Center for Advanced Materials, Department of Chemical and Nuclear Engineering, One University Avenue, University of Massachusetts, Lowell, MA 01854, U.S.A.
ABSTRACT
Electrically conducting organic polymers are a novel class of ‘synthetic metals’ that combine the chemical and mechanical properties of polymers with the electronic properties of metals and semiconductors. Electronically conducting polymers have been studied extensively owing to their applications in energy conversion devices, sensors, electro chromic devices, electromagnetic interference shielding (EMI), electronic circuits etc. Polyaniline - an organic conducting polymer - has been blended with poly methyl methacrylate and the blends have been electrospun to produce conducting nanofibers. The electrospun blends have been characterized to study fiber morphology and formulate conditions for nanofiber formation.
INTRODUCTION
Polyaniline is an organic polymer, but is totally unmoldable and insoluble. It is a conducting
polymer and exists in three oxidation states [1]. It has varied applications; its first applications were to make conducting coating of plastic materials i.e. printed circuit board production and also corrosion protection. Electrospinning is a process by which sub-micron polymer fibers can be produced using an electrostatically driven jet of polymer solution [2]. The fibers are collected as a non-woven mat or membrane with high surface area to volume ratio. Since, polyaniline is insoluble in most organic solvents it cannot be spun by itself, as for electrospinning a polymer solution is required. Therefore it has to be blended with other polymers to form a polymer solution for spinning. In this study we have blended polyaniline (PANI) with poly methyl methacrylate (PMMA) to form electrospun fibers.
EXPERIMENTAL DETAILS
Polyaniline is made conducting by doping with protonating acids like campor sulfonic acid D2.7.2
(CSA) to make it conducting. Polyaniline of the emeraldine base form (Aldrich M.W. 65,000) was doped with CSA (Aldrich) in ratio of 0.5:0.5 wt % polymer repeating unit [3]. The PANI- CSA complex thus formed was mixed with desired amount of PMMA (Aldrich M.W. 120,000) in chloroform (Aldrich) solvent. The resulting mixture thus formed was electrospun to form fibers. Solutions were prepared with 2 – 12 wt % PANI-CSA and 5 – 16 wt % PMMA. In electrospinning an electrode connected to a high voltage power supply is inserted into a polymeric solution contained within a pipette as shown in Figure 1. A grounded collection plate is kept at a suitable distance from tip of the pipette to collect the fibers. The formation of fibers depends upon the voltage applied, concentration of polymers in the solution, tip-target distance and flow rate of solution from the pipette [4]. For the first phase of this research we have studied the effect of polymer concentrations and spinning voltage applied on the formation of fibers. The electrospun fibers were characterized by scanning electron microscope (Amray AMR 1000), transmission electron microscope (Philips EM 400 T) and atomic force microscope (PSIA model XE-100. The photomicrographs obtained were then image processed by image processing software (GAIA blue) to calculate fiber thickness, bead diameter, bead length and bead density.
RESULTS AND DISCUSSION
During electrospinning of PANI-CSA/PMMA blends we found formation of beads along
with fibers. Beads can be described as an unwanted by-product of electrospinning [4]. The morphology of the fibers formed after electrospinning was characterized based on the shape and size of the fibers in terms of bead density, bead length, bead diameter and fiber thickness.
Figure 1. Electrospinning Set-Up
D2.7.3
Effect of Polymer Concentration
Figure 2 shows a plot of bead diameter, bead length, fiber thickness and bead density at various polymer concentrations. We can see that as the total polymer concentration (polyaniline and poly methyl methacrylate) increases, the bead diameter, length and fiber thickness decrease, which is desirable for fiber formation. Also increasing polymer concentration results in decrease of bead density as shown in the SEM micrographs in Figure 3. Since, our polymer solution is a blend of two polymers to make optimum blend for nanofiber formation we have to look at effect of individual polymer concentration in the blend on fiber formation (table 1). We can see that increasing the PANI-CSA concentration leads to a reduction in bead size and fiber thickness which is desirable but increasing PMMA concentration leads to increase in bead size and fiber thickness which is undesirable, therefore based on results shown in Figure 2 and Table 1 we can summarize that 8 wt% PANI-CSA 12 wt% PMMA and 12 wt% PANI-CSA 5 wt % PMMA are good blend ratios for fiber formation which would be further studied to optimize the other electrospinning parameters. The fibers obtained are in the sub-micron to nanometer range with the thinnest being 100 nm shown in TEM micrographs in Figure 4. Figure 5 shows the AFM phase images of the electrospun fibers.
30 40 Bead Diameter Bead length Bead Density 35 25 Fiber Thickness Bead diameter , length and Fiber thickness in micrometer
Figure 2. Effect of polymer concentration on bead diameter, length and density
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Table 1. Effect of individual polymers on fiber formation
Polymer Concentrations Bead Density Bead Diameter Bead Length Fiber Thickness
PANI-CSA
PMMA
Figure 3. SEM micrographs showing reduction in bead density with increasing polymer concentration: (a) 4 wt% PANI-CSA 10 wt % PMMA,(b) 8 wt% PANI-CSA – 12 wt% PMMA and (c)12 wt% PANI-CSA – 5 wt% PMMA.
Figure 4. TEM micrographs of 12 wt% PANI-CSA 5 wt% PMMA showing nanofibers of fiber thickness 100nm and very small beads. D2.7.5
Figure 5: AFM topography (left) and phase images showing distribution of two polymers in the fibers.
Effect of Spinning Voltage
Based on the results obtained for various polymer concentrations we investigated the effect of spinning voltage on fiber formation at three different blend compositions. We observed that fibers appear to form at an applied voltage of 15 kV and as you further increase the voltage up to 25 kV the bead density and fiber thickness decrease as shown in Figure 6. Therefore based on our experiments we can say that an applied voltage of 25 kV is optimum for nanofiber formation.
CONCLUSIONS
We have demonstrated for the first time formation of nanofibers of PANI-CSA/PMMA
blends with fiber thickness ranging from 2.28µm to 100nm depending on concentration of polymers used in the blend. Higher spinning voltage favors formation of thinner fibers with fewer beads. The concentration of polymers in the polymer blend has a significant effect on morphology of formed fibers and as our ultimate goal is to make conducting nanofibers, blends with higher PANI-CSA concentrations are an optimum choice and would be further characterized by electrostatic force microscopy to measure charge distribution and conductivity of the fibers. D2.7.6
Figure 6: Effect of spinning voltage on bead density
ACKNOWLEDGMENTS
The authors would like to acknowledge the financial support received by them from National Science Foundation (NSF) for this research project under OMI-0200498. The authors would like to express their gratitude to Ms Samira Farboodmanesh for having helped in setting up the electrospinning equipment and Ms Bongwoo Kang for assisting with the various characterization techniques.
REFERENCES
1. B. Wessling, Synthetic Metals 85, 1313-1318 (1997).
2. J. M. Deitzel, J. Kleinmeyer, D. Harris and N.C. Beck Tan, Polymer 42, 261-272 (2001). 3. C. Y. Yang, Y. Cao, Paul Smith and A. J. Heeger, Synthetic Metals 53, 293-301 (1993). 4. H. Fong, I. Chun, D. H. Renekar, Polymer 40, 4585-4592 (1999).
