Materials Letters 63 (2009) 569571

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Crosslinking of the electrospun polyethylene glycol/cellulose acetate composite bers as shape-stabilized phase change materials
Changzhong Chen a,b, Linge Wang c,, Yong Huang d,
a

Guangzhou Institute of Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China Graduate School of Chinese Academy of Sciences, Beijing 100049, China Department of Chemistry, University of Shefeld, Shefeld S3 7HF, UK d State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China
b c

a r t i c l e

i n f o

a b s t r a c t
In a previous study, polyethylene glycol/cellulose acetate (PEG/CA) composite ultrane bers have been prepared by electrospinning. In order to improve their water-resistant ability and thermal stability for potential thermal storage applications, in this study, the electrospun PEG/CA bers were crosslinked by using toluene-2, 4-diisocyanate (TDI). The morphology and thermal properties of the crosslinked bers were investigated via SEM, DSC and TG, respectively. The results showed that the brous morphology of the crosslinked bers was well preserved even after 24 h immersing in deionized water. Meanwhile, the crosslinking also led to an improvement on the thermal stability, but brought a decrease of the enthalpy compared with the original electrospun bers. 2008 Elsevier B.V. All rights reserved.

Article history: Received 15 July 2008 Accepted 18 November 2008 Available online 24 November 2008 Keywords: Electrospinning Fiber Crosslinking Composites materials Thermal properties

1. Introduction Phase change materials (PCMs) have been applied in many different areas because of their capability of storing or releasing large amounts of latent heat thermal energy as they change from one physical state to another. Since PCMs melt and crystallize repeatedly during use, there is a risk of PCM leakage. Therefore, shape-stabilized PCMs or form stable PCMs [14], a kind of compound material of PCM and supporting material (commonly using polymer-matrix), was developed for their attractive advantages such as direct use without additional encapsulation, cost-effective, and easily prepared with desirable dimensions [514]. Recently, with the development of nano science and technology, a novel class shape-stabilized PCM, ultrane bers of PCM/polymer composite [1518], have been developed via electrospinning technique. McCann et al. have developed a method based on melt coaxial electrospinning for preparing phase change nanobers consisting of long-chain hydrocarbon cores and TiO2Poly (vinyl pyrrolidone) (PVP) sheaths [15]. Chen et al. have reported the preparation of the ultrane bers of the polyethylene glycol/cellulose acetate (PEG/CA) composite (in which PEG acts as the PCM and CA acts as the matrix) from the mixture solution of PEG and CA by conventional electrospinning method [16]. And the composite bers showed a good thermal stability and reliability with the supporting effect and shielding effect of the polymer (CA) matrix.

Here, in order to further improve the thermal stability as well as the water-resistant ability (because PEG is water soluble polymer) of the electrospun PEG/CA composite bers, the bers were surface crosslinked by using toluene-2,4-diisocyanate (TDI) as a crosslinking agent. The morphology and the thermal properties of the crosslinked bers were investigated using scanning electron microscopes (SEM), differential scanning calorimeter (DSC) and thermogravimeter (TG), respectively. 2. Experimental part 2.1. Materials _ CA (M n = 29,000 g/mol, degree _ of substitution, DS = 2.45) and TDI were obtained from Aldrich. PEG (M n = 10,000 g/mol) was purchased

Corresponding authors. E-mail addresses: linge.wang@shef.ac.uk (L. Wang), yhuang@iccas.ac.cn (Y. Huang). 0167-577X/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2008.11.033

Scheme 1. The crosslinking reaction of electrospun PEG/CA composite bers.

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C. Chen et al. / Materials Letters 63 (2009) 569571 Table 1 Thermal properties of the original and the crosslinked electrospun PEG/CA bers before and after 100 heating-cooling cycles Sample Original Cycled original Crosslinked Cycled crosslinked Melting point (C) 58.47 57.59 52.14 52.12 Latent heat of melting (J/g) 86.03 85.91 36.79 36.72 Crystallization point (C) 38.96 38.23 40.99 40.98 Latent heat of crystallization (J/g) 65.15 64.95 25.92 25.85

(TS2-60, Baoding Changjing Pump Ltd., China) at a rate of 5 ml/h. The metallic needle (0.8 mm diameter) was connected to a high voltage supply (BPS-20, Beijing Electrostatic Facility Ltd., China) with a xed voltage at 14 kV, and a piece of aluminum at sheet (placed 15 cm to the tip of the needle) was grounded and used as the collector [20]. The collected electrospun bers were dried under vacuum at the room temperature for 24 h to remove residual solvent. 2.3. Crosslinking The crosslinking reaction was showed in Scheme 1. Electrospun PEG/CA composite bers (~ 0.1 mm thickness) were immersed in 10 wt.% TDI/toluene solution at 40 C. And then the catalyst, dibutyltin dilaurate (1 wt.%, respect to TDI), was dropped in the solution. After 4 h, the bers ltered from the reaction system were Soxhlet extracted with ether for 24 h and dried under vacuum at 30 C for 24 h. 2.4. Dissolvability test Both the bers of before and after crosslinking were cut into a small size of 3 2 cm2 and soaked in deionized water for 24 h to investigate their water-resistant ability. 2.5. Thermal cycle test The appropriate amounts of bers were placed into the empty aluminum pans and then placed onto a hot stage (STC200, Instec, USA). A typical thermal cycle is consisted of heating the bers above PEG's melting temperature and cooling the samples at room temperature (in the temperature interval 20 C to 100 C). The heating and cooling process times were maintained at approximately 20 and 30 min, respectively. Thermal cycling test was continued until 100 consecutive melting and freezing processes. 2.6. Characterization The bers were gold-coated and the morphology was observed by SEM (JSM-6700F, JEOL, Japan) at an acceleration voltage of 20 kV

Fig. 1. SEM micrographs of the original electrospun PEG/CA composite bers (a), and immersed in deionized water for 24 h (c) and (e); the crosslinked electrospun PEG/CA composite bers (b), and immersed in deionized water for 24 h (d) and (f). (e) and (f ) are high resolution images.

from Guangzhou Chemical Agent Company, China. The catalyst, dibutyltin dilaurate, was purchased from Sinopharm Group Chemical Reagent Co., Ltd, China. All chemicals were used as received without further purication. 2.2. Electrospinning The PEG/CA composite bers were electrospun by following our previously developed procedure [16]. Briey, a 15 wt.% CA solution in 2/1 (w/w) acetone/dimethylacetamide (DMAc) was prepared [19] and then PEG with equal weight of CA was added to the CA solution (PEG/ CA = 1/1, w/w) under constant stirring for 2 h. The as-prepared solution was placed in a 10 ml syringe and was fed by a syringe pump

Fig. 2. DSC curves of (a) the original and (b) the crosslinked electrospun PEG/CA bers before (solid line) and after (dashed) 100 heating-cooling cycles.

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Fig. 3. TG (a) and DTG (b) curves of the original (dashed) and the crosslinked (solid line) electrospun PEG/CA bers.

under low vacuum. Thermal analysis was performed using a DSC (DSC-100, P-E, USA). Thermograms was obtained at a heating and cooling rate of 10 C /min at temperature range 20 C to 120 C and in nitrogen atmosphere. Thermal stability of the samples was measured by a TG (Pyris 1, P-E, USA) from 0 C to 600 C at a 10 C /min heating rate under nitrogen atmosphere.
3. Results and discussion As reported earlier [16], ultrane PEG/CA composite bers (with average ber diameter about 1500 nm) have been successfully prepared by electrospinning, and PEG is distributed not only on the surface but also within the core of the PEG/CA composite bers themselves. Due to the supporting effect and shielding effect of the polymer (CA) matrix as well as the hydrogen bonding interactions between the PEG and CA chains, only trace of PEG distributed on the ber surface would be degraded by atmospheric oxygen. One way to address this problem (the thermo-oxidative degradation of PEG) is to crosslink the bers to isolate PEG from air. By placing the electrospun PEG/CA bers into the TDI solution, the bers could be crosslinked via the reaction of the OH of PEG and CA with the isocyanate group of TDI. Typical SEM images obtained from the electrospun PEG/CA bers before and after crosslinking are shown in Fig. 1a and b. There is no obvious size change after the bers been crosslinked (Fig. 1b), the crosslinked PEG/CA bers show cylindrical shape with a smooth surface which is similar with the morphology of the original bers (Fig. 1a). Meanwhile, some crosslinks or cohesion occurred between the ber junctions, as shown in Fig. 1b, demonstrating the bers has formed a dense network membrane by the crosslinking. This result is also conrmed by the morphological change of the bers after water resistant tests. Since PEG is a water-soluble polymer and CA is not, the PEG distributed on the surface of the electrospun PEG/CA composite bers will be very easily washed from the bers [16]. As shown in Fig. 1c and e, a number of pores and grooves appear on the washed PEG/CA bers surface, which demonstrating the original electrospun PEG/ CA bers have a very poor water-resistant ability. Contrastively, the morphology the crosslinked PEG/CA bers is well preserved after the soaking treatment (Fig. 1d and f), the bers still show smooth surface and no obvious grooves appear on the surface. It suggests that the water-resistant ability of the electrospun PEG/CA is enhanced after the crosslinking, complementing similar result found in the literature [21]. Beside the morphology, the change of the thermal properties (stability) of the bers is also studied by the thermal tests. Fig. 2 shows a comparison of the DSC thermograms of the original and the crosslinked electrospun PEG/CA composite bers before and after 100 heating-cooling cycles. The data of the corresponding phase transition temperature and enthalpy are summarized in Table 1. For the original composite bers, their enthalpies are slightly decreased following thermal treatment. This is attributed to partial thermo-oxidative degradation of PEG [22] on the ber's surface after the thermal cycles [16], even the hydrogen bonding interactions between the PEG and CA chains hamper the oxidation of PEG to a certain extent. In contrast, as shown in Table 1 and Fig. 2, the enthalpies for the crosslinked composite bers are quite identical before and after the thermal cycles, which is due to the thermo-oxidative degradation of PEG is precluded from the shielding effect of the crosslinking. It indicates that the crosslinked PEG/CA bers show a more reliable thermal stability than that of the original bers. Meanwhile, the comparison from TG and differential thermalgravometry analysis (DTG) curves (Fig. 3) of the original and the crosslinked PEG/CA bers are also in accordance with the conclusion. From Fig. 3, the onset temperatures of the original bers are 156.59 C and 341.99 C, respectively, while those of the crosslinked bers are 255.16 C and 360.27 C, respectively. In addition, the peak point of decomposition temperature of the bers increases more than 10 C after be crosslinked. Beside the improvement of the thermal stability of the electrospun PEG/CA bers, however, the crosslinking also leads an

appreciable decrease in the enthalpy. From Table 1, the enthalpies of the crosslinked bers drop more than 50% compared to that of the original bers which can be account for the restriction of the PEG phase. The presence of the interchain crosslinks within the molecules connes the free movement of the molecular chains of PEG on the bers' surface during the melting process and the crystallization process [23,24]. The thermal tests results indicate the crosslinking enhances the thermal stability of the electrospun bers, but it also sacrices the enthalpy of the bers.

4. Conclusion Crosslinked electrospun PEG/CA composite bers have been prepared by using TDI as crosslinking agent. The crosslinked PEG/CA bers showed cylindrical shape with a smooth surface which was similar with the morphology of the original composite bers. It was found that the crosslinking enhanced the water-resistant ability and the thermal stability of the bers, but brought a decrease of the enthalpy of the bers. As a whole, the crosslinked PEG/CA composite bers are promising in serving as a shape-stabilized PCM for thermal energy storage at wider temperature ranges compare with the original composite bers. Acknowledgement Financial support by National Natural Science Foundation of China (Nos. 50521302 and 50473057) is greatly appreciated. References
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