applied

sciences
Article
Thermal Performance Evaluation of Fatty Acid Ester
and Paraffin Based Mixed SSPCMs Using Exfoliated
Graphite Nanoplatelets (xGnP)
Hwayoung Lee, Su-Gwang Jeong, Seong Jin Chang, Yujin Kang, Seunghwan Wi and
Sumin Kim *
Building Environment & Materials Lab, School of Architecture, Soongsil University, Seoul 156-743, Korea;
yoooung@ssu.ac.kr (H.L.); wjdtnrhkd@ssu.ac.kr (S.-G.J.); tjdwls329@ssu.ac.kr (S.J.C.); jin_002@ssu.ac.kr (Y.K.);
dnltmdghks@ssu.ac.kr (S.W.)
* Correspondence: skim@ssu.ac.kr; Tel.: +82-2-820-0665; Fax: +82-2-816-3354

Academic Editor: Mohammed Mehdi Farid

Received: 22 February 2016; Accepted: 4 April 2016; Published: 12 April 2016

Abstract: Phase change materials (PCMs) have been used in various fields including the materials
of buildings. In this research, mixed shape-stabilized PCMs (Mixed SSPCMs) were prepared by
impregnating coconut oil and n-hexadecane into exfoliated graphite nanoplatelets (xGnP) through
a vacuum impregnate method. Coconut oil is fatty acid ester PCM which is relatively economical
in comparison to other PCMs, and n-hexadecane is paraffin PCM that has high latent heat capacity.
Drawbacks include leakage in a liquid state and low thermal conductivity resolved by xGnP.
When preparing Mixed SSPCMs, coconut oil and n-hexadecane were impregnated at different
proportions, namely 70:30, 50:50, 30:70 wt %. Mixed SSPCMs were analyzed through SEM, FT-IR,
DSC, TGA and TCi. As a result, we confirmed the microstructure, chemical stability, thermal
properties, thermal stability and thermal conductivity of Mixed SSPCMs. Latent heat capacity of
Mixed SSPCMs were 89.06, 104.30 and 124.50 J/g while those of SSPCMs containing single PCM were
82.34 and 96.40 J/g. Thermal conductivity of Mixed SSPCMs was more than 284% higher than that of
pure coconut oil and n-hexadecane. Finally, we confirmed that coconut oil and n-hexadecane were
impregnated into xGnP, and the Mixed SSPCMs have high thermal durability.

Keywords: mixed SSPCM; fatty acid ester PCM; paraffin PCM; thermal performance; thermal storage;
xGnP; impregnation

1. Introduction
Thermal energy storage (TES) for space heating and cooling of buildings is becoming more and
more important due to the rising cost of fossil fuels and environmental concerns. It saves premium
fuels and leads to the system being more cost effective by reducing the waste of energy and capital
costs [1,2]. Sensible heat storage (SHS) using thermal mass of the structural elements is the most
common way to storage thermal energy in buildings. It can be used for the storage and release of
thermal energy in a passive way. However, in comparison to latent heat storage, a much larger volume
of material is required to store the same amount of energy by changing the phase of a storage material.
Therefore, an effective way to reduce the building’s energy consumption for heating and cooling is by
incorporating phase change materials (PCMs) in latent heat thermal energy storage (LHTES) systems
of various building elements such as walls, windows, ceilings and floors [3,4].
PCMs are generally divided into organic PCM, inorganic PCM, and eutectic PCM. Typical inorganic
PCMs include water, aqueous solution, salt hydrate, and molten salt, while organic PCMs include
paraffin, fatty acid, ester and sugar alcohol. Besides, eutectic mixtures of two or more miscible pure

Appl. Sci. 2016, 6, 106; doi:10.3390/app6040106 www.mdpi.com/journal/applsci

Appl. Sci. 2016, 6, 106 2 of 10

PCM constituents that solidify simultaneously out of the liquid at a minimum freezing point have
been widely developed to enrich the diversity of PCMs [5].
Commonly, inorganic PCMs suffer from decomposition and supercooling, which can further affect
their phase change properties [6]. In contrast, organic PCMs are more stable and incorrodible than
inorganic PCMs in the surrounding container [7]. In particular, paraffin PCMs are more widely used for
application in building because they possess large latent heat capacity, low vapor pressure, and good
thermal stability [8,9]. Also, many fatty acid ester PCMs have lower latent heat capacity than paraffin
PCMs, but most of them are more commercial and economical than paraffin PCMs [10]. However,
fatty acid ester and paraffin PCMs also have low thermal conductivity and leakage of liquid problems
that disturb their application to energy storage [11–13]. Manufacturing shape-stabilized PCM (SSPCM)
by impregnating the PCMs into high thermal conductivity materials such as carbon materials with
porous structure resolves these problems. Exfoliated graphite nanoplatelets (xGnP) which are porous
and nano-sized carbon materials are suitable [14–18]. Additionally, they have a layered structure and
are very cost effective. The low coefficient of thermal expansion of xGnP, is a desirable property for
composite structural applications [19–22].
In this research, we prepared Mixed SSPCMs by impregnating two types of PCMs, coconut
oil and n-hexadecane into the xGnP at different proportions to improve thermal performance and
investigate the difference between their performances. We used a vacuum impregnation process that
guarantees high heat storage of fatty acid ester PCM and paraffinic PCM due to capillary forces and
surface tension forces during the incorporation process [23]. Further, we analyzed the microstructure,
chemical stability, thermal storage performance, thermal stability, and thermal conductivity of the
Mixed SSPCMs by using SEM, FT-IR, DSC, TGA, and TCi.

2. Experimental

2.1. Materials
In this research, we used fatty acid ester PCM and paraffin PCM, which possess different melting
points. Fatty acid ester PCM is coconut oil and paraffin PCM is n-hexadecane in this research.
The melting point and latent heat capacity at solid-liquid melting of pure coconut oil are 26.78 ˝ C and
110.4 J/g, and those of pure n-hexadecane are 20.84 ˝ C and 254.7 J/g [23,24]. The coconut oil is obtained
from the Korea Similac Corporation in Gyeonggi, South Korea, and the n-hexadecane is obtained
from the Celsius Korea Corporation in Seoul, South Korea. The exfoliated graphite nanoplatelets
(xGnP) were arranged from sulfuric acid-intercalated expandable graphite (3772) obtained from Asbury
Graphite Mills, Inc., in Asbury, NJ, USA by applying a cost- and time-effective exfoliation process
initially proposed by Drzal's group [19]. Table 1 shows the physical properties of coconut oil and
n-hexadecane, and Table 2 shows those of xGnP.

Table 1. Physical properties of coconut oil and n-hexadecane [23,24].

Value
Property
Coconut Oil n-Hexadecane
Melting point (˝ C) 26.78 20.84
Latent heat of melting (J/g) 110.4 254.7
Thermal conductivity (W/mK) 0.321 0.154

Table 2. Physical properties of xGnP [14].

Property Value
Surface area (m2 /g) 20.41
Bulk density (g/cm3 ) 0.0053–0.010
Pore volume (cm3 /g) 0.081
Thermal conductivity (W/mK) 2–300
Specific heat capacity (J/kgK) 710
Appl. Sci. 2016, 6, 106 3 of 10

2.2. Preparation
We prepared the Mixed SSPCMs by impregnating the coconut oil and n-hexadecane into xGnP
at different proportions: 70:30 wt %, 50:50 wt %, and 30:70 wt %. To prepare the Mixed SSPCMs,
we mixed the coconut oil and n-hexadecane in each proportion at room temperature and strongly
stirred. The xGnP was then dried at 105 ˝ C for 24 h in a vacuum oven. Next, we used the vacuum
impregnation process according to following procedure. The xGnP was put inside a filtering flask,
which was connected to a water tromp apparatus to evacuate air from the porous structure. Then,
a valve between the flask and a container with a total of 100 g of liquid coconut oil and n-hexadecane
was opened, to allow the liquid PCMs to flow into the flask and cover the nanoparticles of xGnP.
After the vacuum process was continued for 90 min, the air was allowed to enter the flask again, to
force the liquid PCMs to penetrate the porous structure of the xGnP. In this process, excess PCMs
which were not impregnated remained in the flask. Those were removed through a filtering process.
The·coconut oil + n-hexadecane Mixed SSPCMs in the colloidal state were filtered through 1 µm
filter paper until a granule type of sample appeared on the filter paper, and then those were dried in
a vacuum drier at 80 ˝ C for 48 h.

2.3. Characterization Techniques

The microstructure of the Mixed SSPCMs were analyzed through scanning electron microscopy
(SEM, JSM-6360A, JEOL, Tokyo, Japan) at room temperature. The SEM images of the samples
were obtained with an accelerating voltage of 12 kV and a working distance of 12 mm, and the
samples were gold coated at a few nanometers in thickness to increase their electrical conductivity [19].
Fourier transform infrared spectroscopy (FT-IR, Nicolet 6700, Thermo Scientific, Waltham, MA, USA)
was used to confirm the change of chemical groups of the Mixed SSPCMs at room temperature.
Clear potassium bromide (KBr) disks were made from powder and used as backgrounds. The Mixed
SSPCMs were analyzed over the range of 650–4000 cm´1 , with a spectrum resolution of 8 cm´1 .
All spectra were averaged over 32 scans. This analysis of the Mixed SSPCMs was performed by
point-to-point contact with a pressure device [25]. Thermal properties of the Mixed SSPCMs, such
as melting and freezing point and latent heat capacities, were analyzed by the differential scanning
calorimetry (DSC, DSC-Q1000, TA instrument, New Castle, PA, USA). The melting and freezing point
were measured by drawing a line at the point of maximum slope of the leading edge of the peak
and extrapolating to the base line, and the latent heats of the Mixed SSPCMs were analyzed as total
by numerical integration of the area under the peaks that represents the solid-solid and solid-liquid
phase transition [17]. The DSC measurements were performed at a 3 ˝ C/min heating and cooling rate
and a temperature range of ´20 to 80 ˝ C. Thermal stability of the Mixed SSPCMs was analyzed by
thermogravimetric analysis (TGA, Q-5000 IR, TA Instruments, New Castle, PA, USA) on approximately
11–14 mg of the samples within the range from 20 to 600 ˝ C at a heating rate of 10 ˝ C/min under
a nitrogen flow of 20 mL/min. The TGA was measured with the composites placed in a high quality
nitrogen (99.5% nitrogen, 0.5% oxygen content) atmosphere to prevent unwanted oxidation [26].
The thermal conductivity of the Mixed SSPCMs were measured by TCi thermal conductivity analyzer
(C-Therm Technologies Ltd., Fredericton, NB, Canada) at the temperature of 10 ˝ C. The TCi is a device
for conveniently measuring the thermal conductivity of a small sample by using the Modified Transient
Plane Source (MTPS) method. It is the advantage of the TCi that can measure the thermal conductivity
of materials in the states of solid, liquid, powder, and mixed [27].

3. Results and Discussion

3.1. Microstructure of the Fatty Acid Ester and Paraffin Based Mixed SSPCMs
Scanning electron microscopy (SEM) observations were performed for the coconut oil + n-hexadecane
Mixed SSPCMs. Figure 1 shows the microstructure of the Mixed SSPCMs and xGnP that were
investigated by SEM analysis. Figure 1a–c show the Mixed SSPCMs and Figure 1d shows the porous
Appl. Sci. 2016, 6, 106 4 of 10

structure of the xGnP. We found some nano particles of xGnP in Figure 1d. Through the SEM4 of 10 
Appl. Sci. 2016, 6, 106  analysis,
we confirmed that the coconut oil and n-hexadecane were fully filled into the xGnP. As shown in
analysis,  we  confirmed  that  the  coconut  oil  and  n‐hexadecane  were  fully  filled  into  the  xGnP.  As 
Figure 1a–c, liquid PCMs were well impregnated into the each layer of the xGnP. The porous structure
shown  in  Figure  1a–c,  liquid  PCMs  were  well  impregnated  into  the  each  layer  of  the  xGnP.  The 
of the xGnP is good for impregnation of the PCMs. The microstructure of the Mixed SSPCMs are
porous structure of the xGnP is good for impregnation of the PCMs. The microstructure of the Mixed 
similar to one another, regardless of the ratio of the PCMs. Consequently, heat storage of the PCMs are
SSPCMs are similar to one another, regardless of the ratio of the PCMs. Consequently, heat storage 
maintained in the Mixed SSPCMs despite loading the xGnP.
of the PCMs are maintained in the Mixed SSPCMs despite loading the xGnP. 

 
(a)  (b)

 
(c)  (d)
Figure 1. SEM images of (a) 70 wt % coconut oil + 30 wt % n‐hexadecane Mixed shape‐stabilized phase 
Figure 1. SEM images of (a) 70 wt % coconut oil + 30 wt % n-hexadecane Mixed shape-stabilized phase
change materials (SSPCM), (b) 50 wt % coconut oil + 50 wt % n‐hexadecane Mixed SSPCM, (c) 30 wt 
change
%  materials (SSPCM,
coconut  oil  +  70  wt (b) 50 wt % coconut
%  n‐hexadecane  oilSSPCM, 
Mixed  % n-hexadecane
+ 50 wt and  (d)  exfoliated Mixed SSPCM,
graphite  (c) 30 wt %
nanoplatelets 
coconut oil
(xGnP). + 70 wt % n-hexadecane Mixed SSPCM, and (d) exfoliated graphite nanoplatelets (xGnP).

3.2. FT‐IR Analysis of the Fatty Acid Ester and Paraffin Based Mixed SSPCMs 
3.2. FT-IR Analysis of the Fatty Acid Ester and Paraffin Based Mixed SSPCMs
MostMost of the edible oils, including coconut oil, are composed of triglycerides. As shown in Figure 
of the edible oils, including coconut oil, are composed of triglycerides. As shown in Figure 2,
2, a triglyceride is a fatty acid ester formed by esterifing glycerol with three fatty acids. Coconut oil 
a triglyceride is a fatty acid ester formed by esterifing glycerol with three fatty acids. Coconut oil
consists of medium‐chain triglycerides (MCTs), which are triglycerides that possess 8 to 12 carbons 
consists of medium-chain triglycerides (MCTs), which are triglycerides that possess 8 to 12 carbons of
of fatty acids. So the coconut oil contains –CH3, –CH2, C=O, and C–O bonding. As shown in Figure 3, 
fatty the FT‐IR absorption spectrum of the Mixed SSPCMs appears with nearly the same absorption peaks. 
acids. So the coconut oil contains –CH3 , –CH2 , C=O, and C–O bonding. As shown in Figure 3,
the FT-IR
There absorption spectrum
are  absorption  peaks of
of the Mixed SSPCMs
2919–2920  cm−1  and appears
2850–2851 with
cm−1nearly the same
  occurred  by  –CHabsorption peaks.
3  and  –CH2 
Therebonding, and 1735–1744 cm 2919–2920 cm´1−1and
are absorption peaks of−1 and 1149–1160 cm 2850–2851 cm ´1 occurred by –CH and –CH
 occurred by C=O, and C–O bonding of ester groups. 
3 2
bonding, and 1735–1744
However,  cm
the  30  wt  %  ´1 andoil 
coconut  1149–1160
+  70  wt  % cm ´1 occurred
n‐hexadecane  by C=O,
Mixed  and
SSPCM  C–O
that  bonding
contains  of ester
a  small 
percentage of coconut oil gives rise to small peaks in C=O, and C–O bonding of ester groups. The n‐
groups. However, the 30 wt % coconut oil + 70 wt % n-hexadecane Mixed SSPCM that contains
hexadecane is a paraffin PCM that is consists of 16 carbons and 34 hydrogens of single chain. The 
a small percentage of coconut oil gives rise to small peaks in C=O, and C–O bonding of ester groups.
condensed structure formula of that is CH
The n-hexadecane (CH2)14CHof
is a paraffin PCM that is3consists 3. So the n‐hexadecane also generate the peaks 
16 carbons and 34 hydrogens of single chain.
of –CH3 and –CH2 bonding. The FT‐IR absorption peaks of the Mixed SSPCMs are shown in Table 3. 
The condensed structure formula of that is CH3 (CH2 )14 CH3 . So the n-hexadecane also generate the
In this experiment, we mixed two types of PCMs and impregnated the mixed PCMs into xGnP 
peaks of –CH3 and –CH2 bonding. The FT-IR absorption peaks of the Mixed SSPCMs are shown
to enhance thermal performance. Through the FT‐IR analysis, we confirmed the chemical stability of 
in Table 3.
the Mixed SSPCMs. As shown the result, the both absorption peaks of coconut oil and n‐hexadecane 
In this experiment, we mixed two types of PCMs and impregnated the mixed PCMs into xGnP
are appeared in all Mixed SSPCMs. So we reason that the coconut oil and n‐hexadecane did not join 
to enhance thermal
together  performance.
chemically.  Through
In  addition,  the FT-IR
by  reviewing  analysis,
previous  work we confirmed
[24,28],  the chemical
we  confirmed  stability of
the  chemical 
the Mixed SSPCMs. As shown the result, the both absorption peaks of coconut oil and n-hexadecane
are appeared in all Mixed SSPCMs. So we reason that the coconut oil and n-hexadecane did not join
Appl. Sci. 2016, 6, 106 5 of 10

together chemically. In addition, by reviewing previous work [24,28], we confirmed the chemical
Appl. Sci. 2016, 6, 106  5 of 10 
Appl. Sci. 2016, 6, 106  5 of 10 
stability of the PCMs in xGnP. According to [24,28], the FT-IR spectrum of coconut oil/xGnP and
stability of the PCMs in xGnP. According to [24,28], the FT‐IR spectrum of coconut oil/xGnP and n‐
n-hexadecane/xGnP SSPCMs is the same as the each pure PCMs. This means that there are not
stability of the PCMs in xGnP. According to [24,28], the FT‐IR spectrum of coconut oil/xGnP and n‐
hexadecane/xGnP SSPCMs is the same as the each pure PCMs. This means that there are not chemical 
chemical incorporations between coconut oil and xGnP, and n-hexadecane and xGnP. Therefore, we
hexadecane/xGnP SSPCMs is the same as the each pure PCMs. This means that there are not chemical 
incorporations 
reasonably measured between 
incorporations  between  that coconut 
the coconut
coconut  oil 
oil oiland 
and  xGnP,  and 
xGnP,  and n‐hexadecane 
+ n-hexadecane n‐hexadecane 
Mixed SSPCMs and 
are
and  xGnP.  Therefore, 
chemically
xGnP.  we we 
stable.
Therefore, 
reasonably measured that the coconut oil + n‐hexadecane Mixed SSPCMs are chemically stable. 
reasonably measured that the coconut oil + n‐hexadecane Mixed SSPCMs are chemically stable. 

   
Figure 2. Chemical formation of triglyceride by esterification of glycerol with fatty acids. 
Figure 2. Chemical formation of triglyceride by esterification of glycerol with fatty acids. 
Figure 2. Chemical formation of triglyceride by esterification of glycerol with fatty acids.

-CH 3 / -CH 2
-CH 3 / -CH 2 70wt% coconut oil + 30wt% n-hexadecane Mixed SSPCM
70wt% coconut oil + 30wt% n-hexadecane Mixed SSPCM
50wt% coconut oil + 50wt% n-hexadecane Mixed SSPCM
50wt%coconut
30wt% coconutoiloil+ +70wt%
50wt% n-hexadecane
n-hexadecane Mixed
Mixed SSPCM
SSPCM
30wt% coconut oil + 70wt% n-hexadecane Mixed SSPCM
C=O C-O
C=O C-O
Absorbance
Absorbance

4000 3000 2000 1000

-1
4000 3000 Wavenumbers2000
(cm ) 1000  
-1
Wavenumbers (cm )  
Figure 3. Fourier transform infrared spectroscopy (FT-IR) absorption spectra of Mixed SSPCMs.
Figure 3. Fourier transform infrared spectroscopy (FT‐IR) absorption spectra of Mixed SSPCMs. 
Figure 3. Fourier transform infrared spectroscopy (FT‐IR) absorption spectra of Mixed SSPCMs. 
Table 3. FT‐IR absorption spectra peaks of Mixed SSPCMs. 
Table 3. FT-IR absorption spectra peaks of Mixed SSPCMs.
Table 3. FT‐IR absorption spectra peaks of Mixed SSPCMs. 
Bonding  Wave number range (cm−1) 
Bonding Wave Number Range ´1 )
(cm2919–2920 
–CH3 
Bonding  Wave number range (cm −1) 
–CH2  –CH3 2919–2920 2850–2851 
–CH3  2919–2920 
C=O  –CH2 2850–2851 1735–1744 
–CH2  C=O 1735–1744 2850–2851 
C–O  1149–1160 
C=O  C–O 1149–1160 1735–1744 
C–O 
3.3. Thermal Properties Analysis  1149–1160 
3.3. Thermal Properties Analysis
Figure 4 shows the heating and freezing curves from DSC measurements of the coconut oil + n‐
3.3. Thermal Properties Analysis 
hexadecane 
Figure 4 shows Mixed  SSPCMs. 
the heatingTable 
and 4  represents 
freezing the  phase 
curves from transition  temperature of
DSC measurements and  latent 
the heat  oil +
coconut
Figure 4 shows the heating and freezing curves from DSC measurements of the coconut oil + n‐
capacity  of  coconut  oil  +  n‐hexadecane  Mixed  SSPCMs  and  Table  5  represents  those  of  coconut 
n-hexadecane Mixed SSPCMs. Table 4 represents the phase transition temperature and latent heat
hexadecane  Mixed  SSPCMs.  Table  4  represents  the  phase  transition  temperature  and  latent  heat 
oil/xGnP and n‐hexadecane/xGnP SSPCMs. As shown in Figure 4, the phase transition of the Mixed 
capacity of coconut oil + n-hexadecane Mixed SSPCMs and Table 5 represents those of coconut
capacity 
SSPCMs  of during 
coconut  oil  + and 
heating  n‐hexadecane  Mixed at 
melting  occurred  SSPCMs  and 
the  lower  Table  5  represents 
temperature  those 
of  the  each  of  coconut 
melting  and 
oil/xGnP and n-hexadecane/xGnP SSPCMs. As shown in Figure 4, the phase
oil/xGnP and n‐hexadecane/xGnP SSPCMs. As shown in Figure 4, the phase transition of the Mixed transition
freezing point of the coconut oil and n‐hexadecane. The Mixed SSPCMs display a tendency that the  of the Mixed
SSPCMs during heating and
and melting
melting occurred
occurred  at
at  the lower temperature 
temperatureof  ofthe 
theeach 
more the Mixed SSPCM contains a high rate of n‐hexadecane, the greater the melting and freezing 
SSPCMs  during  heating  the  lower  eachmelting 
melting and
and 
freezing of the coconut oil and n-hexadecane.
points. The melting temperatures at peak points of the Mixed SSPCMs were 12.53 °C, 14.51 °C, and  the
point The Mixed SSPCMs display
freezing point of the coconut oil and n‐hexadecane. The Mixed SSPCMs display a tendency that the  a tendency that
more the Mixed SSPCM contains a high rate of n-hexadecane, the greater the melting and freezing
16.92 °C, while the freezing temperatures at peak points of them were 5.55 °C, 6.54 °C, and 10.31 °C. 
more the Mixed SSPCM contains a high rate of n‐hexadecane, the greater the melting and freezing 
points. The melting temperatures at peak points of the Mixed SSPCMs were 12.53 ˝ C, 14.51 ˝ C, and
The difference between melting and freezing points of the Mixed SSPCMs is because of supercooling 
points. The melting temperatures at peak points of the Mixed SSPCMs were 12.53 °C, 14.51 °C, and 
16.92 of PCMs. 
˝ C, while the freezing temperatures at peak points of them were 5.55 ˝ C, 6.54 ˝ C, and 10.31 ˝ C.
16.92 °C, while the freezing temperatures at peak points of them were 5.55 °C, 6.54 °C, and 10.31 °C. 
The difference between melting and freezing points of the Mixed SSPCMs is because of supercooling 
of PCMs. 
 Appl. Sci. 2016, 6, 106  6 of 10 

The noticeable result in this research is the latent heat capacity of Mixed SSPCMs. The latent heat 
capacities of the Mixed SSPCMs were 89.06, 104.30, and 124.50 J/g during melting, and those of during 
freezing were 92.82, 106.20, and 123.40 J/g. Although these values are lower than pure PCMs because 
Appl. Sci. 2016, 6, 106 6 of 10
3‐dimentional network structure of xGnP disturbs the heat flow of PCMs, these are the high values 
in consideration of the latent heat capacities of coconut oil/xGnP and n‐hexadecane/xGnP SSPCMs 
The difference between melting and freezing points of the Mixed SSPCMs is because of supercooling
that contain single PCM. The latent heat capacities of the Mixed SSPCMs also appear to follow the law 
of that the more the Mixed SSPCM contains a high rate of n‐hexadecane, the greater the latent heat capacity. 
PCMs.

70wt% coconut oil + 30wt% n-hexadecane Mixed SSPCM

50wt% coconut oil + 50wt% n-hexadecane Mixed SSPCM
30wt% coconut oil + 70wt% n-hexadecane Mixed SSPCM

1
Heat Flow(W/g)

Cooling Curve

Heating Curve

-1

-20 0 20 40 60 80
o
Temperature( C)  
Figure 4. Differential scanning calorimetry (DSC) graphs of Mixed SSPCMs.
Figure 4. Differential scanning calorimetry (DSC) graphs of Mixed SSPCMs. 

Table 4. DSC analysis of Mixed SSPCMs.

Table 4. DSC analysis of Mixed SSPCMs. 

Mixed SSPCM (coconut oil: 
Mixed SSPCM (Coconut Latent Heat (J/g) 
Latent Heat (J/g)
Melting point (°C) 
Melting Point (˝ C) Freezing point (°C) 
Freezing Point (˝ C)
n‐hexadecane) 
Oil: n-hexadecane) Melting  Freezing 
Melting Freezing
70:30 (wt %)  12.53  5.55  89.06  92.82 
70:30 (wt %)
50:50 (wt %)  12.53
14.51  5.55
6.54  89.06
104.30  92.82
106.20 
50:50 (wt %) 14.51 6.54 104.30 106.20
30:70 (wt %)  16.92  10.31  124.50  123.40 
30:70 (wt %) 16.92 10.31 124.50 123.40

Table 5. DSC analysis of coconut oil/xGnP and n‐hexadecane/xGnP SSPCMs [24,28]. 
Table 5. DSC analysis of coconut oil/xGnP and n-hexadecane/xGnP SSPCMs [24,28].
Latent Heat (J/g) 
SSPCM  Melting point (°C)  Freezing point (°C) 
Melting 
Latent Heat (J/g)Freezing 
SSPCM Melting Point (˝ C) Freezing Point (˝ C)
Coconut oil/xGnP  26.93  14.95  82.34  Freezing
Melting 77.64 
n‐hexadecane/xGnP  21.80  14.60  96.40  94.80 
Coconut oil/xGnP 26.93 14.95 82.34 77.64
n-hexadecane/xGnP 21.80 14.60 96.40 94.80
3.4. Thermal Stability Analysis 

TheTGA  analysis 
noticeable was  in
result performed  for  thermal 
this research stability 
is the latent heatof  the  coconut 
capacity oil  + 
of Mixed n‐hexadecane 
SSPCMs. Mixed 
The latent heat
SSPCMs at temperatures of 20 to 600 °C. Because xGnP is a carbon material that has high thermal 
capacities of the Mixed SSPCMs were 89.06, 104.30, and 124.50 J/g during melting, and those of during
durability,  it  does  not  decompose  at  temperatures  under  600  °C.  So  only  the  coconut  oil  and  n‐
freezing were 92.82, 106.20, and 123.40 J/g. Although these values are lower than pure PCMs because
hexadecane of the Mixed SSPCMs decompose in the test temperature range. Figure 5 and Table 6 
3-dimentional network structure of xGnP disturbs the heat flow of PCMs, these are the high values in
show the TGA results of the Mixed SSPCMs. As shown in Figure 5, the TGA graphs of the all Mixed 
consideration of the latent heat capacities of coconut oil/xGnP and n-hexadecane/xGnP SSPCMs that
SSPCMs appear 2 degradation curves caused by thermal decomposition. The first degradation curves 
contain single PCM. The latent heat capacities of the Mixed SSPCMs also appear to follow the law that
of  the  graphs  represent  the  decomposition  of  n‐hexadecane.  The  first  degradation  peaks  of  the  n‐
thehexadecane 
more the Mixed SSPCM
occurred  contains
at  the  a high rate
temperature  of n-hexadecane,
of  165.14  °C,  172.62  the
°C, greater the latent
and  178.38  heatsecond 
°C.  The  capacity.
degradation curves of the graphs represent the decomposition of coconut oil. The second degradation 
3.4. Thermal Stability Analysis
peaks  of  the coconut  oil  occurred at  temperatures  of  363.68  °C, 357.68 °C, and  339.79  °C.  In  other 
TGA analysis was performed for thermal stability of the coconut oil + n-hexadecane Mixed SSPCMs
words, the coconut oil has a greater thermal durability than the n‐hexadecane. 
at temperatures of 20 to 600 ˝ C. Because xGnP is a carbon material that has high thermal durability, it does
not decompose at temperatures under 600 ˝ C. So only the coconut oil and n-hexadecane of the Mixed
SSPCMs decompose in the test temperature range. Figure 5 and Table 6 show the TGA results of the
Mixed SSPCMs. As shown in Figure 5, the TGA graphs of the all Mixed SSPCMs appear 2 degradation
curves caused by thermal decomposition. The first degradation curves of the graphs represent the
Appl. Sci. 2016, 6, 106
Appl. Sci. 2016, 6, 106  77 of 10 
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It is also possible to compute the percentages of impregnated coconut oil and n‐hexadecane in 
decomposition of n-hexadecane. The first degradation peaks of the n-hexadecane occurred at the
xGnP  by  investigating ˝the  total  decomposition  rates.  The  three  Mixed  SSPCMs  appeared  similar 
temperature of 165.14 C, 172.62 ˝ C, and 178.38 ˝ C. The second degradation curves of the graphs
values of total decomposition rate. The total decomposition rate were 71.59%, 70.73%, and 68.53%. In 
represent the decomposition of coconut oil. The second degradation peaks of the coconut oil occurred
the  case  of  the  Mixed  SSPCMs,  xGnP  remained  in  them  although  the  two  PCMs  were  fully 
at temperatures of 363.68 ˝ C, 357.68 ˝ C, and 339.79 ˝ C. In other words, the coconut oil has a greater
decomposed. This means that the two PCMs were impregnated into xGnP, and the Mixed SSPCMs 
thermal durability than the n-hexadecane.
have high thermal durability. 

100 70wt% coconut oil + 30wt% n-hexadecane Mixed SSPCM

50wt% coconut oil + 50wt% n-hexadecane Mixed SSPCM
30wt% coconut oil + 70wt% n-hexadecane Mixed SSPCM

80
68.53

70.73
Weight(%)

60
71.59

40
Decomposition of n-hexadecane

20
Decomposition of coconut oil

0
0 200 400 600
o
Temperature( C)  
Figure 5. Thermogravimetric analysis (TGA) graphs of Mixed SSPCMs.
Figure 5. Thermogravimetric analysis (TGA) graphs of Mixed SSPCMs. 

Table 6. TGA analysis of Mixed SSPCMs.

Table 6. TGA analysis of Mixed SSPCMs. 

Mixed SSPCM (Coconut First peak of 

First Peak of Derivative Second peak of 
Second Peak of Total Decomposition
Mixed SSPCM (coconut oil:  Total decomposition 
Oil: n-hexadecane) Weight (˝ C)
derivative weight  Weight (˝ C)
derivative weight 
Derivative Rate (%)
n‐hexadecane)  rate (%) 
70:30 (wt %) (°C) 
165.14 (°C) 
363.68 71.59
50:50 (wt %)
70:30 (wt %)  172.62
165.14  357.68
363.68  70.73
71.59 
30:70 (wt %) 178.38 339.79 68.53
50:50 (wt %)  172.62  357.68  70.73 
30:70 (wt %)  178.38  339.79  68.53 
It is also possible to compute the percentages of impregnated coconut oil and n-hexadecane in
xGnP by investigating the total decomposition rates. The three Mixed SSPCMs appeared similar values
3.5. Thermal Conductivity Analysis 
of total decomposition rate. The total decomposition rate were 71.59%, 70.73%, and 68.53%. In the
The thermal conductivity analysis of the coconut oil + n‐hexadecane Mixed SSPCMs using TCi 
case of the Mixed SSPCMs, xGnP remained in them although the two PCMs were fully decomposed.
at the temperature of 10 °C is shown in Figure 6. As shown in Figure 6, the thermal conductivities of 
This means that the two PCMs were impregnated into xGnP, and the Mixed SSPCMs have high
the Mixed SSPCMs are 1.70, 1.61, and 1.23 W/mK. The Mixed SSPCMs appear to follow the tendency 
thermal durability.
that the more coconut oil they contain, the greater the thermal conductivity because the pure coconut 
oil  has 
3.5. larger 
Thermal thermal  conductivity 
Conductivity Analysis than  pure  n‐hexadecane.  The  thermal  conductivities  of  pure 
coconut  oil  and  n‐hexadecane  are  0.321  and  0.154  W/mK,  respectively  [23,24].  The  overall  Mixed 
The thermal conductivity analysis of the coconut oil + n-hexadecane Mixed SSPCMs using TCi at
SSPCMs have larger thermal conductivities which are 284% higher than the pure PCMs. This implies 
the temperature of 10 ˝ C is shown in Figure 6. As shown in Figure 6, the thermal conductivities of the
that the xGnP led to an enhancement of the thermal conductivity of coconut oil and n‐hexadecane. 
Mixed SSPCMs are 1.70, 1.61, and 1.23 W/mK. The Mixed SSPCMs appear to follow the tendency that
Consequently, we concluded that Mixed SSPCMs can be usefully applied to various categories such 
the more coconut oil they contain, the greater the thermal conductivity because the pure coconut oil
as buildings. 
has larger thermal conductivity than pure n-hexadecane. The thermal conductivities of pure coconut
oil and n-hexadecane are 0.321 and 0.154 W/mK, respectively [23,24]. The overall Mixed SSPCMs have
larger thermal conductivities which are 284% higher than the pure PCMs. This implies that the xGnP
led to an enhancement of the thermal conductivity of coconut oil and n-hexadecane. Consequently, we
concluded that Mixed SSPCMs can be usefully applied to various categories such as buildings.
Appl. Sci. 2016, 6, 106
Appl. Sci. 2016, 6, 106  8 of 10
8 of 10 

1.70
1.61

1.5

Thermal conductivity (W/mK)

1.23

1.0

0.5

0.0
70 : 30 (wt%) 50 : 50 (wt%) 30 : 70 (wt%)
Mixed SSPCM (coconut oil : n-hexadecane)  
Figure 6. Thermal conductivity of Mixed SSPCMs.
Figure 6. Thermal conductivity of Mixed SSPCMs. 

4. Conclusions 
4. Conclusions
With  the rising
With the rising cost
cost ofof  fossil 
fossil fuels 
fuels and and  additional 
additional environmental 
environmental concerns, 
concerns, the  importance 
the importance of 
of latent
latent heat thermal energy storage (LTES) for space heating and cooling is increasing. Accordingly, 
heat thermal energy storage (LTES) for space heating and cooling is increasing. Accordingly, phase
phase change materials (PCMs) have been used in various fields. Among the PCMs, fatty acid ester 
change materials (PCMs) have been used in various fields. Among the PCMs, fatty acid ester PCMs are
PCMs  are economical
relatively relatively  economical 
and paraffin and  paraffin 
PCMs have PCMs 
higherhave 
latenthigher  latent  heat 
heat capacities capacities 
than other PCMs.than So
other 
we
PCMs. So we prepared coconut oil + n‐hexadecane mixed shape‐stabilized PCMs (Mixed SSPCMs) 
prepared coconut oil + n-hexadecane mixed shape-stabilized PCMs (Mixed SSPCMs) using exfoliated
using exfoliated graphite nanoplatelets (xGnP) through a vacuum impregnation method to enhance 
graphite nanoplatelets (xGnP) through a vacuum impregnation method to enhance their thermal
their thermal performance with supplementation of drawbacks of PCMs such as the leakage in liquid 
performance with supplementation of drawbacks of PCMs such as the leakage in liquid state and
state  and  low 
low thermal thermal  conductivity. 
conductivity. When preparing When  thepreparing  the  Mixed 
Mixed SSPCMs, SSPCMs,  we the
we impregnated impregnated  the 
coconut oil and
coconut oil and n‐hexadecane at different proportions, namely 70:30, 50:50, 30:70 wt %. We analyzed 
n-hexadecane at different proportions, namely 70:30, 50:50, 30:70 wt %. We analyzed the microstructure,
the microstructure, chemical stability, thermal properties, thermal stability, and thermal conductivity 
chemical stability, thermal properties, thermal stability, and thermal conductivity of the samples using
of the samples using SEM, FT‐IR, DSC, TGA, and TCi. Through the SEM analysis, we confirmed that 
SEM, FT-IR, DSC, TGA, and TCi. Through the SEM analysis, we confirmed that both of the PCMs were
both of the PCMs were well impregnated into the porous structure of the xGnP. The FT‐IR graphs 
well impregnated into the porous structure of the xGnP. The FT-IR graphs show all peaks of the bonding
show all peaks of the bonding of both of the PCMs. So, we confirmed that there was no chemical 
of both of the PCMs. So, we confirmed that there was no chemical interaction in the all Mixed SSPCMs.
interaction 
From the DSC in  the  all  Mixed 
analysis, SSPCMs. that
we confirmed From 
thethe  DSC 
latent analysis, 
heat capacitywe ofconfirmed 
the coconutthat  the 
oil + latent  heat 
n-hexadecane
capacity of the coconut oil + n‐hexadecane Mixed SSPCMs was higher than the coconut oil/xGnP and 
Mixed SSPCMs was higher than the coconut oil/xGnP and n-hexadecane/xGnP SSPCMs containing
n‐hexadecane/xGnP SSPCMs containing single PCM. The values of latent heat during melting were 
single PCM. The values of latent heat during melting were 89.06, 104.30, and 124.50 J/g while those of
89.06, 104.30, and 124.50 J/g while those of SSPCMs containing single PCM were 82.34 and 96.40 J/g. 
SSPCMs containing single PCM were 82.34 and 96.40 J/g. The greater the amount of n-hexadecane, the
The  greater 
greater the  amount 
the latent of  n‐hexadecane, 
heat capacity becomes. Also, the we
greater  the  latent 
analyzed heat  capacity 
the decomposition becomes.  Also, 
temperatures and we 
the
analyzed  the  decomposition 
total decomposition rates of Mixedtemperatures  and  the TGA
SSPCMs through total analysis.
decomposition  rates 
As a result, weof  Mixed  SSPCMs 
confirmed that the
through  TGA 
coconut oil andanalysis.  As  a were
n-hexadecane result,  we  confirmed 
impregnated that  the 
into xGnP, and coconut 
the Mixed oil  and  n‐hexadecane 
SSPCMs were 
have high thermal
impregnated 
durability. Theinto  xGnP, 
thermal and  the  Mixed 
conductivities of theSSPCMs  have  high 
Mixed SSPCMs thermal 
analyzed by TCidurability. 
were overThe 
284% thermal 
higher
conductivities  of  the 
than those of pure Mixed 
coconut oilSSPCMs  analyzed 
n-hexadecane. by  TCi  were 
Consequently, weover  284% 
expect higher SSPCMs
the Mixed than  those  of useful
to be pure 
coconut oil n‐hexadecane. Consequently, we expect the Mixed SSPCMs to be useful in applications 
in applications in various fields due to their high thermal performances. For example, considering
in various fields due to their high thermal performances. For example, considering their phase change 
their phase change temperatures, they can be applied to improve energy loss in building design and
temperatures,  they  can 
operation in countries be  aapplied 
with contained,to  improve  energy 
microthermal loss  in  building  design  and  operation  in 
climate.
countries with a contained, microthermal climate. 
Acknowledgments: This work was supported by the National Research Foundation of Korea(NRF) grant funded
by the Korea government(MSIP) (No.NRF-2014R1A2A1A11053829).
Acknowledgments:  This  work  was  supported  by  the  National  Research  Foundation  of  Korea(NRF)  grant 
Author Contributions: Hwayoung Lee, Su-Gwang Jeong, Seong Jin Chang, Yujin Kang and Seunghwan Wi
funded by the Korea government(MSIP) (No.NRF‐2014R1A2A1A11053829). 
designed and conducted the experiment. Sumin Kim designed the project. All authors contributed to the analysis
Author  Contributions:  Hwayoung  Lee,  Su‐Gwang  Jeong,  Seong  Jin  Chang,  Yujin  Kang  and  Seunghwan  Wi 
and conclusion.
designed and conducted the experiment. Sumin Kim designed the project. All authors contributed to the analysis 
Conflicts of Interest: The authors declare no conflict of interest.
and conclusion. 

Conflicts of Interest: The authors declare no conflict of interest. 
Appl. Sci. 2016, 6, 106 9 of 10

Abbreviations
The following abbreviations are used in this manuscript:
PCM Phase change material
SSPCM Shape-stabilized phase change material
xGnP Exfoliated graphite nano platelets
TES Thermal energy storage
SHS Sensible heat storage
LHTES Latent heat thermal energy storage
SEM Scanning electron microscopy
FT-IR Fourier transform infrared spectroscopy
DSC Differential scanning calorimetry
TGA Thermogravimetric analysis

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