Solar Energy Materials & Solar Cells 123 (2014) 183–188

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Solar Energy Materials & Solar Cells

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

Preparation and characteristics of microencapsulated palmitic acid

with TiO2 shell as shape-stabilized thermal energy storage materials
Lei Cao, Fang Tang, Guiyin Fang n
School of Physics, Nanjing University, Nanjing, Jiangsu 210093, China

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

Article history: Microencapsulated palmitic acid (PA) with titanium dioxide (TiO2) shell as shape-stabilized thermal
Received 1 August 2013 energy storage material was synthesized through a sol–gel process. Scanning electron microscope (SEM),
Received in revised form Fourier transformation infrared spectroscope (FT-IR), X-ray diffractometer (XRD) and X-ray photoelec-
13 November 2013
tron spectroscopy (XPS) were used to determine the morphology, chemical structure, crystalloid phase
Accepted 8 January 2014
Available online 2 February 2014
and chemical state of the microcapsules, respectively. The thermal properties and thermal stability were
investigated by a differential scanning calorimeter (DSC) and a thermogravimetric analyzer (TGA). The
Keywords: microcapsules have relatively spherical shape and average size of 200–400 nm. The FT-IR, XRD and XPS
Thermal energy storage materials results showed that the PA was well encapsulated in the TiO2 shell. The DSC results indicated that the
Microencapsulation
typical microcapsules melt at 61.7 1C with a latent heat of 63.3 kJ/kg and solidify at 56.7 1C with a latent
Titanium dioxide
heat of 47.1 kJ/kg. The TGA results confirmed that the microcapsules have good thermal stability,
Characteristics
Thermal properties resulting from the TiO2 shells. Based on all results, it can be concluded that the prepared microcapsules
have good energy storage potential due to their non-inflammability, nontoxicity and good thermal
stability.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction protecting PCMs from outside environment, increasing the heat

transfer efficiency and controlling the volume changes during the
In recent decades, the increasing energy consumption and period of phase change [13–16]. Therefore, these features make
shortage of fossil fuels have been a big challenge for the develop- them more excellent than the traditional PCMs in many applica-
ment of human society. Hence the investigation of new energy tions such as functional fibers, heat transfer, solar energy storage,
resources as well as efficient ways of energy storage and recovery and building materials.
has attracted much attention [1,2]. Phase change materials (PCMs) Many attempts have been carried out to encapsulate PCMs with
have received great interest in solar heating systems, building different shell materials via solution casting [17], spray-drying
energy conservation and air-conditioning systems owing to their [18,19], coacervation [20,21], suspension polymerization [22],
high energy storage density and slowly release the latent heat [3–5]. interfacial polymerization [23] and in-situ polymerization [24].
A large number of PCMs including salt hydrates, paraffin wax, Polymethyl methacrylate (PMMA), polyurea (PU), polycarbonate
fatty acids and alkanes have been investigated for different (PC) and other organic polymers have been used as shell materials
applications [6–9]. The palmitic acid (PA) is widely used as PCM in previous investigations [2,17]. However, the application of the
due to its suitable phase change temperature range, high energy MPCMs in polymeric shells is usually restricted due to their
storage density, little or no supercooling during the phase transi- flammability, toxicity, low heat conductivity and poor thermal
tion, nontoxicity and good thermal reliability [7]. In spite of these stability. Therefore, many attentions have been focused on inor-
desirable properties of palmitic acid, the low thermal conductivity ganic shell materials. Zhang et al. [15] and Chen et al. [25]
and the leakage of melted palmitic acid limit its application to a prepared phase-change microcapsules with inorganic silica gel
large extent [3,10–12]. Recently, encapsulation of PCMs in a solid polymer as shell material, respectively. Lin et al. [26] reported a
shell has been found to be a good way to enlarge the utility fields novel micro-PCM with AlOOH as shell material, while it has a low
of the PCMs. Microencapsulated PCMs (MPCMs) have several latent heat value. However, the silica gel polymer as shell material
advantages, such as preventing the leakage of melted PCMs, has poor mechanical properties, and the shell of microencapsu-
lated phase change material cracked easily. The TiO2 shell can
improve the thermal stability of the microcapsules, lower the
n
Corresponding author. Tel.: þ 86 25 51788228; fax: þ 86 25 83593707. flammability of the microencapsulated palmitic acid and prevent
E-mail address: [email protected] (G. Fang). the leakage of the melted palmitic acid. Up to now, the synthesis

0927-0248/$ - see front matter & 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.solmat.2014.01.023
184 L. Cao et al. / Solar Energy Materials & Solar Cells 123 (2014) 183–188

and thermal properties of the microencapsulated palmitic acid measured by an X-ray diffractometer (XRD, D/MAX-Ultima III,
with titanium dioxide shell is little reported. Rigaku Corporation, Japan). The XRD patterns were obtained with
In this paper, the microcapsules with the palmitic acid as core continuous scanning mode at a rate of 51 (2θ)/min and operating
material and the TiO2 as shell material were prepared using a conditions of 40 kV and 40 mA. The chemical composition was
sol–gel method. The TiO2 as shell material was prepared by determined by X-ray photoelectron spectroscopy (XPS, Thermo
hydrolysis-condensation reaction of the tetra-n-butyl titanate Fisher Scientific) with Al Kα X-ray as the radiation source.
(TNBT). The morphologies and thermal properties of the MPCMs A scanning electron microscope (SEM, S-3400NII, Hitachi Inc.,
were investigated. Japan) was used to observe the morphology and microstructure
of the microencapsulated PA with TiO2 shell. A differential scan-
ning calorimeter (DSC, Pyris 1 DSC, Perkin-Elmer) was used to
2. Experimental analyze the thermal properties of the microencapsulated PA with
TiO2 shell at 5 1C/min under a constant stream of argon. The
2.1. Materials accuracy of temperature measurements was 70.2 1C and the
enthalpy accuracy was 7 5%. The thermal stability of the micro-
Palmitic acid (Reagent grade) was used as core material and encapsulated PA with TiO2 shell was investigated by a thermo-
obtained from Sinopharm Chemical Reagent Company. Tetra-n- gravimetric analyzer (Pyris 1 TGA, Perkin-Elmer) from room
butyl titanate (Reagent grade, Nanjing Chemical Reagent Com- temperature to 700 1C with a linear heating rate of 20 1C/min
pany) was used as the precursor. Anhydrous ethanol (Analytical under a constant stream of nitrogen.
grade, Nanjing Chemical Reagent Company) and deionized water
were used as solvent. Sodium dodecyl sulfate (SDS) (Analytical
grade) was used as emulsifier (Jiangsu Huakang Chemical Reagent
Company). The hydrochloric acid (Analytical grade, Nanjing Che-
mical Reagent Company) was used to control the pH value. 3. Results and discussion

2.2. Preparation of the MPCMs with TiO2 shell 3.1. Morphology of the MPCMs with TiO2 shell

The palmitic acid, SDS and deionized water were mixed The morphology and microstructure of the microcapsules were
together in a beaker according to the ratio listed in Table 1. determined by SEM. Fig. 1 shows the SEM photographs of the
In order to form an O/W emulsion, the mixture was continuously obtained microcapsules. As seen in Fig. 1, the microcapsules have
stirred at a rate of 1000 rpm for 40 min with a magnetic stirrer relatively spherical shape. It was observed from the SEM images
while the temperature was controlled at 75 1C. Finally, the palmitic that the average size of the microcapsules is about 200–400 nm.
acid was dispersed uniformly in the O/W microemulsion. The
pH value was adjusted to 2–3 by adding a little hydrochloric acid.
In another beaker, the TNBT and anhydrous ethanol were
mixed together to form the precursor solution. Then the solution 3.2. FT-IR analysis of the MPCMs with TiO2 shell
was added into the obtained microemulsion drop by drop, while
the stirring rate was kept at 800 rpm and the temperature was The FT-IR spectra of the PA, TiO2 and MPCMs are presented in
controlled at 75 1C using a constant temperature bath for 1 h. The Fig. 2. As shown in Fig. 2a, the two strong absorption peaks at
formation process of TiO2 shell is as follows: the TNBT hydrolyzed 2917 cm  1 and 2849 cm  1 represent the asymmetric and sym-
to form the sol solution. Then, the condensation reaction between metric stretching vibrations of –CH2 group, while the relatively
the titanic acid took place to form the oligomers. Finally, the weak absorption peaks at 2954 cm  1 and 2871 cm  1 signify the
oligomers of TiO2 polymerized to build the TiO2 shell on the asymmetric and symmetric stretching vibrations of –CH3 group in
surface of the palmitic acid micro-droplets. After the mixture was PA, respectively. The strong absorption peak at 1703 cm  1 is
cooled to room temperature, the resultant MPCMs were washed attributed to C ¼ O stretching vibration. The absorption peaks
by distilled water and anhydrous ethanol twice respectively, and around 1471 cm  1 and 1295 cm  1 are attributed to the bending
then were dried at 45 1C for 24 h in vacuum oven. Three kinds of vibrations of –CH3 and –CH2 groups. The peak at 941 cm  1 is
microcapsules were obtained, and named as MPCM1, MPCM2 assigned to the –OH out-of-plane rocking vibration, and the in-
and MPCM3. plane rocking vibration of –CH2 group is represented by the
absorption peak at 719 cm  1. In Fig. 2b, the absorption bands
2.3. Characterization of the MPCMs with TiO2 shell around 3200 cm  1 and 1622 cm  1 belong to the stretching
vibration and deformation vibration of the –OH functional group
The chemical structure analysis of the microencapsulated PA in H2O, while the characteristic absorption peaks of TiO2 are
with TiO2 shell was performed on a Fourier transformation around the far infrared region.
infrared spectroscope (FT-IR, Nicolet Nexus 870), and the spectra As shown in Fig. 2, all the characteristic peaks of the PA and
were recorded from 400 cm  1 to 4000 cm  1 with a resolution of TiO2 can be found in the spectra of the MPCMs, and no peak shift is
2 cm  1 using KBr pellets. The crystalloid phase of the MPCMs was observed. The absorption peaks of C¼ O in carboxylic acid groups
are in the region of 1665–1760 cm  1 due to the stretching
Table 1 vibration of the C ¼O bond. However, the absorption peaks of
The compositions of the PA emulsion and solution of the TNBT. C¼ O group in a carboxylate (salt of the carboxylic acid) are in the
region of 1530–1580 cm  1 due to the effect of metal ion. In the
Samples PA emulsion Solution of TNBT
synthesis process, a small amount of titanium palmitate (a salt
PA (g) Deionized water (ml) SDS (g) TNBT (g) Ethanol (g) consists of C15H31COO  and Ti4 þ ) was generated, and the absorp-
tion peak at 1531 cm  1 in the spectra of the MPCMs is corre-
MPCM1 20 300 3.5 25 80 sponding to the stretching vibration of the C¼ O in the titanium
MPCM2 15 300 2.5 25 80
MPCM3 15 300 2.5 25 100
palmitate. These specific peaks in the spectra of the MPCMs
indicated the PA in the obtained microcapsules.
 L. Cao et al. / Solar Energy Materials & Solar Cells 123 (2014) 183–188 185

Fig. 1. SEM images of the (a) MPCM1 (20k  ), (b) MPCM2 (20k  ), (c) MPCM3 (20k  ) and (d) MPCM1 (5k  ).

Fig. 2. FT-IR spectra of the (a) PA, (b) TiO2, (c) MPCM1, (d) MPCM2 and (e) MPCM3. Fig. 3. XRD patterns of the (a) PA, (b) TiO2, (c) MPCM1, (d) MPCM2 and (e) MPCM3.

3.3. XRD and XPS analyses of the MPCMs with TiO2 shell 458.2 eV, which are very close to the reported binding energy of
Ti 2p in TiO2 (463.6 eV and 458.5 eV) [27,28]. Fig. 4(b) illustrates
The XRD patterns of the PA, TiO2 and MPCMs are shown in that O 1s peaks appear at 529.8 eV and 531.6 eV. The O 1s peak at
Fig. 3. The XRD peaks at 12.51, 20.41, 21.61, 24.21 and 36.31 of the 529.8 eV is assigned to the lattice oxygen atom of TiO2, and the
PA are due to its regular crystallization. As shown in Fig. 3b, the peak at 531.6 eV is corresponding to the oxygen in the surface
TiO2 has a flat peak at around 20.41, which indicates its non- hydroxyl groups. These results confirm that the chemical compo-
crystalline and amorphous structure. As seen in Fig. 3, the XRD sition of the shells of the MCPMs is TiO2.
patterns of the MPCMs contain both the peaks of the PA and the
flat peak of the TiO2. This result indicates that the crystal structure 3.4. Thermal properties of the MPCMs with TiO2 shell
of the PA remains unchanged after encapsulated PA in the
TiO2 shell. DSC analyses have been conducted to determine the thermal
In order to investigate the chemical states of shells of the properties of the MPCMs. Figs. 5 and 6 show the DSC curves for the
MPCMs, Ti 2p and O 1s binding energies are measured by the melting and solidifying process of the PA and the MPCMs, and the
XPS spectra. Fig. 4 shows the XPS spectra of MPCM1. As seen in results are given in Table 2. The melting and solidifying tempera-
Fig. 4(a), the Ti 2p1/2 peak and Ti 2p3/2 peak constitute Ti 2p peak. tures are measured to be 62.6 and 60.5 1C for the PA, and 61.7 and
The binding energy of the Ti 2p1/2 and Ti 2p3/2 are 463.7 eV and 56.7 1C for the MPCM1. The latent heats are found to be 208.5 kJ/kg
186 L. Cao et al. / Solar Energy Materials & Solar Cells 123 (2014) 183–188

Fig. 6. The solidifying DSC curves of the PA and MPCM1–MPCM3.

Table 2
DSC data of the PA and MPCM1–MPCM3.

Samples Melting Solidifying Encapsulation

ratio of PA (%)
Temperature Latent Temperature Latent
(1C) heat (1C) heat
(kJ/kg) (kJ/kg)

PA 62.6 208.5 60.5 207.4 100

MPCM1 61.7 63.3 56.7 47.1 30.4
MPCM2 60.7 23.2 44.2 7.2 11.1
MPCM3 60.7 33.1 51.8 16.2 15.9

for the PA and 63.3 kJ/kg for the MPCM1. The phase change
characteristics of the MPCMs are very close to those of the PA.
The melting and solidifying temperatures of the MPCMs are lower
than those of the PA. The reason can be explained by the Gibbs–
Thomson effect. For PCM confined in porous or narrow structure,
the depression of the phase transition temperature can be
described as Eq. (1) according to the Gibbs–Thomson thermody-
namic equation.
Fig. 4. XPS spectra of the MPCM1. 2  Δs  υ  T 0
ΔT ¼ T  T 0 ¼ ð1Þ
Hf  R

where T is phase change temperature of the MPCM, T0 is the bulk

phase change temperature of the PA, υ is the molar volume of the
liquid phase, Hf is the bulk enthalpy of fusion, R is the radius of the
pore and Δs is the difference between the solid/wall interfacial
energy and the liquid/wall interfacial energy. It is seen from Eq. (1)
that the sign of the temperature shift is determined by the
difference of solid/wall interfacial energy and the liquid/wall
interfacial energy. In cases of confined geometry, such as the PA
in the MPCM, this effect will lead to a depression in the freezing
point/melting point that is inversely proportional to the pore size,
as given by the Gibbs–Thomson equation [29,30].
The enthalpy values of the MPCMs become lower than that of
the PA because only PA absorbs thermal energy during the heating
process. Higher content of the PA in the microcapsules results in a
higher latent heat storage capacity. The encapsulation ratio of the
PA is calculated by the following equation:
ΔH MPCM
η¼  100% ð2Þ
ΔH PCM
where η is the encapsulation ratio of the PA, ΔHMPCM and ΔHPCM
represents the melting latent heat of the MPCMs and PA, respec-
Fig. 5. The melting DSC curves of the PA and MPCM1–MPCM3. tively. The calculated results are listed in Table 2. As expected,
 L. Cao et al. / Solar Energy Materials & Solar Cells 123 (2014) 183–188 187

Table 3
Comparison of the MPCMs with TiO2 shell with results of other inorganic shell material.

MPCMs Melting point (1C) Melting latent heat (kJ/kg) Average diameter (μm) Encapsulation ratio (wt%) Reference

n-Octadecane/CaCO3 29.19 84.37 5 40.35 [31]

n-Octadecane/SiO2 27.1 140.9 7–16 65.4 [15]
Paraffin/SiO2 57.10 97.41 40–60 51.0 [25]
PA/AlOOH 16.0 27.8 0.2 69 [26]
PA/TiO2 61.7 63.3 0.2–0.4 30.4 Present study

encapsulation ratio is induced by the amount of the anhydrous

ethanol in the synthesis process. So, the amount of the anhydrous
ethanol has an effect on the encapsulation ratio of the MPCMs. As
is known, the anhydrous ethanol dilutes the TNBT solution, hence
the hydrolysis reaction of the TNBT will be retarded, which favors
the evenly formation of the TiO2 shells. However, excess anhy-
drous ethanol will prevent the titanic acid monomers from
polymerizing to build the shell. Therefore, the TiO2 shell could
be well formed by adjusting the amount of the anhydrous ethanol.
In this work, the maximum encapsulation of PA is 30.4%. In order
to enhance the encapsulation ratio, new precursor should be
found to prepare the TiO2 shell or other synthesis method has to
be investigated.
Table 3 presents the comparison of the MPCMs with TiO2 shell
with results of other inorganic shell material. It can be found that
the PA/TiO2 MPCM has a much smaller average diameter and
appropriate phase change temperature for waste heat recovery
systems, solar heating systems and building energy conservation
Fig. 7. TGA curves of the PA and MPCM1–MPCM3.
systems. Microcapsules with small average diameter can greatly
improve heat transfer efficiency because of the large surface-to-
volume ratio of the MPCMs and the interaction of particles with
particles or fluid, which significantly increases the capability and
heat transfer efficiency of the MPCMs. Therefore, the PA/TiO2
MPCM has an important potential application in thermal energy
storage system.

3.5. Thermal stability of the MPCMs with TiO2 shell

The TGA and DTG curves of the PA and the MPCMs are
presented in Figs. 7 and 8, the charred residue amount and the
temperature of maximum weight loss rate are listed in Table 4.
Fig. 7 shows that the weight loss of the PA starts at 220 1C and
ends at 270 1C. The TGA curve of the PA is sharp and is only one
step due to its linear alkane structure with a low decomposing
temperature. As for the MPCMs, there are two-step thermal
decomposition processes. The first step of decomposition occurs
between 230 1C and 400 1C, which corresponds to the thermal
decomposition of the PA molecular chains. The second step of
weight loss takes place between 400 1C and 500 1C, corresponding
Fig. 8. DTG curves of the PA and MPCM1–MPCM3. to the thermal degradation of the TiO2 gel and the crystal
transition of TiO2 from the amorphous state to anatase phase.
The temperatures of maximum weight loss rate are measured
as 316.0 1C, 313.4 1C and 302.2 1C for the MPCMs in the first step of
Table 4
TGA data of the PA and MPCM1–MPCM3. weight loss, which are much higher than that of the PA (265.3 1C).
This implies the TiO2 shells can prevent the PA from decomposi-
Samples Tpeak1 (1C) Tpeak2 (1C) Charred residue amount (%) tion. It is also noted that the weight loss is limited under 2.7% at
(670 1C)
the working temperature of the MPCMs. These results indicate
PA 265.3 – 1.9 that the thermal stability of the PA can be improved by micro-
MPCM1 316.0 448.5 21.0 encapsulating PA in TiO2 shell. The thermal cycling test is also
MPCM2 313.4 455.6 27.2 important to investigate the stability and durability of the MPCMs.
MPCM3 302.2 460.1 30.6 This work will be performed in next investigation.

larger amount of the PA used in the synthesis process will lead to a 4. Conclusions
higher encapsulation ratio. As seen in Table 2, the encapsulation
ratios of the MPCM1, MPCM2 and MPCM3 were determined to be Microencapsulated PA with TiO2 shell as shape-stabilized
30.4%, 11.1% and 15.9%, respectively. This difference in the thermal energy storage material was successfully prepared by
188 L. Cao et al. / Solar Energy Materials & Solar Cells 123 (2014) 183–188

the sol–gel method. From the SEM, FT-IR, XRD and XPS results, it is [12] X.L. Qiu, W. Li, G.L. Song, X.D. Chu, G.Y. Tang, Fabrication and characterization of
found that the PA has been well encapsulated in the TiO2 shell. The microencapsulated n-octadecane with different crosslinked methylmethacrylate-
based polymer shells, Sol. Energy Mater. Sol. Cells 98 (2012) 283–293.
microcapsules have relatively spherical shape and average size of [13] Z.H. Chen, F. Yu, X.R. Zeng, Z.G. Zhang, Preparation, characterization and
200–400 nm. The DSC and TGA results indicate that the typical thermal properties of nanocapsules containing phase change material n-
microencapsulated PA melts at 61.7 1C with a latent heat of dodecanol by miniemulsion polymerization with polymerizable emulsifier,
63.3 kJ/kg and solidifies at 56.7 1C with a latent heat of 47.1 kJ/kg Appl. Energy 91 (2012) 7–12.
[14] W. Li, G.L. Song, G.Y. Tang, X.D. Chu, S.D. Ma, C.F. Liu, Morphology structure and
as the microencapsulation ratio is 30.4%. The TiO2 shells can thermal stability of microencapsulated phase change material with polymer
prevent the leakage of the microencapsulated PA and improve shell, Energy 36 (2011) 785–791.
the thermal stability. Based on all results, it is concluded that the [15] H.Z. Zhang, X.D. Wang, D.Z. Wu, Silica encapsulation of n-octadecane via sol–
prepared microencapsulated PA with TiO2 shell has potential for gel process: a novel microencapsulated phase-change material with enhanced
thermal conductivity and performance, J. Colloid Interface Sci. 343 (2010)
thermal energy storage applications. 246–255.
[16] W. Li, X.X. Zhang, X.C. Wang, G.Y. Tang, H.F. Shi, Fabrication and morphological
characterization of microencapsulated phase change materials (MicroPCMs)
Acknowledgements and macrocapsules containing MicroPCMs for thermal energy storage, Energy
38 (2012) 249–254.
[17] T. Zhang, Y. Wang, H. Shi, W.T. Yang, Fabrication and performances of new kind
This work was supported by the National Natural Science
microencapsulated phase change material based on stearic acid core and
Foundation of China (Grant no. 51376087) and the Priority Academic polycarbonate shell, Energy Convers. Manage 64 (2012) 1–7.
Program Development of Jiangsu Higher Education Institutions. [18] 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.
References [19] M.N.A. Hawlader, M.S. Uddin, M.M. Khin, Microencapsulated PCM thermal-
energy storage system, Appl. Energy 74 (2003) 195–202.
[1] A. Sharma, V.V. Tyagi, C.R. Chen, D. Buddhi, Review on thermal energy storage [20] Y. Ozonur, M. Mazman, H.O. Paksoyn, H. Evliya, Microencapsulation of coco
with phase change materials and applications, Renewable Sustainable Energy fatty acid mixture for thermal energy storage with phase change material, Int.
Rev. 13 (2009) 318–345. J. Energy Res. 30 (2006) 741–749.
[2] A. Sari, C. Alkan, A. Karaipekli, Preparation, characterization and thermal [21] S.S. Deveci, G. Basal, Preparation of PCM microcapsules by complex coacerva-
properties of PMMA/n-heptadecane microcapsules as novel solid–liquid tion of silk fibroin and chitosan, Colloid Polym. Sci 287 (2009) 1455–1467.
microPCM for thermal energy storage, Appl. Energy 87 (2010) 1529–1534. [22] L.S. Silva, J.F. Rodriguez, A. Romero, A.M. Borreguero, M. Carmona, P. Sanchez,
[3] G.Y. Fang, H. Li, Z. Chen, X. Liu, Preparation and characterization of flame Microencapsulation of PCMs with a styrene-methly methacrylate copolymer
retardant n-hexadecane/silicon dioxide composites as thermal energy storage shell by suspension-like polymerization, Chem. Eng. J. 157 (2010) 216–222.
materials, J. Hazard. Mater. 181 (2010) 1004–1009. [23] G.L. Zou, Z.C. Tan, X.Z. Lan, L.X. Sun, T. Zhang, Preparation and characterization
[4] X.L. Qiu, W. Li, G.L. Song, X.D. Chu, G.Y. Tang, Microencapsulated n-octadecane of microencapsulated hexadecane used for thermal energy storage, Chin.
with different methylmethacrylate-based copolymer shells as phase change Chem. Lett. 15 (2004) 729–732.
materials for thermal energy storage, Energy 46 (2012) 188–199. [24] J.K. Chio, J.G. Lee, J.H. Kim, H.S. Yang, Preparation of microcapsules containing
[5] L.B. Garcia, L. Ventola, R. Cordobilla, R. Benages, T. Calvet, M.A.C. Diarte, Phase phase change materials as heat transfer media by in-situ polymerization,
change materials (PCM) microcapsules with different shell compositions: J. Ind. Eng. Chem. 7 (2001) 358–362.
preparation, characterization and thermal stability, Sol. Energy Mater. Sol. [25] Z. Chen, L. Cao, G.Y. Fang, F. Shan, Synthesis and characterization of micro-
Cells 94 (2010) 1235–1240. encapsulated paraffin microcapsules as shape-stabilized thermal energy
[6] C. Barreneche, A.I. Fernandez, M. Niubo, J.M. Chimenos, F. Espiell, M. Segarra, storage materials, Nanoscale Microscale Thermophys. 17 (2013) 112–123.
C. Sole, L.F. Cabeza, Development and characterization of new shape-stabilized [26] P. Lin, Q.H. Tao, S.D. Zhang, S.S. Wang, J. Zhang, S.H. Wang, Z.Y. Wang,
phase change material (PCM)-polymer including electrical arc furnace dust
Z.P. Zhang, Preparation, characterization and thermal properties of micro-
(EAFD), for acoustic and thermal comfort in buildings, Energy Build. 61 (2013)
encapsulated phase change materials, Sol. Energy Mater. Sol. Cells 98 (2012)
210–214.
66–70.
[7] A. Sari, A. Karaipekli, Preparation, thermal properties and thermal reliability of
[27] D. Leinen, A. Fernández, J.P. Espinós, J.P. Holgado, A.R. González-Elipe, An XPS
palmitic acid/expanded graphite composite as form-stable PCM for thermal
energy storage, Sol. Energy Mater. Sol. Cells 93 (2009) 571–576. study of the mixing effects induced by ion bombardment in composite oxides,
[8] M.M. Farid, A.M. Khudhair, S.A.K. Razack, S. Al-Hallaj, A review on phase Appl. Surf. Sci. 68 (1993) 453–459.
change energy storage: materials and applications, Energy Convers. Manage [28] P.Y. Jouan, M.C. Peignon, Ch. Cardinaud, G. Lempérière, Characterisation of TiN
45 (2004) 1597–1615. coatings and of the TiN/Si interface by X-ray photoelectron spectroscopy and
[9] W.L. Cheng, R.M. Zhang, K. Xie, N. Liu, J. Wang, Heat conduction enhanced Auger electron spectroscopy, Appl. Surf. Sci. 68 (1993) 595–603.
shape-stabilized paraffin/HDPE composite PCMs by graphite addition: pre- [29] J. Warnock, D.D. Awschalom, M.W. Shafer, Geometrical supercooling of liquids
paration and thermal properties, Sol. Energy Mater. Sol. Cells 94 (2010) in porous glass, Phys. Rev. Lett. 57 (1986) 1753–1756.
1636–1642. [30] R. Evans, Fluids adsorbed in narrow pores: phase equilibria and structure,
[10] K.A.R. Ismail, C.L.F. Alves, M.S. Modesto, Numerical and experimental study on J. Phys. Condens. Matter 2 (1990) 8989–9007.
the solidification of PCM around a vertical axially finned isothermal cylinder, [31] S.Y. Yu, X.D. Wang, D.Z. Wu, Microencapsulation of n-octadecane phase change
Appl. Therm. Eng. 21 (2001) 53–77. material with calcium carbonate shell for enhancement of thermal conduc-
[11] J.F. Su, X.Y. Wang, S.B. Wang, Y.H. Zhao, Z. Huang, Fabrication and properties of tivity and serving durability: synthesis, microstructure, and performance
microencapsulated-paraffin/gypsum-matrix building materials for thermal evaluation, Appl. Energy 114 (2014) 632–643.
energy storage, Energy Convers. Manage 55 (2012) 101–107.