Materials Letters 62 (2008) 3555–3557

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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 e v i e r. c o m / l o c a t e / m a t l e t

Electrospun crosslinked polyvinyl alcohol membrane
Enlong Yang ⁎, Xiaohong Qin, Shanyuan Wang
College of Textile, Donghua University, Shanghai, 201620, China

A R T I C L E

I N F O

A B S T R A C T
The electrospinning of polyvinyl alcohol (PVA) was performed with maleic anhydride (MA) as a cross linker to fabricate slightly soluble nanofiber membrane. The solubility, morphology and thermal behavior of electrospun PVA and PVA/MA membranes were characterized by water durability test, scanning electron microscope (SEM) and differential scanning calorimeter (DSC), respectively. Water durability test demonstrated that 8% PVA/MA (20/1, mole/mole) membrane had the least average mass loss and standard deviation. SEM images showed that fibers in PVA/MA membrane had a larger average diameter compared to those in PVA membrane. DSC investigated that crystal structure was formed in PVA/MA membrane. The results show that rapid evaporation of water and high electric field during electrospinning process may promote crosslinking of PVA and MA. © 2008 Elsevier B.V. All rights reserved.

Article history: Received 21 January 2008 Accepted 20 March 2008 Available online 28 March 2008 Keywords: Nanomaterials Polymers Electrospinning Polyvinyl alcohol Maleic anhydride Crosslink

1. Introduction Electrospinning is quite a simple method for fabricating submicron fibers. In general, fibers with diameter less than 1000 nm are called nanofiber in electrospinning [1,2]. The electrospinning process is that a polymer solution or melt is placed into a syringe with a millimetersize nozzle and is subjected to high electric field. Under the applied electrostatic force, the polymer is ejected from the nozzle, whose diameter is reduced significantly as it is transported to and deposited on a collector, which also serves as the ground for the electrical charges. Due to unique properties such as high surface area to volume ratio, small pore sizes, high porosity and so on, the ultrafine fiber membranes prepared by electrospinning process have been extensively studied and widely used for its potential applications in filter media, composite materials, biomedical applications, etc [3–5]. PVA is a polyhydroxy polymer that has been studied intensively because of its good film forming and physical properties, high hydrophilicity, processability, biocompatibility, and good chemical resistance [6–8]. When the electrospun PVA nanofiber membrane was immersed in water, it would dissolve because PVA is a water soluble polymer. Therefore, it is necessary to crosslink the PVA polymer and stabilize the electrospun nanofiber membranes in wet condition [9]. All multifunctional compounds capable of reacting with the hydroxyl group may be used as a cross linker of PVA. Thus, dialdehydes, dicarboxylic acids, dianhydrides, etc. Dicarboxylic acid crosslinked PVA deserves more attention. Gohil et al. crosslinked PVA/MA cast membrane by heat treatment [10]. Ding et al. [11]

prepared electrospun PVA/glyoxal membranes then crosslinked them by heat treatment. Choi [12] prepared electrospun soluble polymer/crosslinking agent membranes then crosslinked them by heat or ultra violet (UV) lights treatment. In the present work, we

⁎ Corresponding author. Tel.: +86 21 67792700; fax: +86 21 67792627. E-mail address: yel@mail.dhu.edu.cn (E. Yang). 0167-577X/$ – see front matter © 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2008.03.049

Fig. 1. Schematic diagram of electrospinning apparatus.

Distilled water was purchased from Pinjiang Chemical Co. The thermal behavior of PVA and PVA/MA membranes was investigated by differential scanning calorimeter (PYRIST DSE) over the temperature of 30–300 °C and at a heating rate of 10 °C min− 1. Average diameter of fibers in PVA and PVA/MA membranes is about 193 nm and 238 nm. so no clear cold crystallization and melting endothermic peak was shown in thermogram of PVA membrane. Experimental PVA powder (Mw = 88. mole/mole) membranes are shown in Fig. The prepared PVA/MA membranes were slightly soluble in boiling water. 2. 21/1. 21/1. The crystallinity and molecular orientation of electrospun 8% PVA were in a low degree.13 0. respectively. The polymer solutions were electrospun at a positive voltage of 20 kV. The electrospinning apparatus is schematically shown in Fig. Results and discussion To evaluate solubility. 8% PVA/MA (20/1. 3.92 20/1 3. this is mainly due to the efficient crosslinking of PVA and MA during electrospinning. 6%. and 10/1. 2. Another possible reason is attributed to the decrease of hydrophilic hydroxyl groups. 2. electrospun PVA membrane can dissolve in water Fig.. SEM images of electrospun 8% PVA and 8% PVA/MA (20/1. But three dimensional structural molecules and crystal structure were formed in electrospun 8% PVA/MA (20/1. 3. Accelerating voltage of 10 kV was employed to take the SEM photographs. 19/1. Maleic anhydride and sulfuric acid (98%) were purchased from Sinopharm Chemical Reagent Co. Mass loss of 8% PVA/MA (10/1. / Materials Letters 62 (2008) 3555–3557 Table 1 Average mass loss and standard deviation of electrospun 8% PVA/MA membranes PVA/MA (mole/mole) Average mass loss (%) Standard deviation (%) 30/1 Soluble 21/1 5. mole/mole) was added into the prepared PVA solutions respectively with vigorous stirring to get homogenous PVA/ MA solutions. 20/1.000 g mol− 1. Ltd. so clear melting endothermic peak was shown in thermogram of PVA/ MA membrane.37 1. so average diameter of fibers in PVA/MA membrane is larger. 20/ 1. crosslinking of it may be the most efficient. 1. 19/1 and 10/1.5 J g− 1. It can be seen from thermogram of PVA/MA membrane that clear melting endothermic peak appears around 250 °C and the enthalpy is 248. The crosslinking chemical agent forms three dimensional structural molecules which can prevent the polymer from dissolving in water [12]. the collected fibers are nearly dry. As they reach aluminum plate. In fact. It is generally believed that the melting endothermic peak (Tm) of PVA appears around 257 °C [13]. mole/mole) membrane.18 found that PVA and MA crosslinked efficiently during electrospinning process instead of heat treatment or UV radiation. A syringe pump connected to the hypodermic syringe controlled the flow rate. mole/mole) membranes are shown in Fig. DSC thermograms of a) electrospun 8% PVA membrane. The results show that slightly soluble PVA/MA nanofiber membrane can be fabricated by electrospinning directly. 9% and 10% PVA solutions were prepared from PVA powder and distilled water.95 1. After the solution was cooling down. Fig. Crystal structure was destroyed when PVA powder dissolved in water. b) electrospun 8% PVA/MA (20/1. the prepared electrospun PVA and PVA/MA membranes were boiled in water for 1 h. but there is no clear melting endothermic peak in thermogram of PVA membrane. As demonstrated in Table 1.3556 E. The morphology of PVA and PVA/MA membranes was observed by JSM-5600LV scanning electron microscopy (SEM). Then MA (PVA/MA = 30/1. 3. a tip-tocollector distance of 20 cm. Compared to 8% PVA/MA (21/1 and 19/1. 2a and b was separately calculated.68 19/1 4. A small piece of membrane was placed on the SEM sample holder and sputter-coated with gold. mole/mole) membrane was soluble because the crosslinking was not efficient. Yang et al.03 10/1 8. mole/mole) membranes.28 0. The results show that mass loss of electrospun PVA membrane was 100%. proper amount of sulfuric acid was added into it to control the pH value within the range of 2–3 [11]. PVA/MA solutions were electrospun immediately after being prepared. Average mass loss and standard deviation of electrospun 8% PVA/MA (30/1.. Obviously the later average diameter is larger than the former. mole/mole) membrane. electrospun 8% PVA/MA (30/1. mole/ mole) membranes are shown in Table 1. Electrospun 8% PVA/MA (20/1. and variable high voltage power supply. SEM images of membranes of a) electrospun 8% PVA membrane. 5%. completely at room temperature in a short period of time. The rapid solidification process of stretched chains under high elongation rate during the later stages of electrospinning may hinder the development of crystal as the chains do not have time to form crystalline registration [14]. mole/mole) membrane had the least average mass loss and standard deviation. Ltd. The electrospinning apparatus used in this study consist of a hypodermic syringe. PVA powder was added into distilled water slowly at room temperature. mole/mole) membrane. Average diameter of twenty fibers in Fig. 7%. b) electrospun 8% PVA/ MA (20/1. The mixture was stirred at 80 °C for 2 h to get homogenous solutions. mole/mole) membrane is slightly soluble after boiling in water for 1 h. 88% hydrolyzed) was purchased from J & K Chemical ®. mole/mole) membrane was larger because unreacted MA dissolved in boiling water. Most of water evaporates rapidly in jet region and instability region during electrospinning. DSC thermograms of electrospun 8% PVA and 8% PVA/MA (20/1. 8%. The crosslinking of PVA and MA during electrospinning enhances solution viscosity. syringe needle. aluminum collecting plate. .

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