Solar Energy Materials & Solar Cells 126 (2014) 42–50

Contents lists available at ScienceDirect

Solar Energy Materials & Solar Cells

journal homepage: www.elsevier.com/locate/solmat

Micro/nano-encapsulated n-heptadecane with polystyrene

shell for latent heat thermal energy storage
Ahmet Sarı n, Cemil Alkan n, Derya Kahraman Döğüşcü, Alper Biçer
Department of Chemistry, Gaziosmanpaşa University, 60240 Tokat, Turkey

art ic l e i nf o a b s t r a c t

Article history: This study is focused on the preparation, characterization and determination of latent heat thermal
Received 3 January 2014 energy storage (LHTES) properties of polystyrene (PS)/n-heptadecane micro/nano-capsules as a novel
Received in revised form encapsulated phase change material (EPCM). The micro/nano-EPCM was synthesized via emulsion
31 January 2014
polymerization method and characterized chemically using Fourier transform infrared (FTIR) spectro-
Accepted 11 March 2014
scopy. The surface morphology and particle size of the micro/nano-capsules were investigated by
particle size distribution (PSD) analysis, polarized optical microscopy (POM) and scanning electron
Keywords: microscopy (SEM) techniques. From differential scanning calorimetry (DSC) analysis, the melting
Micro/nano-EPCM temperature and latent heat of the prepared EPCM were measured as 21.48 1C and 136.89 J/g,
n-heptadecane
respectively. The results of thermogravimetric (TG) analysis showed that the fabricated micro/nano-
Emulsion polymerization
EPCM had good thermal durability. Thermal reliability, chemical stability, thermal conductivity and
Polystyrene
Latent heat phase change reversibility of the micro/nano-EPCM were also studied. All of the results revealed that the
Thermal energy storage fabricated PS/n-heptadecane micro/nano-capsules had promising LHTES potential especially for passive
solar thermal regulation of textile, building, food storage container, medical and electronic materials.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction can appreciably affect their LHTES characteristics. Therefore, these

Phase change materials (PCMs) are very alluring materials for
solar passive LHTES applications because of their capabilities to
store high latent heat per unit volume via phase change at a nearly
invariable temperature [1]. PCMs are classified basically into two
groups as organic and inorganic materials [2]. Organic PCMs are
basically known as paraffin and non-paraffin. Paraffins, i.e, n-alkanes
are chemically inert and reliable, non-corrosive, nontoxic and com-
mercially accessible at rational cost. These kinds of PCMs have also no
phase segregation, low vapor pressure, little or no sub-cooling and
good thermal durability properties, and high latent heats of fusion
and proper solid–liquid phase change temperatures for many LHTES
applications [3–7]. However, they have some drawbacks such as
low thermal conductivity, flammability and high volume change
during phase change [8–10]. Moreover, inorganic PCMs
have large high latent heat capacity and good thermal conductivity,
non-flammable and low-cost properties in comparison with organic
PCMs. On the other hand, they are corrosive and show unstable
phase change behaviors and high sub-cooling degrees, which
n
Corresponding authors.
E-mail addresses: ahmet.sari@gop.edu.tr (A. Sarı),
cemil.alkan@gop.edu.tr (C. Alkan).
problems regarding organic and inorganic PCMs can be overcome
substantially by their encapsulation into a capsule matrix in macro-
[11–13], micro- [14–16] and even nano-sizes [17,18]. The encapsu-
lated PCM (EPCM) is described as a very small bicomponent system
consisting of a core material (PCM), and an outer shell or capsule wall
material. Besides, the use of EPCM helps dramatically to solve the
problems mentioned above; it provides some advantages ordered as
[19–23]: (i) lessening the reactivity of PCM with its close environ-
ment, (ii) expanding the heat transfer area, (iii) preventing the
leakage problem of PCM during its phase changing from solid to
liquid, and (iv) resisting against the volume change of PCM. There-
fore, in recent decades, the utility of EPCMs have drawn attention in
the preparation of thermal regulating fabric [24–29], foam [30,31],
building [32–35] and electronic materials [36]. Recent investigations
have been generally focused on the development of a cheap and
technically feasible process to be used in the fabrication of organic
EPCMs. The most common methods employed to produce organic
EPCMs are complex coacervation, interface, in-situ and emulsion
(or miniemulsion) polymerization methods [37]. Among these,
miniemulsion polymerization is a simple, cheap, stable and eco-
friendly method for the preparation of EPCMs with appropriate
particle sizes [38].
In recent years, several works have been realized about the
encapsulated paraffin wax or n-alkanes as EPCMs using various

http://dx.doi.org/10.1016/j.solmat.2014.03.023
0927-0248/& 2014 Elsevier B.V. All rights reserved.
 A. Sarı et al. / Solar Energy Materials & Solar Cells 126 (2014) 42–50
polymer shells such as melamine–formaldehyde resin [39,40],
urea–formaldehyde resin [41,42], polyurea [43–45], and acrylic-
based polymers [46–50]. Among these, especially melamine–
formaldehyde and urea–formaldehyde resins-based EPCMs may
contain irrepressible residue formaldehyde and isocyanides after
shell forming reaction, which have negative effects on the envir-
onment and health. It is also hard to find useful ways to eradicate
the wastes that are dissociative and can be incessantly released
from the products.
Polystyrene (PS) is one of the aromatic polymers made from
monomer styrene in the chemical industry. It is very inexpen-
sive and therefore commonly used in several trading applica-
tions [51,52]. Polystyrene foams are also suitable for the
insulation of building concrete materials and panel systems. It
has also reasonably good mechanical and protective properties
against the exterior environment. All of these advantages have
facilitated it to be considered as shell material in the fabrication of
new EPCMs [53–56]. Therefore, the utilization scale of PS can be
extended by its usage in different passive solar LHTES systems. n-
Heptadecane known as a hydrocarbon with linear chain has a
desirable melting temperature of about 21 1C and relatively high
latent heat of fusion (about 216 J/g). By taking into account the
literature survey, it can be noted that there is no study about the
preparation and thermal characterization of micro/nano-encapsu-
lated n-heptadecane using PS shell. With this purpose, the present
work was focused on the syhnthesis of PS/n-heptadecane micro/
nano-capsules as novel EPCM using emulsion polymerization
method and chemical characterization by FT-IR spectroscopy techni-
que. The morphology and particle size of the fabricated EPCM were
investigated using SEM, POM and PSD analyses. The LHTES proper-
ties, thermal reliability and thermal durability were determined
using DSC and TG techniques. In addition, the chemical stability,
Fig. 1. Photograph images of experimental apparatus used in the synthesis processes and the obtained final product.
43
thermal conductivity and phase change reversibility properties of the
prepared EPCM were studied.
2. Experimental
2.1. Materials
The chemicals used in the synthesis of micro/nano-capsules
include monomer styrene (Sigma-Aldrich Company), n-heptadecane
(Merck Company), divinylbenzene (Merck Company), Triton X100
(Merck Company), and ferrous sulfate heptahydrate and ammonium
persulphate (Sigma-Aldrich Company). The monomer styrene was
washed three times with an aqueous solution of 10 wt% NaOH prior to
use. The other chemicals were used without further purification.
2.2. Preparation of the PS/n-heptadecane micro/nano-capsules
PS/n-heptadecane micro/nano-capsules were synthesized using
the experimental set-ups shown in Fig. 1(a and b). For the prepara-
tion of PS/n-heptadecane(2:1) micro/nano-capsules, the initial
weight ratio of styrene monomer/n-heptadecane was selected as
about 67%/33% (w/w). According to this ratio, 6.7 g monomer and
2 g divinylbenzene as cross linking agents were mixed with 40 mL
deionized water in the three-necked glass reactor (Fig. 1a). 3.3 g
n-heptadecane in melted state was added to the reactor. This
mixture was homogenized using a homogenizer at 12,000 rpm for
15 min. Then, 3 g Triton X-100 surfactant was added to the mixture
and the solution was re-homogenized at 50 1C for 60 min at the
same homogenization rate. In the next step, 1 mL initiator (freshly
prepared by solving ferrous sulfate heptahydrate (0.15 g) and
ammonium persulphate (0.1 g) into 100 mL deionized water) was
44 A. Sarı et al. / Solar Energy Materials & Solar Cells 126 (2014) 42–50
added to the reaction medium. This resultant blend was stirred to
form an oil-in-water emulsion system at 70 1C for 6 h at 500 rpm
using a mechanical stirrer (Fig. 1b). When the mixture was of the
consistency of honey, the polymerization reaction was ended and it
was filtered using a filter paper. The filtrate was washed several
times and dried at 40 1C in an oven to evaporate the water. The
same synthesis procedure was also repeated in the preparation of
the micro/nano-capsules with two different styrene/n-heptadecane
combinations as 1:1 (corresponds to 50%/50% (w/w)) and 1:2
(corresponds to about 33%/67% (w/w)). The dried product is also
shown in Fig. 1c.
2.3. Characterization of PS/n-heptadecane micro/nano-capsules
The spectroscopic analyses of the synthesized PS/n-heptadecane
micro/nano(1:2)-capsules were carried out using an FT-IR spectro-
photometer (Jasco 430 model). The morphological investigations of
the micro/nano-capsules were made using a SEM (LEO 440 model)
and POM instruments (Leica model). The PSD analysis of the capsules
was performed using a Malvern Mastersizer 2000 instrument in a
diluted dispersion of the particles using deionized water.
Phase change characteristics of PS/n-heptadecane micro/nano
(1:2)-capsules were measured using a Perkin Elmer Jade model
DSC instrument. The DSC peaks were obtained at 3 1C/min heating
and cooling rates. Thermal degradation temperatures of the
n-heptadecane, PS and the PS/n-heptadecane micro/nano(1:2)-
capsules were determined using a TG analyzer (Perkin Elmer
TGA7 model) at a heating rate of 10 1C/min.
In order to achieve knowledge about the thermal reliability and
chemical stability of the prepared PS/n-heptadecane micro/nano
Fig. 2. FT-IR spectra of (a) n-heptadecane, (b) PS, and (c) n-heptadecane/PS micro/nano-capsules(1:2).
(1:2)-capsules, they were also exposed to thermal cycling test
using a thermal cycler (BIOER TC-25/H model). The thermal
cycling test was continued until the number of consecutive
heating/cooling processes was reached 5000.
The temperature–time histories of fabricated PS/n-heptadecane
micro/nano(1:2)-capsules were also determined by using same
experimental set-up and method as given in literature [57]. The
temperature–time variations obtained during the heating and
cooling process of the micro/nano-capsules were recorded using
a data logger (Nova5000 model). In addition, the thermal con-
ductivities of n-heptadecane, PS and PS/n-heptadecane micro/
nano(1:2)-capsules were measured at 25 1C using a thermal
property analyzer (KD2 model).
3. Results and discussion
3.1. Spectroscopic analysis of PS/n-heptadecane
micro/nano-capsules
FT-IR spectroscopy has been commonly used to verify whether
the microcapsules were successfully synthesized or not [29]. In this
study, the FT-IR spectra of n-heptadecane, styrene and the synthe-
sized PS/n-heptadecane micro/nano(1:2)-capsules were taken and
the results were shown in Fig. 2(a–c). In the spectrum of pure
n-heptadecane (Fig. 2a), the peaks at 2956 and 2936, and 2862 cm
1
correspond to the symmetrical C–H stretching vibration of –CH3 and
–CH2 groups, respectively. The peaks observed at 1379 and
1482 cm
1 represent the C–H deformation vibration bands. As seen
from Fig. 2b, the absorption peaks at 3025, 3054 and 3089 cm
1
 A. Sarı et al. / Solar Energy Materials & Solar Cells 126 (2014) 42–50 45

were associated with the C–H stretching vibration bands. The
peak seen at 1412 cm
1 is attributed to the C–H deformation
vibration. The peaks detected at 1522 and 1462 cm
1 were assigned
as aliphatic and aromatic CQC stretching vibration bands of the
benzene ring, respectively. As also clearly seen from the spectrum of
synthesized EPCM (Fig. 2c), the C–H stretching peaks of PS are
overlapped with the same group peaks of n-heptadecane observed in
the range of 2920, 3030 and 3044 cm
1. The peak detected at
1482 cm
1 was regarding CQC stretching vibration bands of the
benzene ring. Moreover, the stretching vibration band related with
the aliphatic vinyl C–H group bonded the benzene ring (at
1522 cm
1) disappeared due to the polymerization of styrene. All
these spectroscopic results confirm the presence of n-heptadecane as
core material and the formation of PS as shell material around the
core material.
3.2. Morphological and PSD analysis of micro/nano-capsules
The morphology and particle size of the synthesized PS/n-
heptadecane micro/nano(1:2)-capsules were investigated using SEM,
POM and PSD analysis methods. The obtained SEM microphotographs
with 30.00  magnification and POM images are presented in
Fig. 3a and b, respectively. As clearly seen from micrographs, the
PS/n-heptadecane micro/nano(1:2)-capsules are not completely
sphere-shaped in appearance and some of them have partially
rough external surface or cluster-structure. On the other hand, the
reason for not being able to observe such type of cluster-structures
in POM micrographs (Fig. 3a) is due to the fact that the particles
were dispersed in aqueous medium prior to taking the micro-
graphs. Moreover, based on the scales on the SEM and POM
micrographs, it can be realized that the fabricated EPCM relatively
consisted of nano-spheres. Thus, such a micro/nano type structure
can present extended surface area, which acts to accelerate heat
transfer rate in LHTES systems [29].
The PSD analysis results (Fig. 4) show the prepared PS/n-
heptadecane micro/nano-capsules have unimodal particle
size distributions with relatively narrow interval (0.01–60 mm,
0.01–30 mm and 0.01–40 mm for EPCM with the combination of
2:1, 1:1 and 1:2, respectively). The particle sizes are mainly in the
range of 1–15 mm, 1–12 mm and 1–20 mm for the prepared EPCMs
with the combination of 2:1, 1:1 and 1:2, respectively. Moreover,
the mean sizes of the particles was found to be 6.3, 6.1 and 5.4 mm.

Fig. 3. (a) POM micrographs of n-heptadecane/PS micro/nano-capsules(1:2) and (b) SEM micrographs n-heptadecane/PS micro/nano-capsules(1:2).

Fig. 4. Particle size distribution of prepared micro/nano-capsules with different styrene/n-heptadecane ratios.
46 A. Sarı et al. / Solar Energy Materials & Solar Cells 126 (2014) 42–50
Fig. 5. DSC thermograms of n-heptadecane and prepared micro/nano-capsules with different styrene/n-heptadecane ratios.
These results showed that the increase in the combination ratio of
the paraffin did not influence the particle sizes of the capsules. In
addition, the particle sizes of the EPCMs determined by PSD
analysis are slightly higher than that observed from SEM and
POM micrographs. This is due to the formation of cluster struc-
tures thus being detected as a single sphere by the PSD instru-
ment. However, even if the prepared PS/n-heptadecane micro/
nano-capsules(1:2) have spheres with cluster state, they can be
used for LHTES purposes.
3.3. Thermal properties and thermal stability of micro/nano-capsules
Fig. 5 shows the DSC curves of n-heptadecane and the micro/
nano-EPCM fabricated at different monomer/PCM ratios. The
LHTES properties obtained for n-heptadecane and the micro/
nano-EPCMs from the DSC curves were also presented in
Table 1. By considering these data, it can be clearly stated that
all of the micro/nano-capsules exhibit very stable and reversible
phase change behaviors during both their heating and cooling
periods. The n-heptadecane has solid–solid peaks at 10.87 1C (for
heating period) and 9.86 1C (for cooling period) and also melting
peak at 21.36 1C, and freezing peak at 21.30 1C. In the similar trend,
the prepared PS/n-heptadecane micro/nano(1:2)-capsules show
solid–solid transitions at 10.93 1C (for heating period) and 8.83 1C
(for cooling period), and a melting phase change at 21.48 1C and
freezing phase change at 21.37 1C. The sub-cooling degree of the
PS/n-heptadecane micro/nano(1:2)-capsules was found to be
0.11 1C. The little sub-cooling provides an important advantage
for reversible LHTES processes. Moreover, the melting temperature
of the prepared PS/n-heptadecane micro/nano(1:2)-capsules
makes it a promising LHTES material for thermal regulating aim
in textile, building, food storage container, medical and electronic
applications.
The latent heat capacity of an EPCM is dependent on the mass
fraction of its PCM content. In this work, in order to achieve the
maximum encapsulation ratio, the micro/nano-EPCMs were
prepared by changing the weight combination ratio of styrene/
n-heptadecane. As also clearly seen from Table 1, the latent heat
values of prepared micro/nano-EPCM were raised proportion-
ally with increasing the mass fraction of PCM content. Espe-
cially, the micro/nano-EPCM with combination ratio of 1:2 (w/
w) has a latent heat of melting of 136.89 J/g while n-heptade-
cane storages latent heat of fusion as 216.21 J/g. This result
indicated that the fabricated PS/n-heptadecane micro/nano
(1:2)-capsules had good LHTES potential for thermal regulation
objectives in textile, building, food storage, medical and elec-
tronic applications.
On the other hand, the actual encapsulation percentage
of n-heptadecane by PS can be calculated as below
 
ΔH PS=heptadecane
Encapsulation of n
heptadecane ð%Þ ¼  100
ΔH heptadecane
where, ΔH PS=heptadecane and ΔH heptadecane correspond to the measured
latent heat values of synthesized EPCM and n-heptadecane,
respectively. By using this equation, the real encapsulation ratio
of n-heptadecane by PS shell was found as 63.3%. This result
means that the actual PCM content is almost same as the
calculated percentage of PCM content (about 67%) based on the
initial combination ratio. On the other hand, in the previous study,
the latent heat capacity and encapsulation ratio for n-heptade-
cane/poly(methyl methacrylate) micro-capsules were found as
81.5 J/g and 38 wt%, respectively [20]. The encapsulation ratio
 A. Sarı et al. / Solar Energy Materials & Solar Cells 126 (2014) 42–50
Table 1
Measured LHTES properties of n-heptadecane and the prepared EPCMs at different weight ratios of monomer/PCM using DSC analysis method.
Micro/nano-EPCM Heating period
Solid–solid phase Solid–liquid phase Latent heat of
transition change (melting) melting (J/g)
temperature (1C) temperature (1C)
n-Heptadecane 10.87 21.36 216.21
PS/heptadecane(2:1) 9.20 21.46 63.74
PS/heptadecane(1:1) 9.45 21.44 81.60
PS/heptadecane(1:2) 10.93 21.48 136.89
After thermal cycling
PS/heptadecane(1:2) 10.88 21.75 128.27
found in this study was also higher than that obtained for various
micro-EPCMs including PS shell and other core materials such as
n-octadecane [16,55], n-tetradecane and n-nonadecane [54].
3.4. Thermal reliability and chemical stability of micro/nano-
capsules
Effective utilization of a LHTES system depends noticeably on
the thermal reliability and chemical stability of PCM used. Thermal
confidence of a PCM is determined by evaluating the change in its
LHTES properties after expanded number of thermal (melting/
freezing) cycles. The chemical stability of PCM can be defined as
whether its chemical structure is changed or not after a large
number of repeated melting/freezing processes. Thus, extensive
information about thermal reliability and chemical stability prop-
erties of PCM with respect to cycling number is necessary to
guarantee the long-term performance and economic practicability
of the LHTES system.
In this regard, the prepared PS/n-heptadecane micro/nano
(1:2)-capsules were exposed to a thermal cycling test. The
endothermic and exothermic DSC curves obtained for the micro/
nano-capsules after 5000 cycles were shown in Fig. 6. As also seen
from Table 1, the melting temperature of the PS/n-heptadecane
micro/nano(1:2)-capsules was changed from 21.48 1C to 21.75 1C
after the cycling test. In addition, its latent heat of melting was
decreased from 136.89 J/g to 128.27 J/g after repeated thermal
cycling. This decrease may be due to a little number of damaged
capsules from the cycling process, thus leaving a slight amount of
paraffin from the capsule shell via evaporation. These results mean
that the variations in the melting temperature and latent heat
capacity of the synthesized PS/n-heptadecane micro/nano(1:2)-
capsules were not considerably high for a LHTES application.
Therefore, the prepared EPCM(1:2) has good long-thermal perfor-
mance and economical possibility for actual LHTES systems.
The chemical stability of PS/n-heptadecane micro/nano(1:2)-
capsules after repeated thermal cycling was also evaluated by
comparing the FT-IR analysis results obtained before and after
thermal cycling test. As clearly seen from Fig. 7, the characteristic
peaks regarding the PS/n-heptadecane micro/nano(1:2)-capsules
were detected at the same wavenumbers even after the cycling.
Any change in the shapes of the peaks did not occur and also, no
new peak was observed in the spectrum taken after thermal
cycling. All of these results indicated that the PS/n-heptadecane
micro/nano(1:2)-capsules protected its chemical structure even
when it was subjected to a great number of melting/freezing cycles.
3.5. Thermal durability of micro/nano-capsules
Thermal durability property is one of the characteristic para-
meters described for a PCM and should be known before its usage
47
Cooling period
Solid–solid phase Liquid–solid phase Latent heat of
transition change (freezing) freezing (J/g)
temperature (1C) temperature (1C)
9.86 21.30
213.96
4.05 21.01
59.70
6.04 21.18
79.46
8.83 21.37
134.67
8.89 21.32
127.12
Fig. 6. DSC thermogram of n-heptadecane/PS micro/nano-capsules(1:2) after
thermal cycling.
in an actual LHTES application. The thermal durability or thermal
degradation temperature limits of a newly developed PCM can be
determined using TG analysis. The TG technique is based on
measuring the weight loss in the sample depending on tempera-
ture increase. Fig. 8 shows the TG curves of n-heptadecane, PS and
the synthesized PS/n-heptadecane micro/nano(1:2)-capsules. As
observed from these curves, the n-heptadecane and PS were
degraded at only one-step which corresponds to the temperature
range of 140–255 1C and 360–420 1C, respectively. On the other
hand, the PS/n-heptadecane micro/nano(1:2)-capsules have two
thermal degradation stages. The first one occurring at the tem-
perature range of 145–220 1C is related with the evaporation of the
n-heptadecane content of the EPCM(1:2) while the second one
taking place at 325–490 1C range is attributed to the degradation
of the PS shell. Moreover, the weight loss percentage regarding the
first step was found to be 61.6% that agrees with the encapsulation
ratio (63.3%) calculated for n-heptadecane based on the DSC
results. In addition, the initial temperature value of first degrada-
tion step of the micro/nano-EPCM(1:2) is fairly above its working
temperature or melting temperature.
3.6. Thermal conductivity values and phase change reversibility
of micro/nano-capsules
Thermal conductivity is known as one of the most important
criteria used in the selection of a PCM in addition to its other
LHTES properties. Low thermal conductivity of PCM leads to low
heat transfer rate during the heat charging and discharging
processes of LHTES systems [51,57]. The thermal conductivity of
synthesized PS/n-heptadecane micro/nano-capsules was mea-
sured at solid state and compared with those of core and shell
materials. It was measured as 0.22, 0.14 and 0.17 W/m K for n-
heptadecane, PS and PS/n-heptadecane micro/nano(1:2)-capsules,
48 A. Sarı et al. / Solar Energy Materials & Solar Cells 126 (2014) 42–50
Fig. 7. FT-IR spectra of n-heptadecane/PS micro/nano-capsules(1:2): (a) before thermal cycling and (b) after thermal cycling.
Fig. 8. TG curves of n-heptadecane, PS and the prepared n-heptadecane/PS micro/
nano-capsules(1:2).
respectively. As expected, the thermal conductivity value of the
EPCM(1:2) was in the range of the values measured for the core
and shell materials. In addition, it can be seen as a reasonable
value compared with that (in the range of 0.16–0.19 W/m K at solid
state) of some organic PCMs such as fatty acids, their mixture and
esters.
On the other hand, the phase change stability and reversibility
of the prepared PS/n-heptadecane micro/nano(1:2)-capsules dur-
ing heating and cooling periods were established by evaluating the
temperature–time variations. As clearly seen from the tempera-
ture–time curves shown in Fig. 9, the melting and solidification
temperature ranges of fabricated micro/nano-EPCM(1:2) (20–
22.5 1C for heating period and 20–22 1C for cooling period) nearly
correspond to its onset-peak temperature range (20.5–22.5 1C for
heating period and 20–21 1C for cooling period) obtained from
DSC curves. This result indicates that the micro/nano-EPCM(1:2)
reveals stable and reversible phase change behaviors during its
both thermal periods. Moreover, since the latent heats regarding
Fig. 9. Temperature–time curves obtained during the heating and cooling periods
of the prepared PS/n-heptadecane micro/nano-capsules(1:2).
the solid–solid phase change of the EPCM(1:2) are very low
compared to its latent heats of solid–liquid phase change, they
could not be observed from the temperature–time curves.
4. Conclusions
In this work, PS/n-heptadecane micro/nano-capsules were
synthesized as novel EPCM using the miniemulsion polymeriza-
tion method. The FT-IR spectroscopic characterization confirmed
that PS/n-heptadecane micro/nano(1:2)-capsules were succes-
sively synthesized. The SEM and POM results revealed that the
micro/nano-capsules did not have complete sphere-shaped
appearances and some of the capsules had partially rough external
surface and cluster-structure. The PSD analysis results showed that
the particle sizes of the capsules were intensively between 1 and
20 mm. However, according to the SEM and POM results, it can be
concluded that the fabricated EPCM(1:2) is relatively consisted of
nano-spheres. The DSC analysis showed that the prepared EPCM
 A. Sarı et al. / Solar Energy Materials & Solar Cells 126 (2014) 42–50
(1:2) with 63.3 wt% n-heptadecane content had a melting tem-
perature of 21.48 1C and latent heat of 136.89 J/g, and a sub-
cooling degree as little as 0.11 1C. The thermal cycling test and TG
analysis exhibited that the synthesized EPCM(1:2) had good
thermal reliability and durability properties. Furthermore, the
fabricated PS/n-heptadecane micro/nano(1:2)-capsules had rea-
sonable thermal conductivity values and reversible phase change
behaviors during heating and cooling periods. By taking into
consideration all results, it was concluded that the prepared PS/
n-heptadecane micro/nano(1:2)-capsules could be considered as
promising EPCM for temperature regulating applications in textile,
building, food storage, medical and electronic fields.
Acknowledgments
The author would like to acknowledge the Scientific and
Technological Research Council of Turkey (TÜBİTAK) for financial
support (Project no.: KBAG-112T864). Authors also thank Ayşe
Altıntaş, Cahit Bilgin, Çınar Kızıl and Ayşegül Nazlı Özcan for their
help in some parts of the experiments.
References
[1] I. Dincer, On thermal energy storage systems and applications in buildings,
Energy Build. 34 (2002) 377–388.
[2] A. Sharma, V.V. Tyagi, C.R. Chen, D. Buddhi, Review on thermal energy storage
with phase change materials and applications, Renew. Sustain. Energy Rev. 13
(2009) 318–345.
[3] M. Hadjieva, St. KanevJ. Argirov, Thermophysical properties of some paraffins
applicable to thermal energy storage, Sol. Energy Mater. Sol. Cells 27 (1992)
181–187.
[4] R. Yang, Y. Zhang, X. Wang, Y. Zhang, Q. Zhang, Preparation of n-tetradecane
containing microcapsules with different shell materials by phase separation
method, Sol. Energy Mater. Sol. Cells 93 (2009) 1817–1822.
[5] E.Y. Kim, H.D. Kim, Preparation and properties of microencapsulated octade-
cane with waterborne polyurethane, J. Appl. Polym. Sci. 95 (2005) 1596–1604.
[6] X. Qiu, W. Li, G. Song, X. Chu, G. Tang, Fabrication and characterization of
microencapsulated n-octadecane with different crosslinked methylmethacrylate-
based polymer shells, Sol. Energy Mater. Sol. Cells 98 (2012) 283–293.
[7] K. Kaygusuz, A. Sarı, Thermal energy storage system using a technical grade
paraffin wax as latent heat energy storage material, Energy Sources 27 (2005)
1535–1546.
[8] D. Zhou, C.Y. Zhao, Experimental investigations on heat transfer in phase
change materials (PCMs) embedded in porous materials, Appl. Therm. Eng. 31
(2011) 970–977.
[9] C.Y. Zhao, Z.G. Wu, Heat transfer enhancement of high temperature thermal
energy storage using metal foams and expanded graphite, Sol. Energy Mater.
Sol. Cells 95 (2011) 636–643.
[10] C.Y. Zhao, G.H. Zhang, Review on microencapsulated phase change materials
(MEPCMs): fabrication, characterization and applications, Renew. Sustain.
Energy Rev. 15 (2011) 3813–3832.
[11] C. Chen, S. Liu, W. Liu, Y. Zhao, Y. Lu, Synthesis of novel solid–liquid phase
change materials and electrospinning of ultrafine phase change fibers, Sol.
Energy Mater. Sol. Cells 96 (2012) 202–209.
[12] C. Chen, L. Wang, Y. Huang, Morphology and thermal properties of electro- spun
fatty acids/polyethylene terephthalate composite fibers as novel form-stable
phase change materials, Sol. Energy Mater. Sol. Cells 92 (2008) 1382–1387.
[13] C. Alkan, A. Sari, Fatty acid/poly(methyl methacrylate) (PMMA) blends as
form-stable phase change materials for latent heat thermal energy storage,
Sol. Energy 82 (2008) 118–124.
[14] L. Pan, Q. Tao, S. Zhang, S. Wang, J. Zhang, S. Wang, Z. Wang, Z. Zhang,
Preparation, characterization and thermal properties of micro-encapsulated
phase change materials, Sol. Energy Mater. Sol. Cells 98 (2012) 66–70.
[15] S. Gschwander, P. Schossig, H.-M. Henning, Micro-encapsulated paraffin in
phase-change slurries, Sol. Energy Mater. Solar Cells 89 (2005) 307–315.
[16] R. Yang, H. Xu, Y. Zhang, Preparation, physical property and thermal physical
property of phase change microcapsule slurry and phase change emulsion, Sol.
Energy Mater. Sol. Cells 80 (2003) 405–416.
[17] Y. Wang, Y. Zhang, T.D. Xia, W.J. Zhao, W.H. Yang, Effects of fabricated
technology on particle size distribution and thermal properties of stearic–
eicosanoic acid/polymethylmethacrylate nanocapsules, Sol. Energy Mater. Sol.
Cells Part B 120 (2014) 481–490.
[18] A.R. Shirin-Abadi, A.R. Mahdavian, S. Khoee, New approach for the elucidation
of PCM nanocapsules through miniemulsion polymerization with an acrylic
shell, Macromolecules 44 (2011) 7405–7414.
49
[19] W. Li, G.L. Song, G.Y. Tang, X.D. Chu, S.D. Ma, Morphology, structure and
thermal stability of microencapsulated phase change materials with copoly-
mer shell, Energy 36 (2011) 785–791.
[20] A. Sarı, C. Alkan, A. Karaipekli, Preparation, characterization and thermal
properties of PMMA/n-heptadecane microcapsules as novel solid–liquid
microPCM for thermal energy storage, Appl. Energy 87 (2010) 1529–1534.
[21] Y. Özonur, M. Mazman, H. Paksoy, H. Evliya, Microencapsulation of coco fatty
acid mixture for thermal energy storage with phase change material, Int. J.
Energy Res. 30 (2006) 741–749.
[22] C. Alkan, A. Sarı, A. Karaipekli, O. Uzun, Preparation, characterization, and
thermal properties of microencapsulated phase change material for thermal
energy storage, Sol. Energy Mater. Sol. Cells 93 (2009) 143–147.
[23] A. Sarı, C. Alkan, A. Karaipekli, O. Uzun, Microencapsulated n-octacosane as
phase change material for thermal energy storage, Sol. Energy 83 (2009)
175–1763.
[24] S. Alay, F. Göde, C. Alkan, Preparation and characterization of poly(methyl-
methacrylate-coglycidyl methacrylate)/n-hexadecane nanocapsules as a fiber
additive for thermal energy storage, Fiber Polym. 11 (2010) 1089–1093.
[25] X.Y. Gao, N. Han, X.X. Zhang, W.Y. Yu, Melt-processable acrylonitrile-methyl
acrylate copolymers and melt-spun fibers containing MicroPCMs, J. Mater. Sci.
44 (2009) 5877–5884.
[26] F. Salaün, E. Devaux, S. Bourbigot, P. Rumeau, Development of phase change
materials in clothing Part I: formulation of microencapsulated phase change,
Text. Res. J. 80 (2010) 195–205.
[27] E. Onder, N. Sarier, E. Cimen, Encapsulation of phase change materials by
complex coacervation to improve thermal performances of woven fabrics,
Thermochim. Acta 467 (2008) 63–72.
[28] S. Alay, C. Alkan, F. Göde, Steady-state thermal comfort properties of fabrics
incorporated with microencapsulated phase change materials, J.Text. Inst. 103
(2012) 757–765.
[29] S. Alay, C. Alkan, F. Gode, Synthesis and characterization of poly(methyl
methacrylate)/n-hexadecane microcapsules using different cross-linkers and
their application to some fabrics, Thermochim. Acta 518 (2011) 1–8.
[30] N. Sarier, E. Onder, Thermal insulation capability of PEG-containing polyur-
ethane foams, Thermochim. Acta 475 (2008) 15–21.
[31] M. You, X.X. Zhang, X.C. Wang, L. Zhang, W. Wen, Effects of type and contents
of microencapsulated n-alkanes on properties of soft polyurethane foams,
Thermochim. Acta 500 (2010) 69–75.
[32] S.G. Jeong, J. Jeon, J. Seo, J.H. Lee, S. Kim, Performance evaluation of the
microencapsulated PCM for wood-based flooring application, Energy Convers.
Manag. 64 (2012) 516–521.
[33] J.F. Su, X.Y. Wang, S.B. Wang, Y.H. Zhao, Z. Huang, Fabrication and properties of
microencapsulated-paraffin/gypsum-matrix building materials for thermal
energy storage, Energy Convers. Manag. 55 (2012) 101–107.
[34] V.V. Tyagi, S.C. Kaushik, S.K. Tyagi, T. Akiyama, Development of phase change
materials based microencapsulated technology for buildings: a review, Renew.
Sustain. Energy Rev. 15 (2011) 1373–1391.
[35] P. Schossig, H.-M. Henning, S. Gschwander, T. Haussmann, Micro-encapsulated
phase-change materials integrated into construction materials, Sol. Energy
Mater. Sol. Cells 89 (2005) 297–306.
[36] W.B. Jackson, R.D. Gould, J.C. Mulligan, Performance of an octacosane based
micropcm fluid for cooling EV electronics, in:Proceedings of the 8th AIAA/
ASME Joint Thermophysics and Heat Transfer Conference, 24 –26 June 2002,
(Chapter) http://dx.doi.org/10.2514/6.2002-3226.
[37] M. Delgado, A. Lázaro, J. Mazo, B. Zalba, Review on phase change material
emulsions and microencapsulated phase change material slurries: materials,
heat transfer studies and applications, Renew. Sustain. Energy Rev. 16 (2012)
253–273.
[38] Y.W. Luo, X.D. Zhou, Nanoencapsulation of a hydrophobic compound by a
microemulsion polymerization process, J. Polym. Sci. 42 (2004) 2145–2154.
[39] J.F. Su, L.X. Wang, L. Ren, Fabrication and thermal properties of microPCMs:
used melamine formaldehyde resin as shell material, J. Appl. Polym. Sci. 101
(2006) 1522–1528.
[40] X.X. Zhang, X.M. Tao, K.L. Yick, Y.F. Fan, Expansion space and thermal
stability of microencapsulated n-octadecane, J. Appl. Polym. Sci. 97 (2005)
390–396.
[41] Z.G. Jin, Y. Wang, J.G. Liu, Z.Z. Yang, Synthesis and properties of paraffin
capsules as phase change materials, Polymer 49 (2008) 2903–2910.
[42] Y.H. Tseng, M.H. Fang, P.S. Tsai, Y.M. Yang, Preparation of microencapsulated
phase-change materials (MCPCMs) by means of interfacial polycondensation,
J. Microencapsul. 22 (2005) 37–46.
[43] Y. Shin, D. Yoo, K. Son, Development of thermoregulating textile materials
with microencapsulated phase change materials (PCM): IV. Performance
properties and hand of fabrics treated with PCM microcapsules, J. Appl.
Polym. Sci. 97 (2005) 910–915.
[44] H. Zhang, X. Wang, Synthesis and properties of microencapsulated n-
octadecane with polyurea shells containing different soft segments for heat
energy storage and thermal regulation, Sol. Energy Mater. Sol. Cells 93 (2009)
1366–1376.
[45] J. Su, L. Wang, L. Ren, Preparation and characterization of polyurethane
microcapsules containing n-octadecane with styrene-maleic anhydride as a
surfactant by interfacial polycondensation, J. Appl. Polym. Sci. 102 (2006)
4996–5006.
[46] Y. Wang, T.D. Xia, H.X. Feng, H. Zhang, Stearic acid/polymethylmethacrylate
composite as form-stable phase change materials for latent heat thermal
energy storage, Renew. Energy 36 (2011) 1814–1820.
50 A. Sarı et al. / Solar Energy Materials & Solar Cells 126 (2014) 42–50
[47] X. Qiu, G. Song, X. Chu, X. Li, G. Tang, Preparation, thermal properties and
thermal reliabilities of microencapsulated n-octadecane with acrylic-based
polymer shells for thermal energy storage, Thermochim. Acta 551 (2013)
136–144.
[48] L. Sanchez-Silva, J. Tsavalas, D. Sundberg, P. Sanchez, J.F. Rodriguez, Synthesis
and characterization of paraffin wax microcapsules with acrylic-based poly-
mer shells, Ind. Eng. Chem. Res. 49 (2010) 12204–12211.
[49] C. Alkan, A. Sarı, A. Karaipekli, Preparation, thermal properties and thermal
reliability of microencapsulated n-eicosane as novel phase change material for
thermal energy storage, Energy Convers. Manag. 52 (2011) 687–692.
[50] X. Qiu, G. Song, X. Chu, X. Li, G. Tang, Microencapsulated n-alkane with p(n-
butyl methacrylate-co-methacrylic acid) shell as phase change materials for
thermal energy storage, Sol. Energy 91 (2013) 212–220.
[51] A. Sarı, C. Alkan, A. Biçer, A. Karaipekli, Synthesis and thermal energy
storage characteristics of polystyrene-graft-palmitic acid copolymers as
solid–solid phase change materials, Sol. Energy Mater. Sol. Cells 95 (2011)
3195–3201.
[52] S. Doroudiani, M.T. Kortschot, Expanded wood fiber polystyrene composites
processing-structure-mechanical properties relationships, J. Thermoplast.
Compos.: Mater. 17 (2004) 13–30.
[53] S.J. Park, K.S. Kim, S.K. Hong, Preparation and thermal properties of polystyr-
ene nanoparticles containing phase change materials as thermal storage
medium, Polym. Korea 29 (2005) 8–13.
[54] L. Sánchez, P. Sánchez, A. Lucas, M. Carmona, J.F. Rodríguez, Microencapsula-
tion of PCMs with a polystyrene shell, Colloid Polym. Sci. 285 (2007)
1377–1385.
[55] Y. Fang, S. Kuang, X. Gao, Z. Zhang, Preparation and characterization of novel
nanoencapsulated phase change materials, Energy Convers. Manag. 49 (2008)
37043707.
[56] L. Sa´nchez-Silva, J.F. Rodrı´guez, M. Carmona, A. Romero, P. Sa´nchez, Thermal
and morphological stability of polystyrene microcapsules containing phase-
change materials, J. Appl. Polym. Sci. 120 (2011) 291–297.
[57] S. Karaman, A. Karaipekli, A. Sarı, A. Bicer, Polyethyleneglycol (PEG)/diatomite
composite as a novel form-stable phase change material for thermal energy
storage, Sol. Energy Mater. Sol. Cells 95 (2011) 1647–1653.