1 Abstract Formation of superhydrophobic materials from polystyrene will provide a material that is able to separate miniscule amounts of water from organic fluids that normally would not be able to be separated by mechanical means. By using polystyrene, not only is cost reduced due to the large amount of polystyrene available, but the problem of finding an efficient method of recycling polystyrene is also resolved. Samples were created using varying electrospinning conditions, ranging from five weight percent polystyrene in dimethylformimide to thirty weight percent. Electrospinning conditions were also varied between ten and thirty kilovolts. Samples were tested for water contact angle as well as under a scanning electron microscope to determine fiber diameter and structure. Samples were defined as superhydrophobic if the water contact angle was greater than 150°. Superhydrophobic nanofibers were achieved using polystyrene by ranging electrospinning conditions between ten and twenty weight percent polystyrene in dimethylformimide and ranging the voltage between ten and twenty kilovolts. 2 Table of Contents Executive Summary ................................................................................................................................ 4 Introduction............................................................................................................................................. 6 Procedure ................................................................................................................................................ 7 Discussion/Results ................................................................................................................................ 10 Conclusion ............................................................................................................................................ 20 Bibliography ......................................................................................................................................... 22 Appendix A: Water Contact Angle Raw Data ........................................................................................ 23 3 Executive Summary The goal of this project was to develop superhydrophobic nanofibers from polystyrene via electrospinning. Formation of superhydrophobic nanofibers is currently a growing field for developing material for water and organic filters. These nanofibers allow for the separation of miniscule amounts of water from organic fluids that are not able to be separated by mechanical means, such as in a centrifuge or gravity separation. Use of polystyrene to generate superhydrophobic materials is not only cost effective due to the low cost and availability of polystyrene, but polystyrene can be recycled to form the superhydrophobic nanofibers. This allows for green engineering of filters using the superhydrophobic polystyrene nanofibers. Superhydrophobic nanofibers were able to be generated from polystyrene. Nanofibers were produced from polymer solutions with a weight percentage of polystyrene to dimethylformamide between ten and twenty pumped at a volumetric flow rate of one milliliter per hour electrospun at a voltage between twenty and thirty kilovolts. Supherhydrophobic nanofibers were produced at four total sets of conditions: 10wt% and 20kv, 10wt% and 30kV, 20wt% and 20kV, and 20wt% and 30kV. Water contact angles observed were 154.8±7.03°, 157.0±3.23°, and 154.1±4.18° for 10wt% and 20kV, 10wt% and 30kV, and 20wt% and 20kV, respectively. Samples spun at 20wt% and 30kV were unable to be tested for water contact angle due to the inability to determine the droplet on the surface of the material using the Krűss Drop Shape Analyzer model DSA20E. Sample diameters ranged depending on electrospinning conditions, and were measured with a scanning electron microscope. These ranges were 200500nm, 300-500nm, 500-900nm, and 1100-1700nm for 10wt% and 20kV, 10wt% and 30kV, 20wt% and 20kV, and 20wt% and 30kV, respectively. All samples were beaded nanofibers except for samples spun at 20wt% and 30kV which were smooth nanofibers. Mass per unit area was determined for each sample to determine the amount of polystyrene necessary to develop superhydrophobic properties. These values were measured as 28.00±5.11 g/m 2, 35.56±3.08g/m2 , 25.33±5.11 g/m2, and 37.33±4.36g/m2 for 10wt% and 20kV, 10wt% and 30kV, 20wt% and 20kV, and 20wt% and 30kV, respectively. The optimal conditions for forming superhydrophobic nanofibers determined from this research were a volumetric flow rate of one milliliter per hour, a distance of twenty centimeters between the needle and ground, a solution weight percent of polystyrene to dimethylformamide of twenty weight percent and a voltage of twenty kilovolts. These conditions allowed for the 4 formation of superhydrophobic materials while minimizing the amount of polystyrene that was required to be spun. During this research I further developed my skills with working with bench scale testing and design of experiments. I also learned a new method for developing new materials. I furthered my experience with being able to start with a wide goal and over the course of the project narrow the methods to obtain the goal set forth originally by the project. Further research is suggested in determining a cross-linking agent that can be spun with the polystyrene to develop a cross linked superhydrophobic nanofiber network. A possible cross linking agent to be further researched with polystyrene is divinyl benzene. It is also suggested for further research into water droplet tilt angle testing and water droplet velocity testing on the superhydrophobic polystyrene nanofibers. 5 Introduction Formation of superhydrophobic nanofibers is currently a growing field for developing material for water and organic filters. Fibers become superhydrophobic by creating increased surface area (Kim, 2008). Spinning samples to nanofiber diameters increases the surface roughness, which can also be further modified by spinning material that generates nanofibers, beaded nanofibers, or nanospheres (Kim, 2008). These nanofibers allow for the separation of miniscule amounts of water from organic fluids that are not able to be separated by mechanical means, such as in a centrifuge or gravity separation (Kim, 2008). These nanofibers create a surface area for the water molecules to collect while allowing for the organic fluids to pass through. Polystyrene was initially chosen to be tested due to its natural hydrophobic properties. Use of polystyrene to generate superhydrophobic materials is not only cost effective due to the low cost and availability of polystyrene, but polystyrene can be recycled to form the superhydrophobic nanofibers. This allows for green engineering of filters using the superhydrophobic nanofibers. The superhydrophobic nanofibers are able to be formed using an electrospinning process. The goal of the research described in this report was to determine the conditions necessary to electrospin superhydrophobic polystyrene nanofibers. The conditions varied included voltage, solution weight percent of polystyrene in dimethylformimide, and the solution flow rate while spinning. 6 Procedure The electrospinning of the polystyrene first involved creating a solution of polystyrene in dimethylformamide. Polystyrene used during this research came from clean recycled materials to simulate the ability to form superhydrophobic nanofibers from recycled polystyrene. Dimethylformimide was used to dissolve polystyrene as described in previous work (Minsung Kang, 2008). The weight percent of polystyrene was varied between five and twenty percent. A five milliliter luer locker syringe was then filled with the solution of polystyrene. The syringe was then placed in a syringe pump that controlled the flow rate between one milliliter per hour and five milliliter per hour. The sample was spun through a twenty one gauge syringe connected to a voltage source. The voltage source was used to control the applied voltage between ten kilovolts and thirty kilovolts. Two sample slides were placed on a formed tray of aluminum that was placed at a distance of twenty centimeters from the tip of the syringe. This distance was held constant throughout all experiments. The electrospinning setup is shown below in Figure 1. Figure 1: Electrospinning Set-up 7 Once the samples were spun, multiple tests were conducted to develop a list of properties for each sample that was spun. Testing included water contact angle, surface structure of the fibers, mass per area of fibers, and percent spun from solution. The contact angle of water was measured on a Krűss Drop Shape Analyzer model DSA20E. The samples that were tested on the DSA20E were tested using multiple drop sizes. The drops size ranged from one micro-liter to five micro-liter. Drop size was varied to show if the water contact angle of the water droplet decreased with droplet size. The DSA20E is shown below in Figure 2. Figure 2: DSA20E Samples were tested for surface structure via Scanning Electron Microscope (SEM). This was conducted to determine whether the samples spun were nanofibers, beaded nanofibers, or electrosprayed nanospheres. The range of fiber size was also collected for each sample from the SEM. The samples were also tested for mass per unit area on the sample slides. These values were calculated by determining the amount of polystyrene spun onto the slide divided by the 8 surface area of the sample slide. The surface area of the sample slide was calculated by multiplying the width of the slide by the length of the slide. The amount of polystyrene spun onto the sample slide was calculated as the difference of the weight of the sample slide with spun polystyrene and the weight of the sample slide without spun polystyrene. The percent of polystyrene spun from the solution to the slide was also calculated as the ratio of the polystyrene that was spun onto the sample slide divided by the total weight of polystyrene spun. This ratio is defined as the efficiency of the electrospinning of a given sample during this research. 9 Discussion/Results The goal of the testing of the electrospun polystyrene was to develop a nanofiber material that held a water contact angle greater than 150°. Initial testing was conducted to determine a range of voltages, flow rates, and solution concentrations for further testing. These initial samples and their conditions are shown below in Table 1. Table 1: Initial Testing Conditions Sample Voltage (kV) Conc. (wt%) Flow Rate (mL/hr) Result 1 20 5 5 Wet Sample, No Fibers 2 20 5 1 No Fibers, No WCA 3 20 10 1 Fibers, WCA of 140.9±3.22 4 30 10 1 Fibers, WCA of 149.5±2.60 5 10 10 1 Dripped instead of spinning, voltage too low Based upon these results, it was determined that a flow rate of 5ml/hr was too fast to develop fibers of polystyrene and to allow enough time for the dimethylformamide to evaporate from the polystyrene. It was also determined that a voltage of 10kV did not supply enough electrical potential to form polystyrene nanofibers over the 20cm distance between the syringe and the sample slides. Further testing was conducted by making the solution flow rate constant at 1mL/hr, varying the voltage between 20kV and 30kV, and varying the polystyrene concentration between 10wt% and 20wt%. At each of these conditions a total of four sample slides were evaluated for water contact angle, surface structure, mass per area, and percent of polystyrene spun. The samples and their conditions are shown below in Table 2. 10 Table 2: Sample Synthesis Conditions Slide 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 8 Sample A B C D E F G H I J K L M N O P Voltage (kV) 20 20 20 20 30 30 30 30 20 20 20 20 30 30 30 30 Conc. (wt%) 10% 10% 10% 10% 10% 10% 10% 10% 20% 20% 20% 20% 20% 20% 20% 20% Flow Rate (mL/hr) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Water contact angles were tested on the DSA20E with droplet sizes varying from one to five micro liters. Samplees E, M, N, O, and P, were unable to be tested for water contact angle on the DSA20E either because the sample was damaged (E) or because the surface of the sample (M, N, O, and P) was very rough due to large fiber size. The average water contact angles and standard deviations for each testing condition are shown below in Table 3 and Table 4, respectively. WCA °s (AVG) 10wt% 20kV 10wt% 30kV 20wt% 20kV Table 3: Water Contact Angle Averages 5μL 4μL 3μL 2μL 154.8 152.4 150.6 146.1 157.0 157.7 160.8 155.5 154.1 149.1 148.0 143.5 1.5μL 1μL 143.4 153.0 141.5 140.9 151.1 137.2 Table 4: Water Contact Angle Standard Deviations WCA °s StDEV 5μL 4μL 3μL 2μL 1.5μL 1μL 10wt% 20kV 7.03 3.59 3.21 2.81 4.37 2.27 10wt% 30kV 3.23 1.93 5.59 5.16 3.17 0.87 20wt% 20kV 4.18 11.77 10.34 10.15 11.65 9.07 11 Below are the graphs of the water contact angle vs. droplet size. Figure 3 represents the testing condition 10wt% 20kV, Figure 4 represents the testing condition 10wt% 30kV, and Figure 5 represents the testing condition 20wt% 20kV. Contact Angle (degrees) 10wt% 20kV Droplet Size vs. Contact Angle 175.0 165.0 155.0 145.0 135.0 125.0 0 1 2 3 4 5 6 5 6 Droplet Size (m icroliter) Figure 3: WCA vs. Droplet Size, 10wt% 20kV Contact Angle (degrees) 10wt% 30kV Droplet Size vs. Contact Angle 175.0 165.0 155.0 145.0 135.0 125.0 0 1 2 3 4 Droplet Size (m icroliter) Figure 4: WCA vs. Droplet Size, 10wt% 30kV 12 Contact Angle (degrees) 20wt% 20kV Droplet Size vs. Contact Angle 175.0 165.0 155.0 145.0 135.0 125.0 0 1 2 3 4 5 6 Droplet size (m icroliter) Figure 5: WCA vs. Droplet Size, 20wt% 20kV From the figures above, it is observed that the trend of the water contact angle decreases with the decrease in droplet size. This testing was done to view how the superhydrophobic properties of the nanofibers depend upon the water droplet size. With smaller droplet sizes, lower water contact angles are observed. This is due to the surface energy of the water droplet lowering with droplet size, allowing for the water droplet to sink into the fiber matrix due to the porosity , and of the fiber matrix. This is also shown below in Figures 6,7, and 8. The SEM images show larger pore sizes on samples spun at 20wt% 20kV, which in Figure 5 the water contact angle dropped at a faster rate. This is compared to samples spun at 10wt% 20kVand 10wt% 30kV having water contact angles that drop slower with droplet size when the pore sizes observed in Figures 6 and 7 are smaller. A statistical analysis of regression was performed to determine the t-Stat values and Pvalues to determine if there was statistical correlation between the samples tested for water contact angle. The t-Stat values and P-values are shown below in Table 5 and Table 6, respectively. 13 Table 5: t-Stat Analysis t-Stat wt% kV 5μL -0.30159 0.914039 4μL -0.9798 1.559823 3μL -0.9798 1.559823 2μL -0.81782 2.954591 1.5μL -0.5309 2.759408 1μL -1.46119 3.97479 Table 6: P-value Analysis P-Value wt% kV 5μL 0.765565 0.369788 4μL 0.336957 0.131892 3μL 0.336957 0.131892 2μL 0.421506 0.006911 1.5μL 0.600367 0.010908 1μL 0.156933 0.000562 Statistical significance was observed if the t-Stat value is greater than one while the Pvalue is less than 0.05 indicating 95% confidence. Values that showed this are highlighted in yellow in Tables 5 and 6, respectively. This statistical model shows that voltage played the largest role in determining water contact angle. A second regression analysis was performed by removing the weight percent affect on the statistics. The weight percent dependence in the analysis was removed due to the t-Stat values being below one. The results from the second regression analysis are shown below in Table 7. Table 7: Second Regression Analysis kV t-Stat P-Value 5μL 4μL 3μL 2μL 1.5μL 1μL 1.253 0.221 2.368 0.025 4.041 0.0004 3.909 0.0006 3.544 0.002 5.314 1.66E-05 This second analysis once again supports that the dominating factor on the water contact angle is the voltage that the sample is electrospun at. A further t-test analysis was performed to discern the large standard deviations between samples and droplet size. These values are shown below in Table 8, 9, and 10 for samples 10wt% 20kV, 10wt% 30kV, and 20wt% 20kV, respectively. 14 10wt% 20kV 5μL 4μL 3μL 2μL 1.5μL 1μL Table 8: 10wt% 20kV t-Test Analysis SE n mean stdev Mean 9 9 9 9 9 9 154.84 152.38 150.57 146.1 143.39 140.9 7.03 3.59 3.21 2.81 4.37 2.27 2.34 1.2 1.07 0.94 1.46 0.76 95%CI (149.44,160.25) (149.62,155.14) (148.10, 153.03) (143.94,148.26) (140.03,146.75) (139.16,142.65) Table 9: 10wt% 30kV t-Test Analysis 10wt% 30kV 5μL 4μL 3μL 2μL 1.5μL 1μL n mean stdev SE Mean 95%CI 9 9 9 9 9 9 157.03 157.67 160.81 155.53 153.03 151.06 3.23 1.93 5.59 5.16 3.17 0.87 1.08 0.64 1.86 1.72 1.06 0.29 (154.55,159.52) (156.18,159.15) (156.51,165.11) (151.57,159.50) (150.6,155.47) (150.39,151.72) Table 10: 20wt% 20kV t-Test Analysis 20wt% 20kV 5μL 4μL 3μL 2μL 1.5μL 1μL n mean stdev SE Mean 95%CI 9 9 9 9 9 9 154.12 149.06 148.03 143.49 141.53 137.17 4.18 11.77 10.34 10.15 11.65 9.07 1.39 3.92 3.45 3.38 3.88 3.02 (150.91,157.34) (140.01,158.11) (140.09,155.98) (135.68,151.29) (132.58,150.49) (130.20,144.14) Comparing the standard error mean we can determine the accuracy of the water contact angle for each sample for each water droplet size. Table 8 shows that for the 10wt% 20kV sample the largest standard error mean is at a droplet size of 5μL with a value of 2.34. Comparing this to the raw data shown in Appendix A it is visible that one sample slide was slightly undervalued compared to other sample slides. Table 9 shows that the 10wt% 30kV samples were all within reasonable values of each other. Table 9 shows that at 20wt% 20kV the standard error mean is above 3 for multiple droplet sizes. Comparing this to the raw data shown in Appendix A it is visible that one sample slide was slightly undervalued compared to other sample slides. 15 From these regressions, equations to determine water contact angle for a given voltage and drop size were determined. These equations are shown below for calculating the water contact angle for 5µL, 4µL, 3µL, 2µL, 1.5µL, and 1 in Equations 1, 2, 3, 4, 5, and 6, respectively. Eqn 1: Eqn 2: Eqn 3: Eqn 4: Eqn 5: Eqn 6: For these equations, the water contact valuein degrees, y, is dependent upon the voltage in kV, x. From sample to sample, it is viewed that water contact angle generally increases with higher voltages and with higher weight percent solutions. Water contact angle is generally derived from the surface structure of the nanofibers. During electrospinning the structure of the material can range between nanofibers, beaded nanofibers, or nanospheres. By increasing the roughness of the surface structure of the material, greater contact angles and super-hydrophobic properties are able to be obtained. Shown below are SEM images showing the surface structure of different electrospinning conditions in Figures 6, 7, 8, and 9. 16 Figure 6: 10wt% 20kV Figure 8: 20wt% 20kV Figure 7: 10wt% 30kV Figure 9: 20wt% 30kV *Note that Figures 6 and 7 have a scale of 5μm, while Figure 8 has a scale of 10μm and Figure 9 has a scale of 20μm* From sample to sample, it is viewed that the surface roughness of the samples varies dependent on the electrospinning conditions. Samples run at 10wt% 20kV, 10wt% 30kV, and 20wt% 20kV formed nanofibers and beaded nanofibers. Samples run at 20wt% 30kV formed only nanofibers. Higher weight percent solutions and higher voltages resulted in higher diameter samples, as shown in Table 11. 17 Condition 10wt% 20kV 10wt% 30kV 20wt% 20kV 20wt% 30kV Table 11: Fiber Diameters Diameter Average (nm) 332.7 435.3 668.0 1527.8 Diameter StDEV (nm) 134.2 66.8 157.2 127.8 Fibers spun at different conditions also showed different ranges for fiber diameters. Samples spun at 10wt% 20kV showed a fiber diameter range from 200-500nm. Fibers spun at 10wt% 30kV showed a fiber diameter range from 300-500nm. Fibers spun at 20wt% 20kV showed a fiber diameter range from 500-900nm. Fibers spun at 20wt% 30kV showed a fiber diameter range from 1100-1700nm. A general trend is observed that as solution weight percent increases fiber diameter increases. This can be explained as the higher amount of available polystyrene causes there to be wider fibers formed. Another general trend is observed that as voltage increases surface structure is varied. Lower voltages result in more beaded nanofibers and nanospheres, while higher voltages result in smoother nanofibers or microfibers. This can be explained as the higher energy potential forces the polystyrene to elongate, causing the fibers to not collect in one area to form beads or nanospheres. Samples were also tested to determine the mass of polystyrene per unit area, as well as to determine the efficiency of the electrospinning. The efficiency of the electrospinning for the samples spun during this research was defined as the ratio of the amount of polystyrene that was spun onto the sample slide over the amount of polystyrene in the solution that was spun. The mass per unit area for each sample is shown below in Table 12. The efficiency of the electrospinning for each sample is shown below in Table 13. 18 Table 12: Mass Per Unit Area Voltage (kV) 20 30 20 30 Voltage (kV) 20 30 20 30 Concentration (wt%) 10 10 20 20 Mass/Area (g/m 2) 28.000 ± 5.106 35.556 ± 3.079 25.333 ± 5.106 37.333 ± 4.355 Table 13: Electrospinning Efficiencies Concentration (wt%) Percent Spun (%) 10 11.41% ± 2.08% 10 14.49% ± 1.26% 20 13.54% ± 2.30% 20 14.89% ± 1.74% In Table 12 it is shown that by increasing the voltage increases the mass per unit area. This can be explained that due to the higher voltage the polystyrene is drawn to the sample slide with greater energy. This is also shown due to the higher efficiency of the higher voltage samples shown in Table 13. 19 Conclusion Superhydrophobic nanofibers were able to be generated from polystyrene. The conditions that allowed for formation of these nanofibers included varying the weight percent of polystyrene to dimethylformamide between ten and twenty weight percent, a volumetric flow rate of one milliliter per hour, and varying the voltage between twenty and thirty kilovolts. Four total samples showed superhydrophobic properties, including 10wt% 20kv, 10wt% 30kV, 20wt% 20kV, and 20wt% 30kV. Samples spun at 10wt% and 20kV resulted in a contact angle of 154.8±7.03°, a surface structure of beaded nanofibers ranging from 200-500ηm, and a mass per unit area of 28.00±5.11 g/m2. Samples spun at 10wt% and 30kV resulted in a contact angle of 157.0±3.23°, a surface structure of beaded nanofibers ranging from 300-500ηm, and a mass per unit area of 35.56±3.08g/m 2. Samples spun at 20wt% and 20kV resulted in a contact angle of 154.1±4.18°, a surface structure of beaded nanofibers ranging from 500-900ηm, and a mass per unit area of 25.33±5.11 g/m2. Samples spun at 20wt% and 30kV in a surface structure of nanofibers ranging from 1100-1700ηm, and a mass per unit area of 37.33±4.36g/m 2. Samples spun at 20wt% and 30kV were unable to be tested for water contact angle due to the inability to determine the droplet on the surface of the material using the Krűss Drop Shape Analyzer model DSA20E. The optimal conditions for forming superhydrophobic nanofibers determined from this research were a volumetric flow rate of one milliliter per hour, a distance of twenty centimeters between the needle and ground, a solution weight percent of polystyrene to dimethylformamide of twenty weight percent and a voltage of twenty kilovolts. These conditions allowed for the formation of superhydrophobic materials while minimizing the amount of polystyrene that was required to be spun. 20 Further research is suggested in determining a cross-linking agent that can be spun with the polystyrene to develop a cross linked superhydrophobic nanofiber network. A possible cross linking agent to be further researched with polystyrene is divinyl benzene. Divinyl benzene is a current cross linking agent used with polystyrene. Research will need to be conducted to determine if the divinyl benzene will need to be spun with polystyrene or coated on the nanofibers after they are electrospun. Curing conditions will also need to be researched. It is also suggested for further research into water droplet tilt angle testing and water droplet velocity testing on the superhydrophobic polystyrene nanofibers. These values can be used to further determine physical properties of the materials spun as well as defining optimal electrospinning conditions. 21 Bibliography Kim, S. H. (2008). Fabrication of Superhydrophobic Surfaces. Journal of Adhesion Science and Technology , 235-250. Minsung Kang, R. J.-S.-J. (2008). Preparation of Superhydrophobic Polystyrene Membranes by Electrospinning. Colloids and Surfaces A: Physicochem. Eng. Aspects , 411-414. 22 Appendix A: Water Contact Angle Raw Data Sample Slide A B C F G H I K L 5μL 161.1 159.2 158.4 161.0 158.2 159.0 146.1 145.4 145.2 155.2 155.7 156.9 161.2 161.2 160.9 153.0 154.0 155.2 151.1 148.3 153.2 153.8 151.9 151 158.2 160 159.6 4μL 152.4 152.5 153.6 157.2 156.3 155.1 148.7 147.8 147.8 158.7 156.8 157.3 160.3 160.0 159.1 155.2 156.2 155.4 134.8 135 132.7 150.5 152.3 155.1 162 160.9 158.2 3μL 151.5 151.0 149.5 156.0 152.1 153.8 147.9 146.6 146.7 162.7 163.9 164.4 164.5 165.5 165.9 153.1 153.1 154.2 133.2 134.6 135.8 156.1 155.8 158.6 153.8 151.9 152.5 2μL 142.8 141.4 143.2 147.2 148.7 148.6 147.7 147.4 147.9 160.9 159.0 159.0 160.1 157.1 157.1 149.5 149.0 148.1 130 129.8 131.2 147.1 147.9 147.2 153.8 151.9 152.5 23 1.5μL 135.0 140.3 140.0 147.2 147.2 148.7 145.1 144.3 142.7 155.2 156.7 153.6 154.2 156.2 154.2 148.6 148.4 150.2 132.2 129.2 130.7 136.3 136.7 139.2 156.5 155.7 157.3 1μL 138.8 139.3 140.4 143.5 144.0 144.1 139.2 139.5 139.3 151.7 150.1 150.7 152.2 151.7 152.1 150.4 150.0 150.6 127.9 129.7 127.7 136.8 133.8 134.8 147.7 142.5 153.6
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