is studied using the EDX elemental mapping. The ele- RT, a temperature accuracy of ± 0.2 °C and temperature reproducibility
mental mapping shows the homogeneous dispersion of indium particles of ± 0.1 °C. The effect of cooling rate on the enthalpy of solid transition
in the PE with some areas of almost pure PE. The blue arrows in the EDS and degree of supercooling studied by analyzing the DSC data at dif-
plot represent the areas with pure PE. Red dots within red circle in EDS ferent cooling rates of 5, 10, 20 and 40 °C /min. The properties of the
plot represent the indium particles dispersed in PE (Fig. 2). prepared PCM samples before and after 500 thermal cycles reported in
The thermal cycling test conducted to test the feasibility of using the this experimental work.
PE/LMM composite PCM for long-term thermal storage application.
The thermal cycling of the prepared PCM samples performed using a
laboratory hotplate having a capacity of 1.5 kW. The hot plate surface 2.3. Heat transfer study

2.3.1. Experimental setup

The representation sketch of the experimental setup used for heat
transfer experiment shown in Fig. 3. The exhaust gas from a single
cylinder, four stroke, air cooled, diesel engine (Make: Kirloskar, bore
87.5 mm, stroke 110 mm, rated power 7.4 kW at 1500 rpm) passed
through a shell and tube type heat exchanger. The heat exchanger in-
corporated three copper tubes of 20 mm inner diameter and 60 cm
length in a mild steel shell of 75 mm diameter. The convection and
radiation heat loss during the charging and discharging process reduced
by insulating the shell using glass wool and asbestos. The space sur-
rounding the copper tubes in the shell filled with about 3 kg of PCM by
Fig. 2. EDX mapping of PE + 0.5 wt. % In (Indium-red) (For interpretation of manual packing (packing pressure: 0.2 MPa) at a packing density of
the references to colour in this figure legend, the reader is referred to the web 1.5 g/cm3. The PCM absorbs the heat of the hot exhaust gas passing
version of this article). through the copper tubes during the heating cycle. The cold circuit

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K. Venkitaraj, et al. Thermochimica Acta 680 (2019) 178343

Fig. 3. Representation diagram of the experimental setup for heat transfer study.

consists of a pump which continuously pumps the coolant (thermal oil) time.
through the copper tubes during the discharging cycle. The heat The heat absorbed by the PCM stored in the heat exchanger calcu-
transfer fluid absorbs the heat released by the PCM. The temperature of lated as the sum of sensible heat and heat of absorption of solid-soild
PCM at the front end, center and trailing end of the heat exchanger as transition of the PCM.
well as the inlet, exit temperatures of the exhaust gas and the circu-
Qst = Qsen + Qlat = mp cp, p (Ttrs Tamb) + mp htrs , kJ (2)
lating heat transfer fluid were monitored by using K-type thermo-
couples. A multi-channel data acquisition system (KEYSIGHT 34972A where, mp - mass of the PCM (pentaerythritol), Ttrs - solid - solid tran-
LXI) used to record the various temperatures monitored sition temperature of pentaerythritol, Tamb - ambient temperature, htrs -
The constructional details of the heat exchanger are given in Fig. 4. enthalpy of absorption at solid - solid transition, c p, pcm - specific heat of
Fig. 5 shows the representation sketch of the actual shell and tube PCM.
type heat exchanger used in this experimental work. The quantity of heat recovered estimated as the heat absorbed by
the heat transfer fluid circulated through the heat exchanger during the
2.3.2. Experimental procedure discharge process by using the equation,
The heat transfer experiments conducted using pure PE and PE and Q re = mw c p, w (To,w – Ti,w ), kJ (3)
PE added with 0.1, 0.5, and 1,0 wt.% of LMM as the energy storage
medium. The energy storage performance of each PCM tested at dif- where mw - the mass flow rate of heat transfer fluid, c p, w -specific heat
ferent engine load condition ranging from no load to full load. The of water, To,w and Ti,w - exit and entry temperatures of heat transfer
engine exhaust gas passed through heat exchanger filled with the pre- fluid.
pared PCM in the shell side. The hot exhaust gas flowing through the The charging efficiency defined as the ratio of the heat stored (Q st )
copper tubes exchanges heat with the PCM filled in the shell side of the to the heat supplied (Q sp) , i.e.,
heat exchanger. The temperature of PCM increases due to the absorp- Q st
tion of heat and the same at the leading end, center and trailing end of Charging efficiency (%) = x 100
Q sp (4)
the heat exchanger along with the inlet/exit exhaust gas temperatures
recorded by using a data logger. The charging process continued till the The energy savings by using the PCM calculated as the ratio of heat
temperature of the PCM reached slightly above the solid-solid transition stored to energy supplied by the fuel,
temperature. The charging process stopped by switching off the engine,
Q st
and the cold fluid line opened, allowing the thermal oil to flow through Energy saved (%) = x 100
mf C v (5)
the copper tubes. The cold thermal oil receives the heat discharged by
the PCM. Again, the temperature of the PCM at the leading end, center Where mf mass of fuel is supplied, C v - calorific value of the fuel.
and trailing end of the heat exchanger along with the inlet/exit tem-
peratures of the heat transfer fluid recorded by using a data logger. 2.3.4. Uncertainty in the experiment
The primary parameter monitored during the thermal cycling and
2.3.3. Data reduction thermal storage performance tests were the PCM sample temperatures,
The data obtained from the experiments LMM used to evaluate the where K type thermocouples connected to a multi-channel data acqui-
thermal energy storage performance of pure PE, PE + 0.1 wt.% LMM, sition system (KEYSIGHT 34972A LXI) were used to record the sample
PE + 0.5 wt.% LMM, and PE + 1.0 wt. %. temperatures. These K-type thermocouples were calibrated using a
The heat supplied by the exhaust gas during the charging process is handheld dry-well calibrator (Fluke 9100S) having temperature accu-
given by, racy of ± 0.25 °C. The root sum squares (RSS) method was used to
evaluate the uncertainty in the temperature measurement. In RSS
Qsp = mg c pg (Ti,g T0,g ) t, kJ (1)
method, a realistic value for uncertainty obtained by combining the
where mg -exhaust gas mass flow rate (kg/s), c p,g - exhaust gas specific bias and precision elemental errors within the instrument. The K-type
heat, Ti,g and T0,g - inlet and exit exhaust gas temperature, t - storage thermocouples used in this experimental study had a standard limit of

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K. Venkitaraj, et al. Thermochimica Acta 680 (2019) 178343

Fig. 4. Constructional features of the shell and tube heat exchanger.

an accuracy of ± 0.25 °C. Now, the overall uncertainty associated with

temperature measurement computed by combining the errors of ther-
mocouple and data acquisition system and the drywell calibrator.
Fig. 5. The photograph of the shell and tube heat exchanger.
e Temp = ((ethermocouple) 2 + eDAQ) 2 + (ecalibrator )2
error of ± 2.2 °C. The LabView resolution set at ± 0.01 °C. Thus the e Temp = (2.2)2 + (1.0) 2 + (0.25) 2
zero order uncertainty associated with it was ± 0.005 °C. The un- e Temp = ± 2.23°C
certainty related to thermocouples calculated:
The temperature and enthalpy of solid-solid transition of the PCM
ethermocouple = (e bias)2 + (e precision)2 samples determined using the Mettler Toledo DSC 822e, having an
uncertainty of ± 0.2 °C for the temperature and ± 2% of the enthalpy
ethermocouple = (2.2) 2 + (0.005)2
change. The DSC was industry calibrated using Indium and Zinc stan-
ethermocouple = ± 2.2 °C
dards. The uncertainties in the flow meter reading are specified by the
manufacturer as ± 1% of full flow. The uncertainties in the energy
The data logger used in this experimental study had a bias error of
measurements are calculated using the temperature and flow rate un-
± 1 °C and a resolution of 0.1 °C. Therefore, the uncertainty associated
certainties. The uncertainty in the heat supplied/recovered (δQ) was
with data acquisition system calculated as:
calculated using the know uncertainty values of temperature ( T) and
eDAQ = (e bias) 2 + (e precision) 2 mass flow rate of the HTF ( m) . Therefore,

eDAQ = (1.0) 2 + (0.05) 2 Q = tc p,htf ( T m )2 + 2 (m T)

2

e DAQ = ± 1 °C
where
The drywell calibrator used for calibrating the thermocouples had m the mass flow rate of the HTF , c p,htf specific heat of the HTF , ΔT

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K. Venkitaraj, et al. Thermochimica Acta 680 (2019) 178343

–the difference between the inlet and exit fluid temperatures, t- Time of Table 1
charging/discharging Thermal conductivity variation with temperature in PE added with LMM.
The uncertainty in the heat stored is given by Temperature Average Thermal conductivity (W/m-K)
range (oC) Temp (oC)
δQ = M cp,pcm (ΔT x δT) + M (δh) PE PE + 0.1% PE+ PE+
LMM 0.5% 1.0%
where
LMM LMM
M -the mass of the PCM used, δh- the uncertainty in the enthalpy
change given by the DSC equipment. 40-95 67.5 0.112 0.119 0.126 0.135
cp,pcm- specific heat of the PCM. 95-150 122.5 0.108 0.115 0.122 0.128
150-205 177.5 0.104 0.109 0.119 0.122
Using the above relations, the average uncertainties in heat sup-
plied, heat stored and heat recovered were estimated as 6.9%, 6.5%,
and 7.1% respectively.
temperature = 7.5 °C), 95 to 150 °C (average temperature=122.5 °C),
and 150 to 205 °C (average temperature = 177.5 °C). The thermal
3. Results and discussions conductivity of pure PE decreased from 0.112 to 0.104 W/mK in the
temperature ranges considered in this study. In the case of PE + 0.1 wt.
3.1. Thermal conductivity and specific heat of PE added with LMM % LMM, thermal conductivity varied between 0.119 W/m-K and
0.109 W/m-K. The thermal conductivity of PE +0.5 wt.% decreased
The thermal conductivity and specific heat of PE, PE + 0.1 wt.% from 0.126 to 0.119 W/mK and the thermal conductivity of PE
LMM, PE + 0.5 wt.% LMM and PE + 1.0 wt.% LMM before and after +1.0 wt.% decreased from 0.135 to 0.122 W/mK. Thus it is very evi-
thermal cycling were obtained by the T-history method. The thermal dent that the thermal conductivity of all test samples decreased with
conductivity of pure PE obtained as 0.106 W/m-K. After 500 thermal increase in temperature. The reason for the decreasing trend can be
cycles, the thermal conductivity reduced to 0.1 W/m-K. The thermal explained with the help of the classical theory of heat transfer in solids.
conductivity of pentaerythritol found to increase to 0.110 W/m-K, According to this, the heat transfer in solids occurs through the
0.119 W/m-K, and 0.132 W/m-K corresponding to 0.1, 0.5 and, 1.0 wt. movement of phonons. The movement of these phonons restricted at
% of LMM. The thermal conductivity values after 500 thermal cycles for elevated temperature because of the increased thermal vibrations.
PE + 0.1 wt.% LMM, PE + 0.5 wt.% LMM and PE + 1.0 wt.% LMM Thus, the restricted motion of the phonon resulted in decreased thermal
were calculated as 0.108, 0.111 and, 0.128 W/mK respectively. The conductivity at a higher temperature. Table 1 summarizes thermal
specific heat capacity of PE before and after 500 thermal cycles ob- conductivity dependence on temperature.
tained as 2.78 kJ/kg-K and 2.61 kJ/kg-K respectively. The specific heat
values of PE + 0.1 wt.% LMM, PE + 0.5 wt.% LMM and PE + 1.0 wt.% 3.2. Enthalpy of solid-solid transition of PE added with LMM
LMM after 500 thermal cycles obtained at 2.33, 2.12 and, 2.01 kJ/kg-K
respectively. The temperature and enthalpy of solid-solid transition of the PCM
Thus was quite evident that the higher the weight proportion of the samples obtained using the DSC data.
LMM in the PE, greater was the thermal conductivity enhancement. The Fig. 6 illustrates the DSC plot obtained for pure PE sample. The two
probable reasons for the enhancement of thermal conductivity of pen- peaks seen in the DSC curve represent the phase change process in PE.
taerythritol are the natural Brownian motion, surface morphology, in- The first peak corresponds to the solid to solid phase change and the
terparticulate diffusion, energy transfer potential and the clustering of second peak corresponds to the solid-liquid phase change.
the particle. Again the specific heat value of PE was observed to be During the endothermic charging process, the solid to solid phase
decreasing with the addition of LMM. It is very clear from the experi- change began at 181.4 °C. The peak of the solid to solid phase change
mental results that thermal cycling has a significant effect on thermal appeared at 187.8 °C, and the process ended at 193.6 °C. The enthalpy
conductivity and specific heat of PE. The change in thermal properties change during the solid to solid phase change estimated from the area
was found more significant as the number of cycles increases. The T- of the peak as 263.9 kJ/kg. The second peak representing the solid to
history data also used to study the temperature dependence of the liquid change started at 258.1 °C, and the peak of this phase change
thermal conductivity of PCM samples. Fig. 6 shows the variation in appeared at a temperature of 261.1 °C. The enthalpy of solid to liquid
thermal conductivity with temperature. The thermal conductivity of phase change calculated from the area of the peak as 42.7 kJ/kg. During
each sample measured in three temperature ranges 40 to 95 °C (average the cooling process, the liquid to solid phase change began at 247.5 °C.
The peak temperature during the liquid to solid phase change obtained
at 246.2 °C and the process ended at 243.5 °C. The solid-solid phase
change during the cooling process started at 169.1 °C with the peak
appeared at 168.6 °C. The solid to solid phase change process ended at
163 °C. The enthalpy change is corresponding to the solid to solid phase
change during the cooling process estimated at 238.92 kJ/kg.

3.2.1. The effect of thermal cycling on enthalpy of transition

The DSC results indicated that the heat flow due to solid-solid phase
change in PE decreased with the addition of the LMM. The purpose of
adding LMM was to accelerate the rate of energy transfer in PE by
improving its thermal conductivity. As reported in the previous section
on thermal property measurement, the thermal conductivity of PE en-
hanced by the addition of LMM. However, the inclusion of LMM did not
contribute to the enthalpy change corresponding to the solid-solid
transition of PE. Table 2 summarizes DSC results for the uncycled PCM
samples.
The heat flow in PE not affected because indium did not take part in
Fig. 6. DSC curve of pure PE. the solid-solid transition process. Since the melting point of indium

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K. Venkitaraj, et al. Thermochimica Acta 680 (2019) 178343

Table 2
Enthalpy and temperature of solid-solid transition of PE blended with LMM.
PCM Charging Cycle (10 °C/min) Discharging Cycle (10 °C/min)

Onset (°C) Peak (°C) Endset (°C) Heat Flow (kJ/kg) Onset (°C) Peak (°C) Endset (°C) Heat Flow (kJ/kg)

PE 181.4 187.8 193.6 264 169.1 168.6 163.0 239

PE+0.1 wt% LMM 180.7 187.0 194.2 262 167.9 165.6 162.0 230
PE+0.5 wt% LMM 181.1 187.5 192.6 255 168.2 166.8 163.3 217
PE+1.0wt% LMM 181.8 188.3 191.9 249 168.9 167.5 163.8 210

Table 3
Temperature and enthalpy of transition of PE added with LMM after 500 thermal cycles.
PCM Charging Cycle (10 °C/min) Discharging Cycle (10 °C/min)

Onset (°C) Peak (°C) Endset (°C) Heat Flow (kJ/kg) Onset (°C) Peak (°C) Endset (°C) Heat Flow (kJ/kg)

PE 186.8 190.7 194.1 241 171.3 169.4 164.1 212

PE+0.1 wt. % LMM 181.4 188.1 193.5 235 168.9 166.6 163.1 208
PE+0.5 wt. % LMM 180.8 187.6 192.2 230 167.2 165.9 162.5 201
PE+1.0 wt. % LMM 180.1 186.9 191.4 222 166.9 165.2 161.8 195

(156.6 °C) is lower than the transition temperature of PE, the indium
added to PE received only the sensible heat during the phase transition
in PE. Due to this the heat flow of PE added with LMM is lower than
that of pure PE. i.e., the decrease in the heat flow is because of the non-
involvement of indium in the process phase change of PE. The tem-
perature and heat flow of the solid-solid transition PCM samples un-
derwent 500 thermal cycles are displayed in Table 3.
The experimental results of DSC analysis discussed above revealed
that the addition of the LMM has resulted in a slight decrease in the
enhancement of the heat of transition during the charging process.
Pentaerythritol, being a solid-solid PCM, undergoes a transition from a
body-centered tetrahedral structure to a face-centered cubic structure at
189 °C and the heat of absorption accompanied by this phase change is
utilized to store thermal energy. The idea of adding LMM was to en-
hance the thermal energy storage performance of PE by improving its
thermal conductivity. Though the thermal conductivity of PE improved,
the addition of indium does not contribute to the heat absorption
during the solid-solid phase transition in PE. The reason for this is be-
cause indium, being a low melt metal, is in a liquid state (melting at
156.6 °C) during the occurrence of a solid-solid transition in PE. Thus,
the indium mixed with PE will receive only the sensible heat during the Fig. 7. Variation of enthalpy of solid-solid transition with cooling rate.
solid-solid phase transition, and this causes the slight decrease in the
enthalpy change of PE added with LMM compared to pure PE. In other 10, 20 and 40 °C/min respectively. An enthalpy change of 221 kJ/kg
words, the reduction in the enthalpy is due to the non-participation of observed in the case of PE + 0.1 wt% LMM when the sample cooled at
additives in the phase transition process of PE. Another important ob- 5 °C/min. The enthalpy change found increased to 230, 238 and
servation was that the enthalpy of transition during the recharging 247 kJ/kg when the PCM sample cooled at 10, 20 and 40 °C/min re-
process was less than the corresponding value in charging process. The spectively.
results show that the onset temperature of PE with additive was less In the case of PE + 0.5 wt.% LMM, enthalpy of transition of 210,
than that of pure PE. This indicated that the solid-solid-solid transition 217, 225 and 234 kJ/kg observed corresponding to the cooling rates of
during discharging cycle occurred at a lower temperature when indium 5, 10, 20 and 40 °C/min respectively. The enthalpy change of 203, 210,
added to PE. The additive, indium (melts at 156.6 °C), is in a liquid state 216, 224 kJ/kg observed when PE + 1.0 wt. % LMM tested at cooling
at the time of transition and therefore, it does not have any role in the rates of 5, 10, 20 and 40 °C/min respectively. The variation of enthalpy
crystal structure changes in PE. Due to this, the effective temperature at of transition with a weight fraction of indium at different cooling rates
which the solid-solid transition occurs gets decreased. plotted in Fig. 8. The enthalpy of transition decreased with increase in
weight fraction at all cooling rates.
Table 4 shows the % decrease in enthalpy of transition at different
3.2.2. The effect of cooling rate and weight fraction on enthalpy of solid-
solid transition cooling rates.
It is very evident from the Table 4 that the %decrease in enthalpy of
Fig. 7 shows the variation of enthalpy of solid-solid transition with
transition increases with increase in weight fraction of indium at all
cooling rate. The graph shows that the heat flow corresponding to the
cooling rates considered in this study. For example, at a cooling rate of
solid-solid transition in pentaerythritol increases with an increase in
5 °C/min, the % decrease in enthalpy of transition corresponding to 0.1,
cooling rate for all weight fractions of Indium added to it.
0.3 and, 0.5% wt fraction obtained as 2.6, 7.5 and, 10.6 respectively.
The pure pentaerythritol showed an enthalpy change of 227 kJ/kg
corresponding to 5 °C/min cooling rate. The heat flow value found in-
creased to 239, 245 and, 255 kJ/kg, when the cooling rate increased to

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K. Venkitaraj, et al. Thermochimica Acta 680 (2019) 178343

accelerate the phase transition process in PE causing a reduction in

supercooling. It observed that the degree of supercooling decreases
with increase in particle loading.
The pure PE, when cooled at 5 °C/min, showed a supercooling of
21.6 °C, and a maximum supercooling of 27.7 °C observed when the
sample cooled at 40 °C/min. The observed supercooling in PE + 0.1 wt.
% LMM was 20.6 °C and 26.5 °C corresponding to cooling at 5 °C/min
and 40 °C/min respectively. In the case of PE + 0.5 wt. % LMM, the
supercooling in PE reduced to 18.4 °C and 24.2 °C corresponding to the
cooling rates 5 °C/min and 40 °C/min respectively. The lowest values of
supercooling of 16.9 °C and 22.9 °C recorded when the PCM sample
PE + 1.0 wt. % LMM cooled at 5 °C/min and 40 °C/min respectively.
Therefore, at higher cooling rate, more supercooling observed. This
meant that crystallization processs is delayed as the cooling rate in-
creased [20,21].
The results indicated that degree of supercooling, which char-
acterizes the overall rate of crystallization, decreased with the addition
of indium. Again, the degree of super cooling was found decreasing
with the increase in wt. % of indium. Since the degree of supercooling
affect the nucleation and crystal growth,
Fig. 8. The enthalpy of solid-solid transition as a function of the weight fraction temperature and time range at which the crystallization occurs gets
of indium. lowered at higher cooling rates. This means that the incorporation of a
heterogeneous nucleating agent is a very useful way to increase the
Table 4 crystallization and crystallinity. The nucleating agent serves as a pri-
The change in the enthalpy of transition at different cooling rates. mary crystalline nucleus to promote crystal growth, and as a result,
provides a function of reducing crystal size and increasing the crystal-
Sample % Decrease in enthalpy of transition
lization speed. By adding a nucleating agent, the nucleating density
o
Cooling rate, C/min 5 10 20 40 increases, and the spherulite size decrease so that the crystallization
PE + 0.1% wt. In 2.6 3.8 2.9 3.1 rate increased. The nucleating agent provides a surface that reduces the
PE + 0.5% wt. In 7.5 9.2 8.1 8.2 free energy barrier to the primary nucleation, and, thus, the nucleation
PE + 1.0% wt. In 10.6 12.1 11.8 12.2
density increased [39].

3.2.3. The effect of cooling rate and weight fraction on the degree of 3.3. Heat Transfer performance of pentaerythritol with LMM additive
supercooling
The DSC results showed that the solid-solid transition during the The heat transfer performance of PE added with 0.1, 0.5 and, 1.0 wt.
discharging cycle occurs at a temperature lower than the corresponding % of LMM was studied by performing experiments utilizing the exhaust
temperature during the charging cycle. This meant that the PCM su- heat from an internal combustion engine. The tests were performed to
percooled below the phase change temperatures causing a reduction in store the heat of a diesel engine exhaust using a heat recovery heat
the enthalpy change. Fig. 9 shows the variation of the degree of su- exchanger (HRHE) filled with PE added with LMM. The heat stored by
percooling with the cooling rate for different weight percentage of in- the PCM then recovered by the cold fluid circulating through the heat
dium added to PE. It is very evident from the figure that the addition of exchanger. The experimental data obtained using pure PE and PE added
indium causes a reduction in the degree of supercooling in PE. This with 0.1, 0.5 and, 1.0 wt. % of LMM analyzed. The effect of adding
indicated that the indium particles act as a nucleation agents and thus LMM on the heat transfer performance of PE studied by evaluating and
comparing the charging efficiency, energy savings with and without
LMM additives.
Fig. 10 displays the time dependence of the PCM temperature
during heating and cooling period at the different locations of the heat
exchanger with the engine working at maximum load. Initially, the hot
exhaust gas from the engine passed through the heat exchanger. The
PCM filled in the shell side of HRHE absorbed heat from the hot exhaust
gas and got heated to a temperature above the solid-solid transition
point. The temperature of PCM in different locations in the heat ex-
changer increased steadily from room temperature to the temperature
of solid-solid transition. The PCM temperature at the leading end,
center and trailing end of the heat exchanger were recorded and com-
pared. The test results showed a reduction in the charging time of
pentaerythritol because of the addition of LMM. This reduction in the
heat storage time is because of the increased heat transfer rate arose
from the enhanced thermal conductivity of pentaerythritol due to the
presence of LMM. The highest charging rate observed at the leading end
and the lowest rate at the trailing end of the heat recovery heat ex-
changer. The time for heat storage with the shell side filled with pure
PE during the charging cycle corresponding to the maximum load of
4 kg was respectively 12.8 min, 13.6 min, and 14.2 min.
The tests repeated with the shell side filled with PE added with 0.1,
Fig. 9. Degree of supercooling as a function of cooling rate. 0.5, and 1.0 wt.% of LMM. When the shell side filled with PE + 0.1 wt.

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K. Venkitaraj, et al. Thermochimica Acta 680 (2019) 178343

Fig. 10. Time dependence of charging and discharging time of PE with and
without LMM.

% LMM, the charging time at the leading, center and trailing ends were Fig. 11. Energy supplied/stored and PCM temperature at different engine
respectively 12.4 min, 12.8 min, and 13.2 min. The time for energy loads.
storage at the leading, center and trailing ends decreased to 12.2 min,
12.4 min, and 12.9 min respectively when the heat exchanger was 2, 3, 4 kg loads applied on the brake drum.
loaded with PE + 0.5 wt.% LMM. In the case of PE + 1.0 w.% LMM, the The tests result in the case of pure PE, PE + 0.1 wt.% LMM,
charging time at the leading, center and trailing ends further reduced to PE + 0.5 wt.% LMM and PE + 1.0 wt.% LMM were compared to study
11.7 min, 12.1 min, and 12.4 min. The average time energy storage the thermal performance of PE added with LMM. The heat supplied by
using PE, PE + 0.1 wt.% LMM, PE + 0.5 wt.% LMM and PE + 1.0 wt.% the exhaust gas to pure PE and the heat absorbed by PE at no load
LMM obtained as 13.5 min, 12.8 min, 12.5 min and 12.0 min respec- condition estimated as 2549.6 kJ and 253.1 kJ respectively. When the
tively. Thus, the time for energy storage using PE showed 5.2, 7.4 and, engine loaded with 25% of full load, the heat supplied and heat stored
10.4% reduction corresponding to 0.1, 0.5 and 1.0 wt.% of LMM. were estimated as 2727.1 kJ and 353.9 kJ respectively. The heat sup-
The variation of the PCM temperature with time during the energy plied and stored in the case of pure PE at 50% load condition obtained
release period also shown in Fig. 10. The test results show that the time as2864.4 kJ and 418.8 kJ respectively. The quantity of heat supplied
for energy release by PCM during the cooling period decreased with the and stored at 75% load condition calculated as 2832.9 kJ and 508.9 kJ
addition of LMM as a result of the enhanced heat transfer rate. The time respectively and at full load condition, the energy supplied and stored
for discharging in the case of pure PE and PE added with 0.1, 0.5, and were respectively 2742 kJ and 1051 kJ.
1.0 wt.% of LMM recorded and analyzed. The results showed that the In the case of PE + 0.1 wt.% LMM, the heat supplied and stored
time for heat release at the leading end of the heat exchanger with the under no load condition 2455.2 kJ and 263.1 kJ respectively. The ex-
shell side filled with pure PE, PE + 0.1 wt.% LMM, PE + 0.5 wt.% LMM periment with 25% of the full load showed the heat supplied and heat
and PE + 1.0 wt.% LMM was 15.3 min, 15.0 min, 14.2 min, and stored at 2853.8 kJ and 387.9 kJ respectively. The calculated heat
13.3 min respectively. At the center of the heat exchanger, the energy supplied and heat stored at 50% load condition obtained as 2937.8 kJ
discharge took place in 15.6 min, 15.3 min, 14.6 min, and 13.9 min and 498.3 kJ respectively. The quantity of heat supplied and stored at
corresponding to PE, PE + 0.1 wt.% LMM, PE + 0.5 wt.% LMM and 75% load condition calculated as 2769.9 kJ and 589.8 kJ respectively
PE + 1.0 wt.% LMM. The time for energy discharging at the trailing end and at full load condition, the energy supplied and stored were re-
of the heat exchanger with the shell side filled with pure PE, spectively 2686 kJ and 1123.1 kJ.
PE + 0.1 wt.% LMM, PE + 0.5 wt.% LMM and PE + 1.0 wt.% LMM was The experimental results of PE + 0.5 wt.% LMM, the heat supplied
15.9 min, 15.6 min, 14.9 min, and 14.5 min respectively. The average and stored under no load condition estimated as 2460.2 kJ and 80.9 kJ
time energy discharge using PE, PE + 0.1 wt.% LMM, PE + 0.5 wt.% respectively. When the engine operated at 25% load condition, the heat
LMM and PE + 1.0 wt.% LMM obtained as 15.6 min, 15.3 min, 14.6 min supplied and stored obtained as 2869.9 kJ and 473.1 k J respectively.
and 13.9 min respectively. Therefore, it obtained that the time for en- The heat supplied and stored under 50% load condition estimated as
ergy discharge reduced by 3.2, 7.6 and, 12% respectively when the shell 2930.3 kJ and 615.4 kJ respectively. The amount of heat supplied and
side of the heat exchanger filled with 0.1, 0.5 and, 1.0% weight frac- stored when the engine loaded with 75% of full load calculated to be
tions of LMM. 2775.2 kJ and 778.9 kJ respectively. When the engine operated under
The amount of heat supplied and stored by the PCM estimated to full load condition, the quantity of heat supplied and stored estimated
study the effect of adding LMM on thermal energy storage performance to be 2670.7 k J and 1204.7 kJ respectively.
of PE. The tests conducted with PE, PE + 0.1 wt.% LMM, PE + 0.5 wt.% In the case of PE + 1.0 wt% LMM, heat supplied and stored with the
LMM and PE + 1.0 wt.% LMM at different load conditions on the en- engine is running at no load estimated to be 2459.8 kJ and 302.3 kJ
gine. It observed from the experimental results that the quantity of heat respectively. When the engine operated at 25% load condition, the heat
supplied and stored increased as the load on the engine increased. The supplied and stored obtained as 2878.7 kJ and 576.3 k J respectively.
reason for this increased heat quantity at higher loads was because of The heat supplied and stored under 50% load condition estimated as
the higher temperature of exhaust gas. 2931.3 kJ and 745.6 kJ respectively. The amount of heat supplied and
The variation of energy supplied and storage with engine load de- stored when the engine loaded with 75% of full load calculated to be
picted in Fig. 11. The quantity of heat supplied by the exhaust gas and 2776.2 kJ and 899.4 kJ respectively. When the engine operated under
the heat stored by the PCM estimated at no load condition and with 1,

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K. Venkitaraj, et al. Thermochimica Acta 680 (2019) 178343

% LMM used for energy storage. The energy saved using pure PE at no
load, 25% load, 50% load, 75% load and full load conditions obtained
to be 4.3%, 6.4%, 8.2%, 9.7%, and 18.5% respectively. The energy
savings of PE +0.5 wt.% LMM at no load, 25% load, 50% load, 75%
load and full load conditions obtained to be 4.6%, 7.8%, 10.1%, 12.8%,
and 19.8% respectively. The average energy savings using 0.5 wt.%
addition of LMM found to be 11.1%. In the case of PE +1.0 wt% LMM,
the energy savings at no load, 25% load, 50% load, 75% load and full
load conditions estimated to be 5.0%, 9.5%, 12.3%, 14.8%, and 21.8%
respectively. The average energy savings of about 12.7% obtained
corresponding to 1.0 wt.% addition of LMM. It is very evident from the
above discussion that the average energy savings of PE increased with
increase in weight fraction of LMM. The increase in the energy saving
was because of the increased rate of heat transfer resulted from the
enhanced thermal conductivity of pentaerythritol added with LMM.
The energy stored by the PCM during the charging period trans-
ferred to the circulating cold fluid during the discharge period. The
amount of energy discharge during the cooling cycles found to be lesser
than the heat stored during the heating cycle. The reduced heat release
Fig. 12. The charging efficiency and % energy saved at various engine loads.
was because of the decreased enthalpy of solid-solid transition of the
PCM during the discharge period resulted from the supercooling effect.
full load condition, the quantity of heat supplied and stored estimated The test results of pure PE showed an amount of 460 kJ heat recovered
to be 2669.1 k J and 1321.8 kJ respectively. Thus it observed from the out of the 1051 kJ heat stored corresponding to the maximum load
above discussion on the experimental results that the heat storage condition. The recovered heat from pure PE is 43.8% of the total heat
under no load condition enhanced by 3.9%, 10.9% and 19.4% corre- stored in it during the charging cycle. When 0.1 wt.% LMM added to PE,
sponding to 0.1, 0.5 and, 1.0 wt.% of LMM added to PE. When the the heat recovery increased to 48.9% of the total heat stored. The ad-
engine operated at maximum load condition, the enhancement in heat dition of 0.1 wt.% LMM resulted in a heat recovery of 550 kJ out of
storage corresponding to 0.1, 0.5 and, 1.0 wt.% of LMM found to be 1123 kJ. In the case of PE + 0.5 wt.% LMM, 675 kJ of heat recovered
6.9%, 14.6% and, 25.8% respectively. out of 1205 kJ heat stored during the heating cycle. This indicated an
The charging efficiency is another parameter used to study the increase of about 7.1% in heat recovery when 0.5 wt.% LMM added to
thermal performance of PE added with LMM. The charging efficiency is PE. The heat recovery using PE + 1.0 wt.% LMM found to be 823 kJ out
defined as the ratio of heat stored by the PCM during the heating cycle of the 1322 kJ stored during the charging period. It is very evident from
to the maximum energy that can be stored. The Fig. 12 shown below the above discussion that, the percentage of heat recovery increased
depicts a variation of the charging efficiency of pure PE and PE added with the increase in the weight fraction of LMM. The main reason for
with 0.1, 0.5. 1.0 wt.% LMM under different engine loads. It observed the enhanced heat transfer was because of the improved thermal con-
from the experimental results that the charging efficiency improved ductivity of PE due to the presence of thermal conductive LMM parti-
with the increase in the load applied to the brake drum. The charging cles. In addition to that, it also observed that the degree of supercooling
efficiency of pure PE under no load, 25% load, 50% load, 75% load and in PE decreased with the increase in weight fraction of LMM. The de-
full load estimated to be 9.9%, 13.0% 14.6%, 17.9% and, 38.3% re- crease in the degree of supercooling also increased the amount of heat
spectively. recovered during the cooling period.
The charging efficiency of 10.6%, 13.6%, 16.9%, 21.3%, and 41.8% The results of the experimental investigation discussed in the pre-
obtained corresponding to no load, 25% load, 50% load, 75% load and ceding sections revealed that the incorporation of indium enhanced the
full load condition when the shell side of the heat exchanger filled by thermal energy storage performance of pentaerythritol. The enhanced
PE + 0.1 wt% LMM. The obtained values indicated that the charging energy storage and release performance can be attributed to the im-
efficiency of PE increased by 2.1% on the average when 0.1 wt. % LMM proved thermal conductivity of PE due to the presence of conductive
added to pure PE. The charging efficiency of PE +0.5 wt% LMM under indium as reported in the section on thermal property measurement.
no load, 25% load, 50% load, 75% load and full load estimated to be The greatest performance was obtained corresponding to 1.0 wt. % of
11.4%, 16.5%, 21.0%, 28.1% and, 45.1% respectively. The average indium. This indicated that the charging and discharging occurs more
enhancement in the charging efficiency of PE added with 0.5 wt.% efficiently at higher weight % of the heat transfer enhancement ad-
LMM estimated to be7.1%. When the weight fraction of LMM increased ditives. Higher the weight % of indium particles, greater is the en-
to 1.0%, the average enhancement in the charging efficiency obtained hancement in the thermal conductivity which resulted in the heat
as 9.2%. The charging efficiency of PE +1.0 wt% LMM under no load, transfer at an enhanced rate.
25% load, 50% load, 75% load and full load estimated to be 12.3%, During the charging process, the hot HTF transfers heat to the PCM
20.1%, 25.4%, 32.4% and, 49.5% respectively. filled in the shell side of the heat exchanger. Initially, heat is transferred
The energy saved is the third parameter estimated to study the effect from the circulating hot exhaust gas to the inner surface of the tubes
of adding LMM on thermal storage performance of PE. The energy through convection. The heat is then conducted through the tube ma-
saving accounted as the percentage of fuel energy supplied to the en- terial by conduction. The PCM layer in contact with the outer surfaces
gine. The variation of % energy saved load corresponding to PE, of the tube receives this heat by conduction and then flows outwards
PE + 0.1 wt.% LMM, PE + 0.5 wt.% LMM and PE + 1.0 wt.% LMM into the bulk of the PCM. The continuous heating of the PCM due to the
displayed in Fig. 12. The energy saved by pure PE and PE added with transfer of the heat from the exhaust gas causes the temperature to
0.1, 0.5, and 1.0 wt.% LMM estimated at different engine loads. The increase linearly. When the temperature of PE reaches its solid-solid
energy saved using pure PE at no load, 25% load, 50% load, 75% load transition temperature, the added heat causes the breaking of me-
and full load conditions obtained to be 4.2%, 5.8%, 6.9%, 8.4%, and tastable hydrogen bonds in the PE molecules. The breaking of hydrogen
17.3% respectively. The test results of pure PE indicated an average bonds is an endothermic process involving a large enthalpy change.
energy saving of about 8.91%. Thus, a considerable amount of heat is absorbed by the PCM during the
Average energy saving of about 9.42% obtained when PE + 0.1 wt. breaking of bonds. At ordinary temperature, PE has the body-centered

10
K. Venkitaraj, et al. Thermochimica Acta 680 (2019) 178343

tetragonal (BCT) crystal structure. At the transition temperature, the Centre (STIC), Cochin University of Science and Technology, Kochi for
crystal structure changes to face-centered cubic (FCC). If the PCM is providing the testing facility of DSC.
further heated above this transition temperature, the PCM receives heat
again by sensible heating. References
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