Energy and Buildings 90 (2015) 106–113

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Energy and Buildings

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Synthesis and characterization of micro/nano capsules of

PMMA/capric–stearic acid eutectic mixture for low
temperature-thermal energy storage in buildings
Ahmet Sarı ∗ , Cemil Alkan ∗ , Ayşegül Nazlı Özcan
Department of Chemistry, Gaziosmanpaşa University, 60240 Tokat, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: In this work, polymethylmethacrylate(PMMA)/capric–stearic eutectic mixture (C-SEM) micro/nano cap-
Received 9 October 2014 sules were synthesized effectively using emulsion polymerization method. POM and SEM analysis results
Received in revised form showed that the synthesized PMMA/C-SEM micro/nano capsules were consisted with spherical shape
19 December 2014
with uniform structure. The PSD analysis indicated that the mean diameter of the capsules was 1.3 ␮m
Accepted 9 January 2015
Available online 17 January 2015
and 28.1%-part of the capsules can be characterized as nano-sized spheres. DSC analysis exposed that
the synthesized PMMA/C-SEM (1:2) micro/nano capsules has a melting temperature of 21.37 ◦ C, which
can be suitable for free cooling of buildings depending on the climatic conditions. It has a latent heat of
Keywords:
PMMA melting of 116.25 J/g, which can be enough to integrate with conventional building materials. TGA results
Capric acid exhibited that the thermal degradation temperature of the micro/nano capsules is very much higher its
Stearic acid melting temperature. Moreover, the synthesized PMMA/C-SEM micro/nano capsules have good ther-
Eutectic mal reliability, chemical stability and thermal conductivity. By taking into consideration all results, it
Micro/nano encapsulation can be also concluded that the micro/nano encapsulated C-SEM can be used to fabricate new building
PCM components.
Latent heat © 2015 Elsevier B.V. All rights reserved.
Thermal energy storage
Building

1. Introduction
Growing energy prices and environmental respects induced
the investigations regarding with the potential applications to be
reduced the operational expenses from heating and cooling sys-
tems used in buildings [1]. The latent heat storage (LHS) method is
an alternative for thermal energy storage with respect to decrease
the operation time of heating, ventilation, and air Conditioning
(HVAC) systems, save energy and reduce fossil fuel consumption
and also the pollutant emissions [2]. The LHS process is occurred via
phase change of a phase change material (PCM) at constant temper-
ature. This method is an efficient way to get better thermal comfort
of buildings and diminish the energy utilization because it allows
storing high amounts of thermal energy as at a designated tem-
perature and low volume change [3]. The use of LHS system in a
building can lessen temperature fluctuation, and thus enable the
passive control of temperature in buildings [4]. The PCMs can be
∗ Corresponding authors. Tel.: +90 036625216116.
E-mail addresses: ahmet.sari@gop.edu.tr, asari@gop.edu.tr (A. Sarı),
cemil.alkan@gop.edu.tr (C. Alkan).
used to store thermal energy in active and passive LHS applications
in buildings such as heating and cooling of is one of the most effi-
cient ways [5–8]. The integration of PCMs with the construction
materials makes available lightweight structures with advantages
of passive solar gaining and decrease the energy requirement to
maintain the indoor temperature within the comfort range in build-
ings.
With the advent of PCM implemented in conventional building
materials (bricks, mortar, concrete, cement, lime, artificial marble,
sealants, paints and other coatings material), LHS can be part of the
building structure even for light weight buildings Several forms of
bulk encapsulated PCMs have been developed for active and pas-
sive solar applications in building including direct heat gain [9–13].
Moreover, the encapsulated PCMs also directly used to fabricate
new building elements (ceiling panel, sandwich panel, facade panel,
plasterboard, gypsum wallboard, concrete wall etc) with increased
LHS capacity. The usage of such kind of building components in
buildings reduces temperature swings, which increases occupant
comfort and can reduce cooling load changed with climatic condi-
tions [14–16].
PCMs can be combined with building materials using differ-
ent techniques such as impregnation and encapsulation. The direct

http://dx.doi.org/10.1016/j.enbuild.2015.01.013
0378-7788/© 2015 Elsevier B.V. All rights reserved.
 A. Sarı et al. / Energy and Buildings 90 (2015) 106–113
impregnation method includes several high risks in terms of leak-
age and material loss for PCM, mechanical strength and undesired
odors for final product and poor adhesion of paint coatings to the
surface [17–19]. These problems can be solved by the encapsu-
lation of PCMs before their absorption in construction materials.
Microencapsulation of PCMs with polymeric shells has been con-
sidered for the best way in the encapsulation applications [20–22].
PCMs can be encapsulated into different polymeric shell materi-
als. Smaller PCM particles give larger surface-to-volume ratio, thus
the heat transfer efficiency is greatly improved [23–26]. More-
over, the choice of shell material for the encapsulation has a very
significant function in specifying the structural and thermal prop-
erties of the micro/nano capsules. With this regard, the several
polymers or copolymers such as arabic-gum [27], polyurea [28],
melamine-formaldehyde [29], styrenedivinylbenzene co-polymer
[30], styrene-buthylacrylate copolymer [31], methylmethacrylate-
based copolymers [32], polystyrene [33,34] and etc have been used
as shell material in the production of micro or nano encapsulated
PCMs. In addition, poly(methylmethacrylate) (PMMA) has been
evaluated as shell material in the preparation of novel encapsu-
lated PCMs due to its being transparent, lightweight, easy process
able, environmental stable, and low cost [35–39].
On the other hand, suitable phase change temperature, high
energy storage capacity, good chemical compatibility with poly-
meric shell material are the most important criteria, which should
be considered in the selection of core material acted as energy stor-
ing PCM into the capsules. Fatty acids and their eutectic mixtures
have the advantageous LHS properties mentioned above [40–43].
Therefore, the investigations on the encapsulation of these PCMs
as organic core materials by using polymeric shells have been
attracted in recent years. Özonur et al. [25] microencapsulated
coco fatty acid mixture with jelatin and gum arabic mixture. Sarı
et al. [44] prepared and characterized the LHS properties of micro-
nanoencapsulated some fatty acids by polystyrene shell. Konuklu
et al. [45] microencapsulated fatty acid with poly(melamine-urea-
formaldehyde).
The one of important choice criterion for a PCM to be used for
LHS purposes in buildings is its servicing temperature. For build-
ing envelopes, the defined comfort levels which is between 23 ◦ C
and 27 ◦ C for summer season [46]. Therefore, for free cooling sys-
tems, the melting temperature of the PCM should be between 19 ◦ C
and 24 ◦ C [47]. In another study, it is reported that free cooling of
buildings coupled with PCM storage unit performs efficiently in
the climatic conditions where the diurnal temperature range is in
range of 12–15 ◦ C [48]. Moreover, different criteria have been used
to choose the melting point of PCM [49,50]. It can be concluded
from the literature that the applicability of the PCM for free cooling
of buildings depends mainly on the climatic conditions.
Stearic acid and capric acid as fatty acids have little super-
cooling and no phase segregation during the phase change process,
good thermal reliability, thermal stability and compatible prop-
erty for absorption in various building materials [10,19,25,41].
Although stearic acid as PCM had relatively high latent heat capac-
ity (252.7 J/g) [51], its melting temperature (68.86 ◦ C) is too higher
than the comfortable temperature range for buildings. In this
regard, this study is aimed firstly to achieve lower temperature
value to be preferred for cooling process of building envelopes.
With this purpose, the phase transition temperature of stearic acid
was tailored to the desired value by preparing its mixtures with
capric acid, which has a melting temperature of 31.14 ◦ C. More-
over, as seen from the literature research, there is no study on
the preparation and characterization of micro/nano encapsulated
capric–stearic acid eutectic mixture (C-SEM) with polymethyl-
methacrylate(PMMA) shell. In this regard, The PMMA/C-SEM
micro/nano capsules were synthesized effectively via emulsion
polymerization technique. The chemical characterization of the
107
Fig. 1. Photograph images of the MMA monomer, the prepared C-SEM and the
synthesized PMMA/C-SEM (1:2) micro/nano capsules
synthesized micro/nano capsules were carried out using Fourier
transform infrared (FTIR) spectroscopy method. The morphology
and particle size of the micro/nano capsules were investigated
using polarized optical microscopy (POM), scanning electron
microscopy (SEM) and particle size distribution (PSD) analysis tech-
niques. The LHS properties and thermal stability of the micro/nano
encapsulated PMMA/C-SEM were measured using DSC and TGA
methods, respectively. Furthermore, thermal conductivity and
phase change reversibility of the encapsulated PMMA/C-SEM were
determined.
2. Experimental
2.1. Materials
Capric acid and stearic acid were obtained from Merck Company.
MMA monomer, Triton-X100, ethylene glycol dimethylacrylate,
ammonium persulphate and ferrous sulphate heptahydrate were
supplied from Sigma-Aldrich Company. The monomer was washed
with NaOH solution (10 wt/v%) before the polymerization reaction.
2.2. Preparation of capric–stearic acid eutectic mixture (C-SEM)
The eutectic composition ratio and melting temperature for the
binary mixture of capric–stearic (C–S) acid was determined theo-
retically based on the “phase equilibrium theory” [52,53] prior to
prepare the C–S eutectic mixture (C-SEM). After that, eight mixtures
of C–S was prepared around the theoretical eutectic combination
ratio by using the same method reported in literature [54–58].
Each mixture sample were analyzed thermally using DSC analy-
sis and the eutectic composition ratio and eutectic phase change
temperature were determined by evaluating the DSC thermograms
obtained for the samples.
2.3. Synthesis of the PMMA/C-SEM micro/nano capsules
The emulsion polymerization method was used to synthesis
micro/nano PMMA/C-SEMs capsules. The synthesis process was
firstly for treated for 1:1 (w/w) MMA monomer:C-SEM ratio. For
this purpose, 5 g C-SEM, 5 g MMA monomer in liquid state and were
mixed in deionized water (40 mL) into a three-neckled glass reac-
tor. 2 g ethylene glycol dimethacrylate as cross linking agent was
added to this combination and mixed at 12000 rpm for 15 min using
a homogenizer. Then, 3 g surfactant material (Triton X-100) was put
in the mixture and was re-homogenized at 50 ◦ C for 60 min at the
same rate. After this step, 1 mL freshly prepared aqueous initia-
tor solution was inserted gradually to the reactor and the mixture
was stirred at 70 ◦ C for 6 h at 500 rpm to attain oil-in-water emul-
sion system using a mechanical stirrer. The obtained filtrate after
the completion of the polymerization reaction was washed several
times using hot water (40 ◦ C) to eliminate unencapsulated C-SEM
from the final product. The photograph images of MMA monomer,
the prepared C-SEM and the obtained PMMA/C-SEM (1:2) product
are shown in Fig. 1. The experimental ratio for the encapsulation of
108 A. Sarı et al. / Energy and Buildings 90 (2015) 106–113
Fig. 2. FT-IR spectra of the prepared C-SEM and the synthesized PMMA/C-SEM (1:2)
micro/nano capsules.
dried C-SEM was calculated by taking into account the measured
latent heat capacity of the product. By considering this encapsu-
lation percentage the synthesis reaction was repeated to fabricate
the higher monomer:C-SEM combination ratios with 1:2 or 1:3.
2.4. Characterization of PMMA/C-SEM micro/nano capsules
The polymerization reaction regarding the transformation of
MMA to PMMA around the C-SEM used PCM core material was
checked with FT-IR spectroscopic (Jasco 430 model FT-IR instru-
ment) analysis. The geometric shapes of the fabricated capsules
were characterized using LEO 440 model SEM and Leica model
POM instruments. The particle size distribution (PSD) of the pre-
pared capsules was determined using a Malvern Mastersizer 2000
model instrument. The sample was diluted with deionized water
to disperse the particles and thus make easy its PSD analysis.
The LHS properties of the synthesized PMMA/C-SEM capsules
were characterized using a Perkin Elmer Jade model DSC instru-
ment. The measurements were carried out at 3 ◦ C/min during both
heating and cooling periods. The thermal stability of the micro/nano
capsules were evaluated using a Perkin Elmer TGA7 model instru-
ment. The analyses of the capsules were conducted at heating run
of 10 ◦ C/min. The chemical stability and long-term energy storage
Fig. 3. POM and SEM micrographs of the synthesized PMMA/C-SEM micro/nano capsules.
performance of the encapsulated PCM were estimated by perform-
ing a thermal cycling test using with a BIOER TC-25/H model ther-
mal cycler and the cycling process was continued to until the num-
ber of accelerated heating/cooling processes was 5000. Further-
more, the thermal conductivity of the synthesized micro/nano cap-
sules were measured using a KD2 model thermal property analyzer.
3. Results and discussion
3.1. Spectroscopic characterization of PMMA/C-SEM micro/nano
capsules
The FT-IR spectral data of C-SEM and MMA monomer and
the synthesized micro/nano capsules were examined to prove
the polymerization reaction regarding the formation of PMMA
shell around the C-SEM. As shown in Fig. 2, the prepared C-
SEM has three characteristic bands, the symmetrical stretching
vibration of C H, C O and C O groups which were recorded at
2927, 1381 cm−1 and 1704 cm−1 , respectively. The MMA monomer
has typical C O, C O, C C bands and OH band regarding with
water remained into monomer, respectively detected at 1590 cm−1 ,
1124 cm−1 , 1629 cm−1 and 3450 cm−1 , respectively [38]. Moreover,
the representative FT-IR peaks for the PMMA and C-SEM con-
stituents of the synthesized micro/nano capsules was overlapped at
2932–2846 cm−1 , 1372 and 1621 cm−1 which are attributed. Also,
the vibration band of vinylic C C group of the MMA monomer at
1590 cm−1 was not observed after its polymerization reaction. All
these results clearly proved the formation of PMMA shell around
C-SEM acted as core material.
3.2. Morphological and PSD analysis results of PMMA/C-SEM
micro/nano capsules
Particle size and shape can noticeably change physical and real
properties of an encapsulated PCM. In this sense, the geometric
shape of the synthesized PMMA/C-SEM micro/nano capsules was
examined using POM and SEM techniques. Fig. 3 shows the POM
and SEM micrographs of PMMA/C-SEM (1:2) capsule sample. As
shown from these images, the capsules have spherical profile with
fairly uniform structure and compact surfaces. However, very lit-
tle some of capsules are adhered each other and aggregated, which
result in a larger mean diameter in PSD curves. The large major-
ity of the capsules to be resembling indicate that the C-SEM was
successfully encapsulated by PMMA due to the good compatibility
between the core and shell materials. The SEM and POM micropho-
tographs showed that the synthesized capsules have spherical form
 A. Sarı et al. / Energy and Buildings 90 (2015) 106–113
Fig. 4. PSD diagram of the synthesized PMMA/C-SEM (1:2) micro/nano capsules.
with fairly uniform structure and compact surfaces. However, very
little some of capsules are adhered each other and aggregated. In
addition, it can be resulted from the measurement scales onto both
SEM and POM microphotographs, the encapsulated particles are
somewhat consisted of nano-sized spherical capsules.
On the other hand, the size of capsule can be in charge of the
function of encapsulated PCM. The larger capsules than 0.5–10 ␮m
and 10–100 ␮m micro size are not proper for carrier thermal flu-
ids due to the probable high viscosity and crushing problem to
be encountered during its pumping stage [59]. The nano capsules
present a further contribution to the surface area per volume, which
enhances heat transfer rate into the PCMs [60]. As can be evidently
seen from the PSD diagram in Fig. 4, the synthesized PMMA/C-
SEM (1:2) sample has relatively narrow size distribution in the
range of 0.01–15 ␮m. The particle size of the capsules was also
determined averagely as 1.3 ␮m and also 28.1%-part of the par-
ticles are consisted of nano-sized spheres. Thus, the PSD results
are well conformity with the POM and SEM results. Additionally, it
can be deduced from the morphological findings results that the C-
SEM was effectively encapsulated with PMMA shell in nano size
in addition to micro size. Therefore, the encapsulated C-SEM in
micro/nano size can be considered as an appropriate LHS material
to be used in the preparation of lightweight composite structures
with advantages of reducing the energy demand to keep the indoor
temperature within the comfort range in buildings.
3.3. Thermal properties of C-SEM and synthesized PMMA/C-SEM
micro/nano capsules
In order to determine the eutectic combination ratio and melt-
ing temperature of mixture capric–stearic (C–S) acid mixture, eight
binary mixtures prepared at different combination ratios were
analyzed by DSC technique. As can be seen from Fig. 5, the DSC
thermograms of each of the mixtures includes two phase change
peaks (main peak and small peak) representing the phase change
temperatures of each component in the mixture, while the eutectic
mixture with the combination ratio of 86–14 wt% ratio (C–S) show
only one peak. The on-set temperature value (26.06 ◦ C) of this peak
corresponds to the eutectic phase change temperature, which is
relatively lower than the melting temperatures of the other mix-
tures. Moreover, by integration of the area under the eutectic peak
using the DSC software, its latent heat of melting was calculated
as 176.68 J/g. As a result, the eutectic melting temperature value
and latent heat of the prepared C–S eutectic mixture (C-SEM) make
it potential PCM as core material for its micro-nanoencapsulation
with polymeric shell materials.
On the other hand, as clearly observed from the DSC thermo-
grams in Fig. 6, the synthesized PMMA/C-SEM micro/nano capsules
had similar melting and freezing behavior with that of prepared
109
Fig. 5. DSC thermograms of prepared capric–stearic acid binary mixtures at differ-
ent combination ratios.
C-SEM. In other words, there is no change in the peak number
in the DSC signals of the prepared micro/nano capsules synthe-
sized at different monomer/C-SEM ratios. This means that there
was no occurred any chemical reaction among the reaction con-
stituents except the transformation reaction of MMA monomer
to PMMA polymer shell around the eutectic mixture used as core
material. The on-set temperature values of the DSC peaks obtained
during the heating and cooling periods were taken as melting and
freezing temperatures of the micro/nano capsules. As seen from
Table 1, melting temperatures of PMMA/C-SEM (2:1), PMMA/C-
SEM (1:1) and PMMA/C-SEM (1:2) were determined as 21.03, 21.37
and 20.20–21.37 ◦ C, respectively, while their freezing temperatures
were determined to be 22.04, 20.17 and 20.14 ◦ C, respectively.
Compared to the prepared C-SEM, the decline occurred in the phase
change temperatures of the micro/nano capsules could be due to
the effect of PMMA polymer shell formed around the C-SEM. How-
ever, the phase change temperatures of the encapsulated PCMs can
be considered to be within free cooling temperature range desired
in buildings depending on the climatic conditions [46–50].
Additionally, as can be seen from Table 1, the latent heat of melt-
ing were measured as 51.98, 73.34 and 116.25 J/g for PMMA/C-SEM
(2:1), PMMA/C-SEM (1:1) and PMMA/C-SEM (1:2), respectively,
while the latent heat of freezing were determined to be −50.27,
−68.40 and −111.95 J/g, respectively. As clearly seen from these
results, the latent heat capacities of phase change of the micro/nano
capsules were increased with increasing the amount of the core
material encapsulated by the shell material. Moreover, especially,
the latent heat capacity of the fabricated PMMA/C-SEM (1:2)
micro/nano capsules has facilitated it to be considered as potential
PCM for passive solar space cooling or decreasing indoor tempera-
ture fluctuations in buildings depending on the climatic conditions.
Furthermore, the maximum encapsulation percent of C-SEM into
the PMMA shell was found to be 65.8 wt% by dividing the latent
heat value of the encapsulated C-SEM to the latent heat value of
the unencapsulated C-SEM. The ratio was found to be almost equal
to the weight ratio of C-SEM (66.3 wt%) which was selected before
the synthesis process.
On the other hand, based on the literature, the synthesized
PMMA/C-SEM (1:2) micro/nano capsules had enough high latent
heat capacity to compare with several microencapsulated PCMs
including fatty acid or its derivative as core material and includ-
ing different shell kind. For instance, the latent heat value of
some micro capsules, caprylic acid/urea-formaldehyde, caprylic
acid/melamine-formaldehyde and caprylic acid/urea-melamine-
formaldehyde resins were measured as in the rage of 69–94 J/g,
110 A. Sarı et al. / Energy and Buildings 90 (2015) 106–113

Fig. 6. DSC thermograms of the prepared C-SEM and the synthesized PMMA/C-SEM (1:2) micro/nano capsules.

16–26 J/g and 57–63 J/g, respectively [61]. It was measured as
88.0 for poly(MUF)/decanoic acid [62], 80.0 J/g for polyurea/butyl
stearate microcapsules [63] and 52.3–53.5 J/g for poly(urethane-
urea/fatty acid ester [64]. Moreover, when compared the latent
heat capacity of synthesized PMMA/C-SEM (1:2) micro/nano cap-
sules were higher than the data reported for the microencapsulated
PCMs including PMMA as shell material and different PCMs as core
materials [24,26,36,37,39,60].
3.4. The LHS reliability and chemical stability of PMMA/C-SEM
micro/nano capsules
The effectiveness of a LHS system is directly related with ther-
mal reliability and chemical stability of PCM after a large number
of thermal cycling [65]. Therefore, to ensure long run-life and cost-
performance of LHS system, it is important to have expansive
information about these properties for a new developed PCM. With
this aim, in the present work, a thermal cycling test consisted of
5000 melting/freezing process was conducted to the encapsulated
C-SEM to detect quantitatively repeatability of its LHS properties
and prove the unchangeablity in its chemical structure. The DSC
data to be obtained after thermal cycling test indicated that the
melting temperature of the synthesized PMMA/C-SEM (1:2) was
21.40 ◦ C and the corresponding latent heat value was 94.79 J/g.
By considering both the DSC data obtained before after thermal
cycling, it can be noticed that the changes in LHS properties of
the encapsulated PCM are in insignificant order and thus it has a
good long-term LHS performance and economic option for passive
solar thermal energy storage applications in buildings. Addition-
ally, the invariability in the chemical structure of the synthesized
PMMA/C-SEM (1:2) micro/nano capsules was confirmed by com-
paring the FT-IR results obtained before and after the cycling test. As
obviously seen from Fig. 7, the spectral wavenumber data and peak
profiles regarding the typical bands was remained unchanged and
any new peak was not observed in its spectrum after the cycling.
These results verified that the chemical structure of the synthesized
micro/nano capsules was not affected by a large number of thermal
cycling and thus had an excellent chemical stability.

Table 1
Measured LHS properties of the prepared C-SEM and the synthesized PMMA/C-SEM (1:2) micro/nano capsules.

PCM Melting temperature (◦ C) Latent heat of melting (J/g) Freezing temperature (◦ C) Latent heat of freezing (J/g)

C-SEM (86–14%) 26.04 176.68 25.12 −172.46

PMMA/C-SEM (2:1) 21.03 51.98 22.04 −50.27
PMMA/C-SEM (1:1) 21.37 73.34 20.17 −68.40
PMMA/C-SEM (1:2) 20.20 116.25 20.14 −111.95
 A. Sarı et al. / Energy and Buildings 90 (2015) 106–113
Fig. 7. FT-IR spectra of the synthesized PMMA/C-SEM (1:2) micro/nano capsules
before and after thermal cycling.
Fig. 8. TGA curves of the prepared C-SEM and the synthesized PMMA/C-SEM (1:2)
micro/nano capsules.
3.5. Thermal degradation temperature limit and thermal
conductivity of PMMA/C-SEM micro/nano capsules
Thermal data regarding with degradation temperature limit is
one of the choice parameters defined for a new PCM. Therefore, it
is needed to have knowledge on its practical temperature limit for
successful LHS applications in buildings. A PCM can be degraded
thermally in the form of decomposition, sublimation, evaporation.
The TGA is the most widespread techniques used in the determining
the thermal degradation temperature limit (TDTL) of a PCM. Fig. 8
showed the TGA curves the prepared C-SEM and the synthesized
PMMA/C-SEM (1:2) micro/nano capsules. The TDTL range of PMMA
was 300–440 ◦ C [38,66] as a 99.8%wt-part of the unencapsulated
C-SEM evaporated in the temperature ranges of 120–240 ◦ C, indi-
cating that it behaved like a pure PCM. As also noticed from Fig. 8,
the synthesized PMMA/C-SEM(1:2) micro/nano capsules has two
TDTL values. The first one corresponds to 80–220 ◦ C range, which is
111
attributing the evaporation of the C-SEM encapsulated into the cap-
sules while the other is occurred in the range of 220–430 ◦ C, which
is leaving of PMMA shell from the capsules thoroughly evapora-
tion or degradation. Moreover, the weight loss percent regarding
the first TDTL was determined as about 71%, which is in well agree-
ment with the encapsulation ratio (65.8%) of the C-SEMs calculated
by considering the DSC data. In light of the TGA results, it can
also remarkably noted that the synthesized PMMA/C-SEM (1:2)
micro/nano capsules has high thermal durability since its TDTL
value of the first degradation stage is very much higher than its
melting temperature.
Besides the other thermo-physical properties, thermal conduc-
tivity is one of the preference criteria to be taken into account
for a PCM used in building applications because it has apprecia-
bly effect on the energy charging/discharging rates to/from a TES
system [67]. In this respect, the thermal conductivity values of the
C-SEM and the synthesized PMMA/C-SEM (1:2) micro/nano cap-
sules were measured and compared. It was measured as 0.19 W/m K
for the unencapsulated C-SEM while to be 0.15 W/m K for the syn-
thesized capsules. As expected, it is between the value measured
for the core material and the value (0.13 W/m K) measured for the
PMMA shell material [66]. In addition, the thermal conductivity of
the synthesized PMMA/C-SEM (1:2) micro/nano capsules is in rea-
sonable grade enough to be compared with that of some fatty acids
(0.16–0.19 W/m K) [68] and some paraffins (0.19–0.24 W/m K) [69].
4. Conclusions
PMMA/C-SEMs micro/nano capsules for LHS applications in
buildings were synthesized using the emulsion polymerization
technique. The chemical characterization, geometric shape, mor-
phology, size distribution, LHS properties, thermal reliability,
thermal durability and thermal conductivity of the synthesized
micro/nano capsules were investigated by FT-IR, POM, SEM, PSD,
DSC and TGA techniques. The morphological analysis results
showed that the synthesized capsules has spherical form with fairly
uniform structure and but very little some of capsules are adhered
each other. The PSD results indicated that the mean diameter of
the capsules was determined as 1.3 ␮m and 28.1%-part of the cap-
sules is consisted of nano-sized spheres. The DSC analysis results
revealed that the synthesized PMMA/C-SEM (1:2) micro/nano cap-
sules has a melting temperature of 21.37 ◦ C which can be suitable
for free cooling temperature range in buildings depending on the
climatic conditions. It has a latent heat of melting of 116.25 J/g,
which is enough to compare with several microencapsulated PCMs
in literature. The maximum encapsulation ratio of C-SEM into the
PMMA shell was calculated as 65.8 wt% by considering the DSC data.
The TGA measurements exposed that the encapsulated C-SEM has
good thermal durable up to 80 ◦ C, which is very much higher its
melting temperature. Moreover, the micro/nano encapsulated PCM
has good thermal reliability, chemical stability and good thermal
conductivity. By taking into account all results, it can be also con-
cluded that the micro/nano encapsulated PCM can be incorporated
with different building components (such as panels, plasterboards,
and wallboards) to decrease indoor temperature swing in buildings
depending on the climatic conditions.
Acknowledgments
The author would like to acknowledge by Scientific and Tech-
nological Research Council of Turkey (TÜBİTAK) for financial
support (Project No.: 112T864). Authors also thank Derya Kahra-
man Döğüşcü, Çınar Kızıl, Cahit Bilgin, Ayşe Altıntaş and Alper Biçer
for their helps in some parts of the experiments.
112 A. Sarı et al. / Energy and Buildings 90 (2015) 106–113
References
[1] P. Zhang, Z.W. Ma, R.Z. Wang, An overview of phase change material
slurries: MPCS and CHS, Renewable Sustainable Energy Rev. 14 (2010)
598–614.
[2] V.V. Tyagi, S.C. Kaushik, S.K. Tyagi, T. Akiyama, Development of phase change
materials based microencapsulated technology for buildings: a review, Renew-
able Sustainable Energy Rev. 15 (2011) 1373–1391.
[3] B. Zalba, J.M. Marin, L.F. Cabeza, H. Mehling, Review on thermal energy storage
with phase change: materials, heat transfer analysis and applications, Appl.
Therm. Eng. 23 (2003) 251–283.
[4] S.G. Jeong, J. Jeon, J. Cha, J. Kim, S. Kim, Preparation and evaluation of thermal
enhanced silica fume by incorporating organic PCM, for application to concrete,
Energy Build. 62 (2013) 190–195.
[5] A. Pasupathy, L. Athanasius, R. Velraj, R.V. Seeniraj, Experimental investigation
and numerical simulation analysis on the thermal performance of a build-
ing roof incorporating phase change material (PCM) for thermal management,
Appl. Therm. Eng. 28 (2008) 556–565.
[6] M. Pomianowski, P. Heiselberg, Y. Zhang, Review of thermal energy storage
technologies based on PCM application in buildings, Energy Build. 67 (2013)
56–69.
[7] T. Toppi, L. Mazzarella, Gypsum based composite materials with micro-
encapsulated PCM: experimental correlations for thermal properties esti-
mation on the basis of the composition, Energy Build. 57 (2013)
227–236.
[8] P. Lamberg, J. Jokisalo, K. Sirén, The effects on indoor comfort when using phase
change materials with building concrete products, in: Proceedings IEA, ECES IA
Annex 10, Sixth Workshop, November, 2000, Stockholm, Sweden, 2000, pp.
22–24.
[9] A.M. Khudair, M.M. Farid, A review on energy conservation in building applica-
tions with thermal storage by latent heat using phase change materials, Energy
Convers. Manage. 45 (2007) 263–275.
[10] V. Sharma, V.V. Tyagi, C.R. Chen, D. Buddhi, Review on thermal energy stor-
age able with phase change materials and applications, Renewable Sustainable
Energy Rev. 13 (2009) 318–345.
[11] V.V. Tyagi, D. Buddhi, PCM thermal storage in buildings: a state of art, Renew-
able Sustainable Energy Rev. 11 (2007) 1146–1166.
[12] S.H. Lee, S.J. Yoon, Y. Gu Kim, Y.C. Choi, J.H. Kim, J.G. Lee, Development of build-
ing materials by using micro-encapsulated phase change material, Korean J.
Chem. Eng. 24 (2007) 332–335.
[13] D.P. Bentz, R. Turpin, Potential applications of phase change materials in con-
crete technology, Cem. Concr. Compos. 29 (2007) 527–532.
[14] L.F. Cabeza, C. Castellon, M. Nogues, M. Medrano, R. Leppers, O. Zubillaga, Use
of microencapsulated PCM in concrete walls for energy savings, Energy Build.
39 (2007) 113–119.
[15] L. Royon, L. Karim, A. Bontemps, Thermal energy storage and release of a new
component with PCM for integration in floors for thermal management of
buildings, Energy Build. 63 (2013) 29–35.
[16] M. Koschenz, B. Lehmann, Development of a thermally activated ceiling panel
with PCM for application in lightweight and retrofitted buildings, Energy Build.
36 (2004) 567–578.
[17] A.M. Borreguero, I. Garrido, J.L. Valverde, J.F. Rodríguez, M. Carmona, Devel-
opment of smart gypsum composites by incorporating thermoregulating
microcapsules, Energy Build. 76 (2014) 631–639.
[18] 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.
[19] M. Kenisarin, K. Mahkamov, Solar energy storage using phase change materials,
Renewable Sustainable Energy Rev. 11 (2007) 1913–1965.
[20] Z. Chen, F. Shan, L. Cao, G.Y. Fang, Preparation and thermal properties of n-
octadecane/molecular sieve composites as form-stable thermal energy storage
materials for buildings, Energy Build. 49 (2012) 423–428.
[21] B. Boh, B. Šumiga, Microencapsulation technology and its applications in build-
ing construction materials, RMZ—Mater. Geoenviron. 55 (2008) 329–344.
[22] M.N.A Hawlader, M.S. Uddin, M.M. Khin, Microencapsulated PCM thermal
energy storage system, Appl. Energy 74 (2003) 195–202.
[23] A. Waqas, Z. Ud Din, Phase change material (PCM) storage for free cooling of
buildings—a review, Renewable Sustainable Energy Rev. 18 (2013) 607–625.
[24] A. Sarı, C. Alkan, A. Karaipekli, Preparation, characterization and thermal prop-
erties of PMMA/n-heptadecane microcapsules as novel solid-liquid microPCM
for thermal energy storage, Appl. Energy 87 (2010) 1529–1534.
[25] 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.
[26] C. Alkan, A. Sarı, A. Karaipekli, O. Uzun, Preparation, characterization, and ther-
mal properties of microencapsulated phase change material for thermal energy
storage, Sol. Energy Mater. Sol. Cells 93 (2009) 143–147.
[27] L. Bayes-Garcıa, L. Ventol, R. Cordobilla, R. Benages, T. Calvet, M.A. Cuevas-
Diarte, Phase change materials (PCM) microcapsules with different shell
compositions: preparation, characterization and thermal stability, Sol. Energy
Mater. Sol. Cells 94 (2010) 1235–1240.
[28] 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.
[29] B. Alic, U. Sebenik, M. Krajnc, Microencapsulation of butyl stearate with
melamine-formaldehyde resin: effect of decreasing the pH value on the com-
position and thermal stability of microcapsules, eXPRESS Polym. Lett. 6 (2012)
826–836.
[30] M. Fuensanta, U. Paiphansiri, M.D. Romero-Sánchez, Á.M. López-Buendía, K.
Landfester, C. Guillem, Thermal properties of a nove nano encapsulated phase
change material for thermal energy storage, Thermochim. Acta 565 (2013)
95–101.
[31] L. Sanchez-Silva, J.F. Rodríguez, A. Romero, A.M. Borreguero, M. Carmona,
P. Sanche, Microencapsulation of PCM with a styrene-methyl methacrylate
copolymer shell by suspension-like polymerization, Chem. Eng. J. 157 (2010)
216–222.
[32] X. Qiu, W. Li, G. Song, X. Chu, G. Tang, Microencapsulated n-octadecane with dif-
ferent methylmethacrylate-based copolymer shells as phase change materials
for thermal energy storage, Energy 46 (2012) 188–199.
[33] Y. Fang, S. Kuang, X. Gao, Z. Zhang, Preparation and characterization of novel
nanoencapsulated phase change materials, Energy Convers. Manage. 49 (2009)
3704–3707.
[34] A. Sarı, C. Alkan, D. Kahraman Döğüşcü, A. Biçer, Micro/nano-encapsulated n-
heptadecane with polystyrene shell for latent heat thermal energy storage, Sol.
Energy Mater. Sol. Cells 126 (2014) 42–50.
[35] 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.
[36] 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. Manage. 52 (2011) 687–692.
[37] 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.
[38] A. Sarı, C. Alkan, A. Biçer, A. Altuntas, C. Bilgin, Micro/nanoencapsulated n-
nonadecane with poly(methyl methacrylate) shell for thermal energy storage,
Energy Convers. Manage. 86 (2014) 614–621.
[39] 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.
[40] T. Wei, B. Zheng, J. Liu, Y. Gao, W. Guo, Structures and thermal properties of
fatty acid/expanded perlite composites as form-stable phase change materials,
Energy Build. 68 (2014) 587–592.
[41] A. Sharma, A. Shukla, C.R. Chen, S. Dwived, Development of phase change mate-
rials for building application, Energy Build. 64 (2013) 403–407.
[42] Y. Wang, T.D. Xia, H. Zheng, H.X. Feng, Stearic acid/silica fume composite as
form-stable phase change material for thermal energy storage, Energy Build.
43 (2011) 2365–2370.
[43] Z. Chen, L. Cao, F. Shan, G. Fang, Preparation and characteristics of microencap-
sulated stearic acid as composite thermal energy storage material in buildings,
Energy Build. 62 (2013) 469–474.
[44] A. Sarı, C. Alkan, A. Altıntaş, Preparation, characterization and latent heat
thermal energy storage properties of micro-nanoencapsulated fatty acids by
polystyrene shell, Appl. Therm. Eng. 73 (2014) 1158–1166.
[45] Y. Konuklu, H.O. Paksoy, M. Unal, S. Konuklu, Microencapsulation of a fatty acid
with poly(melamine-urea-formaldehyde), Energy Convers. Manage. 80 (2014)
382–390.
[46] U. Stritih, V. Butala, Energy saving in building with PCM cold storage, Int. J.
Energy Res. 31 (2007) 1532–1544.
[47] V. Butala, U. Stritih, Experimental investigation of PCM cold storage, Energy
Build. 41 (2009) 354–359.
[48] V. Raj, R. Velraj, Review on free cooling of buildings using phase change mate-
rials, Renewable Sustainable Energy Rev. 14 (2010) 2819–2829.
[49] K. Yanbing, J. Yi, Z. Yinping, Modeling and experimental study on an innovative
passive cooling system-NVP system, Energy Build. 35 (2003) 417–425.
[50] S. Medved, C. Arkar, Correlation between the local climate and the free-cooling
potential of latent heat storage, Energy Build. 40 (2008) 429–437.
[51] A. Sarı, A. Bicer, O. Lafcı, M. Ceylan, Galactitol hexa stearate and galactitol hexa
palmitate as novel solid–liquid phase change materials for thermal energy
storage, Sol. Energy 85 (2011) 2061–2071.
[52] P. Kauranen, K. Peippo, P.D. Lund, An organic PCM storage system with
adjustable melting temperature, Sol. Energy 46 (1991) 275–278.
[53] Y. Zhang, Y. Su, X. Ge, Predication of the melting temperature and the fusion
heat of (Quasi-) eutectic PCM, J. China Univ. Min. Technol. 25 (1995) 474–478.
[54] A. Sarı, Eutectic mixtures of some fatty acids for low temperature solar heating
applications: thermal properties and thermal reliability, Appl. Therm. Eng. 25
(2005) 2100–2107.
[55] S.L. Lv, N. Zhu, G.H. Feng, Eutectic mixtures of capric acid and lauric acid
applied in building wallboards for heat energy storage, Energy Build. 38 (2006)
708–711.
[56] A. Sharma, A. Shukla, C.R. Chen, T.N. Wu, Development of phase change materi-
als (PCMs) for low temperature energy storage applications, Sustainable Energy
Technol. Assess. 7 (2014) 17–21.
[57] N. Zhang, Y. Yuan, Y. Yuan, T. Li, X. Cao, Lauric-palmitic-stearic acid/expanded
perlite composite as form-stable phase change material: preparation and ther-
mal properties, Energy Build. 82 (2014) 505–511.
[58] J. Zuo, W. Li, L. Weng, Thermal performance of caprylic acid/1-dodecanol
eutectic mixture as phase change material (PCM), Energy Build. 43 (2011)
207–210.
 A. Sarı et al. / Energy and Buildings 90 (2015) 106–113
[59] A. Jamekhorshid, S.M. Sadrameli, M.M. Farid, A review of microencapsulation
methods of phase change materials (PCMs) as a thermal energy storage(TES)
medium, Renewable Sustainable Energy Rev. 31 (2014) 531–542.
[60] Y. Wang, Y. Zhang, T.D. Xia, W.J. Zhao, W.H. Yang, Effects of fabricated tech-
nology on particle size distribution and thermal properties of static-eicosanoic
acid/polymethylmethacrylate nanocapsules, Sol. Energy Mater. Sol. Cells 120
(2014) 481–490.
[61] Y. Konuklu, M. Unal, H.O. Paksoy, Microencapsulation of caprylic acid with dif-
ferent wall materials as phase change material for thermal energy storage, Sol.
Energy Mater. Sol. Cells 120 (2014) 536–542.
[62] Y. Bao, W. Pan, T. Wang, Z. Wang, F. Wei, F. Xiao, Microencapsulation of fatty
acid as phase change material for latent heat storage, J. Energy Eng. 137 (2011)
214–219.
[63] C. Liang, X. Lingling, S. Hongbo, Z. Zhibin, Microencapsulation of butyl stearate
as a phase change material by interfacial polycondensation in a polyurea sys-
tem, Energy Convers. Manage. 50 (2009) 723–729.
[64] A.A. Aydin, In situ preparation and characterization of encapsulated high-chain
fatty acid ester-based phase change material (PCM) in poly(urethane–urea) by
using amino alcohol, Chem. Eng. J. 231 (2013) 477–483.
113
[65] K.M. Rathod, J. Banerjee, Thermal stability of phase change materials used in
latent heat energy storage systems: a review, Renewable Sustainable Energy
Rev. 18 (2013) 246–258.
[66] A. Sarı, C. Alkan, C. Bilgin, Micro/nano encapsulation of some paraffin eutectic
mixtures with poly(methyl methacrylate) shell: preparation, characterization
and latent heat thermal energy storage properties, Appl. Energy 136 (2014)
217–227.
[67] S. Kim, S.J. Chang, O. Chung, S.G. Jeong, S. Kim, Thermal characteristics of
mortar containing hexadecane/xGnP SSPCM and energy storage behaviors of
envelopes integrated with enhanced heat storage composites for energy effi-
cient buildings, Energy Build. 70 (2014) 472–479.
[68] Y. Yuan, N. Zhang, W. Tao, X. Cao, Y. He, Fatty acids as phase change
materials: a Review, Renewable Sustainable Energy Rev. 29 (2014) 482–
498.
[69] S. Kim, L.T. Drzal, High latent heat storage and high thermal conductive phase
change materials using exfoliated graphite nanoplatelets, Sol. Energy Mater.
Sol. Cells 93 (2009) 136–142.