Solar Energy Materials and Solar Cells 200 (2019) 110037

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Solar Energy Materials and Solar Cells

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

Solvent-free preparation of bio-based polyethylene glycol/wood flour T

composites as novel shape-stabilized phase change materials for solar
thermal energy storage
Bin Lianga, Xiang Lub,∗∗, Renpu Lia, Weiping Tuc, Zhuohong Yanga,∗∗∗, Teng Yuana,c,∗
a
Department of Applied Chemistry, College of Materials and Energy, South China Agricultural University, Guangzhou, 510642, China
b
Key Laboratory of Polymer Processing Engineering of the Ministry of Education, South China University of Technology, Guangzhou, 510641, China
c
Guangdong Provincial Key Lab of Green Chemical Product Technology, South China University of Technology, Guangzhou, 510640, China

ARTICLE INFO ABSTRACT

Keywords: Vacuum adsorption was conducted to fabricate bio-based polyethylene glycol (PEG)/wood flour (WF) compo-
Polyethylene glycol sites as novel shape-stable phase change materials (SSPCMs). The structure–property relationships and com-
Wood flour prehensive performance of PEG/WF phase change materials (PCMs) prepared with different average molecular
Vacuum adsorption weights of PEG and different length-to-diameter ratios of WF were investigated through various characterization
Shape-stabilized
techniques. The relationship between the average molecular weight and mass content of PEG with the properties
Phase change materials
Solar thermal energy storage
and structure of the prepared PEG/WF PCMs was evaluated. Leakage test results showed that WF with a high
length-to-diameter ratio (HWF) exhibited much higher adsorption capacity for PEG than that of WF with a low
length-to-diameter ratio (LWF). The maximum adsorption content of PEG was found to be 70 wt% in those PEG/
HWF PCMs and both proceeded with excellent shape stability without leakage when the average molecular
weight of PEG was more than 4000. The maximum content of PEG1000 in novel PEG/HWF PCMs without any
leakage above the melting point of PEG was 75 wt%. Fourier transform infrared (FT-IR) spectroscopy results
indicated that physical interactions occurred between WF and PEG, but chemical reactions did not take place. X-
ray diffraction (XRD) analysis demonstrated that the crystallization of PEG in SSPCMs decreased. Differential
scanning calorimetry (DSC) analysis demonstrated that the phase transition temperature did not depend on the
content and length-to-diameter ratio of the WF. Simultaneously, the highest melting latent heat of the prepared
PEG/HWF SSPCM was 108.6 J/g, and its enthalpy efficiency reached more than 75.05%. Thermal cycling test
and TGA analysis results demonstrated that PEG/WF SSPCMs had good thermal reliability and chemical stability
and showed potential for applications in solar thermal energy storage and biomass energy.

1. Introduction thermal mode of constant or near-constant temperature [4,5].

An imbalance between energy demand and supply has become a
critical issue in energy consumption and current industrial develop-
ment. Energy efficiency improvement is a key to ensuring the sustain-
able development of a country's economy and society. New and efficient
energy-saving technologies have been widely explored to address these
problems [1,2]. However, thermal storage technology is the fastest
developed among the methods for improving energy efficiency [3]. In
comparison with sensible heat, latent heat storage based on phase
change materials (PCMs) has received considerable attention on ac-
count of its high-energy storage density, high thermal efficiency, and
Polyethylene glycol (PEG) has been extensively investigated be-
cause of its high phase transition enthalpy, low thermal hysteresis, good
chemical and thermal stability, good biodegradability, nontoxicity, and
adjustable average molecular weight [6–12]. However, PEG is a typical
solid–liquid PCM, which has a risk of leakage during phase transition
[13]. Therefore, various strategies, such as microcapsule and vacuum
adsorption technologies based on porous materials, have been used to
prepare PEG-based shape-stable PCMs (SSPCMs) and consequently
overcome this leakage problem [8,14–19]. Benmoussa et al. [20] en-
capsulated PEG with poly (methacrylic acid) (PMA) through radical
polymerization in the presence of methylene-bis-acrylamide (MBA) as a

∗
Corresponding author. Department of Applied Chemistry, College of Materials and Energy, South China Agricultural University, Guangzhou, 510642, China.
∗∗
Corresponding author.
∗∗∗
Corresponding author.
E-mail addresses: luxiang_1028@163.com (X. Lu), yangzhuohong@scau.edu.cn (Z. Yang), yuant@scau.edu.cn (T. Yuan).

https://doi.org/10.1016/j.solmat.2019.110037
Received 16 April 2019; Received in revised form 1 June 2019; Accepted 30 June 2019
0927-0248/ © 2019 Elsevier B.V. All rights reserved.
B. Liang, et al.
crosslinking agent. They modified the obtained microcapsules through
amidation with ethylenediamine as a spacer molecule. The micro-
capsules have a spherical structure with an average diameter of 10 μm
and a thermal stability of less than 500 °C. However, large-scale pre-
paration is difficult to achieve because this process requires high
technology. Wang et al. [21] prepared expanded graphite (EG) at high
temperature and blended it with PEG through vacuum adsorption to
obtain PCMs and found that the percentage of PEG is as high as 90 wt%
and the melt has no leakage. In addition to EG Refs. [22,23], the in-
fluence of the pore structure of porous carbon materials (e.g., EG, ac-
tivated carbon, and ordered mesoporous carbon to prepare SSPCMs) on
the phase change behavior of PEG/porous carbon composites has been
studied [17,24]. The shape stability of micrometer-sized pores has the
same level and nanometer size, but large pores can minimize enthalpy
loss because some PEG fragments are limited by the interaction be-
tween pores and PEG chains in the pores of EG Ref. [25]. In summary,
the preparation of PEG/porous SSPCMs via the adsorption of porous
materials on PEG and simple vacuum adsorption method has broad
application prospects. Although in the above report the porous minerals
have good adsorption to PEG and found that the adsorption by the
porous material can also be used to prepare a shape-stable PEG-based
PCMs, that materials do not belong to biomass. Renewable natural
biomass resources provide a sufficient source of raw materials for future
development and application, and the use of biomass as raw materials
for the preparation of energy storage materials is beneficial to the en-
vironment, society, and human health. Therefore, a simple, rapid,
green, and efficient preparation method should be developed to utilize
biomass materials efficiently.
Wood flour (WF) is a porous matrix of biomass material that com-
prehensively exists in nature. The waste of wood, such as residues of
Chinese traditional medicine, sawdust, root, straw and forestry scrap, is
mainly used to prepare WF. WF has high porosity, low density, high
absorption capacity, inert characteristics, environmentally friendly,
degradable and inexpensive properties, and its structure is composed of
cellulose fibers in an amorphous matrix of cellulose, lignin and hemi-
cellulose, it also contains a great many of hydroxyl groups [17,26,27].
Although WF can be used in reinforced polymer composites, such as
natural fiber-reinforced composites or wood plastic composites, it is
mainly used in automotive, furniture, construction, package and 3D
printing materials [28–31]. Different kinds of SSPCMs have been pre-
pared by using WF, because organic PCMs can be incorporated into WF
by capillary force, hydrogen-bond interaction, and surface tension force
to prevent the leakage during the phase transition process [32–34].
Liang et al. [32] selected WF with an average porous size of 58.5 μm as
a support material to prepare fatty acid (FA)/WF SSPCMs through
blending and adsorption. They found that the melting and freezing la-
tent heat of hexadecanoic acid/WF PCM and encapsulation ratio can
reach 102.6 J/g, 103.5 J/g, and 51.6%, respectively. A hydrophilic
functional group, such as –OH, on the surface of WF has a strong H
bonding interaction with an organic substance, such as FA, and its
porous structure and organic substance have strong capillary adsorp-
tion. Therefore, WF can be used to adsorb PEG for the preparation of
PEG and biomass-based SSPCMs. However, few previous studies re-
ported that WF is used as supporting materials to encapsulate organic
PCMs, such as PEG, for the preparation of PEG-based SSPCMs. The
adsorption of porous activated carbon on PEG with different average
molecular weights is significantly different, and adsorption influences
the crystallinity, phase change temperature, and enthalpy of PEG be-
cause the H bonding interaction and capillary adsorption of the inter-
action between porous activated carbon and PEG chains with different
average molecular weights are different. WF, as a kind of porous bio-
mass material, may have different adsorption effects on those PEGs
with different average molecular weights, and its adsorption effect may
conversely affect the crystallinity, phase change temperature, and
phase change enthalpy of PEG as well. The adsorption effect of WF
particles with different morphologies on PEG may change [17,32,34].
2
Solar Energy Materials and Solar Cells 200 (2019) 110037
However, the mechanism of these differences remains unclear and
should be investigated.
In this study, PEG/WF SSPCMs were prepared via a simple vacuum
adsorption process. The structure–property relationships and compre-
hensive performance of PEG/WF PCMs prepared with different average
molecular weights of PEG and different length-to-diameter ratio of WF
were investigated. The relationship between the average molecular
weight and content of PEG with the properties and structure of the
composites was evaluated. The prepared PEG/WF SSPCMs were as-
sessed through Fourier transform infrared (FT-IR) spectroscopy, X-ray
diffraction (XRD), scanning election microscopy (SEM), differential
scanning calorimetry (DSC), and thermogravimetric (TG) analysis.
2. Experimental
2.1. Materials
Polyethylene glycol (LR; Mn = 1000, Mn = 4000, Mn = 10,000), a
white waxy crystalline solid powder, was purchased from Damao
Chemical Reagent Tianjing Co., Ltd. The wood-flour from eucalyptus
were obtained from Pengjian Mineral Products Processing Plant (Hebei,
China), one is WF (HWF) with a high length-to-diameter ratio, and the
other is WF (LWF) with a low length-to-diameter ratio.
2.2. Preparation of PEG/WF PCMs
PEG/HWF PCMs were prepared through a simple one-step vacuum
adsorption method. First, PEG was melted at 80 °C. Then, HWF was
added to the melted PEG through vigorous stirring at 80 °C. The sam-
ples were placed in a vacuum oven at 80 °C and vacuum adsorbed for
24 h at a pressure of −80 kPa. To investigate the effect of HWF on the
performances of PCMs, the HWF content was adjusted by changing the
mass ratio, the HWF mass contents in PEG/HWF PCMs were set to 15 wt
%, 20 wt%, 25 wt%, 30 wt%, and 35 wt% to optimize the maximum
absorption ratio without causing the melted PEG to leak from the
composites. To investigate the structure–property relationships, PEG/
LWF PCMs were also prepared in the same way. The obtained PEG/
HWF and PEG/LWF PCMs with different PEG average molecular
weights and WF mass contents were labeled as PEGx/yWF, where x is
the average molecular weight of PEG, and y is the mass fraction of WF.
The synthetic route of PEG/WF PCMs is shown in Scheme 1.
2.3. Characterization
The particle size distribution of WF was characterized by HORIBA
Laser Scattering Particle Size Distribution Analyzer at 25 °C. The testing
particle size ranges were from 0.01 to 5000 μm. Prior to testing process,
WF was kept for ultrasound for 30 min to obtain a better dispersion in
water. Although the pore size distribution of WF was also measured at
low and high pressure (0.10–33000.00 psia) using a mercury intrusion
meter (0701-(10) 5 Bulb, 1.131 Stem, Flour) with applying the Barret-
Joyner-Halenda (BJH) method.
The morphologies and microstructures of HWF, LWF, PEG/HWF
and PEG/LWF SSPCMs were investigated using SEM (Hitachi SE3400 N,
Japan) with an accelerated voltage of 5.00 kV. Accurately weighed
0.5 g, used a tablet press to press the sample into a circular sheet with a
diameter of 13 mm at a pressure of 30 kPa. All samples were gold-
sputtered to prevent the occurrence of electrostatic charge during ob-
servation.
The chemical groups of PEG, HWF, LWF, PEG/LWF and PEG/HWF
SSPCMs were characterized by a Fourier transform infrared (FT-IR)
spectrometer. FT-IR spectras were characterized with a Thermo-Nicolet
Nexus 670 FT-IR spectrometer, and the spectra were characterized in
the range of 400–4000 cm−1. All samples were tested using KBr tablet
method.
The crystal structures of PEG, LWF, HWF, PEG/LWF and PEG/HWF
B. Liang, et al.
Scheme 1. Synthetic route of the PEG/WF PCMs.
SSPCMs were investigated by the XRD (X Pert pro MPD, Netherlands)
with Cu Ka at 40 kV and 40 mA. The scans were made in the 2θ ranging
from 3 to 60° at a scanning rate of 10°/min.
The phase change temperature (melting and freezing), enthalpy and
latent heat of the prepared PEG/WF SSPCMs were investigated using a
Q8000 DSC (Thermal Analysis Corporation, Netzsch, Germany) at a
heating or cooling rate of 10 °C/min under nitrogen atmosphere with
the weight of all samples about 8–10 mg. Before testing process, the
samples were heated from 0 to 100 °C and kept at 100 °C for 5 min to
eliminate the thermal history. All samples were heated from 0 to 100 °C
and kept at 100 °C for 5 min, and subsequently cooled to 0 °C and kept
at 0 °C for 5 min. The DSC curves of all samples recorded the onset
temperatures of melting and freezing, as well as melting and freezing
latent heats.
Thermal gravity analysis (TGA) was investigated by a NETZSCH TG
209 F1 Libra (Netzsch, Germany) analyzer. The samples were scanned
in the range of 30–650 °C at a heating speed of 10 °C/min under a ni-
trogen atmosphere with 20 ml/min.
In order to characterize the thermal reliability, stability and reusa-
bility of the prepared PEG/WF SSPCMs, the accelerated thermal cycling
testing was conducted in high-low temperature stages with 100 cycles.
Each thermal cycling composed of a temperature programming from 10
to 100 °C and a cooling process from 100 to 10 °C. The time of thermal
cycling program was set to be about 25 min for each heating and
cooling process. Afterwards, the phase change temperatures, latent heat
and chemical stability of the thermal treated PEG/WF SSPCMs were
investigated by FT-IR, XRD and DSC, respectively.
The light-thermal conversion performance and temperature-regu-
lated performance of the prepared PEG/WF SSPCMs were characterized
by simulated solar irradiation using an infrared thermography camera
(FLIR, SC 3000). The temperature of sample (PEG1000/25% HWF
PCM) and ambient during these periods were recorded by P01 and P02,
respectively.
3. Results and discussion
3.1. Characterization of WF
In this study, HWF and LWF with different length-to-diameter ratios
were used as auxiliary materials for the synthesis of PCMs. The particle
size and porosity distributions of the original HWF and LWF should be
determined before SSPCMs were prepared. The particle size distribu-
tions of HWF and LWF are shown in Fig. 1(a). HWF had a distinct bi-
modal distribution in the particle size distribution curve with an
average particle size of 341.9 μm, and LWF had a distinct monomodal
distribution in the particle size distribution curve with an average
3
Solar Energy Materials and Solar Cells 200 (2019) 110037
particle size of 68.4 μm. Fig. 1(b) shows the porosity distributions of
HWF and LWF. An apparent unimodal distribution is observed in the
porosity distribution curve. The average pore diameters (4 V/A) of HWF
and LWF were 15.76 and 10.25 μm, respectively. HWF and LWF were
polydisperse in size in a range of several tens of microns, and their total
pore areas were 1.54 and 1.41 m2/g, respectively. The porosities of
HWF and LWF were 87.0% and 80.5%, respectively, which were due to
the absorption of melted PEG. These findings showed that HWF is more
porous than LWF in terms of porosity, average pore diameters, pore
areas and specific surface area, and the adsorption behavior of HWF for
PEG may be stronger than that of LWF [35].
The morphological characteristics and microstructure of HWF and
LWF were evaluated. The microstructure of HWF with typical fibrous
materials are shown in Fig. 2(a), (b), and (c). In Fig. 2(a), pure HWF
showed irregular strip fiber fragments at 250 × magnification of SEM.
In Fig. 2(b) and (c), a large number of tunnel-like and gully-like vein
fragments were detected on the surface of pure HWF, indicating that
PEG could fill the HWF surface with nonuniformity and porosity
through capillary forces, hydrogen-bond interactions, and surface ten-
sion forces [36]. In comparison with the HWF with a rough surface, the
pure LWF exhibited a disordered irregular flaky slag (Fig. 2(d)), and the
distribution was uneven. A large amount of gully was found on the
surface of LWF (Fig. 2(e) and (f)), also indicating that the surface
porosities and inhomogeneity of LWF could be filled by PEG [36]. The
large particle size, high pore volume, and porosity guaranteed that the
density of the thermal energy storage for HWF was higher than that for
LWF. Thus, HWF and LWF were suitable supporting materials for the
preparation of PEG/HWF and PEG/LWF SSPCMs.
3.2. Leakage test of PEG/WF PCMs
Leakage tests were performed for PCMs with different PEG/HWF
and PEG/LWF PCMs to optimize the maximum absorption weight ratio
without causing the melted PEG to leak from the PCM composites. The
photos of PEG/HWF and PEG/LWF PCMs with different PEG average
molecular weights and different HWF contents at 80 °C for 60 min are
shown in Fig. S1 and Fig. 3. The PEG segments in PEG1000/15 wt%
HWF composites rapidly melted into liquid and leaked, whereas the
PEG segments in PEG1000/25 wt%HWF PCMs could maintain the in-
itial shape without liquid leakage during the whole heating process
(Fig. 3(a)). However, for PEG 4000 and PEG 10,000, the prepared PEG/
HWF composites could maintain their shape only when the WF content
was greater than 30 wt%. For PEG4000 and PEG10000, 50 wt% LWF in
PEG/LWF composites should maintain their shape and avoid leakage
(Fig. 3(b)). However, only 35 wt% LWF was required for PEG1000.
These findings indicated that the adsorption capacity of HWF and LWF
B. Liang, et al.
Fig. 1. Particle size distribution and porosity distribution of HWF and LWF.
for low-molecular-weight PEG was better. For PEG with the same
average molecular weight, the adsorption capacity of HWF was better
than that of LWF, and this observation might be related to the pore
diameter and porosity of WF with different length-to-diameter ratios.
The reason may be that the low molecular weight PEG chain is shorter,
and its viscosity at high temperature is lower, which may be more fa-
vorable to be adsorbed into these holes in WF through capillary force or
surface tensions interactions. Meanwhile, under the same mass fraction,
the PEG with lower molecular weight should bear more molar amount
of –OH groups, which is more beneficial for the hydrogen bond ad-
sorption of PEG onto WF. It is therefore convincingly believed that PEG
with lower molecular weight may be more easily adsorbed by WF and
the leakage performance is better.
3.3. Microstructure of PEG/WF PCMs
Fig. 4 shows the SEM images of PEG/WF SSPCMs. In comparison
with the rough and irregular surface of HWF (LWF), the surface of
PEG10000/HWF (LWF) SSPCMs was smooth and even. The porous
spaces of HWF (LWF) were filled with PEG and had significantly less
visible pores at different magnifications, indicating the successful ab-
sorption of PEG into HWF (LWF). Fig. 4(c) –(f) show that the micro-
structure of porous HWF and LWF changed, indicating that PEG was
successfully absorbed into the pore structure of HWF and LWF. WF with
different length-to-diameter ratios had different adsorption effects on
PEG, and the hydrogen bond interaction and capillary adsorption be-
tween HWF and PEG chains with different average molecular weights
Fig. 2. SEM images of HWF (a–c) and LWF (d–f).
4
Solar Energy Materials and Solar Cells 200 (2019) 110037
were stronger than those of LWF, which are consistent with the particle
size distribution and porosity distribution results.
3.4. FT-IR and XRD characterization of PEG/WF PCMs
The chemical composition and structure of PEG, LWF, PEG/LWF,
HWF, and PEG/HWF SSPCMs were evaluated to determine the probable
interactions through FT-IR spectroscopy. The FT-IR spectra of
PEG10000, HWF, PEG10000/30%HWF, LWF, and PEG10000/30%LWF
SSPCMs are presented in Fig. 5. For the pure PEG10000 (Fig. 5(a)), the
broad peak at approximately 3435 cm−1 corresponds to the O–H
stretching vibration, the peak at approximately 1107 cm−1 corresponds
to the C–O–C symmetric stretching vibration of PEG, and the char-
acteristic peaks at 2889 cm−1 are attributed to the C–H stretching vi-
bration of –CH2– groups [37]. In Fig. 5(b) and (d), the broad char-
acteristic peak at 3405 cm−1 is assigned to the O–H stretching vibration
of HWF and LWF, the characteristic peaks at 2902 cm−1 are attributed
to the C–H stretching vibration of –CH2– and –CH3– groups, and the
main absorption band at 1059 cm−1 is ascribed to the stretching vi-
bration of C–O group [26,32]. In Fig. 5(c) and (e), in comparison with
the characteristic peaks of PEG and HWF (LWF), the peaks at 3420 and
1059 cm−1 are ascribed to the characteristic absorption peaks of HWF
or LWF, and the peaks of PEG/HWF and PEG/LWF at 2902, 1967, 962,
and 842 cm−1 are attributed to the characteristic absorption peaks of
PEG. These results demonstrated the existence of HWF and LWF in
PEG/HWF and PEG/LWF SSPCMs. No additional characteristic ab-
sorption peaks appear in the FT-IR spectra of PEG/HWF and PEG/LWF
B. Liang, et al. Solar Energy Materials and Solar Cells 200 (2019) 110037

Fig. 3. Photographs of leakage test of PEG/HWF (a) and PEG/LWF (b) PCMs.

SSPCMs, indicating that physical interactions occur between PEG and

HWF/LWF, but chemical reactions did not take place. Similar results
are obtained in Fig. 5(c) and (e), suggesting that only physical inter-
actions occur between PEG and LWF or HWF.
The XRD patterns of PEG, HWF, PEG/HWF PCM, LWF, and PEG/
HWF SSPCMs are displayed in Fig. 6. In Fig. 6, the 2θ positions of the
peaks in the X-ray scan of PEG/HWF and PEG/LWF PCMs are similar to
that of pure PEG, indicating that the introduction of porous HWF (LWF)
does not affect the crystal structure of PEG. In Fig. 6, the diffraction
peaks of HWF and LWF appear at 22.44°, 15.14°, and 22.28°. However,
these diffraction peaks are weak, suggesting that the crystallinity of
HWF (LWF) crystalline cellulose is low. Pure PEG shows sharp dif-
fraction peaks at 18.92° and 23.08° because of its complete crystal-
lization. For PEG10000/30%HWF PCMs, the characteristic XRD peaks
of pure PEG and HWF are presented, and the characteristic XRD peaks
of HWF are superimposed over that of PEG. PEG10000/50LWF SSPCMs
is also behaving the same result. This finding suggests that the crys-
tallinities of PEG/WF PCMs decrease, and WF acts as an impurity in
PEG that interferes with its crystal growth. In the composites with a low Fig. 5. FT-IR spectra of (a) PEG10000; (b) HWF; (c) PEG10000/30%HWF; (d)
PEG content, most PEG segments are confined within the pores of WF or LWF; (e) PEG10000/30%LWF.
adsorbed on the surface of WF, which hinders their ability to crystallize

Fig. 4. SEM images of PEG10000/30%HWF (a–c) and PEG10000/50%LWF (d–f) PCMs.

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B. Liang, et al. Solar Energy Materials and Solar Cells 200 (2019) 110037

Table 1
Latent heat storage properties of PEG, PEG/HWF and PEG/LWF SSPCMs.
PCMs Melting process Freezing process

o
Tm ( C) △Hm (J/g) Tf (oC) △Hf (J/g)

PEG1000 48.9 144.7 23.1 141.4

PEG1000/25%HWF 47.7 108.6 22.2 108.2
PEG1000/35%LWF 45.8 96.6 25.6 87.3
PEG4000 62.7 185.6 35.6 162.7
PEG4000/30%HWF 60.5 137.0 34.2 113.4
PEG4000/50%LWF 58.7 88.9 32.8 77.3
PEG10000 63.7 189.2 39.1 167.3
PEG10000/30%HWF 62.8 128.1 39.6 120.5
PEG10000/50%LWF 60.2 99.1 38.0 87.0

influence of HWF (LWF). Clearly, the endothermic and exothermic

Fig. 6. XRD curves of PEG10000, HWF, PEG10000/30%HWF, LWF and
PEG10000/50%LWF.
and agglomerate [38]. The diffraction peak strength of PEG/HWF PCMs
is significantly higher than that of PEG/LHF due to high PEG loading.
3.5. Phase change performance of PEG/WF SSPCMs
DSC was used to measure the phase change properties of PEG/HWF
and PEG/LWF SSPCMs. The DSC curves of PEG, PEG/HWF, and PEG/
LWF are shown in Fig. 7. The corresponding detailed melting points
(Tm), freezing points (Tf), melting latent heat (ΔHm), and freezing latent
heat (ΔHf) are summarized in Table 1. In Fig. 7, Tm of PEG/HWF and
PEG/LWF SSPCMs (except PEG1000/25%HWF) decreases slightly
compared with that of pure PEG and slightly affects the thermal energy
storage of PCM. The change in the interactions between PCMs and WF
leads to the shift of Tm. For a strong interaction between PCMs and
porous materials, Tm increases, whereas Tm decreases with a weak in-
teraction [25,39,40]. FT-IR and XRD results indicate that PEG and WF
largely retain their original forms in the composites. PEG chains can
interact with porous WF through capillary force and hydrogen bonding.
Thus, these interactions result in low Tm. However, Tm of PEG1000/
25%HWF is higher than that of pure PEG1000, indicating that PEG1000
strongly interacts with HWF in terms of hydrogen-bond interactions
and capillary interaction because the low HWF content enables PEG and
HWF to interact completely.
A blunt peak was observed in the melting and freezing curves
compared with that of pure PEG, indicating that the phase change
properties of PEG/HWF and PEG/LWF are affected by the addition of
HWF (LWF) because of the existence of imperfect crystallites under the
peaks of PCMs become small, and the latent heat of the phase change of
SSPCMs is obtained via the area of the exothermic peak. The results for
the SSPCMs with different contents and average molecular weights of
PEG are summarized in Table 1. The fusion latent heat of PCMs de-
creases, and the decrease in this parameter is lower in the PEG/HWF
composites than in the PEG/LWF composites. Another factor leading to
the loss of latent heat is the interaction between PEG and WF, which
hinder PEG from crystallizing and reduce the enthalpy of PCMs as
suggested by the low PEG crystallinity when porous WF is added. The
decrease in the latent heat of SSPCMs cannot be attributed solely to the
low PEG content. Another factor leading to the loss of latent heat is the
interaction between PEG and WF, thereby preventing PEG crystal-
lization and reducing the enthalpy of SSPCMs.
The phase transition characteristics of SSPCMs prepared in this
study were compared with the previously reported phase change
characteristics of SSPCMs of PEG and porous materials to confirm
whether these characteristics were excellent. To ensure that the data
are comparable, we compare the absolute value of the latent heat of
SSPCMs [46]. Therefore, the relative latent heat efficiency (η) is cal-
culated by using Eq. (1):
= Hm, SSPCMs/ Hm, PEG × 100% (1)
Where ΔHm, SSPCMs and ΔHm, PEG are the values of the melting latent
heat of SSPCMs and used PEG, respectively. A large η indicates the
higher latent heat retention ability of SSPCMs than that of the used pure
PCM. Table 2 lists η of the prepared SSPCMs and previously reported
SSPCMs [3,44,45]. η of the obtained PEG/WF SSPCMs is significantly
higher than that of other porous composite materials with PEG-based
SSPCMs with different average molecular weights (Table 2). The largest
η of PEG1000/HWF SSPCMs is 75.05%, which is significantly higher
than that of other SSPCMs reported in the literature. Therefore, these
results demonstrate that the use of WF as a supporting material to

Fig. 7. DSC curves of PEG, PEG/HWF and PEG/LWF SSPCMs.

6
B. Liang, et al. Solar Energy Materials and Solar Cells 200 (2019) 110037

Table 2
Thermal energy storage characteristics of different SSPCMs in literature and the present study.
SSPCMs ΔHm, PEG (J/g) ΔHm, SSPCMs (J/g) η (%) Reference

PEG1000(83 wt%)/cellulose 180.4 78.6 43.57 [41]

PEG1000(80 wt%)/expanded graphite 163.1 108.2 66.34 [42]
PEG4000(75 wt%)/silica fume 169.7 81.3 47.91 [43]
PEG4000(50 wt%)/diatomite 180.3 88.4 49.03 [44]
PEG10000(50 wt%)/cellulose acetate 177.4 86.0 48.49 [45]
PEG1000(75 wt%)/HWF 144.7 108.6 75.05 present
PEG1000(65 wt%)/LWF 144.7 96.6 66.76 present
PEG4000(70 wt%)/HWF 185.6 137.0 73.81 present
PEG4000(50 wt%)/LWF 185.6 88.9 47.90 present
PEG10000(70 wt%)/HWF 189.2 128.1 67.71 present
PEG10000(50 wt%)/LWF 189.2 99.1 52.38 present

loading PEG is an effective method to prepare novel bio-based SSPCMs Table 3

with high latent heat. Latent heat storage properties of PEG, PEG/HWF and PEG/LWF PCMs after 100
thermal cycling.
3.6. Thermal property of PEG/WF SSPCMs PCMs Melting process Freezing process

Thermal stability and reusability are essential for PCMs because Tm (oC) △Hm (J/g) Tm (oC) △Hm (J/g)

they can be simulated by accelerating the thermal cycling process in PEG1000/25%HWF 47.7 104.9 22.6 102.9
long-term practical applications. The DSC curves before and after PEG1000/35%LWF 43.6 83.2 25.0 75.0
thermal cycling of the prepared PEG/HWF and PEG/LWF SSPCMs are PEG4000/30%HWF 59.0 121.6 35.6 115.0
shown in Fig. 8(a–f). The corresponding detailed data are summarized PEG4000/50%LWF 52.7 85.0 32.7 75.7
PEG10000/30%HWF 64.7 119.4 37.3 113.2
in Table 3. The results show that the phase transition temperatures and PEG10000/50%LWF 57.4 87.8 37.3 74.5
latent heat of PEG/HWF and PEG/LWF SSPCMs are slightly changed
after 100 thermal cycles. These changes are regular, which are not
significant for thermal energy storage applications. These results in- dot line in Fig. 9), indicating that the chemical structure of the prepared
dicate that the prepared PEG/HWF (LWF) PCMs have good thermal PEG/HWF (LWF) SSPCMs is not affected by thermal cycling, and no
reliability in terms of phase transition properties after 100 thermal chemical degradation occurs in PEG/HWF(LWF) SSPCMs during
cycles. thermal cycling. These indicate that the shape-stabilized PEG/wood
The FT-IR spectra of PEG/HWF (LWF) SSPCMs before and after 100 flour PCMs have good chemical stability, thermal reliability and sta-
thermal cycles are presented in Fig. 9. The position and shape of ab- bility.
sorption peaks are consistent before (solid line in Fig. 9) and after (dash

Fig. 8. DSC curves of SSPCMs before and after thermal cycling.

7
B. Liang, et al. Solar Energy Materials and Solar Cells 200 (2019) 110037

Table 4
Degradation date of PEG, PEG/WF PCMs from the TG curves.
PCMs Mass loss (%)

At 100 (oC) At 250 (oC) At 500 (oC)

PEG1000 2.38 3.93 99.08

PEG1000/25%HWF 1.34 2.95 93.78
PEG1000/35%LWF 1.71 3.76 91.41
PEG4000 0.86 0.90 98.74
PEG4000/30%HWF 0.97 1.99 91.53
PEG4000/50%LWF 2.08 3.69 89.24
PEG10000 0.22 0.31 98.23
PEG10000/30%HWF 0.94 2.11 91.80
PEG10000/50%LWF 2.71 4.32 88.93

have apparent weight loss when the temperature is higher than 500 °C.
The weight losses of PEG and the prepared PEG/WF SSPCMs mainly
occur at the temperature between 200 °C and 450 °C. The TG results
indicate that the prepared PEG/WF SSPCMs are stable in the tem-
Fig. 9. FT-IR spectra of PEG10000/30%HWF and PEG10000/50%LWF PCMs
perature range of the phase transition for thermal energy storage ap-
before (solid line) and after (dash dot line) thermal cycling.
plications.

3.7. Thermal stability of PEG/WF SSPCMs

3.8. Light-thermal conversion and temperature regulation performance

Thermal stability is an important factor in the research and appli-

The light of a constant power of 250 W was used to simulate solar
cations of PCMs on account of the limiting usability of thermal de-
illumination to perform light-thermal conversion and temperature ad-
gradation. TG analysis is frequently performed to evaluate thermal
justment tests, and the temperature evolution of the sample (P01) and
stability. The TG and derivative TG (DTG) analysis curves of PEGs and
its around environment (P02) were recorded by infrared thermography
the prepared PEG/WF SSPCMs are shown in Fig. 10, and the corre-
camera, the temperature−time curves are showed in Fig. 11 (a). With
sponding data are summarized in Table 4. The DTG curves are sharp,
the solar irradiation time increases, the temperature of P01 and P02
only one-step decomposition occurs in PEG and the prepared PEG/WF
rises rapidly. When the temperature reaches about 35 °C (the initial
SSPCMs (Fig. 10). The peak appears at about 400 °C and corresponds to
temperature of phase transition of PEG), the temperature of P02 con-
the thermal decomposition of PEG segments. All samples have no ap-
tinues to increase rapidly, but the sample temperature (P01) increase
parent weight loss when the temperature is lower than 100 °C, while
slowly (from 50 to 200 s). During the process, PEG molecular segments

Fig. 10. TG and DTG curves of PEG and PEG/WF SSPCMs.

8
B. Liang, et al. Solar Energy Materials and Solar Cells 200 (2019) 110037

Fig. 11. Temperature-time curves of sample and around environment (a) and representative thermal images about the photothermal performance (b–f).

in the sample absorb solar thermal energy and store it through the temperature of the SSPCMs that releases its stored latent heat and
phase transition, the temperature of sample (P01) was maintained be- maintains the temperature. After the latent heat is released, the tem-
tween 35 and 50 °C and it is lower that the temperature of P02. Then, perature continues to drop and further releasing the stored sensible heat
under the continued solar irradiation, the temperature of P01 continues until the material temperature approaches the ambient temperature
to rise and the sensible heat continues to be stored. At about 300s, solar [10].
irradiation is turned off. Subsequent the temperature of P01 and P02
dropped sharply to about 30–35 °C and maintained (the indoor tem-
4. Conclusion
perature). However, the temperature of P01 is always lower than that of
P02. In other words, it shows that the temperature of sample in both
In this study, vacuum adsorption was conducted to fabricate PEG/
endothermic and exothermic processes are lower than the ambient
WF composites as SSPCMs. The studies showed that the adsorption
temperature around it, and the temperature in the sample is always
performance of HWF for PEG was higher than that of LWF, the max-
kept in the most comfortable with the humans, which allows the sample
imum PEG contents of PEG1000, PEG4000, and PEG10000 in PEG/
to be used in the cool energy storage of the building system, when the
HWF SSPCMs were 75 wt%, 70 wt%, and 70 wt%, respectively, but the
ambient temperature is at 30–45 °C.
maximum PEG contents in PEG/LWF SSPCMs were 35 wt%, 50 wt%,
Simultaneously, the light-thermal conversion performance of the
and 50 wt%, respectively. For PEG/WF SSPCMs, no chemical reaction
sample was clearly observed and recorded by the infrared thermal
occurred between PEG and WF during the melt processing, but the
imaging camera. As shown in Fig. 11(b–f), cylindrical sample and round
crystal structure of PEG in SSPCMs by WF component decreased. The
environment both are labeled to P01 and P02, respectively. Red portion
melting latent heat and relative latent heat efficiency of the prepared
and blue portion represent for high temperature and low temperature,
PEG/WF SSPCMs for PEG1000/25%HWF were as high as 108.6 J/g and
respectively. At the beginning (0 s), the sample temperature is close to
75.05%, and the obtained PEG/WF SSPCMs had good thermal relia-
the ambient temperature, so the image is generally blue. Under solar
bility and chemical stability for prolonged applications.
irradiation, the temperature of the sample and its round rises rapidly,
and the color of the image gradually turns red. The result of image
Fig. 11(b–f) is consistent with the result of temperature-time curve. In Author contributions
addition, the shape of the sample does not change throughout the
process, which is in good agreement with DSC test results and the The manuscript was written through contributions of all authors. All
leakage test. The above results show that PEG/WF SSPCMs have ex- authors have given approval to the final version of the manuscript.
cellent light-thermal conversion properties and have great potential
application in solar thermal energy storage.
Notes
The mechanism of solar thermal energy storage about the obtained
PEG/wood flour SSPCMs are described below. When the SSPCMs is
The authors declare no competing financial interest.
irradiated by sunlight, the temperature of the SSPCMs increases (sto-
rage sensible heat) and the temperature continues to rise to the phase
transition temperature of the SSPCMs, while the phase transition pro- Acknowledgements
cess occurs. In this process, the latent heat is stored and the temperature
of the SSPCMs is maintained near the phase transition temperature. This work was supported by the National Natural Science
After the phase transition of the material is completed, the temperature Foundation of China (21808070, 51673075), the Natural Science
continues to rise and the sensible heat continues to be stored. With Foundation of Guangdong Province (2018A030310349), the
leave the sunlight, the temperature of the SSPCMs drops and releases a Science & Technology Program of Guangzhou City (201803030003,
part of sensible heat. When the temperature drops to the crystallization 201704030085), the Research Fund Program of Guangdong Provincial
Key Lab of Green Chemical Product Technology (GC201813).

9
B. Liang, et al.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.solmat.2019.110037.
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