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org/Langmuir © 2010 American Chemical Society
Study of Superhydrophobic Electrospun Nanocomposite Fibers for Energy Systems
Ramazan Asmatulu,*,† Muhammet Ceylan,† and Nurxat Nuraje*,‡
Department of Mechanical Engineering, Wichita State University, 1845 Fairmount, Wichita, Kansas 67260, United States, and ‡Department of Materials Science and Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States Received September 14, 2010. Revised Manuscript Received December 15, 2010
Polystyrene (PS) and polyvinyl chloride (PVC) fibers incorporated into TiO2 nanoparticles and graphene nanoflakes were fabricated by an electrospinning technique, and then the surface morphology and superhydrophobicity of these electrospun nanocomposite fibers were investigated. Results indicated that the water contact angle of the nanocomposite fiber surfaces increases to 178°on the basis of the fiber diameter, material type, nanoscale inclusion, heat treatment, and surface porosity/roughness. This is a result of the formation of the Cassie-Baxter state in the fibers via the nanoparticle decoration, bead formation, and surface energy of the nanofiber surface. Consequently, these superhydrophobic nanocomposite fibers can be utilized in designing photoelectrodes of dye-sensitized solar cells (DSSCs) as self-cleaning and anti-icing materials for the long-term efficiency of the cells.
Research on superhydrophobicity where the contact angle exceeds 150° has accelerated around the globe, and many investigators have taken a keen interest in the fabrication of superhydrophobic materials. Superhydrophobicity, a unique property of materials, has been studied extensively in recent years because it has wide applications in many areas, such as antibiofouling paints for boats,1-3 antistick coatings to repel snow on antennas and windows,4,5 self-cleaning windshields for automobiles,6 metal refining, stain-resistant textiles, antisoiling architectural coatings,7and oil/water separation.8,9 Superhydrophobic surfaces possessing a high advancing contact angle (higher than 150°) and low water contact angle hysteresis is explained by the Cassie-Baxter model.10 Examples of superhydrophobic surfaces including lotus leaves can be widely found in nature.11,12 The surface is usually textured with 3-10-μm-sized hills and valleys that are decorated with nanometer-sized particles of a hydrophobic material;12,13 therefore, the micrometer-sized hills and valleys can provide very low area-to-water contact, and the hydrophobic nanoparticles can prevent water penetration into the hills and valleys. Nature-inspired artificial superhydrophobic
*Corresponding authors. E-mail: email@example.com, nurxat@ mit.edu.
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surfaces have been fabricated by various techniques,13-22 including layer-by-layer approaches,13,14 roughening the surface of hydrophobic materials,15-18 in situ polymerization of monomers in the presence of a porogenic solvent,19 and electrospinning.20-22 Among these techniques, electrospinning is a straightforward, cost-effective method of producing novel fibers with diameters in the range of 3 nm to greater than 100 μm.23,24 The electrospinning technique is applied to fabricate the superhydrophobic surface because it can intrinsically provide at least one length scale of roughness.20-22,25-27 Most of the above techniques are applied in two ways to generate superhydrophobic surfaces. In the first case,23,25-27 roughness resulting from the small diameters of the fibers combined with hydrophobic polymers was sufficient to receive a contact angle of greater than 150°. In the latter case,20-22 the particles introduced a second length scale of structure into the fibrous membrane, which is called “beads on strings.” Electrospinning28-30 is a process in which a high electric field is directly utilized to fabricate microfibers and nanofibers from
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504 DOI: 10.1021/la103661c
Published on Web 12/20/2010
Langmuir 2011, 27(2), 504–507
3.1. The fiber size and morphology were analyzed using scanning electron microscopy (SEM).. K. J. Y. Hong... we determined that the water contact angles were usually higher.-D. Electrospinning is an excellent technique for creating porous films containing both organic and inorganic materials. Results and Discussion In photovoltaic cells. Lee. From the above applications of electrospinning. no attempt was made to obtain a better estimate of the actual sampling depth. and (D) small-diameter PS fibers. This study provides valuable scientific fundamentals for the fabrication of DSSC devices and evaluations of their performances. Nanotechnology 2004.-K. D.-M.. 3. et al. dc voltages. The electrospinning process can provide tunable nanofibers for porosity and superhydrophobicity. Schreuder-Gibson. which in turn is very important for DSSC applications. Wang. Senecal. D. Following the mortar grinder step or pulverizing.31-33 Therefore. D. Lett. Poly(vinyl chloride) (PVC. polymeric solutions. Part A: Pure Appl. 1861.19 These self-cleaning and anti-icing properties are directly linked to superhydrophobicity. polystyrene (PS. Superhydrophobic Behavior of Electrospun Fibers without Inclusions. The electrospinning process31-33 has been successfully exploited to create porous electrodes for dye-sensitized solar cells (DSSCs) and can provide porous films that consist of a controlled nanofiber size and tunable porosity. These products were directly used in the electrospinning process without further purification. In the present work. and surface roughness of fibers and the smaller air packets on the fiber films. 2007. J. Appl. Jeon.. As the gel formed.25 μm. Nanosize graphene (thickness of less than 10 nm with a diameter of 600 nm) and TiO2 nanoparticles (1025 nm) were added to polymeric solutions in varying percentages. and dimethylacetamide (DMAC) were purchased from Sigma-Aldrich... Titania and graphene are the essential materials in the fabrication of photoelectrodes in DSSCs. (C) large-diameter PS fibers. 2. fiber diameters of PVC are between 200 and 500 nm and that of PS are between 400 nm and 1. we designed and studied the superhydrophobicity of porous nanocomposite fiber films because titania and graphene are the most important materials in photoelectrodes of DSSCs.1021/la103661c 2.. J. In the present study.. (33) Kim. Nanoscale graphene with a thickness of less than 10 nm was purchased from Angstron Materials. and spinning distances. Phys.. Electrospun PVC and PS fibers with different diameters were used in the contact angle measurements using a CAM 100 contact angle goniometer. Y. 2002. Kumar. Experimental Section 2. (32) Song. 504–507 505 . 25 kV dc voltage. initial hydrophobicity. I. TiO2 nanoparticles were fabricated in-house. the amorphous TiO2 nanoparticles were annealed at 550 °C for 2 h. Letter Figure 1. (B) small-diameter PVC fibers (scale bar 400 nm). Mw = 150 000 g/ mol). H. Electrospinning experiments were conducted at various pump speeds. PS and PVC were separately dissolved in solvents (dimethylformamide and dimethylacetamide) in a ratio (31) Drew. Langmuir 2011.-K. A.5 mL/h pump speed. of 0..8:0. 15. Yang. E. B.2 prior to the electrospinning process. we investigated the superhydrophobicity of porous films using the above components under different conditions. Using a sol-gel process.. X. Kim. porous photoelectrodes with selfcleaning properties are more desirable. 1085. 27(2). 39. PVC and PS electrospun fibers were obtained at a 2. Samuelson.2.. Choi. Because only a qualitative determination of surface enrichment is sought at this stage. and then 10% HCl solution was added dropwise using a pipet. This may also be attributed to the molecular structure. and 25 cm spinning distance (Figures 1 and 2). Method. H. 91. He. dimethylformamide (DMF). it was dried at 150 °C for 24 h (or until completely solidified).1. SEM images of PVC and PS fibers: (A) large-diameter PVC fibers (scale bar 5 um).. it can be seen that this process has a promising potential application in photovoltaic cells because photovoltaic cells with self-cleaning and anti-icing properties are more desirable for efficient and long-term applications. Macromol. As can be seen. Mw = 230 000 g/mol). The composition of the films was confirmed by thermal gravity analysis (TGA Q50 equipped with a Thermostar mass spectrometer). C..-J. Chem. M. L. J. 163109. which may be due to the fact that the beads that formed on the fiber surfaces became smaller at smaller diameters. Some of these findings are DOI: 10. Sci. Materials. The following procedure was utilized to prepare these nanoparticles: isopropanol and titanium(IV) butoxide were mixed for about 10 min.Asmatulu et al.
Effects of nanoparticles. and 177. 2. and 8) and then electrospun at a 25 cm distance.Letter Asmatulu et al. and graphene nanoflakes on the superhydrophobic properties of PVC and PS fibers were investigated. thus reaching superhydrophobicity on the nanocomposite fiber films. 1. 4. We also investigated the effects when nanosized graphene flakes were added to PVC polymeric solutions at different weight percentages (0. and 4) and then electrospun at a 30 cm distance. However. 156.5. 4935... Figure 4.5. G. (Blue line) PVC nanocomposite fiber films with TiO2 nanoparticles. found that hydrophobicity increased with a reduction in diameter among bead-free fibers and with the introduction of a high density of relatively small diameter beads. Wilkes. Usually. Gupta.5 water contact angle values. This is useful data for confirming the successful fabrication of nanocomposite fibers.0 water contact angles. 2006. 25 kV dc voltage. The PS nanocomposite fibers obtained at 1. such as titania.. One contains only titania nanoparticles in the fibers. M.3. Gleason. With the formation of beads in the fibers. the water droplets sit on the heterogeneous surface of the fiber and the air. in the titania-containing composite fibers. 164. R. Rutledge. The contact angles of bead fibers are higher than that of bead-free fibers. Figure 3. TiO2 nanoparticles (10-25 nm) were added to PVC and PS polymeric solutions at different weight percentages (1.1021/la103661c Langmuir 2011. whereas the PVC nanocomposite fibers (34) Ma. 168. Change in contact angle values of PVC and PS fibers as a function of fiber diameter. 25 kV dc voltage. in the graphene-accompanied PVC fibers (blue line).. Additionally. The highest contact angle value (177. 4.3. P. The brown line represents the titania-included PVC composite fibers.5. Sci. (Green line) PVC nanocomposite fiber films with graphene nanoflakes. Claus. the peaks around 200 and 400 °C indicated dimethylacetamide and PVC coming off of the electrospun fibers separately. three-shouldered peak areas can be detected. and 1.. K. and the other contains graphene nanoflakes. Mao. Contact angle values of an electrospun nanocomposite fiber film as a function of the percentage of TiO2 nanoparticles or graphene nanoflakes. respectively. M. consistent with the literature. as shown in Figure 3.1. Superhydrophobic Behavior of Electrospun Fibers with Inclusions. The concentration of (35) Gupta. R. and 1 mL/h pump speed to determine the effects of inclusions on the contact angle values of nanocomposite fibers. However. 9742. 2. J. in the graphene-contained nanocomposite fibers.. 506 DOI: 10. 2. K. only two peaks can be detected because titania cannot be removed from the electrospun fibers in that temperature range.3. For example.5 mL/h pump speed. Macromolecules 2005. 27(2).34 Ma et al. resulting in a Cassie-Baxter state.35 This structure induces a Cassie-Baxter state in the film. G. respectively.2. and 8% TiO2 nanoparticles give 155.. 504–507 . 164. Figure 2. In both cases. Thermal gravimetric analysis (TGA) of both PVC fibers containing titania nanoparticles (red line) and PVC fibers containing graphene nanoparticles (blue line). the shoulder at 500 °C indicates that the graphene component is removed from the fibers. C. two-shouldered peak areas can be observed. (Red line) PS nanocomposite fiber film containing TiO2 nanoparticles. Appl. The composition of nanocomposite fibers was confirmed using thermal gravity analysis after two different types of fibers were fabricated via the electrospinning process.. the blue line represents the TGA curve for graphene-containing PVC nanocomposite fibers. which may be due to the nanoscale gaps/bumps/voids formed on the fiber in the presence of TiO2 nanoparticles. Figure 4 shows the contact angle values of an electrospun nanocomposite fiber film containing different numbers of TiO2 nanoparticles and graphene nanoflakes. The results show that TiO2 nanocomposite fibers have higher contact angle values. 3. increasing the number of TiO2 nanoparticles in both polymers results in higher contact angle values. Y. and 165. with the same concentrations and spinning conditions give 151. 100. In the titania-included PVC fibers. Polym. 38. Asmatulu.5) was received from the PS nanocomposite fiber obtained at 8% TiO2 nanoparticles.
504–507 DOI: 10. resulting in higher contact angles and superhydrophobicity.1021/la103661c 507 . the chain segment undergoes rotation because of carbon-carbon bonds in the chain that can be twisted easily. John Wiley and Sons: New York. however. H. Effects of Heat Treatment on Superhydrophobicity. The main purpose of adding graphene particles to the polymeric solution was to increase the surface roughness.3. where the surface roughness..acs. glassy solids at room temperature. Both our results and the above studies conceptually mimic the hierarchically roughened nature of superhydrophobic surfaces of the lotus leaf.13 created superhydrophobic multilayer films through the inclusion of silica nanoparticles in layer-by-layer assembled multilayers.5. However. This indicates that graphene inclusions in the polymeric fibers drastically change the surface morphology and chemistry. which was not the case for the TiO2 nanoparticle inclusions. and hydrophobicity of the electrospun fibers to obtain superhydrophobicity. 80. Therefore. Supporting Information Available: PVC electrospun fibers incorporated with 8% TiO2 nanoparticles.Asmatulu et al.5. Conclusions In the present study. Developments in PVC Technology. J. 165. porosity. The tunable properties of titania. Langmuir 2011. shape. However. Ma et al. and 166. Below the Tg point. we have successfully fabricated superhydrophobic nanocomposite fibers using an electrospinning process. However.36 Two bonds can act as an axis of rotation.8. 100. the water contact angle of the fibers is below 140. Titania nanoparticles and graphene nanoflakes were included in the electrospun fibers to induce superhydrophobicity on the surfaces of the fibrous films. which results in lower contact angles on the surfaces of PS fibers.and graphene-based superhydrophobic surfaces and electrodes can play an important role in improving the efficiency of DSSC devices. Table 1. respectively. The investigation of the heat treatment on the fiber film also provides valuable information on building superhydrophobic surfaces. Figure 4 also shows that increasing the graphene concentration in the electrospun fibers gradually increases the water contact angle values. which is the primary motivation of the present study. The same phenomena can occur with PVC. 1. The changes in contact angle values of the nanocomposite films are not significant. In the absence of graphene. Perhaps the rougher surface becomes smoother in this case. 27(2). 3. Whelan. The superhydrophobicity properties of the photoelectrodes are likely to provide selfcleaning and anti-icing surfaces. Above the Tg for the polymer. Table 1 gives the water contact angle values of PS fibers obtained at various temperatures. Tg of polystyrene is around 100 °C. Our results further prove that the microscale and nanoscale beards on the morphology improved the superhydrophobicity of nanofibrous films. and 4% graphene-added nanocomposite fibers are 141. Similar behavior can also be seen in the PS fibers. 4. Zhai et al.3. the contact angle values of PVC nanocomposite fiber films initially increased from 155 to 161° at 80 °C and then decreased to 140° at 100 °C. for a graphene-mixed PVC composite film. and 120 °C in the presence and absence of nanoparticle inclusions.3. 151. and fiber diameters drastically changed the superhydrophobicity of the surfaces. permitting carbon atoms (and the groups attached to them) to rotate. A. Acknowledgment. respectively. polymer chains are rigid and segments of the chains cannot move. The contact angle values of PVC and PS fibers without graphene inclusion decreased to 137 and 101° at 100 and 120 °C. Both high-molecular-weight PS and PVC are hard. (36) Henson. This material is available free of charge via the Internet at http://pubs. voids. it is very difficult to imagine nanoscale morphological changes on the surface of polymeric fibers. These results further explain the effect of graphene on the glass-transition temperature of PVC films.22 also studied the superhydrophobicity of electrospun films created via a layer-bylayer assembly of negatively charged silica nanoparticles with positively charged polyallylamine. We studied the effects of heat treatment on the contact angle values of electrospun PVC and PS fibers at 60. We gratefully acknowledge Wichita State University for the support of this work. The change in the contact angles may be related to the rearrangement of fiber structures in the film at the glass-transition temperature (Tg). the Tg of which is 80 °C. morphology. water contact angle values of 0. and exceeding the Tg can permanently change the size. they become flexible and rubbery. However. the contact angles of the composite films are higher than the contact angles of PVC-only films. 1973. and surface composition of the fibers. concentrations. the polymeric materials become softer and rubbery. Effect of Heat Treatment on the Contact Angle Values of PS and PVC Fiber Films contact angle values at different temperatures (°C) polymeric fibers PVC PVC with 1% graphene PS 60 144 155 156 80 149 161 158 100 138 151 155 120 133 140 101 Letter graphene in the polymeric solution was increased up to 4% because a graphene concentration higher than 4% adversely affected the electrospinability of the polymeric solutions.org. after exceeding the Tg point. Our studies showed that nanoscale inclusions. and voids of the nanocomposite fibers can change considerably on the microscale and nanoscale. 2. when the temperature is higher than the Tg of the polymers. L.
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