Applied Energy 86 (2009) 170174

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Preparation and performance of form-stable polyethylene glycol/silicon dioxide

composites as solidliquid phase change materials
Weilong Wang a,*, Xiaoxi Yang a,b, Yutang Fang a, Jing Ding a
a
Key Lab of Transfer Enhancement and Process Energy Conservation of National Education Ministry, School of Chemical and Energy Engineering, South China University of
Technology, Guangzhou 510640, PR China
b
Dongguan University of Technology, Dongguan 523808, PR China

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

Article history: This work mainly involved the preparation and characterization of form-stable polyethylene glycol
Received 15 October 2007 (PEG)/silicon dioxide (SiO2) composite as a novel solidliquid phase change material (PCM). In this study,
Received in revised form 22 November 2007 the polyethylene glycol/silicon dioxide composites as form-stable, solidliquid phase change material
Accepted 1 December 2007
(PCM) was prepared. In this new material, the polyethylene glycol acts as the latent heat storage material
Available online 13 February 2008
and silicon dioxide serves as the supporting material, which provides structural strength and prevents
the leakage of the melted polyethylene glycol. Results indicated that the composite remained solid when
Keywords:
the weight percentage of silicon dioxide was higher than 15%. Moreover, the polyethylene glycol was
Polyethylene glycol
Silicon dioxide
observed to disperse into the network of the solid silicon dioxide by investigation of the structure of
Heat storage materials the composite PCMs using a scanning electronic microscope (SEM). The properties of the porous materi-
Phase change materials als and phase change materials were characterized using Fourier transformation infrared spectroscope
(FTIR). The transition process was observed using polarizing optical microscope (POM) and dynamic
thermo mechanic analysis (DMA). The melting temperatures and latent heats of the form-stable PEG/
SiO2 composite PCMs were determined using differential scanning calorimeter (DSC).
2008 Elsevier Ltd. All rights reserved.

1. Introduction temperature. The major problem of traditional PCMs, such as inor-

With the rapid development of the society, the demands for the
energy are higher. At the same time, the non-renewable resources
are being exhausted gradually. Therefore, the utilization of new en-
ergy is receiving increasing attention in the research community
worldwide.
Solar energy availability and high utilization periods are differ-
ent. It requires efcient thermal energy storage to collect the ex-
cess heat during the sunny periods of day time and to release it
for using during the night. A similar problem exists in the waste
heat recovery system [1,2]. Thermal energy storage systems can
help to resolve the time mismatch of electric energy supply-and
-demand during the day and night, especially in very cold and
hot climates [3]. Thermal energy storage techniques consist of sen-
sible heat storage and latent heat storage. Sensible heat storage has
a high capacity, which depends on the temperature of the storage
materials. But it is difcult to control the temperature in this meth-
od [2]. The latent heat storage based on the phase change materials
(PCMs) has been studied over the last decade, because it can pro-
vide a high energy storage density and store the heat at a constant
* Corresponding author. Tel.: +46 21 15178; fax: +46 21 101370.
E-mail address: ce_logan@hotmail.com (W. Wang).
ganic salt hydrates, is their separation and super cooling [4,5].
Polyethylene glycol (PEG) has been recommended as a thermal
energy storage material due to its relatively more heat of fusion,
congruent melting behavior, better resistance to corrosion and
suitable melting point [69]. However, there are some difculties
in using PEG for latent heat storage [10]. One major issue is that
PEG belongs to the solidliquid phase change substances, so it
must have special sealed packaging to prevent its leakage in the so-
lidliquid phase transitions. This increases the cost. Another prob-
lem is that PEG has an unacceptably low thermal conductivity, and
hence, heat transfer enhancement techniques are required for its
application [11].
Recently, a new type PCM called shape-stabilized or form-stable
composite PCM was developed [1216]. The form-stable PCMs can
be classied into two categories: solidsolid PCMs and solidliquid
ones. There are several ongoing research projects on the prepara-
tion and investigation of the form-stable phase change materials.
Hong [17] prepared parafn/HDPE composites as form-stable
phase change materials and analyzed its thermal properties and
structure. Sari [18] found the maximum percentage for parafn
without any seepage was as high as 77 wt.%. Liu et al. [19] investi-
gated the preparation and thermal properties of form-stable paraf-
n with silica gel polymer shin.

0306-2619/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2007.12.003
 W. Wang et al. / Applied Energy 86 (2009) 170174 171

In this paper, a novel shape-stabilized composite of PEG and sili- 2. Experiments

con dioxide was prepared. The weight percentage of PEG in microen-
capsulated PCMs was optimized and discussed. The properties of PEG
and composites were measured by means of differential scanning
calorimeter, polarization optical microscope, scanning electronic
microscope, Fourier transformation infrared spectrophotometer.
2.1. Materials
Reagent grade Polyethylene glycol with an average molecular
weight of 10,000 was purchased from Guangzhou Chemical Agent
Company (Guangzhou, China). Silicon dioxide was purchased from
Guangzhou Peoples Chemical Company (Guangzhou, China).

Fig. 1. The SEM photograph of the PEG/SiO2 composite PCM. Fig. 2. The TEM photograph of the PEG/SiO2 composite PCM.

Fig. 3. POM of samples: (a) PEG (60 C); (b) PEG (64 C); (c) PEG (68 C) and (d) PEG/SiO2 (85/15) (110 C).
172 W. Wang et al. / Applied Energy 86 (2009) 170174
Fig. 4. DMA analysis: (a) PEG; (b) PEG/SiO2 (85/15).
2.2. Methods
Silicon dioxide and PEG solution were each prepared by dissolv-
ing silicon dioxide and PEG in water with quick continuous stirring
for 12 h. The prepared solutions were then mixed at room temper-
ature at different weight ratios ranging from 95 wt.% to 5 wt.%.
After stirring for 3 h, the mixed solution was put into a drying cab-
inet and heated at 100 C for 24 h. Then the solid composite was
Fig. 6. DSC curve (heating cycle): (a) PEG; (b) PEG/SiO2 (85/15).
Fig. 5. FTIR spectrum of (a) PEG, (b) SiO2 and (c) composite.
obtained by heating under a reduced pressure at 70 C for 24 h
[20].
2.3. Performance analysis
The melting point and the heat of fusion of the solid compos-
ite were determined using a differential scanning calorimeter
(PerkinsElmer DSC-2C) calibrated with an indium standard in the
range from 30 C to 120 C. The scanning rate was at 10 C/min.
An observation of polarizing optical microscope was performed
on a 12 pol microscope equipped with a digital camera. The sample
was placed between a microscope glass and a cover slip.
Microphotographs were taken of the surface made by fracturing
the specimen in liquid nitrogen and then casting it with gold (AU)
powder.
3. Results and discussion
3.1. Structure analysis of the form-stable composite PCMs
Figs. 1 and 2 show SEM and TEM photographs of the microstruc-
tures of the form-stable PEG/SiO2 composite PCMs. From these g-
ures, it can be seen that the polyethylene glycol is dispersed into the
network of solid SiO2 used as supporting material. This structure
 W. Wang et al. / Applied Energy 86 (2009) 170174
Table 1
Thermal conductivity of the composite PEG (10,000)/SiO2
Samples Weight percentage of Conductivity Increased
SiO2 (%) (W m 1 K 1) percentage (%)
1 0 0.2985 0 trum proved that the reaction was physical [22].
2 20 0.3615 21.0
3 30 0.4126 38.2
4 40 0.4783 60.2
5 50 0.5124 71.7
provided a mechanical strength to the whole compound. Hence, the
composite maintained its shape in the solid state without seepage
of the melted polyethylene glycol.
The maximum mass percentage of polyethylene glycol dis-
persed into the PCM composites was determined as 85 wt.%. There
was no leakage of the PEG from the surface of the composite up to
this mass ratio even when it melts. Namely, when the mass per-
centage of silicon dioxide is less than 15%, the mechanical strength
and the highest enduring temperature of these composites de-
creased and therefore it could not hold melted PEG any more [18].
3.2. Phase change behavior of PEG and PEG/SiO2 composite
To investigate the morphology in the transition process, the
micro-morphology is recorded by POM with a hot stage in a heat-
ing process. Fig. 3 shows POM micrographs of pure PEG and PEG/
SiO2 composite. From the Fig. 3ac, pure PEG was crystalline and
its crystal structure was orbicular at 60 C. When the temperature
reached 64 C, some PEG started to melt and the small droplet ap-
peared. Then PEG would melt totally at 68 C and the bubble also
emerged.
The POM micrograph of the composite at 110 C is shown in
Fig. 3d. It indicated that SiO2 serving as supporting material helped
to prevent leakage of the melted polyethylene glycol [21].
DMA measurements of PEG and PEG/SiO2 composite are dem-
onstrated in Fig. 4a and b, respectively. Fig. 4a shows the thickness
of PEG started to reduce when the temperature reached 69.89 C.
After that, the higher the temperature, the thinner the PEG sample.
The highest rate of melting speed was 429.9 lm C 1. When the
temperature reached 78.61 C, the shape change value was equal
to the thickness of PEG sample, namely, it melted completely.
These behaviors indicated that this transition should be a solidli-
quid phase change. Fig. 4b shows that composite had different
phase change behavior totally. As the temperature rise to 100 C,
40 C higher than the melting point of PEG, no rapid shift occurred
in the integral curve, but little shrinkage of volume happened,
which indicated that the composite remained in the solid state
during the phase transition and exhibited solidsolid phase change
behavior. This special solidsolid phase change behavior of com-
posite was further conrmed by visual observation. After heating
the composite slowly directly to 100 C, it was still observable in
the solid state. No liquid leaked from the sample.
3.3. Chemical properties of the form-stable composite PCMs
The FTIR spectrum of the PEG, SiO2 and the composite are
shown in Fig. 5. Fig. 5a shows the spectrum of PEG. It is obvious
there is a peak at the wave number of 1105 cm 1 caused by
stretching vibration of functional group of CO. Additionally, peak
caused by stretching vibration of functional group of OH is also
found at 3447 cm 1. Peaks at 2889 cm 1 and 962 cm 1 represent
the stretching vibration of functional group of CH2 and crystal
peak of PEG. Fig. 5b shows the spectrum of SiO2. Peaks at the wave
number of 1093 cm 1, 801 cm 1, 473 cm 1 are caused by bending
vibration of functional group of SiO. Peak at 3449 cm 1 represents
the stretching vibration of functional group of OH. Moreover, the
173
function group of SiOH is found at the wave number of 967 cm 1.
Fig. 5c shows the spectrum of the composite. It is easy to nd peaks
at the wave number of 3447 cm 1, 2889 cm 1, 1105 cm 1,
801 cm 1. No signicant new peaks were observed. The FTIR spec-
3.4. Thermal properties of the form-stable composite PCMs
Fig. 6a and b presents the thermal characteristics of PEG and
composite in the heating cycle at a scanning rate of 10 C/min,
respectively.
Fig. 6a shows that the latent heat of PEG is 187.3 J g 1 (melting
temperature Tm = 61.18 C), which proves that PEG has a large la-
tent heat. This is because PEG is a linear polymer chain made up
of (CH2CH2O)n and has hydroxyl groups on two ends. It can be
easily crystallize and has quite large enthalpy because of its simple
structure. From the Fig. 6a, it also can be seen that PEG shows a
melting temperature range. This is because PEG is a mixture of dis-
tributed molecular weight. Fig. 6b indicates that a phase change
with an enthalpy of 162.9 J g 1 happened at 61.61 C. The thermal
characteristics of the composite are very close to those of PEG. It is
proved that there is no chemical reaction between PEG and SiO2
[20,23].
3.5. Thermal conductivity of the form-stable composite PCMs (see
Table 1)
As we know, PEG has an unacceptable low thermal conductiv-
ity. So heat transfer enhancement techniques are required. By
using the thermal conductivity apparatus, the thermal conductiv-
ity in the solid state was estimated as 0.2985 W m 1 K 1. From
the Table 1, it can be seen that with the increase in the mass per-
centage of Sio2, the conductivity of the composite PCMs increased.
With the increase in the mass percentage of SiO2, the conductivity
of the composite PCMs increased. When the mass percentage of
SiO2 was 50%, the composite conductivity was 0.5124 W m 1 K 1.
The thermal conductivity was increased about 71.7%. However,
the suitability of heat storage capacity of the PCM must be consid-
ered simultaneously. Therefore, the sample in the ratio of 20 wt.%
(SiO2) was chosen and the thermal conductivity was
0.3615 W m 1 K 1 with an increase of 21%, respectively. The
improvement in the thermal conductivity was most likely because
of the thermal conductive network formed by the pore structure of
the SiO2.
4. Conclusions
The composite made by PEG blended with SiO2 was a new kind
of form-stable phase change material. PEG and SiO2 were chosen as
phase change material and supporting material, respectively. Be-
cause of the effect of capillary force and surface tension force, there
was no leakage of liquid PEG from the porous of SiO2 network. The
solidsolid transition characteristics of these composites were sen-
sitive to the proportion of components. The maximum weight per-
centage for PEG dispersed in the PCM composites without any
leakage of the melted PEG was found as high as 85%.
The PEG (85%)/SiO2 composite had a large enthalpy of
162.9 J g 1 and suitable melting temperature (Tm = 61.61 C).
Meanwhile, the thermal conductivity was also improved because
of the thermal conductive network formed by the pore structure
of the SiO2. To consider the suitable enthalpy value and conductiv-
ity of the composite PCMs, the combination percentage for com-
posite PCMs was about PEG (80%)/SiO2 (20%). In case of this
composite, the latent heat of the composite was 137.7 J g 1 and
the thermal conductivity for the composite was increased by 21%.
174 W. Wang et al. / Applied Energy 86 (2009) 170174
Acknowledgement
The research was supported by National Science Foundation of
China (No. 90610023).
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