Applied Thermal Engineering 114 (2017) 328–336

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Applied Thermal Engineering

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

Research Paper

Design and preparation of shape-stabilized composite phase change

material with high thermal reliability via encapsulating polyethylene
glycol into flower-like TiO2 nanostructure for thermal energy storage
Yong Deng a, Jinhong Li a,⇑, Hongen Nian b, Yali Li a, Xiaoping Yin a
a
Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology,
China University of Geosciences, Beijing 100083, PR China
b
Qinghai Institute of Salt Lake, Chinese Academy of Sciences, 810008, PR China

h i g h l i g h t s

PEG/FLN-TiO2 ss-CPCM with high thermal reliability was prepared.

FLN-TiO2 benefited encapsulation of PEG and thermal reliability enhancement of PEG/FLN-TiO2 ss-CPCM.

Weak physical interaction and test rates affected phase change temperatures of PEG/FLN-TiO2 ss-CPCM.

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

Article history: Flower-like TiO2 nanostructure (FLN-TiO2) with specific surface area of 117.61 m2/g, pore diameter of
Received 31 August 2016 3.75 nm, and spherical diameter of about 1–2 lm was synthesized by a simple hydrothermal method.
Revised 9 November 2016 The obtained FLN-TiO2 was employed to encapsulate polyethylene glycol (PEG) as phase change material
Accepted 10 November 2016
to overcome liquid leakage during phase transition and enhance the thermal reliability of the PEG/FLN-
Available online 30 November 2016
TiO2 shape-stabilized composite phase change material (ss-CPCM) after a large number of thermal cycles.
SEM analysis results showed that abundant PEG was well enwrapped and dispersed inside the pores and
Keywords:
surfaces of FLN-TiO2 due to the effect of capillary force and surface tension. The maximum encapsulation
Polyethylene glycol
Flower-like TiO2 nanostructure
capacity of PEG with good shape stability was 50.2 wt.%. Excellent chemical compatibility between PEG
Shape-stabilized composite phase change and FLN-TiO2 was confirmed by FT-IR results. DSC results indicated that the phase change temperature of
material the PEG/FLN-TiO2 ss-CPCM in melting and solidification process was respectively 53.6 °C and 20.1 °C and
Thermal reliability enhancement corresponding latent heats were 93.68 J/g and 91.07 J/g, respectively. The weak physical interaction
between the PEG and surface of FLN-TiO2 led to the lower phase change temperatures of PEG/FLN-TiO2
ss-CPCM. Different heating and cooling rates were responsible for the shift of melting/solidification tem-
perature of PEG and PEG/FLN-TiO2 ss-CPCM. Thermal cycling test results showed that the PEG/FLN-TiO2
ss-CPCM exhibited excellent thermal reliability within at least 200 melting/solidifying cycles and demon-
strated that the FLN-TiO2 benefited the thermal reliability enhancement.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Latent heat storage utilizing phase change material (PCM) exhi-
bits a high enthalpy, in a relatively small volume and temperature
variations, and can store or release large amounts of thermal
energy during phase transitions [1,2]. PCM becomes one of the
most efficient and valuable thermal energy storage materials.
Among all the PCMs, organic PCM, such as polyethylene glycol
⇑ Corresponding author.
E-mail address: jinhong@cugb.edu.cn (J. Li).
(PEG), has drawn much attention in the last decades because it
has suitable phase change temperature, high phase change latent
heat, low vapor pressure, excellent chemical stability, and low cost
and shows no phase separation or corrosiveness [3].
As a solid–liquid PCM, liquid leakage during phase transition is
the main drawback of PEG and severely restricts its applications
because liquid PEG may destroy the surrounding materials of
energy storage systems and result in potential dangers. To solve
the problem of shape instability of liquid PEG, shape-stabilized
composite phase change material (ss-CPCM) composed of a work-
ing substance and supporting materials has been developed [4,5].

http://dx.doi.org/10.1016/j.applthermaleng.2016.11.082
1359-4311/Ó 2016 Elsevier Ltd. All rights reserved.
 Y. Deng et al. / Applied Thermal Engineering 114 (2017) 328–336
The working substance serves as the PCM for thermal energy stor-
age and supporting material provides structural strength to pre-
vent the leakage of melted PCM. The preparation method of ss-
CPCM is usually physical blending and impregnation method,
which is more simple and effective than other methods, such as
microencapsulation and sol–gel. The preparation and thermal
energy storage of the ss-CPCM containing PEG as PCM had been
extensively reported [6–9].
The pore structure of supporting material plays a key role in
adjusting thermal energy storage behavior of ss-CPCM and enhanc-
ing its thermal reliability after a large number of thermal cycles.
Guan et al. [10] impregnated paraffin into expanded vermiculite
with modified porous carbon layer (pores diameter: 120 lm) to
form ss-CPCM, and its phase change latent heats in melting and
solidification processes were respectively decreased by 22.6% and
22.4% after 200 melting/solidifying cycles. Zhang et al. [11] found
that the latent heats of RT100/expanded graphite (pores diameter:
approximately 10 lm) ss-CPCM after 200 heating-cooling cycles
were respectively decreased by 7.73% for melting and 6.81% for
solidification. RT100 could not completely melt and crystallize
because the narrow zone of expanded graphite limited its partial
long-chain alkanes. It is believed that the decrease of latent heats
after large numbers of phase change cycles is caused by the
decrease in the component of PCM retained in pore structure of
supporting material. The PCM was adsorbed and encapsulated
inside the pores and surfaces of supporting material due to the
capillary force and surface tension. The capillary force can be calcu-
lated via Young-Laplace equation [12]:
p ¼ 2r cos h=r;
where p is capillary force; r represents the surface tension of
melted PCM; h is the wetting angle between PCM and supporting
material; r represents the radius of supporting material pore. Hence,
if the pore size of supporting material is too large, the capillary force
will be not sufficient to retain the liquid PCM in the phase change
cycles, thus leading to bad thermal reliability. The nanoscale pores
will be optimum and beneficial for stabilizing the shape of PCM to
enhance the thermal reliability of ss-CPCM due to strong capillary
force.
Flower-like TiO2 nanostructure (FLN-TiO2) with unique pore
structure, high specific surface area, high photocatalytic activity,
environmental friendliness, and low cost has been widely used in
environmental management, air purification, sterilization, surface
self-cleaning, etc. Currently, the hydrothermal, solvothermal,
microemulsion, sol–gel, and hydrolysis techniques are used to
form FLN-TiO2 [13,14]. FLN-TiO2 is also applied as supporting
material of ss-CPCM for the purpose of thermal reliability enhance-
ment. The effects of FLN-TiO2 on thermal energy storage behaviors
and thermal reliability of ss-CPCM were seldom reported.
In this study, we synthesized FLN-TiO2 through a simple
hydrothermal reaction from metal Ti powders. Then PEG was
encapsulated within FLN-TiO2 to overcome liquid leakage during
phase transition and enhance the thermal reliability of the PEG/
FLN-TiO2 ss-CPCM after a large number of thermal cycles. The mor-
phology, microstructure, crystalline phase, and pore structure of
FLN-TiO2 were investigated. The microstructure, chemical compat-
ibility, thermal energy storage behavior, and thermal reliability of
the prepared PEG/FLN-TiO2 ss-CPCM were also evaluated in detail.
2. Experimental
2.1. Materials
Polyethylene glycol (PEG, Chemically pure) with an average
relative molecular weight of 6000 was purchased from Xilong
329
Chemical Reagent Beijing Co., Ltd. China. Nitric acid (HNO3,
65–68 wt.%, Analytical reagent (A.R.)), hydrogen peroxide (H2O2,
30 wt.%, A.R.), and sodium hydroxide (NaOH, >96%, A.R.) were
purchased from Beijing Chemical Reagent Co., Ltd. China. Titanium
powder (>99.99%) was obtained from Sinopharm Chemical Reagent
Co., Ltd. China.
2.2. Preparation of FLN-TiO2
FLN-TiO2 was synthesized through a simple hydrothermal
method via self-assembly of the primary nanostructure under the
controlled experimental conditions (Fig. 1(a)). Firstly, 150 mL of
mixed aqueous solution of 0.1 M HNO3 and 10 M H2O2 was vigor-
ously stirred after adding 0.12 g titanium powder and then main-
tained at 80 °C in water bath for 2 h. Secondly, 20 mL of the
above cooled solution and 40 mL of aqueous solution of 10 M
NaOH were mixed for 15 min under vigorous stirring. Then, the
mixture was transferred to a 150-mL Teflon-lined stainless steel
autoclave and maintained at 150 °C for 6 h. Thirdly, the precipi-
tates were filtered and washed to pH 7.0 with 0.1 M HNO3 and then
dried at 80 °C for 12 h. Finally, the dried sample was calcined in air
atmosphere at 550 °C for 2 h to obtain the FLN-TiO2.
2.3. Preparation of PEG/FLN-TiO2 ss-CPCM
The PEG/FLN-TiO2 ss-CPCM was prepared by a physical blend-
ing and impregnation method (Fig. 1(b)). The synthetic FLN-TiO2
was impregnated into abundant PEG and the temperature was
maintained 80 °C for 12 h (Fig. 2(a)). After this, the impregnated
ð1Þ sample was transferred onto filter paper and put into a drying oven
at 80 °C to remove the leaky liquid PEG from FLN-TiO2 (Fig. 2(b)).
Filter paper was replaced continuously until no liquid leakage trace
was observed (Fig. 2(c)). Finally, the PEG/FLN-TiO2 ss-CPCM was
obtained. The maximum adsorption mass fractions of PEG retained
in the pores of FLN-TiO2 could be determined by Eq. (2).
g ¼ ðm1  m0 Þ=m1 ; ð2Þ
where g, m1, and m0 represents the maximum encapsulation mass
fractions of PEG, weight of the PEG/FLN-TiO2 ss-CPCM, and corre-
sponding weight of the FLN-TiO2, respectively. The maximum
encapsulation capacity of PEG with good shape stability reached
50.2 wt.%.
2.4. Characterization
The morphology observations of FLN-TiO2 and PEG/FLN-TiO2 ss-
CPCM were performed under scanning electron microscope (SEM,
S-4800, HITACHI, Japan) at an accelerating voltage of 15 kV. All
samples were gold-coated by sputtering to produce conductive
coatings onto the samples. The microstructure of FLN-TiO2 was fur-
ther analyzed by transmission electron microscope (TEM, Tecnai
G2 F30 S-TWIN, FEI, USA). Nitrogen adsorption-desorption iso-
therms were obtained on a nitrogen adsorption analyzer
(ASAP2020, Micromeritics Instruments, USA). The Brunauer-
Emmett-Teller (BET) specific surface area was determined with
the adsorption data in the relative pressure P/P0 range of 0.11–
0.31 according to a multipoint BET method. The pore size distribu-
tion was calculated according to Barrett-Joyner-Halenda (BJH)
method. X-ray diffraction (XRD, D8 Advance, Bruker, Germany)
technique was applied to investigate the crystal structure of FLN-
TiO2 by using Cu Ka radiation at a scanning rate of 12°/min in
the 2h range of 20–60°. Chemical compatibility between the PEG
and FLN-TiO2 was examined by the Fourier transform infrared
spectroscopy (FT-IR, FTIR8400, SHIMADZU, Japan). The FT-IR test
was carried out over a wavenumber range from 4000 cm1 to
400 cm1. The phase change temperature and enthalpy of the
330 Y. Deng et al. / Applied Thermal Engineering 114 (2017) 328–336

Fig. 1. (a) Schematic diagram of the synthesis process of FLN-TiO2 and (b) preparation process of PEG/FLN-TiO2 ss-CPCM.

Fig. 2. (a) Photographs of FLN-TiO2 impregnated with abundant PEG, (b) PEG/FLN-TiO2 ss-CPCM with liquid leakage trace, and (c) PEG/FLN-TiO2 ss-CPCM with good shape
stability.

samples were measured by using a differential scanning calorime-
ter (DSC, 214 Polyma, NETZSCH, Germany). The samples of PEG and
PEG/FLN-TiO2 ss-CPCM were heated and cooled to the temperature
range between 10 °C and 80 °C at different rates of 10, 5, 2 and
1 °C/min in a nitrogen atmosphere. The samples of PEG/FLN-TiO2
ss-CPCM after phase change cycles were between 10 °C and 80 °C
at 10 °C/min.
3. Results and discussion
3.1. Characterization of FLN-TiO2
The SEM images with different magnifications of the synthe-
sized FLN-TiO2 are shown in Fig. 3(a)–(c). There were a large
amount of non-aggregated spherical FLN-TiO2 particles with high
porosity and large specific surface area. These spherical FLN-TiO2
particles were composed of numerous nanosheets, which were
intercrossed with each other and self-assembled to form a porous
flower-like structure. The energy dispersive X-ray spectroscopy
(EDS) spectrum confirmed the presences of titanium (Ti) and oxy-
gen (O) in the synthesized FLN-TiO2 (Fig. 3(d)). These FLN-TiO2 par-
ticles had the narrow size distribution ranging from 1 lm to 2 lm
and the average diameter (The arithmetic mean of the diameter of
200 spherical FLN-TiO2.) was calculated to be about 1.46 lm (Fig. 3
(e)). The microstructure of the synthesized FLN-TiO2 was further
investigated by TEM (Fig. 4(a) and (b)). The FLN-TiO2 particles
showed an interesting radial morphology with about 10 nm thick
nanosheets coming out from the center and distributed uniformly
in all directions. To examine the porous structure of synthesized
FLN-TiO2, the N2 adsorption-desorption isotherms were used to
determine the BET specific surface area and pore size distribution
(Fig. 5). The Type-IV isotherm in the relative pressure range of
 Y. Deng et al. / Applied Thermal Engineering 114 (2017) 328–336 331

Fig. 3. (a–c) SEM images with different magnifications of the synthesized FLN-TiO2 and (d) the corresponding EDS spectrum; (e) diameter (lm) distribution of the
synthesized FLN-TiO2. (Counting the diameter (lm) of 200 spherical FLN-TiO2 from multiple SEM images of synthesized FLN-TiO2. The frequency distribution histogram
based on diameter (lm) and percent was drawn to represent the size distribution of FLN-TiO2.)

Fig. 4. (a and b) TEM images with different magnifications of the synthesized FLN-TiO2.

0.4–1.0 was observed, indicating the presence of mesopores (by
definition, the size of mesopores is between 2 nm and 50 nm)
[15]. These mesopores were formed by the self-assembly of
nanosheets under the controlled experimental conditions. The
specific surface area of FLN-TiO2 sample was 117.61 m2/g. The
BJH method was used to calculate the pore size distribution (inset
in Fig. 5) and the average pore diameter of FLN-TiO2 was 3.75 nm.
The large specific surface area and unique mesoporous structure
could be expected to adsorb abundant PEG and enhance the ther-
mal reliability of the PEG/FLN-TiO2 ss-CPCM after a large number
of phase change cycles. Fig. 6 shows the XRD pattern of the FLN-
TiO2 sample. The observed two diffraction peaks respectively cor-
respond to the (1 0 1) and (2 0 0) crystal planes of the TiO2 anatase
phase (JCPDS card No. 21-1272).
332 Y. Deng et al. / Applied Thermal Engineering 114 (2017) 328–336
Fig. 5. Nitrogen adsorption-desorption isotherms and corresponding pore-size
distribution curves (inset) of the synthesized FLN-TiO2 sample.
Fig. 6. XRD pattern of the synthesized FLN-TiO2 sample.
3.2. Morphology of PEG/FLN-TiO2 ss-CPCM
The SEM images with different magnifications of PEG/FLN-TiO2
ss-CPCM are shown in Fig. 7(a–c). PEG was uniformly embedded
and encapsulated in the pores and surfaces of FLN-TiO2 due to
the strong capillary action and surface tension force between the
PEG and the porous network of FLN-TiO2, which was beneficial
for thermal reliability enhancement of PEG/FLN-TiO2 ss-CPCM.
The porous structure of FLN-TiO2 provided a reasonable mechani-
cal strength for the whole composite to prevent the seepage of
melted PEG. The PEG/FLN-TiO2 ss-CPCM could maintain its shape
Fig. 7. (a–c) SEM images with different magnifications of the prepared PEG/FLN-TiO2 ss-CPCM.
in the solid state even after it was heated above the melting point
of the PEG. These morphologies indicated that the physical blend-
ing and impregnation method was an effective route to disperse
PEG into the FLN-TiO2.
3.3. Chemical compatibility analysis of PEG/FLN-TiO2 ss-CPCM
Fig. 8 represents the FT-IR spectra of PEG, FLN-TiO2, and PEG/
FLN-TiO2 ss-CPCM. In the spectrum of PEG, the peak at 844 cm1
was attributed to the vibration of interim-CH2-group. The peaks
at 1065 cm1, 1110 cm1, 1145 cm1, and 1239 cm1 corre-
sponded to CAO stretching vibration. The peaks at 1280 cm1,
1343 cm1, and 1468 cm1 were assigned to CAH bending vibra-
tion. The peaks at 964 cm1 and 2888 cm1, and 3423 cm1 were
attributed to CAH stretching vibration of CH2 and OAH stretching
vibration, respectively [8,9]. In the spectrum of FLN-TiO2, the
absorption peak at 504 cm1 corresponded to the stretching vibra-
tion of TiAO bond. The peaks at 1632 cm1 and 3423 cm1 were
ascribed to the deformation and stretching vibration of the AOH
bond [16]. All absorption peaks of PEG and FLN-TiO2 appeared in
the spectra of PEG/FLN-TiO2 ss-CPCM. Moreover, the absorption
peaks in the spectrum of PEG/FLN-TiO2 ss-CPCM did not shift sig-
nificantly from the original positions in the spectra of PEG and
FLN-TiO2. The above results indicated that no chemical reaction
occurred between the PEG and FLN-TiO2 during the phase transi-
tion process, verifying good chemical compatibility.
3.4. Thermal energy storage behavior and thermal reliability
of PEG/FLN-TiO2 ss-CPCM
The DSC curves of PEG and PEG/FLN-TiO2 ss-CPCM before and
after phase change cycles are shown in Fig. 9 and the correspond-
ing phase change temperatures and latent heats are summarized in
Table 1. An endothermic peak and exothermic peak occurred dur-
ing the melting and solidification processes of PEG. The DSC curves
of PEG/FLN-TiO2 ss-CPCM before and after phase change cycles of
100 and 200 times are almost completely overlapped with each
other except slight deviations, indicating that the PEG/FLN-TiO2
ss-CPCM exhibited similar thermal energy storage behavior and
excellent thermal reliability. After 100 and 200 phase change
cycles, the phase change latent heat of PEG/FLN-TiO2 ss-CPCM
was respectively changed by 0.13% and 0.16% in melting process
and 0.34% and 0.21% in solidification process, and the phase change
temperature was seldom changed. The SEM images of the PEG/
FLN-TiO2 ss-CPCM after 200 phase change cycles are presented in
Fig. 10. It was clearly observed that there was no obvious differ-
ence on morphology with before cycles. The PEG observed at the
surface of FLN-TiO2 was also retained, which might be due to the
effect of strong surface tension force of PEG. The above results also
confirmed the excellent thermal reliability of PEG/FLN-TiO2 ss-
CPCM. The comparison of thermal energy storage property and
thermal reliability between PEG/FLN-TiO2 ss-CPCM prepared in
 Y. Deng et al. / Applied Thermal Engineering 114 (2017) 328–336
Fig. 8. FT-IR spectra of PEG, FLN-TiO2, and PEG/FLN-TiO2 ss-CPCM.
Fig. 9. DSC curves of PEG and prepared PEG/FLN-TiO2 ss-CPCM before and after 100
and 200 melting/solidifying cycles.
this study and the recently reported similar ss-CPCMs are provided
in Table 2. The PEG/FLN-TiO2 ss-CPCM exhibited excellent thermal
reliability than previously prepared ss-CPCMs within at least 200
phase change cycles. The thermal reliability of ss-CPCM after expe-
riencing large number of cycles was of great importance for the
service life of thermal energy storage applications. The nanoscale
pores of FLN-TiO2 were beneficial for stabilizing the shape of
melted PEG and enhancing the thermal reliability of PEG/FLN-
TiO2 ss-CPCM due to strong capillary force and surface adsorption.
Although the latent heats of PEG/FLN-TiO2 ss-CPCM in melting and
solidification processes were markedly decreased to almost half of
pure PEG, they were in a reasonable and acceptable level.
Table 1
Phase change temperatures (°C) and latent heat values (J/g) of the PEG and PEG/FLN-TiO2 ss-CPCM during the melting and solidification processes before and after thermal
cycling.a
Samples
PEG
PEG/TiO2 ss-CPCM before thermal cycles
PEG/TiO2 ss-CPCM after 100 thermal cycles
PEG/TiO2 ss-CPCM after 200 thermal cycles
a
Here, the TM and HM respectively represents the phase change temperature (°C) and latent heat values (J/g) in melting process, and the TS and HS respectively represents
the solidification process.
333
The endothermic and exothermic peaks of PEG/FLN-TiO2 ss-
CPCM before and after 100 and 200 melting/solidifying cycles were
significantly shifted to the lower-temperature direction, indicating
that the phase transition processes of encapsulated PEG were sig-
nificantly affected by the pore structure of FLN-TiO2. The decrease
of phase change temperature of PEG/FLN-TiO2 ss-CPCM was prob-
ably caused by the interactions between the PEG molecular chain
and the pore structure of FLN-TiO2. Radhakrishnan and Gubbins
[23] and Radhakrishnan et al. [24] demonstrated that the interac-
tion between the PCM and the inner surface of the porous media
determined the shift direction of phase change temperature and
found that for a strong attractive interaction between melted
PCM and pore surface, an elevated phase change temperature
would appear, and for a weakly attractive interaction, a depressed
phase change temperature would occur. The FT-IR results indicated
that no chemical reaction occurred during the phase transition
process. The PEG segments might interact with the FLN-TiO2
through physical actions, such as capillary force. The weak interac-
tion between the PEG and inner surface of FLN-TiO2 led to the
lower phase change temperatures of PEG/FLN-TiO2 ss-CPCM. The
above results were in agreement with previous studies [25,26].
The DSC curves of PEG and PEG/FLN-TiO2 ss-CPCM at different
heating and cooling rates (10, 5, 2 and 1 °C/min) are presented in
Fig. 11, and the corresponding phase change temperatures and
latent heats are summarized in Table 3. It was clearly observed that
the solidification temperatures shifted towards lower tempera-
tures with increasing cooling rates in the cases of both PEG and
PEG/FLN-TiO2 ss-CPCM. Moreover, the low cooling rates induced
rather narrow crystallization peaks, while the high cooling rates
provoked broad crystallization curves. The results were in agree-
ment with previous studies [27,28]. The possible reasons could
be described as follows: there was no sufficient time to activate
nuclei at higher temperature. The molecular chains of PEG pre-
sented less flexibility and there was shorter time in order to diffuse
into the crystallite lattice and organize the chain configurations
into more perfect crystallites [27]. The PEG gradually changed from
disordered molten state to ordered crystalline state with increas-
ing cooling rates and the faster cooling rate led to a higher degree
of supercooling. It was too late to the regular arrangement of
molecular chains, so the PEG was compelled to crystallize at a
lower temperature. The effect of heating rates on melting temper-
ature was contrary to solidification process. The variation in the
peak temperature with heating rate was governed only by the acti-
vation energy [29–31]. After embedded and encapsulated in the
pores and surfaces of FLN-TiO2, the activation energy of PEG in
the PEG/FLN-TiO2 ss-CPCM changed relative to pure PEG, so the
effect of heating rates on the shift of melting temperature was dif-
ferent between PEG/FLN-TiO2 ss-CPCM and pure PEG. Therefore,
the different heating and cooling rates determined the shift of
melting/solidification temperature, which could also explain the
very big differences of observed DSC curves between PEG and
PEG/FLN-TiO2 ss-CPCM.
Melting process Solidification process
TM (°C) HM (J/g) TS (°C) HS (J/g)
66.4 203.70 32.3 184.10
53.6 93.68 20.1 91.07
53.6 93.56 20.1 90.76
53.6 93.83 20.0 91.26
334 Y. Deng et al. / Applied Thermal Engineering 114 (2017) 328–336

Fig. 10. (a and b) SEM images with different magnifications of the PEG/FLN-TiO2 after 200 melting/solidifying cycles.

Table 2
Thermal energy storage property and thermal reliability comparison between PEG/FLN-TiO2 ss-CPCM prepared in this study and the recently reported similar ss-CPCMs.a

ss-CPCMs Melting process Solidification process Ref.

TM (°C) HM (J/g) TS (°C) HS (J/g)
PCMs Supporting Before 100 200 Before 100 200 Before 100 200 Before 100 200
materials cycles cycles cycles cycles cycles cycles cycles cycles
53.2 wt.% 46.8 wt.% 48.85 – +0.80% 101.14 – 22.61% 53.01 – +0.51% 103 – 22.37% [10]
paraffin expanded
vermiculite with
porous carbon
layer
70 wt.% 30 wt.% 57.03 – +0.98% 122.1 – 6.96% 44.10 – +0.20% 106.8 – 6.81% [17]
polyethylene mesoporous
glycol calcium silicate
71.4 wt.% fatty 28.6 wt.% 32.2 0.56% – 114.6 5.0% – 29.2 +0.34% – 106.8 5.0% – [18]
acid eutectics cellulose
61 wt.% paraffin 39 wt.% calcined 33.04 – +3.27% 89.54 – 4.72% 52.43 – +0.82% 89.80 – 2.76% [19]
diatomite
66.6 wt.% 33.3 wt.% 22.92 – +2.79% 86.4 – 6.83% 21.03 – +1.28% 80.4 – 2.24% [20]
capric- modified
myristic- expanded
stearic acid vermiculite
eutectic
mixture
60 wt.% 40 wt.% semi- 58.51 +0.02% – 99.83 2.47% – 36.62 0.57% – 96.32 +0.49% – [21]
polyethylene interpenetrating
glycol polymer network
65 wt.% stearic 35 wt.% 55.6 – 0.72% 113.02 – 0.60% 50.8 – +0.39% 112.58 – 0.73% [22]
acid polyaniline
PEG – 66.4 – – 203.70 – – 32.3 – – 184.10 – – This
work
50.2 wt.% PEG 49.8 wt.% FLN- 53.6 0 0 93.68 0.13% +0.16% 20.1 0 0.50% 91.07 0.34% +0.21% This
TiO2 work
a
Here, the ‘‘+” and ‘‘” represents the increment and decrement of phase change temperature (°C) and latent heat values (J/g) after thermal cycles compared to before
cycles, respectively.

Fig. 11. DSC curves of (a) PEG and (b) PEG/FLN-TiO2 ss-CPCM at different heating and cooling rates.
 Y. Deng et al. / Applied Thermal Engineering 114 (2017) 328–336
Table 3
Phase change temperatures (°C) and latent heat values (J/g) of the PEG and PEG/FLN-TiO2 ss-CPCM during the melting and solidification processes at different heating and cooling
rates.
Samples Heating/cooling rates (°C/min)
PEG 10
5 61.9
2 59.6
1 58.5
PEG/TiO2 ss-CPCM 10
5 53.1
2 52.3
1 52.6
4. Conclusions
In this study, the synthesized FLN-TiO2 was employed to encap-
sulate PEG in order to overcome liquid leakage during phase
transition and enhance thermal reliability of the prepared PEG/
FLN-TiO2 ss-CPCM after a large number of thermal cycles. Based
on the above discussion, the conclusions can be drawn as follows:
(1) FLN-TiO2 with specific surface area of 117.61 m2/g, pore
diameter of 3.75 nm and spherical diameter of about
1–2 lm was obtained by a simple hydrothermal method.
(2) The PEG was effectively embedded and dispersed into the
pores and surfaces of FLN-TiO2 and the maximum capacity
with good shape stability was 50.2 wt.%. The latent heat
values of PEG/FLN-TiO2 ss-CPCM were in a reasonable and
acceptable level for thermal energy storage applications.
(3) The PEG/FLN-TiO2 ss-CPCM exhibited excellent chemical
compatibility. The weak physical interaction between
the PEG and surface of FLN-TiO2 led to the lower phase
change temperatures of PEG/FLN-TiO2 ss-CPCM. Different
heating and cooling rates were responsible for the shift
of melting/solidification temperature of PEG and PEG/
FLN-TiO2 ss-CPCM.
(4) The FLN-TiO2 benefited the thermal reliability enhancement
of PEG/FLN-TiO2 ss-CPCM. Compared with previously
prepared ss-CPCMs, the PEG/FLN-TiO2 ss-CPCM showed
excellent thermal reliability within at least 200 phase
change cycles.
Acknowledgments
This work was supported by the Fundamental Research Funds
for the Central Universities (Grant Nos. 53200859163 and
2652016086).
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