The energy storage and reuse have attracted considerable attention in recent years

because of the energy crisis, the high cost of fossil fuels, the environmental impacts as
well as the low price [1,2]. Owing to its ability to provide a high storage density at nearly
constant temperature, latent heat thermal energy storage (LHTES) using phase change
materials (PCMs) is considered to be the most effective and promising technique for
solar energy heating and cooling applications [3]. In recent years, PCMs have been
widely employed in various fields including solar energy system, building energy
conservation, thereto-regulated fibers and so on [4–8]. Among the PCMs investigated,
PEG is taken as a promising PCM because of its nontoxicity, relatively large fusion
heat, congruent melting behavior, resistance to corrosion and ease of chemical
modification [9–11]. However, the melted PEG has to be kept in a closed tank or
container to prevent leaching during the phase transition, which not only increases
production costs, but also reduces the heat transfer efficiency. Physical entanglement or
chemically cross-linking of PEG with other substances, it may maintain the original solid
state during phase transition of PEG, namely forms the so-called FSPCMs, which can
effectively solve the above problems. FSPCMs can be prepared by encapsulation of
PCM into inorganic materials with porous lamellar structure or polymers with high
melting point and so on [12–14]. Although inorganic materials can ensure the same
macroscopic shape before and after the phase transition, the PCM is easy to loss by
migrating to the surface after repeated use. Therefore, a considerable amount of
research has been carried out on the preparation of suitable polymer-based FSPCMs
with crosslinking structure. There are two basic approaches: chemical and physical
approach. In the chemical approach, the PCM is bound onto supporting polymeric
materials by chemical grafting and cross-linking copolymerization [9,15]. Li et al. [16]
synthesized a novel solid–solid phase change material (SSPCM) via the two-step
condensation reaction of polyethylene glycol (PEG10000) with pentaerythritol (PE) and
4,40 - diphenylmethane diisocyanate (MDI). The results showed that the novel
polymeric SSPCMs possesses excellent crystal properties and high phase change
enthalpy. Xiang et al. [17] synthesized novel environmentally friendly
poly(hydroxybutyrate-co-hydroxy vale rate) and poly(ethylene glycol) (PHBV/PEG)
copolymer networks as a PCM with PHBV diacrylate (PHBVDA) and polyethylene glycol
diacrylate (PEGDA) as macromonomers. PHBV/PEG copolymer network had a higher
latent heat enthalpy, which didn’t reduce with the components of PHBV increased.
Moreover, PHBV/PEG copolymer network still had good thermal stability even at 300 C.
Li et al. [18] synthesized a novel melamine/formaldehyde/polyethylene glycols (MFPEG)
SSPCMs with crosslinking structure composed of PEG as energy-storage ingredient
and melamine as crosslinking functional reactant. The SSPCMs were synthesized via
two steps of amine-aldehyde condensation reaction and aldolization. The maximal
latent heat enthalpies of heating and cooling cycle were 109.4 and 103.9 J/g,
respectively. In another study, PEG10000/ polyglycidyl methacrylate cross-linked
copolymer as a novel SSPCM was successfully synthesized [19]. The DSC results
indicated that the copolymer imparted balanced and reversible phase change behaviors
at the temperature range of 25–60 C, and it had high latent heat storage capacity of
more than 70 J/g. However, there was a remarkable obstacle in the practical application
for energy storage with chemical methods of synthesizing SSPCMs due to its
complexity. Moreover, owing to the chemical linkage function of the skeleton polymer to
the phase change substance, the phase change enthalpy and the phase change
temperature of these phase changed substance composites obviously reduces. The
other approach is the physical approach in which many researchers aim to construct
cross-linked microstructure in the matrix of polymer-based FSPCMs [16,18]. Here, the
cross-linked microstructure plays an important role in overcoming the leakage of phase
change materials. It is mainly because molecular chain of phase change working
substance is confined in the micro deformation of cross-linked microstructure, so it
migrates into surface of matrix hardly. Chen et al. [20] prepared a series of cross-linked
high-density polyethylene (HDPE) FSPCM with different gel contents. The result
showed that cross-linking can improve the stability of FSPCM with the formation of the
network, which would prevent the paraffin from diffusing to the outside. Moreover, Chen
et al. [21] evaluated the miscibility of the paraffin in the three types of polyethylene. The
atomic force microscopy (AFM) results verified the partial miscibility of paraffin in
polyethylene, and concluded that paraffin is less miscible in HDPE than in LDPE or
LLDPE. In the next paper, to evaluate the leakage behavior of paraffin in PE for future
FSPCMs, Chen et al. [22] explored morphological structures with paraffin leakage
behavior in polyethylene/paraffin binary composites. The paraffin leakage rate from
HDPE was considerably slower than blends produced with LDPE or LLDPE for leakage
test. As one kind of important engineering polymer, Polyacrylonitrile (PAN) possess
solvent resistance, chemical stability, thermal and mechanical stability, high tensile
strength and good insect resistance [23,24]. It has attracted more and more researchers
to explore the PAN as PCM packaging material in recent years [25–28]. Here, we
prepare a novel cross-linked network structure of acrylonitrile copolymer P(AN-co-IA)
with itaconic acid (IA) as comonomer. When compared this method with the others in
literature, it is simple, easy and does not need long time, high temperature and special
catalyst. Thereafter, a novel cross-linked FSPCMs with PEG as work materials and
cross-linked P(AN-co-IA) as cladding layer and supporting material were prepared. The
crosslinked P(AN-co-IA) not only provided a good supporting skeleton to the whole
composites, but also prevented the leakage of solid– liquid PCM during phase change
process. The structure, thermal properties and thermal reliability of cross-linked P(AN-
co-IA)/ PEG were investigated by FTIR, Raman, DSC, XRD, POM, SEM, TGA and
thermal conductivity testing instrument. The results showed that the cross-linked
FSPCMs possess excellent phase change properties. It is easy to achieve desired
shapes and likely to be produced in large scale. Firstly, 1.0 g P(AN-co-IA) (0.00513 mol
ACOOH), 0.65 g (0.0026 mol) MDI (molar ratio of ACOOH to MDI = 2:1) and 70.0 g
DMF were dissolved in a three-neck round-bottom flask with an overhead stirrer. The
reaction mixture was stirred at 65 C for 4 h. Then, 0.25 g (0.001 mol) MDI was dissolved
in the reaction mixture, and slowly heated to 90 C and left to stir for S. Mu et al. / Energy
Conversion and Management 110 (2016) 176–183 177 1 h. At last, 3.0 g dried
polyethylene glycol (PEG, M = 4000) was added and the reaction was continued at 90 C
for 3 h. After the reaction was completed, the crude product was dried in vacuum oven
at 90 C for several hours. The Synthetic route of crosslinked P(AN-co-IA) is shown In
the rest of this paper, the synthesized cross-linked P(AN-co-IA)/PEG is abbreviated as
CFSPCMs and the ratio of P(AN-co-IA). The composition and structure were
characterized by a FT-IR (U.S. Company Perkin Elmer) in the wavenumber range of
4000–400 cm1 . Raman spectra of P(AN-co-IA) and cross-linked P(AN-co-IA) were
measured with a 90 C scattering geometry at the excitation of 532 nm using a green
laser and a spectral resolution of 1 cm1 (XploRA, France). The spectrum was measured
in the range of 100–4000 cm1 . The thermal energy storage of crosslinked FSPCM was
performed using a differential scanning calorimeter thermal analyzer (DSC Q2000) at a
heating rate of 10 C/min over the temperature range of 0–100 C under a nitrogen
atmosphere. Thermal cycling tests were carried out by using a hot stage (STC200,
Instec). A typical thermal cycling consisted of a consecutive heating and cooling
process (in the temperature interval 20–80 C). XRD patterns of the samples were
recorded on a D/max-3B diffractometer (Rigaku Corporation) using with k = 0.1542 nm
target of Cu Ka radiation in the range of 2h = 10– 70 for scanning the sample. The
scanning speed was 4/min, tube voltage of test used was 40 kV, and the tube current
was 40 mA. An observation of polarizing optical microscopy (POM) was performed on a
LEICA DM2500P microscope equipped with a video camera. The sample was placed
between a microscope glass and a cover slip, and heated with hot stage. Microstructure
of the samples was investigated by JSM-5600LV scanning electron microscopy (SEM).
Thermal stability was investigated by a thermogravimetry analysis system (TGA) (TGA
Q50). Temperature programs were run from 30 to 800 C at a heating rate of 10 C/min
under a nitrogen atmosphere. The thermal conductivity of the CFSPCMs was measured
by using a thermal conductivity testing instrument (LFA 457, NETZSCH, accuracy:
±2.0%) s gives the DSC curves of PEG and CFSPCMs with different PEG contents, and
the thermal properties obtained from these curves were also summarized in Table 2. As
can be seen from DSC curves and data, the maximum melting and freezing peak of
PEG in the composites shift toward lower temperatures compared with PEG, this is
mainly because the PEG molecules in cross-linked P(AN-co-IA) networks exhibit a
confined crystallization process in light of the changes of crystallization environments.
Additionally, the decreased Tc of the CFSPCMs composites also confirms that the
P(AN-co-IA) template does not play the role of nucleation agent for the crystallization of
PEG [30]. Moreover, as can be seen from Table 2, there are considerable differences
between the phase transition temperatures of the CFSPCMs obtained from heating and
cooling processes. It is because the subcooling behavior of PEG dispersed into cross-
linked P(AN-co-IA). And the phase transition temperatures of CFSPCMs are in the
range of 23.6–35.5 C for cooling scan and 43.4–53.9 C for heating scan. It can be noted
that these CFSPCMs have proper phase transition temperatures for heating and cooling
applications, and can be used as energy absorbing building material. As can be seen
from Table 2, phase change enthalpies of the CFSPCMs increased with the PEG
content increased. This is due to the increase in the concentration of the crystalline
domains. The latent heat values of the CFSPCMs are in the range of 21.8– 118.5 J/g for
heating process and 19.8–115.7 J/g for cooling process. Especially, the latent heat
capacity of CFSPCM-5 is much higher than those of traditional FSCPMs reported in
literature with the same phase change working ingredient. Table 3 lists the data of
thermal properties of the traditional FSPCMs with different PCMs in literatures. For
comparison, the enthalpy efficiency (u) is introduced here, which is the ratio of practical
and theoretical loading in mixtures. It can be noted that the u value of the CFSPCMs in
present work is much higher than that of the traditional FSPCMs, which indicates that
the introduction of cross-linked P(AN-co-IA) as a supporting material has greatly
increased the thermal storage density of the FSPCMs. To verify the stability of phase
change for CFSPCMs, the 1000 times heating and cooling cycles were carried out, as
shown in From the DSC curves of CFSPCMs-4 after 1000 thermal cycling, the melting
and freezing temperatures were found to be 24.1 C and 20.7 C, and the latent heats of
melting and freezing were calculated as 65.51 J/g and 67.96 J/g. The melting and
freezing temperatures of the CFSPCMs-4 changed in range of 0.75–0.9 C, 1.3–3.3 C,
respectively. Moreover, after the thermal cycling, the latent heat values of melting and
freezing changed by 4.4%, 4.6%, respectively. Based on the results, it is noteworthy
that the CFSPCMs have good heat storage durability in terms of thermal properties after
thermal cycling. In order to validate the shape stability of CFSPCMs during phase
transition, the leakage test were performed as follows: pristine PEG and CFSPCMs
were heated to 80 C simultaneously and kept the temperature constant for 3 min. Then,
the samples were cooled to room temperature. The heating–cooling process was cycled
for 5 times. The photographs of pristine PEG and CFSPCMs at 80 C are showed in.
The appearance of CFSPCMs is brown. The CFSPCMs with the maximum PEG content
of 73 wt% keeps solid state without melted PEG leakage at 80 C. That means the hard
segment of cross-linked P(AN-co-IA) could serve as skeleton to restrict the free
movement of the soft PEG segments, it exhibits a special solid–solid phase change
behavior. When the temperature further increased to 180 C for 10 min, the surface of
CFSPCMs appeared slightly moist phenomenon, which is because the PCM migrate to
the surface. But, the CFSPCMs still keep solid status without leaking melted free PEG
movement. So, the best shape stabilized To reveal the crystallization morphology of
CFSPCMs, WAXD patterns of PEG, P(AN-co-IA), and CFSPCMs are shown in. It is
clearly shown that the broad diffraction pattern of P(AN-co-IA) displays around 2h value
of 16.7, which is a confirmation of its amorphous nature. Moreover, it is easily observed
that pristine PEG and CFSPCMs have similar diffraction patterns, and two strong
diffraction peaks appear at about 19.2 and 23.4. These results indicate that PEG units
in the CFSPCM have similar crystal structure as the pristine PEG. However, the
diffraction peak height of CFSPCMs is lower and the half width is broader than that of
pristine PEG, which means the crystallites become smaller and the degree of
crystallinity decreases. Due to the network structure, rigid benzene ring and cyano
groups of CFSPCM, some segments of PEG cannot form crystals. The crystallinity of
PEG decreases owing to steric hindrance [36]. To further investigate the crystalline
properties of CFSPCMs, the POM was used to record the crystalline morphology of
CFSPCMs and pristine PEG. It is observed from that both PEG and CFSPCMs-4 are
crystalline. However, the crystallites of CFSPCMs are smaller than that of pristine PEG,
which indicates that the PEG chains are limited by the cross-linked network of P(AN-
coIA). The crystalline properties of CFSPCMs are weakened compared with pristine
PEG because the crystallization process of PEG chains becomes confined [37,38].
These results are in good agreement with WXRD results. Similar POM micrographs.
The SEM photographs of PEG and CFSPCMs are shown in PEG with smooth dark gray
surfaces could be seen. From it is believed that the brighter threedimensional network
structure and smooth dark gray area on the SEM images correspond to cross-linked
P(AN-co-IA) matrix and PEG, respectively [39]. This point of view is able to be
confirmed by the SEM observation of water-etched surface of CFSPCMs-4 (i.e. the
sample was soaked in hot water at 80 C for 10 min to dissolve away the PEG located in
surface layer) which presented in Fig. 6f. The obvious three-dimensional network
structure of cross-linked P(AN-co-IA) matrix could be seen from. According to SEM
observations of CFSPCMs composites, the PEG is uniformly encapsulated and
embedded inside the three-dimensional cross-linked P(AN-co-IA) network. Moreover,
we can also find the concentration of network obviously increased with the increase of
mass fraction of the cross-linked P(AN-co-IA). The existence of the cross-linked P(AN-
co-IA) plays a very important role in keeping solid state of CFSPCMs. When heated to
PEG’s melting point, CFSPCMs can only vibrate and rotate but keep its solid state. 3.5.
Thermal stability of CFSPCMs The TGA and DTG analysis curves of pristine PEG and
CFSPCMs are shown in. The degradation temperature data derived from the TGA and
DTG curves are also tabulated in Table 4. It can be observed from that CFSPCMs are
not degraded and almost no weight loss when the temperature is lower than 249 C,
which means that CFSPCMs as a novel PCMs is very stable in the working temperature
region. There is also a wider processing temperature range of CFSPCMs. Only when
the temperature is increased to higher than 249 C, slight thermal decomposition
appears. And it is degraded in two steps, which includes the thermal decomposition of
cross-linked P(AN-co-IA) and PEG chain. The decomposition temperature of them
reaches to maximum at 327 C and 396 C, respectively. Moreover, it can be observed
from that the initial decomposition temperature and peak point of second step of the
CFSPCMs are higher than those of pristine PEG. It is due to the introduction of rigid
phenyl groups and cross-linking network played a very important role in elevating the
thermal resistance of CFSPCMs. Thus, the synthesized novel CFSPCMs with good
heat-resistant performance will have a broad applicable temperature range. 3.6. Heat
transfer properties of prepared PCMs To investigate the effect of the cross-linked P(AN-
co-IA) supporting materials on the thermal conductivity of the PEG, the thermal
conductivities of the samples are measured by using the thermal conductivity testing
instrument. Table 5 presents the thermal conductivity of the CFSPCMs and PEG. The
tests are repeated five times and averaged to obtain the thermal conductivity values. As
seen from Table 5, the thermal conductivity of the CFSPCMs are determined as
0.2360.298 W m1 K1 . And the thermal conductivity of the CFSPCMs increased with
increasing mass fraction of PEG. The thermal conductivity of pure PEG and the
CFSPCMs-1 are determined as 0.297 W m1 K1 and 0.298 W m1 K1 , respectively,
showing CFSPCMs-1 and PEG (0.297 W m1 K1 [40]) have the approximate thermal
conductivity. This indicates that the CFSPCMs have almost equal heat absorption and
release velocity to PEG. 4. Conclusion A novel type of CFSPCMs with cross-linked
network microstructure has been successfully prepared via blending cross-linked P (AN-
co-IA) with PEG. It has been confirmed that the P(AN-co-IA) formed macroscopic
network, the PEG was dispersed into the network. The CFSPCMs has been endowed
with excellent phase change properties and good heat storage durability. The phase
change properties of the CFSPCMs enhances with increasing the weight percentage of
the PEG. Meanwhile, the CFSPCMs has exhibited great thermal