Materials Letters 216 (2018) 220–223

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Preparation and thermal properties of polyethylene glycol/expanded

graphite as novel form-stable phase change material for indoor energy
saving
Yingni Yang, Yao Pang, Yi Liu ⇑, Hongwu Guo ⇑
College of Materials Science and Technology, Beijing Forestry University, Beijing 100083, China

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

Article history: Phase change material (PCM) is a new kind of material for energy storage; its thermal properties are key
Received 10 December 2017 factors in determining the application areas and the actual effect. The polyethylene glycol
Received in revised form 23 December 2017 (PEG)/expanded graphite (EG) composite was prepared as a novel form-stable PCM by vacuum impreg-
Accepted 4 January 2018
nation in this study. Nitrogen adsorption test indicated that EG belonged to materials in mesoporous
Available online 5 January 2018
scale with developed porous structure and prodigious adsorbility. The PEG/EG PCM owned excellent seal-
ing performance and remarkable thermal storage capacity. The phase change temperatures and latent
Keywords:
heats of the PEG/EG PCM were in range of 18.89–25.93 °C and 97.56–98.59 J
g 1 respectively. TGA and
Thermal energy storage
Form-stable phase change materials
thermal performance manifested that the PEG/EG PCM presented good thermal stability and EG per-
Polyethylene glycol formed favorable conductivity and improved the thermal storage efficiency. The obtained PCMs were
Expanded graphite suitable for indoor energy saving and thermal comfort improvement.
Indoor energy saving Ó 2018 Elsevier B.V. All rights reserved.

1. Introduction and it showed that EG improved the thermal conductivity and sta-
bility of stearic acid/EG composites [7]. Compared with other por-
Thermal storage material, especially those using latent heat to ous materials, EG has good adsorption capacity, but less impurity,
store energy, has attracted unprecedented concern due to the less surface free radicals, stable performance, low cost and easy
growing challenges of energy crisis and climate change [1]. Phase preparation [8]. It is obvious that porous materials give an encap-
change material (PCM) with higher thermal storage densities and sulation to PCM by using developed pore structure. If the PCM
nearly isothermal process, has been widely used in aerospace, mil- could be applied into indoor building or decorative materials, the
itary affairs, medical treatment, textile and successfully applied in novel various of functional composites could provide thermostat
building materials area [2–4]. Among the investigated PCMs, and thermal energy conservation properties, and improve the
organic solid-liquid PCMs are more attractive, which includes indoor thermal comfort [9,10].
paraffin, alkyl esters, fatty acids, polyethylene glycol and its deriva- The aim of this study was to prepare a thermostable PEG/EG
tives. However, PCM is sensitive to ambient temperature or pres- PCM for indoor energy saving application. The pore structure of
sure in the practical application, which leads to liquid leakage EG, packing capability and thermal properties of PEG/EG PCM were
problem. Normally, PCM is packaged in the skeleton to avoid this investigated respectively. According to results, PEG/EG PCM exhib-
problem [5]. Polymers and microcapsule are used as skeletons to ited good sealing performance and remarkable thermal storage
coat PCM. However, during the composite process, these skeletons capacity, which were beneficial for energy saving. This provides a
would be riskily ruptured or sunken so that PCM would flow away development direction for the building and household adornment
from the skeleton and losing thermal storage ability [6]. Form- materials.
stable encapsulation of PCM has been regarded as a hot issue in
recent years. Many researchers aim to construct porosity material
adsorption system, which can effectively solve the liquid leakage 2. Materials and methods
problem and protect PCM from external problems. Lately,
researchers have successfully manufactured stearic acid/EG PCM 2.1. Materials and sample preparation

⇑ Corresponding authors. 2.1.1. Materials

E-mail addresses: [email protected] (Y. Liu), [email protected] PEG (AR, the average molecular weight is 800 g/mol) was pur-
(H. Guo). chased from Shanghai Macklin Biochemical Co., Ltd. (Shanghai,

https://doi.org/10.1016/j.matlet.2018.01.025
0167-577X/Ó 2018 Elsevier B.V. All rights reserved.
 Y. Yang et al. / Materials Letters 216 (2018) 220–223 221

China) and stored at room temperature hermetically. Expandable also plotted and analyzed. Thermal storage efficiency testing was
flake graphite (80 meshes) was supplied by Jinrilai graphite Co., carried out by a measurement machine in Fig. 1(b).
Ltd. (Qingdao, China).

3. Results and discussion

2.1.2. Preparation of PEG/EG PCM
Through high-temperature expansion at 800 °C for 60 s, the By BET analysis, EG showed a high specific surface area which
over-dried flake graphite was developed into EG and cooled down was 134.48 m2
g 1. This is highly beneficial for PCMs adsorption.
naturally in a desiccator. PEG was configured as 20% anhydrous EG possesses mesoporous structure with the pore sizes
ethanol solution which was blended with EG by spray at mass concentrated on the 1–10 nm range (Fig. 2(b)). According to the
ratios of 6:1(PCM1), 7:1(PCM2), 8:1(PCM3), 9:1(PCM4), 10:1 hysteresis loop of adsorption/desorption isotherm, the distance
(PCM5) and 11:1(PCM6), respectively. The samples were put in a between the closed point on the upper and lower end of the hys-
vacuum oven at 85 °C for 12 h under pressure of 0.1 MPa. After teresis loop was wide. This indicated EG possesses a wide meso-
the vacuum adsorption process, the PEG/EG PCMs were con- porous aperture distribution. Therefore, EG possessed powerful
structed (Fig. 1(a)). The liquid leakage tests were proceeded to adsorption ability, which was advantageous for PCM to prepare
ensure the packing capability. phase change functional material.
EG had a lamellar, puff and porous structure (Fig. 2(a)), which
was benefit for PEG adsorption. In previous research, EG performed
2.2. Measurement a preferable absorptivity of absorbing stearic acid and the absorp-
tion capacity had reached 90% [7]. Liquid PEG was filled up the
EG porosity was measured by nitrogen adsorption test at 150 °C pores of EG under vacuum by air pressure and pore syphoning.
(Autosorb-iQ, USA) using BET formula to calculate the specific sur- PEG/EG PCM had a relatively smooth surface in PCM4 and PCM6.
face [11]. The morphologies and microstructures were observed by For PCM6, little superfluous PEG on the surface of EG was visible.
a Scanning Electron Microscope (JSM-7001F, Japan). Differential The leakage tests were carried out at 155 °C for 3 h. PEG would
Scanning Calorimeter (DSC Q2000) and Thermogravimetric Ana- enter into the macro pores firstly then permeate into mesoporous
lyzer (TGA Q50) were to characterize thermal properties of sam- under the effect of negative pressure and gradually fill up meso-
ples. Curves of weight loss and derivative weight loss (DTG) were porous of EG during adsorption process. When the PEG mass frac-

Fig. 1. (a) The synthetic route of PEG/EG PCM; (b) the schematic of the temperature measurement system.
222 Y. Yang et al. / Materials Letters 216 (2018) 220–223

Fig. 2. (a) The nitrogen adsorption/desorption isotherm and cumulative pore area versus and diameter curves of EG; (b) Mass loss rate of PEG/EG PCM samples after leakage
test; (c) SEM images of EG, PCM1, PCM4 and PCM6.

Table 1
DSC data of PEG and PEG/EG PCM samples.

Sample Crystallizing Melting

Phase transition temperature Peak temperature Latent heat Phase transition temperature Peak temperature Latent heat
(°C) (°C) (J
g 1) (°C) (°C) (J
g 1)
PEG 24.57 21.69 130.3 25.39 32.39 133.6
PCM1 13.35 12.55 81.50 21.65 30.06 78.06
PCM4 21.10 19.09 97.56 18.89 25.93 98.59
PCM6 20.18 18.74 95.03 17.14 25.81 98.28

tion was not exceeding 90%, the quantity of PEG was under EG mised by mesoporous structure, resulting in the decrease of ther-
adsorption capacity, resulting in the retention of PEG in the macro mal enthalpy compared with PEG. Crucially, PCM4 exhibited high
pores of EG. However, the surface interaction between adsorbate latent heat values with nearly no liquid leakage, while PCM6 had
and adsorbent in macro pores was weaker than that in meso- occurred liquid leakage. This result indicated PEG/EG PCM owns
porous, so the liquid PEG was more tended to leak out. Reversely, the potential for indoor functional composites application.
the leakage phenomenon occurred. This illustrated that leakage It can be found in Fig. 3(b) that slight thermal decomposition of
prevention ability of PEG/EG PCM is in a certain mass range. Com- both PEG and PEG/EG PCM appeared as the temperature was
prehensive the economic material ratio and preferable permeabil- higher than 278 °C. The EG of PCM4 illustrated no decomposition
ity, the relatively better ratio of PEG and EG for PCM preparation and caused the maximum mass loss ratio had reduced 0.2%. The
was 9:1 (Fig. 2(c)). peak temperature decreased from 383 to 378 °C, which was attri-
As it can be seen from DSC test results(Fig. 3(a) and Table 1), the butable to the superior thermal conductivity of EG. Additionally,
latent heat of PCM4 during crystallizing-melting cycles still the internal pressure of pores increased faster when the tempera-
reached up to high value of 97.56–98.59 J
g 1. The temperature ture increasing. Due to ‘‘pressure cooker” action, the practical tem-
range of the solid-liquid phase change process was 18.89–25.93 °C, perature in pores was higher than the apparent temperature.
which shifted downward compared with that of PEG. It was mainly The temperatures were rose from 18.0 to 40.0 °C during the
because PEG molecules in EG exhibited a confined crystallization thermal storage process and cooled down oppositely for thermal
process in light of the changes of crystallization environments. release. PEG used 2490 s for thermal storage while PCM4 spent
Meanwhile, EG had good thermal conductivity and this increased 1810 s, and time of PCM4 had been shortened 27.31% (Fig. 3(c)).
the speed of phase changing process. Thermal enthalpies of PCM Compared with PEG, PCM4 underwent 2370 s and saved 60.5% of
samples increased with the PEG mass fraction increasing due to time during thermal releasing process (Fig. 3(d)). This exhibited
the increase in the concentration of the crystallization domains. the preferable thermal conductivity of EG improved the thermal
On the other hand, the crystallization integrity of PEG was compro- storage efficiency.
 Y. Yang et al. / Materials Letters 216 (2018) 220–223 223

Fig. 3. (a) DSC, (b) TG and DTG, (c) thermal storage and (d) release efficiency curves of PEG and PEG/EG PCM samples.

4. Conclusions [3] S. Mu, J. Guo, S. Zhang, Q. An, D. Wang, Y. Liu, F. Guan, Preparation and thermal
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