Accepted Manuscript

Heat transfer performance of Graphene nano-platelets laden micro-encapsulated

PCM with polymer shell for thermal energy storage based heat sink

B. Praveen, S. Suresh, Vignesh Pethurajan

PII: S1359-4311(18)31998-7
DOI: https://doi.org/10.1016/j.applthermaleng.2019.04.072
Reference: ATE 13662

To appear in: Applied Thermal Engineering

Received Date: 30 March 2018

Revised Date: 7 March 2019
Accepted Date: 18 April 2019

Please cite this article as: B. Praveen, S. Suresh, V. Pethurajan, Heat transfer performance of Graphene nano-platelets
laden micro-encapsulated PCM with polymer shell for thermal energy storage based heat sink, Applied Thermal
Engineering (2019), doi: https://doi.org/10.1016/j.applthermaleng.2019.04.072

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 Heat transfer performance of Graphene nano-platelets laden micro-

encapsulated PCM with polymer shell for thermal energy storage based heat

sink

B Praveen, S Suresh*, Vignesh Pethurajan

Department of Mechanical Engineering, National Institute of Technology, Tiruchirappalli-

620015, India
*(corresponding author) E-mail: ssuresh@nitt.edu
Praveen. B
Research Scholar
Department of Mechanical Engineering
National Institute of Technology Tiruchirappalli
Email: praveennitt15@gmail.com
Mob: +919003362384

Dr. S. Suresh
Associate Professor
Department of Mechanical Engineering
National Institute of Technology Tiruchirappalli
Email: ssuresh@nitt.edu
Mob: +919489066246

Vignesh Pethurajan
Research Scholar
Department of Mechanical Engineering
National Institute of Technology Tiruchirappalli
Email:vignesh.9226@gmail.com
Abstract

Encapsulation of phase change material ( PCM ) prevents from leakage and can evade the
adverse effect of bulk volume expansion. In this study, experimental results on the heat transfer
performance of graphene nano-platelets laden microencapsulated PCM ( ME/GnP PCM ) in a
finned thermal energy storage based heat sink are presented. In-situ polymerization method was
used to prepare the capsules with paraffin/polyurethane as core/shell material. The samples were
characterized by its morphology, capsule size, thermal and chemical stability. To enhance the
heat transfer within the microcapsules, GnP of 0.5, 1 and 3 wt. % were incorporated. The
performance of PCM was compared with a finned heat sink under constant heat load condition of
10W, 15W and 20W. The performance was evaluated based on the heat sink base temperature
with time for set point temperatures and the temperature rise rate (TRR). The thermal
conductivity increased from 0.192 to 0.379 W/m.K and the TRR of the heat sink was delayed
due to the enhanced the heat transfer within the ME/GnP PCM. Moreover, the recovery time of
the heat sink also declined due to reduced thermal resistance and nucleation effect in the
MEPCM by the GnP.

Keywords: Micro-encapsulated PCM; graphene nano-platelets; TES based heat sink;

temperature rise rate; thermal conductance.

Abbreviations

PCM : Phase change material

ME PCM : Micro encapsulated PCM

GnP : Graphene nano-platelets

ME/GnP PCM : GnP laden micro-encapsulated PCM

TES : Thermal energy storage

RT : Room temperature

DSC : Differential scanning calorimetric

TGA : Thermo-gravimetric analysis

PSD : Particle size Distribution

SEM : Scanning electron microscope

TRR : Temperature rise rate, °C/min

C : Thermal conductance, W/K

1. Introduction

In the context of present-day electronics packaging systems, the concept of thermal management
has gained paramount importance among researchers and industrialists, as it directly affects
system performance. The integration of high power density chips imposes severe challenges on
the thermal management design for the next-generation integrated circuits [1-2]. With the
increase in the power density of the electronic components, the heat generated per unit area
increases and hence, the issue of thermal imbalance arises due to inefficient heat removal
techniques or mechanisms. Hence, research is being concentrated in this direction to make
efficient designs of more compact thermal management systems. Additionally, conventional
cooling systems with natural and forced convection methods have their limitations to meet the
required performance demanded by the present high-density electronics packaging.
Active cooling techniques in packaging create internal vibration, noise and increased
power consumption. Thus, the use of active cooling methods is limited and the applicability of
passive cooling methods is now gaining more attention. Among the passive cooling techniques,
the use of Phase Change Material (PCM) based heat sink has been gaining more attention
recently. Recently, researchers have introduced and investigated the PCM based thermal
management techniques experimentally and numerically [3-7]. The PCM have desired properties
for energy storage applications as they are used in heat exchangers and for cooling the heat
source.
Solid-liquid PCM like paraffin, n-eicosane, metallic alloy and gallium are more commonly
used for thermal management applications. Baby and Balaji [3] conducted a transient
experimental study on phase changes due to the heating and cooling of n-eicosane as PCM with
plate finned with a constant power level of 5 – 10W corresponding to a flux of 2 – 4 kW/m2.
They compared the performance of the heat sink with and without the PCM. The PCM was
found to maintain a heat sink temperature within 50 °C for up to 90 min of operation. Pal et al.
[4] had done an experimental and numerical study with n-triacontane under constant heat load.
Their main attention was to study the effect of natural convection in PCM and developed the
correlations. The authors reported that natural convection played a dominant role during the
initial stages of melting. Kandasamy et al. [5] investigated the transient cooling performance of
heat sink with paraffin. They studied the natural convection effect and the results showed that,
for lower power levels, the effect of PCM was not felt due to the higher melting point (55-60 °C)
of PCM. A similar study was performed by Fok et al. [6] with eicosane as PCM and the results
showed that the PCM had effect in the lower power range (3-5 W) because of the lower melting
point of the selected PCM (35 - 40 °C). Yang et al. [7] conducted a numerical study on heat
transfer and heat sink orientation effect with n-eicosane as PCM for a power level of 2-4 W. It
was reported that the presence of PCM in an aluminium heat sink could maintain a stable
operating temperature (50-60 °C) for electronics packaging and orientation has limited effect on
the melting of PCM.
Previous studies reveal the fact that heat sinks integrated with PCM is an effective option
for a passive cooling technique and the performance depends on the PCM characteristics.
However, these solid-liquid PCM face the issue of volume expansion and leakage during
conversion into the liquid phase. This limits the practical applicability of solid-liquid PCM.
Hence, this PCM need to be packed or enclosed to avoid leakage. With this intention,
encapsulation of PCM with thermally and physically stable shell material (generally polymeric
materials) is necessary. The methods to encapsulate a PCM can be broadly classified into three
types- physical, chemical and physio-chemical methods [8]. In the physical method, the
ingredients are not undergoing any chemical reaction and the encapsulation process is carried out
by pan coating or suspension coating or spray drying. In the chemical methods, polymerization
reaction is initiated when the free radicals attack the monomers when there is a change in pH
value of the solution. These chemical methods include suspension, emulsion, interfacial, in-situ
and condensation polymerization technique. Sari et al.[9] synthesized and characterized
micro/nanocapsules of a eutectic mixture of n-tetracosane and n-octadecane with polystyrene
shell material using emulsion polymerization method. The synthesized micro/nanocapsules had
bimodal size distributions within 0.01–115 μm. TGA results demonstrated that the synthesized
capsules had good thermal stability and are suitable for low-temperature thermal energy storage
applications. In recent studies, paraffin encapsulated in shell material such as calcium carbonate
[10] and urea formaldehyde [11] are reported. Jin Z et al. [11] were prepared and characterized
micro-capsules containing paraffin as PCM in the core with shell of urea formaldehyde. The
synthesized micro-capsules were showed thermal stability up to 200 °C. They reported that the
synthesized micro-capsules were being potentially useful in energy conservation and functional
heat storage materials. Zhang H et al. [12] were synthesized and characterized the properties of
n-eicosane as core PCM with silica shell micro-capsules of mean particle size of 17 µm. The
TGA analysis showed no mass degradation up to 250 °C. The DSC results indicated good phase
change properties for potential application in thermal regulating in textiles and fibers. He F et al.
[13] were synthesized silica encapsulated n-octadecane as core PCM. The characterization
results showed that the prepared micro capsules exhibits good phase change performance and
high encapsulation efficiency. In addition to this study, a series of experiments reported towards
the feasibility of micro-encapsulation of PCM for different applications [11]. All the studies
reported that the micro- or nano- encapsulation of PCM could avoid the interference with its
container, has less effect on PCM volume change and have improved heat-transfer due to the
shape, light permeability, and better thermal stability properties. All these studies reported that
the micro- or nano-encapsulation of PCM could avoid the interference with its container, and
thus have a lesser effect on PCM volume change and have improved heat-transfer due to the
shape, light permeability, and better thermal stability properties.

Paraffin has attractive thermal energy properties like the high latent heat of phase transition
(200-230 kJ/kg·K), better thermal durability and thermal stability[14].Moreover, the
encapsulation of paraffin can make the PCM suitable for energy storage applications. However,
paraffin possesses lower thermal conductivity (0.2 - 0.4 W/m·K) which limits its heat transfer
performance. Moreover, encapsulation further decreases the heat transfer in the bulk material.
Addition or incorporation of thermal conductivity enhancers (TCEs) can aid the heat transfer
within the PCM. These TCE facilitate uniform heat diffusion which leads to the uniformity in
melting of bulk PCM and this intern results in better heat transfer performance of the heat sink.
Experimentally reported TCEs are such as metallic fin, porous materials, metallic forms, non-
metallic forms and nano-additives [15]. The concept of TCE by metallic fins was first proposed
by Henze et al. [16]. They reported that the fin in the bulk PCM can significantly affect the heat
transfer within the PCM. Later on Nayank et al. [17] were studied the performance of PCM heat
sink by varying the number fins by 2, 4 and 8. The results showed that the presence of fins
enhanced the heat diffusion consequently decreased the heat sink base temperature by 7 °C.
Hossei- nizadeh et al. [18] also reported more uniform melting of PCM occurs in the heat sink
with the fins. Recently Balaji et al. [19] conducted experiments with pate fin and pin fin heat
sink for 4W power. The heat sink with plate fin and pin were showed reduced temperature for a
long time compared with heat sink without fins.
Researchers reported that the addition of conductive particles is a useful method to enhance
the thermal conductivity of the PCM. The reported additives include oxide particles like Al2O3,
CuO[20], TiO2, SiO2, ZnO[21], metals like Ag [22] and carbon-based additives like MWCNTs,
CNFs and GO [23]. All these studies were performed to utilize the PCM for high-temperature
energy storage applications. Even the PCM having desired properties as explained, their inherent
low range of thermal conductivity slows down the heat transfer performance in the case of heat
sink application. Weinstein et al. [24] conducted a study of thermal performance of heat sink
with paraffin added with graphite nano-fibers of 0.25 to 5 wt.%. They observed improved
thermal performance of heat sink and reduced heat source temperature. Fan et al.[25] studied the
thermal performance of carbon nano-filler in PCM. They prepared the composite PCM by adding
CNT and graphene nano-platelets in 1-hexadecanol and the results showed that the carbon nano-
fillers improved the transient performance of the heat sink. And Sanusi et al. [26] experimentally
investigated the effects of composite PCM of paraffin added with graphite nano-fiber of 10 wt.%
in an aluminum heat sink. They reported that the graphite nano-fiber addition showed a reduction
in maximum temperature in the thermal containment unit by 48%. And Chintakrinda et al. [27]
conducted an experiment with paraffin and graphite nano-fiber of 10 wt.% in an aluminum heat
sink with power levels o 1.93 to 19.3 W/cm2. The results showed a 12% reduction in temperature
of module compared with pure PCM. All the reported investigations reveal that the addition of
conductive particles enhances the thermal conductivity and hence more heat transfer property in
PCM.
Most of the previous works were related to the applications of encapsulated solid-liquid
PCM for thermal energy storage. No attempts have been made till now to experimentally
exposure the performance of micro-encapsulated PCM in TES based heat sink application. Also,
the heat transfer performance of graphene nanoplatelets (GnP) laden micro-encapsulated
composite PCM (ME/GnP PCM) has not been explored experimentally.
This study aims to report the heat energy storage/release and heat transfer performance of
GnP laden micro encapsulated paraffin with polyurethane shell using in-situ polymerization
technique for TES based heat sink application. GnP of 0.5, 1 and 3 wt. % were incorporated as
heat transfer enhancing filler with the encapsulated PCM. Experiments were conducted to study
the thermal stability, chemical stability, heat storage/release behavior and heat transfer
performance of synthesized PCM microcapsules added with GnP. The effect of encapsulation on
phase transition, latent heat capacity and the thermal degradation were studied through DSC and
TGA and techniques. Moreover, the effect of encapsulation and GnP addition on heat storage
and release rate was observed. The transient heat transfer performance of encapsulated and GnP
added PCM with the heat sink was analyzed experimentally.

2. Experimental

2.1 Synthesis of GnP added microencapsulated PCM

The materials used for encapsulation process includes paraffin (melting point = 60 to 62
°C, ρ = 880 kg/m3), deionized water, ammonium chloride ( NH4Cl, molar mass = 53.49 g/mol,
crystalline form ), resorcinol (C6H4(OH)2, molar mass= 110.11 g/mol, crystalline form), sodium
hydroxide (NaOH, molar mass= 40.00 g/mol, pellet form), urea ( CH4N2O, molar form = 60.03
g/mol, crystalline form) and formaldehyde (HCHO, molar mass= 30.03 g/mol, solution) which
were purchased from Spectrum chemical Pvt. Ltd. India. Ethylene-alt-maleicanhydride(EMA)
was commercially supplied by Sigma-Aldrich, US. The GnP of sub-micronparticles (size: 0.5 -
5µm, thickness: 5-20 nm, surface area = 500 m2/g) was purchased from Alfa Aesar, US. All the
chemical have purity range of 99% as mentioned by the manufactures and used as received
without any further purification.
 Ethylene-maleic anhydride (EMA) was chosen as the emulsifier in the encapsulation
process. 2.5 wt. % of EMA solution was mixed with deionized water and the solution was stirred
with a mechanical stirrer for 10 hours at 50 °C to dissolve the emulsifier completely. EMA
initiates the polycondensation process in which the monomers having two functional groups
leads to the formation of the polymer.
In-situ polymerization prepares the microcapsules in an oil-in-water emulsion. Fig. 1(a)
and Fig. 1(b) show the sequence of the process. At room temperature, 200 ml of deionized water
was mixed with 2.5 wt. % aqueous solution of EMA copolymer in a beaker and was kept on a
temperature controlled water bath. The solution was agitated with a mixer having three-bladed
propeller placed at the center of the beaker. During agitation, 5 g urea, 0.50 g ammonium
chloride and 0.50 g resorcinol were dissolved in the solution. To avoid precipitation and to raise
the pH of the solution from 2.60 to 3.50, sodium hydroxide or hydrochloric acid is added drop
wise till the solution remains unsettled. To eliminate the bubble formation, one to two drops of 1-
decanol were added to the solution. Then 10 grams of paraffin wax was added to the emulsion
and it could stabilize for 10 min and then heated up to 80°C. After stabilization, 37 wt.% of
aqueous formaldehyde was added to the solution to obtain 1:2 molar concentration of urea
formaldehyde. The emulsion mixture was further heated up to 55°C at a heating rate of 1 °C/min.
The agitation was continued for the next four hours at the same temperature and then allowed to
cool to ambient temperature. Then the microcapsules were separated under vacuum with a
coarse-fritted filter and rinsed with deionized water and air-dried for 24-48 hours. The
synthesized microencapsulated PCM were mixed with GnP of wt.% 0.5, 1 and 3using low
energy ball milling to ensure uniform distribution.
 (a)

(b)

Fig.1. (a). Encapsulation process of paraffin by In-situ polymerization, (b). Preparation of ME/

GnP PCM

2.2 Characterization

The surface morphology and dispersion of synthesized microcapsule and the composite
were analyzed through SEM imaging (TESCAN VEGA3). The TGA was performed using a
NETZSCH STA 449 F3 Jupiter. TGA studied the thermal degradation of microcapsules up to
450 °C. Powder samples of less than or equal to 2mg were analyzed using alumina crucibles with
a protective gas flow of 100 mL/min in nitrogen atmosphere. The instrument had a temperature
range from ambient to max. 1150 °C and a measurement range ± 350mW at room temperature
with a measurement resolution of 0.04mW at RT, temperature accuracy of ± 0.20 °C and
temperature reproducibility of ±0.1 °C. The PCM samples were subjected to heating and cooling
between the temperature range 30 – 80 °C at 5 °C/min using a thermal cycling chamber before
measurement. The sample is placed in the crucible and ramped from room temperature to 450°C
under the nitrogen inert atmosphere with a flow rate of 60 ml/min with a heating rate of 5
°C/min. Sample Characterization using Thermogravimetric Analysis (TGA) involves the
determination of the change in weight of a sample as a function of temperature and/or time of
heating. These measurements are used to study the thermal stability of samples.

The thermal conductivity of the samples was measured using Laser Flash Analyzer
(NETZSCH LFA 467).The sample is placed inside the manufacture supplier sample holder (2.5
cm diameter and 1 cm thick) and the measurement is conducted with liquid nitrogen cooled
sensor. The measurements were repeated for 5 times for obtaining an accurate reading.
Spectroscopic analysis for chemical compatibility was done by FTIR spectroscopy (Frontier
FTIR, Perkin-Elmer) at mid-IR range (400-4000 cm-1).

Latent heat, melting and solidification points were found using Differential Scanning
Calorimeter (DSC 6000 Perkin Elmer) which works in the temperature range of -100°C to
450°C with a resolution of ± 0.2 °C at room temperature and reproducibility of ±0.1°C. In this
study, the heating and cooling rates were fixed at 5°C/min. All the experiments were performed
under the inert nitrogen atmosphere with a flow rate of 20ml/min. All the weight measurements
were accurate upto 0.01mg in a sealed aluminum cell with piercing. The instrument was
calibrated for heat flow and temperature analysis using indium and zinc standards. In DSC
analysis, the system measures the difference in the amount of heat required to increase the
temperature of a material sample (sample pan) and an empty sample (reference pan) as a
function of temperature.

2.3 Experimental setup and procedure for heat transfer study with heat sink

The experimental setup to study the heat transfer performance consists of aluminum
finned heat sink of dimension 80 × 60 × 40 mm3 with uniform fin thickness of 2 mm as a heat
storage PCM heat sink and the heater arrangement as shown in Fig. 2. At the bottom of the heat
sink, a polyimide film heater (Watlow) of ~1 mm thickness was placed with insulation at the
bottom. The heater was connected to a DC power source for applying the heat load. A copper
plate of 80 mm × 60 mm × 2 mm was placed in between the heater and heat sink which acted as
a heat spreader. At the bottom of the heat sink, three thermocouples (K type, Watlow) of 2 mm
diameter were placed to measure the average heat sink temperature. A thermally conductive
silicon paste (Omegatherm 201, OT 201) was applied in between the interfaces of the heater, in
the thermocouples holes and in between the heat spreader and heat sink to reduce the interface
resistance. All the thermocouples were connected to the data logger (34972A Data Logger,
KEYSIGHT Technologies) to obtain the temperature values during experimentation. The heat
sink assembly was placed inside a convective enclosure to avoid the external convective
disturbance.

Fig. 2. Schematic diagram of the experimental arrangement for heat transfer study
 A transient experiment was conducted to evaluate the heat transfer performance of
encapsulated PCM and ME/GnP PCM with TES based heat sink. The tests were conducted for
both the heating and cooling process. The observations were done for the case of the heat sink
without PCM, with paraffin, with encapsulated paraffin and with GnP (0.5, 1 and 3 wt. %)
incorporated encapsulated paraffin. The heat sink was filled with equal weights for all
combinations of PCM. The experiments were conducted for a heat load of 10W, 15W and 20W
applied through a DC power supply. This power level was adequate to observe the heat transfer
performance of a heat sink as reported [4]. Power was supplied to the heater till the temperature
of heat sink rose up to 80 °C and then the heater power was switched off to cool the heat sink to
the room temperature. The temperatures were recorded at a scan rate of 10s interval by the data
logger. The transient heat transfer performance of each case was analyzed by observing the
variations in the temperature with time, recorded by the thermocouples located at the base of the
heat sink.

3. Result and discussion

3.1 Characterization

3.1.1 Morphology and PSD analysis of microencapsulated PCM

The morphology and particle size of the prepared microcapsules analyzed using SEM
image and particle size distribution (PSD) analyzer are as shown in Fig.3. From the image, it can
be observed that most of the encapsulated PCM are of micron-sized capsules with approximately
spherical shape and some part showing aggregated. The SEM images confirm the spherical shape
of encapsulation with a diameter of about ~ 60 µm. The diameter measurement by SEM image is
also matching with the statistical evaluation method by the PSD analysis. Fig. 4shows the PSD
analysis results for the prepared microencapsulation. The results ensure the homogeneity in
shape of PCM and the average size of the microcapsules are in the range of 60 - 65µm. Micron-
scale PCM capsules providea large surface area for better heat transfer. The uniformity in shape
of the samples was attributed to the ample amount of time given for the shell formation during
the process. The SEM micrographs indicate the successful encapsulation of paraffin wax with
polymer shell. All the synthesis of microcapsules was carried with an agitation rate of 700 rpm,
as the size of encapsulation depends on agitation speed[28]. The geometry of the microcapsule
and the thermal response time has a substantial effect on the heat transfer properties of the PCM.
The spherical shaped geometry of the microcapsules tends to have the improved heat transfer
rate compared to other geometries [28].

Fig.3.SEM image of micro ME PCM (a, b), GnP (c)and GnP added ME PCM (d)

Fig.3(c)shows the SEM image of GnP , and (d) shows the GnP (3 wt.%)with
encapsulated PCM. Most of the microcapsules are not clearly visible due to the covering of GnP
fillers. It can be observed that the GnP are well dispersed and the microcapsules were covered by
the GnP are mostly intact. This reveals that all the microcapsules were wrapped by GnP medium
which makes a continuous path for the heat transfer. The GnP filled the space in between the
spheres which reduces internal thermal resistance. The morphology and particle size analysis
proves that the prepared encapsulated PCM is in micron level spherical shape and the added
GnPwere dispersed over the microcapsules.

Fig. 4. PSD analysis of micro-encapsulated PCM

3.1.2 Thermal stability and chemical compatibility

The TGA analyzes the thermal stability of PCM by measuring the percentage of weight
change as a function of increasing temperature in a controlled atmosphere of nitrogen, helium,
air, or in a vacuum, which exhibits loss or gain of mass due to thermal decomposition,
evaporation, oxidation or dehydration of the sample. The TGA curve for paraffin and
encapsulated paraffin are shown in Fig.5. The paraffin decomposes in a single step between the
temperature range of 200-350 °C. However, for the encapsulated PCM, the decomposition takes
place in two steps. For the detailed evaluation, the TGA curve of PCM is divided into three
Zones. The zone I is in the temperature range up to 200 °C where there is no mass degradation of
PCM occurred. In this zone, a mass degradation of 3.6 % happened in the early stage of heating
up to 100 °C. This degradation percentage and the temperature range shows that this is due to the
evaporation of moisture content left and the unremoved residual particles (low molecular) during
the encapsulation process. The zone II, from 200 °C to 300 °C represents the evaporation of
paraffin in the encapsulation core. At the end of this zone, 54.6 % of total mass were
decomposed. In the zone III, the decomposition of shell material occurs at the temperature range
of above 300 °C. The TGA results give the following information. The mass degradation of
paraffin and encapsulated PCM occurs only after 200 °C, which is within the temperature range
of application. The degradation temperature remains unchanged after encapsulation of the PCM.
The first step of major mass loss was 54.6 % for paraffin, which is almost matching with the
encapsulation ratio of 55.59 % by DSC analysis.

Fig. 5. TGA curve for paraffin and encapsulated paraffin.

Moreover, the shell material protects the paraffin from reacting with the outside
environment and will be able to maintain the temperature stability in a system. Also, the shell
reduces the effect of volume change during the charging and discharging process. This long-term
stability of the synthesized microcapsules makes them a possible candidate for PCM in thermal
energy storage-based applications. The shape stability of the encapsulated PCM with temperature
was observed by placing the samples in same temperature platform. Fig.6 shows the photographs
of paraffin (A), micro-encapsulated paraffin (B) and GnP added micro-encapsulated paraffin (C,
D and E) heated using same temperature source. As seen from the photograph, the paraffin melts
completely after 5 minutes. However, the micro-encapsulated paraffin samples retained their
shape without leakage from the core of PCM. This confirms the shape stability of the prepared
encapsulated PCM well above the melting temperature without the leakage of molten core
paraffin.

Fig. 6. Photograph of PCM heated using the same heat source. (A) paraffin, (B) micro-

encapsulated paraffin, (C) (D) and (E) micro-encapsulated paraffin added with 0.5, 1 and 3 wt.%

GnP respectively.

The chemical stability and displacement in bonds and functional groups are analyzed using
Infrared spectrophotometer (Perkin Elmer). The FTIR spectra for paraffin, GnP, encapsulated
paraffin and GnP added encapsulated paraffin are shown in Fig.7. In the spectrum of paraffin,
peaks appearing at 2920cm-1and 2840 cm-1 are responsible for C-H stretching absorption. The
peak at 1460 cm-1 corresponds to bending vibration resulting due to CH 2 absorption vibration.
Peak appearing at 715 cm-1 absorption vibrations uphold linear saturated aliphatic frame of
paraffin. The peak for encapsulated paraffin occurred at 3313.36 cm-1 which is due to the
stretching frequency of O-H. Similar peaks occurred at 2916.05 cm-1 and 2831.79 cm-1 which
were due to the strong stretching frequency of CH3, CH2,and C-H functional groups. Peaks also
occurred at 1632.74 cm-1 and 1531.64 cm-1 which are due to C=C stretch. In the finger point
region (1500-500 cm-1), peaks appeared at 1371.12 cm-1 and 1025.24 cm-1 which were due to
bending vibration of CH3, CH2,and C-H functional groups. After adding GnP, the FTIR spectra
showed only a minor shift in the peaks due to the surface tension forces between PCM and GnP.
The FTIR spectroscopy results confirm the presence of polymer shell formed after encapsulating
the paraffin. There was no evidence of new peaks formed by the addition of GnP. This reveals
that GnP were dispersed only through physical interaction with the PCM and without forming
any chemical reaction between the shell material.

Fig.7. FTIR spectrum of GnP, paraffin, micro-encapsulated paraffin and GnP added micro-

encapsulated PCM.

3.1. 3 Enthalpy and phase transition temperature

Differential Scanning Calorimetric (DSC) was used to estimate the melting point and latent
heat of the microcapsules. All samples were heated to 100°C and allowed to cool to their
crystallization point and then heated again for collecting the data. The melting point and latent
heat obtained from the second heating cycle and the average value of three DSC experiment
were taken as the final data and are shown in Fig.8.
The DSC curves for paraffin, encapsulated and GnP added samples are shows a main sharp
curve and a small secondary curve. The small primary curve represents solid-solid transition and
the sharp secondary curve represents the solid-liquid (melting) transition of the PCM. The
shoulders of both the curves lie in the same temperature region but with the shifted peaks. The
DSC curve of the encapsulated paraffin shows a melting peak at 62.31°C, whereas, the melting
peak for the paraffin was at 63.15 °C. This variation in melting point of encapsulated samples
was already reported and the impurities captured during the encapsulation process was the reason
explained for this fact [29]. The latent heat of melting was found to be 116.71 J/g for
encapsulated sample and 211.93 J/g for the paraffin sample. The melting point ( Tm) and the
melting enthalpy (△Hm) of the samples are listed in the Table 1. As shown in the Table 1, the
addition of GnPof 0.5 to 3 wt.% had little effect in melting temperature ( 62.45 to 62.71 °C ) and
enthalpy ( 115.20 to 110.71 J/g ).The melting temperature and latent heat value of the
synthesized microcapsules make them suitable for latent heat storage based heat sink
applications.
 Fig.8 DSC curve for paraffin and encapsulated paraffin

The encapsulation ratio(wt.% of PCM in the capsule)is a parameter used to characterize the
phase change performance of microencapsulated PCM which in turn can be calculated from the
DSC data. The PCM percentage inside the encapsulation is one of the key factors of
encapsulation process outcome which determine the percentage of PCM encapsulated in the
microcapsule based on melting enthalpy value and it can be calculated as follows,

△
Paraffin (wt. %) in the encapsulation △

Where ∆Hencap ,∆HParaffin is the melting enthalpy of encapsulated sample and paraffin
respectively. The calculated encapsulation ratio was 55.59 %, which means that encapsulated
microspheres contain 55.59 wt.% of paraffin. This trend of decrease in the value of∆Hencap after
the encapsulation process was reported by the researchers [30] which ensures the validity of the
results obtained in this study.
3.1.4 Thermal conductivity

The thermal conductivities of ME PCM at room temperature are shown in the Table 1.
The measure value thermal conductivity of ME PCM was 0.192 W/mK. The addition of GnP in
to the ME PCM, increased the thermal conductivity to 0.211 W/mK, 0.221 W/mK and 0.379
WmK for 0.5, 1 and 3 wt. % respectively. In percentage calculation, the thermal conductivity
enhanced to 9.89 %, 15.10% and 97.39 % by the addition of GnP. The enhancement in thermal
conductivity can explain, as anticipated due to the presence of higher thermal conductive GnP in
the ME PCM.
Table 1: Thermal properties of ME PCM

PCM Tm, °C △Hm, J/g k, W/mK

ME PCM 62.31 116.71 0.192

ME PCM/GnP @ 0.5 wt.% 62.45 115.20 0.211

ME PCM/GnP @ 1 wt.% 62.53 113.51 0.221

 ME PCM/GnP @ 3 wt.% 62.71 110.71 0.379

3.2 Heat transfer performance with TES based heat sink

3.2.1 Heat transfer performance of encapsulated PCM

This section deals with the results of an experiment conducted to evaluate the performance of
encapsulated and GnP added PCM in TES based heat sink. The temperature variation recorded
by the thermocouples at the bottom of the heat sink was used to evaluate the transient
performance of heat sink with the encapsulated PCM.

Fig.9.(a). Temperature time history of the heat sink without PCM, paraffin and encapsulated

paraffin during heating with 10W.

 Fig.9.(b). Temperature time history of the heat sink without PCM, paraffin and encapsulated

paraffin during cooling.

Experiments with the heat sink without filling any PCM material was used as the base
line evaluation. To evaluate the performance of encapsulated PCM, experiments were conducted
by filling the heat sink with paraffin and encapsulated paraffin and then compared with the
results of the heat sink without PCM. The results of the heat sink without PCM is plotted for a
baseline comparison. The results of heating and cooling process are shown in Fig. 9(a,b). The
temperature of the heat sink without PCM rises at a faster rate as there is no PCM to store or
remove heat from the heat sink. The curves of paraffin and encapsulated paraffin divided were
into two sections as 0-1a, 1a-2a and 0-1b, 1b-2b respectively. During heating, at the region 0-1 a
and 0-1b, the heat sink base temperature rises at a steady rate. During this time, sensible heating
of PCM occurs. Moreover, at the region 1a-2a and 1b-2b, the rate of increase of heat sink
temperature reduces as in this time the PCM changes its phase (melting) by absorbing latent heat
of fusion from the heat sink.
 In the case of encapsulated paraffin, it required a higher temperature as the encapsulation
shell offers some resistance to heat flow to the PCM in the core. Moreover, during this time, the
base temperature of the heat sink increases at a slower rate and the process was ended at 1b and
2b. The time duration for the processes 1a-2a and 1b-2b were 31.4 and 11.3 minutes. This shows
that the heat sink was maintained at a lower temperature for a duration of 31.41 and 11.32
minutes with paraffin and encapsulated paraffin respectively. Shorter duration for encapsulated
PCM was due to its lower enthalpy of melting (110 kJ/kg K) as compared to paraffin (210 kJ/kg
K). As the heating experiment was conducted up to 80°C, the base temperature of the heat sink
was attained within 50.52, 88.20 and 62 minutes for container without PCM, with paraffin and
encapsulated paraffin respectively. With encapsulated PCM, the heat sink base temperature
increases at a fast rate as compared with paraffin. The heat transfer within the encapsulated PCM
is less as compared to the heat transfer within the paraffin, as in encapsulated PCM there is less
thermal contact between the adjacent encapsulated shells due to its spherical shape. Furthermore,
the shape of encapsulated PCM remains stabilized in the heat sink, thus avoiding the chances of
leakage which is one of the objectives of this study.
Results for cooling process are shown in Fig. 9(b). In the graph 0-1a and 0-1b, the heat
sink temperature reduces steeply from 80 to 60 °C. Moreover, in regions 1a-2a and 1b-2b, the
temperature of heat sink reduces at a slower rate as the PCM gets cool by rejecting the latent heat
and thus the heat sink temperature gets down slowly. Duration of 1a-2a and 1b-2b is different
and less for encapsulated paraffin, same as explained in the heating process. The results show
that PCM can keep the heat sink at a lower temperature for a considerable duration of time. The
encapsulated PCM remains solid throughout the duration of the operation.

3.2.2 Effect of GnP addition in encapsulated PCM

To observe the effect of GnP addition, experiments were conducted by adding GnP of 0.5,
1 and3 wt. % with encapsulated PCM. The comparison was made based on temperature variation
of the heat sink with time for 10W, 15W and 20W heating load during heating and cooling. Fig.
10 shows the results. The results of heating at a rate of 10W shows that the temperature of the
heat sink rises very fast at the initial stage as the PCM was under sensible heating. When the
PCM gets starts melting inside the encapsulation, the rate of heat sink temperature rise gets
reduced as PCM absorbs the latent heat. The results for GnP added PCM shows the rate of
reduced temperature rise.
With 10 W power and the encapsulated PCM, the set point temperature of 80°C was
reached within 62 minutes, while GnP added PCM required 64.3, 67.6 and 73.6 minutes. This
proves that the addition of GnP delayed the temperature rise by 2.3 to 11.6 minute for 0.5 to 3
wt.%. Moreover, this delayed effect was also shown for the increased power values of 15W and
20W. Addition of GnP in the encapsulated PCM reduces the heating rate of the heat sink. The
delayed effect is due to increased thermal heat transport within the PCM incorporated with GnP.
Fan et al.[25] reported the same trend of enhanced heat transfer with GnP addition in 1-
Hexadecanol as PCM in the heat sink. As the wt. % of GnP increases, the heat transport in the
PCM increases at a faster rate and hence the heat flux bottleneck at the heat sink base reduces
significantly. The heat sink base temperature was minimum for 3 wt. % GnP addition. The
enhanced heat transfer was due to the space between the encapsulated shells filled with
conductive GnP which creates an easier path to the heat flow within the PCM. Due to this, the
internal heat resistance between the encapsulation shells gets reduced and avoids the heat
accumulation at the bottom of the heat sink. Thus, PCM can absorb the heat at a faster rate from
the heat sink and as an effect, the heat sink maintains a lower temperature for a longer duration.
Fig. 11 (a) and (b) shows the enhancement ratio in operating time to reach the set point
temperatures of 60°C and 80°C concerning the heat load value of 10W, 15W and 20W. The
enhancement in operating time can be expressed by calculating the ratio of time taken by the heat
sink to reach a set point temperature with PCM to that of without PCM. The calculated results
show that the enhancement ratio is above 1 for all the cases, which reveals that the presence of
PCM enhances the operating time of the heat sink in the range of observed set point
temperatures. Moreover, a maximum enhancement ratio of 1.87 and 1.67 are observed for PCM
with 3 wt. % GnP for 15W heat load value at a set point temperature of 60 and 80 °C
respectively. The increased enhancement ratio with power is due to the temperature rise of the
heat sink in a short time with increased power level in the case of without PCM[3]. Moreover, in
the case of the heat sink with PCM, the PCM absorbs heat up to its capacity from the heat sink
thus delaying the heat sink temperature rise. As the GnP (0.5, 1 and 3 wt. %) was added in the
PCM, the enhancement ration also increases from 1.2 to 1.56, 1.4 to 1.87 and 1.2 to 1.47 for
10W, 15W and 20W heat load respectively for set the point temperature of 60 °C. And for 80°C
set point temperature, the enhancement ratio increases from1.22 to 1.43, 1.45 to 1.67 and 1.3 to
1.4 respectively.
Fig. 10. Effect of GnP in encapsulated PCM on the variation of the base temperature of the heat

sink with time for 10W, 15W and 20W.(A)- without PCM, (B)- paraffin, (C)- ME PCM, (D)-

ME PCM+ 0.5 wt.% GnP, (E)- ME PCM+ 1 wt.% GnP and (F)- ME PCM+ 3wt.% GnP

(a)
 (b)

Fig.11. The enhancement in time to reach set point temperatures with respect to heat flux,

(a) 60°C and (b) 80°C

 Fig.12. Calculated temperature rise rate (TRR) of the heat sink.

(A) ME PCM, (B), (C) & (D) ME PCM + 0.5, 1 & 3 wt.% GnP respectively. The inset shows

how the TRR is calculated.

Based on the transient heat transfer experiment results, the factor of temperature rise rate
(TRR) was calculated for comparing the performance of PCM in the heat sink (the term TRR
defined as the temperature rise measured per unit time, °C/min). The TRR denotes how fast the
base temperature of heat sink rises. A lower TRR implies that the heat sink temperature increases
at a slower rate. Fig. 12 shows the TRR calculated for 10W with all combinations of samples.
The TRR was calculated for three sections of observation, RT – 40 ºC, 40 – 60°C and 60 – 80
°C, which corresponds to the initial stage of heating, before the phase transition of PCM and at
the phase transition temperature range of the PCM respectively. The TRR value in case of the
heat sink without any PCM was 1, 1.10 and 0.85 °C/min for the three temperature ranges
respectively. At all the sections of heating, the presence of PCM reduces the TRR of heat sink
compared to the one without the PCM. Moreover, comparing with encapsulated paraffin,
paraffin showed lowest TRR of 0.71, 0.42 and 0.48°C /min because of its high latent heat of
melting. The lowest TRR value of 0.59 °C/min was showed for encapsulated PCM in the
temperature range of 60-80 ºC. Thisis due to the melting point of paraffin which lies in this
temperature range and so the encapsulated PCM can absorb additional heat from the heat sink.
Addition of GnP reduces the TRR up to 0.85, 0.65 and 0.53 °C/min for 3 wt. % with the
corresponding three temperature ranges respectively. However, in the case of paraffin, the TRR
is showed to increase at 60 – 80°C. This is because the paraffin melts in this temperature range
and the convective heat transfer dominates within the PCM. This decreases the heat transfer
within the liquid PCM. However, in the case of encapsulated PCM, the liquid PCM was filled
inside the shell and the heat transfer occurs through conduction across the shell in the bulk PCM.
Moreover, the addition of GnP enhances the heat transfer and hence reduces the TRR.

Fig. 13. Comparison of thermal conductance for different GnP wt. % loading with micro-

encapsulated PCM.
 To evaluate the performance of heat sink with PCM and thermal conductivity enhancer
early researcher were used the term thermal conductance [31]. The thermal conductance shows
the heat transfer rate per unit temperature difference to the room temperature with the GnP
addition. Fig. 13 shows the comparison of thermal conductance with GnP addition for all
observed power levels. The result shows that the thermal conductance is increasing with GnP
loading which reveals more heat transfer within the PCM to the heat sink surface. The
comparison results reveals that for higher power level the thermal conductance increase
significantly with GnP addition.
The mechanism behind the increased thermal conductance is illustrated in Fig.14. The
voids present in between the microcapsules reduce the bulk heat conduction. The added GnP gets
filled in and around the voids between the microcapsules which facilitates additional heat
conductive path. This effect of enhanced heat transfer with conductive fillers was already
reported by the same research group[32]. Moreover, as the wt. % of GnP in the samples
increases, the rate of heat transfer within the PCM also increases due to the improved conductive
path. The Table 2 depicted the previous studies were used graphene additives in PCM for heat
sink application. The previous studies reported an enhanced heat transfer and reduced
temperature rise in the heat sink with the graphene additives.
Table 2. Previous studies using graphene additives in PCM with heat sink

Nano Loading Power

Authors PCM Heat sink design Observations
additives level level
Cube with volume of Improved the thermal response
Graphite 0, 0.25, and reduced the source
Weinstein 131 cm3 with Cu
Paraffin nano- 0.5, 1.0& 3 and 7W temperature.
et al.[24] bottom and Kydex T
fibers 5.0 wt%
Acrylic/PVC side wall
The elapsed time to reach the
set point temperature were
Graphene
reduced from 3600s to 2600-
Fan et al. nano- 0.3, 1 & Aluminum heat sink 40, 80 and
1-hexadcanol 2560, 190 to 200-230 and 120
[25] platelets 3 wt.% 80x80x30 mm3 120 W
to 120-130 for applied power
(GnP)
levels respectively with GnP.

GNF enhancement was shown

Graphite
Aluminum cubes have 4W/cm2 to reduce the maximum
Sanusi et al. nano-
Paraffin 10 wt. % side lengths of 5.08 and temperature in the thermal
[26] fiber
and 10.16 cm 20W/cm2 containment unit (TCU) by
(GNF)
48%.
Aluminum cubic 1.93
Graphite 12 % reduction in temperature
Chintakrind have a side length of W/cm2 to
Paraffin nano- 11 wt. % of module compared with pure
a et al [27] 5.08 cm and a total 19.3
fiber PCM.
volume of 131 cm3 W/cm2
 The reason behind this is, due to the encapsulation of PCM, the shell offers resistance to
heat flow. This is similar to the phenomenon taking place in the case of heating. Addition of GnP
to the encapsulated samples reduces the cooling. Thus, the above experimental observation
proves the fact that the addition of GnP expedites the heat transfer by reducing the inter-spatial
heat resistance within the adjacent encapsulated PCM spheres.

Fig.14. Schematic representation of mechanism behind the enhanced heat transfer in ME PCM

with GnP addition.

 Fig.15. Effect of GnP in ME PCM on the base temperature of heat sink during cooling

The recovery time of heat sink is also significant for its cycles of operation. Fig.15 shows
the temperature variation of heat sink after switching off the heater. The heat sink temperature
starts decreasing with time and attains equilibrium with the RT. At the early stage of cooling, the
temperature drops quickly from 80 – 60 °C after which the rate of reduction in temperature is
comparatively less. In the case of GnP added PCM, the temperature drop in the base of heat sink
becomes more pronounced as compared to the heat sink with pure PCM, and the temperature
drop is increased with increase in GnP wt.%. As explained earlier, due the encapsulation, the
thermal contact between the encapsulated PCM gets reduced due to its spherical shape. The
presence of GnP expedite the heat transferwithin the PCM by creating a conductive path in
between the adjacent encapsulated PCM and hence the heat releases more quickly from the bulk
PCM.
4. Uncertainty measurements

In this study, the primary parameter measured was temperature for evaluating the
properties such as heat storage and release rate, enthalpy of phase transition, the temperature of
mass degradation and heat transfer performance in the heat sink. The major contributor to the
uncertainty in experimental results was the uncertainty involved in temperature measurement by
the thermocouples, the phase transition temperature of PCM by DSC measurement, the enthalpy
value by DSC measurement and thermal conductivity value by LFA equipment.
The thermocouples used were K-type (OMEGA Engineering Inc., USA) and had an
accuracy of ±0.50 ºC in the range of 0-200 ºC. The LFA equipment has an accuracy value of ± 5
% in thermal conductivity measurement. The phase transition temperature and enthalpy change
of the PCM measured using DSC analysis were with an equipment accuracy of ± 0.20 ºC in
temperature and ± 2 % in enthalpy measurement. The equipment had a sensitivity of 0.2 mg in
sample weighing. Repeated experiments were conducted to observe the uncertainty in
repeatability of measurement. The heat sink assembly kept in a sizeable convective enclosure
ensured the natural convection and the external disturbance throughout the experiments was
minimized.
To evaluate the repeatability and reproducibility of the measured data, three separate runs at
different times are carried out. For a parameter, the total uncertainty (µ measure) is estimated by
considering the repetition uncertainty (µrep) and the equipment uncertainty (µeqp) [33]. The
repetition uncertainty is fixed by the statistical analysis of the measure data and the equipment
uncertainty is related to the accuracy of the instrument in the measuring range. The uncertainty in
measurement estimated as :

(1)

Where, µrep µeqp can be calculated as,

µrep = (1.a)

µeqp = (1.b)

Where, S - standard deviation

n - number of repeated measured data

 a - half of the equipment accuracy

Using above Eqs.(1-1.b) the uncertainty in measurement was calculated. The uncertainties

obtained for the measured parameter are listed in the Table 3.

Table 3 Uncertainty in measurement.

Equipment Parameter Accuracy Uncertainty Uncertainty Uncertainty

measured of of in
repetition equipment measurement
(µrep) (µeqp) (µ measure)

K-Type Heat sink ± 0.5 °C 0.22 0.14 0.26

Thermocouple temperature,

Fluke 15B, Voltage 1%+ 3 V 0.03 0.49 0.49

USA

Fluke 15B, Current 1.5%+ 3 A 0.02 0.79 0.79

USA

DSC Analysis Phase transition ± 0.2 °C 0.11 0.05 0.12

temperature, °C

Phase transition ± 2% 0.27 0.67 0.72

DSC Analysis Enthalpy, J/g

Thermal
conductivity,
LFA ± 5% 0.010 0.005 0.011
W/mK

5. Conclusions

This paper investigated the performance of GnP laden microencapsulated( ME/GnP )

paraffin with polyurethane shell in TES based heat sink. The microcapsules were prepared by in-
situ polymerization. The TGA and DSC analysis showed that the encapsulation contains 54 to 56
wt.% of paraffin within the polyurethane shell. The FT-IR analysis verifies the chemical
compatibility of the PCM. The SEM and PSD results showed that the MEPCM has a spherical
shape with capsule size in the range of 60 - 65µm. The TGA results showed that the prepared
ME PCM were thermally stable up to 200 °C. The thermal conductivity of the ME PCM was
increased from 0.192 W/mK to 0.211 W/mK, 0.221 W/mK and 0.379 WmK with GnP addition.
Addition of GnP (0.5, 1 and 3 wt.%) in the PCM increased the thermal response rate during
charging and discharging of PCM. The composite PCM responded quickly during heating and
cooling. The thermal response rate increased up to 11.1, 22.2 and 29.6 % at the set point
temperature of 60 °C during heating with GnP loading. The heat transfer performance of heat
sink for both the encapsulated and GnP added PCM were evaluated experimentally. The
presence of MEPCM delayed the temperature rise of the heat sink by 22.5% up to a temperature
of 80 °C. Moreover, the effect of GnP addition with the MEPCM in enhancing the heat transfer
was observed. The addition of GnP enhanced the heat transfer and as an effect, the time taken to
reach 80 °C gets delayed by 3, 9 and 18% with 0.5, 1 and 3 wt.% for 10W heat load input
respectively. Moreover, for the higher heat value of 15W and 20W, the percentage delay was 4.3,
8 and 15 % and 2.8, 5.6 and 10.9 % respectively. The presence of ME PCM reduced the TRR of
the heat sink from 0.83 °C/min to 0.59 °C/min in the temperature range of 60-80 °C.
Furthermore, the addition of GnP again dragged down the TRR for all the observed temperature
ranges. The comparison of thermal conductance shows that the wt.% of GnP in the ME PCM
increases the thermal conductance and hence the heat transfer with the heat sink. Moreover, the
recovery time during cooling of heat sink also gets reduced significantly with GnP loading which
facilitates the heat sink to be ready for the next cycle of operation. Furthermore, it is interesting
to conduct an expansion work with higher conductivity shell encapsulated PCM based on the
present investigations. The result and discussion of this investigation pointing to the scope of
mentioned future work.
Acknowledgement

This research was supported by the Department of Electronics and Information Technology
(DEITY) funded by The Ministry of Communications and Information Technology, Government
of India.

Declarations of interest

None

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 Graphical abstract

Graphical abstract: Illustrates the steps involved in the process of micro encapsulation of PCM
by In-situ polymerization. To enhance the heat transfer, Graphene nanoplatelets of 0.5, 1 and 3
wt.% was added and dispersed homogenously by low energy ball milling process. The
morphology, shape and the size of the micro capsules were characterized by SEM analysis. The
shape stability of the prepared microcapsules was tested with same temperature exposure. The
presence of GnP reduces the internal heat resistance by filling the voids between the
microcapsules. The heat sink temperature rise rate gets delayed by the composite PCM and the
rate is depend up on the GnP wt.% in the PCM.
Highlights

 Paraffin is microencapsulated with polymer shell by In-situ polymerization.

 Graphene nano-platelets (GnP) of 0.5, 1 and 3 wt. % added to enhance the heat

transfer between the encapsulated PCM.

 The thermal conductance the heat sink increased with GnP wt. %.

 The temperature rise rate (TRR) of heat sink reduced from 1.1 °C/min to 0.85

°C/min at the temperature range of 40 - 60 °C

 The GnP in the encapsulated PCM reduced the recovery time of heat sink.