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Langmuir Article Figure 6. Mechanism for contact triboelectrification of insulating polymers. Shearing the polymer interface heats both surfaces unevenly forming hot spots, due to forced contact on surface hills. Plasticization and melting take place, added to chain breakdown and fragmentation. Homolytic scission produces free radicals with markedly different electronegativities that are converted into fluorocarbanions and hydrocarbocations by electron transfer. Ions are segregated due to the chain size, following Flory−Huggins theory and superseding weak electrostatic interactions between highly spaced charges. ■ ASSOCIATED CONTENT *S Supporting Information Electric potential maps of PTFE and PE samples. Removal of charges from tribocharged PTFE by 1,1-difluoroethane. Electrostatic potential maps of PTFE pressed between cleaved mica sheets. Complete ref 41. This material is available free of ■charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *E-mail: fernagal@iqm.unicamp.br. Notes T■he authors declare no competing financial interest. ACKNOWLEDGMENTS Supported by CNPq and Fapesp (Brazil) through Inomat, National Institute (INCT) for Complex Functional Materials. T.A.L.B., T.R.D.D., and K.J.C. hold fellowships from CNPq, a■nd K.R.F. holds a fellowship from Fapesp. REFERENCES (1) Crowley, J. M. Fundamentals of Applied Electrostatics; Wiley: New York, 1986. (2) Bailey, A. G. The Charging of insulator surfaces. J. Electrostat. 2001, 51−52, 82−90. (3) Harper, W. R. Contact and Frictional Electrification; Laplacian: Morgan Hill, 1998. (4) Castle, G. S. P. Contact charging between insulators. J. Electrostat. 1997, 40, 13−20. (5) Schein, L. B. Recent progress and continuing puzzles in electrostatics. Science 2007, 316, 1572−1573. (6) Loeb, L. B. The basic mechanisms of static electrification. Science 1945, 102, 573−576. (7) Williams, M. W. Triboelectric charging of insulators − Evidence for electrons versus ions. IEEE Trans. Ind. Appl. 2011, 47, 1093−1099. (8) Matsusaka, S.; Maruyama, H.; Matsuyama, T.; Ghadiri, M. Triboelectric charging of powders: A review. Chem. Eng. Sci. 2010, 65, 5781−5807. Figure 7. Macroscopic patterns obtained on PTFE surface. An aluminum sheet mask with drilled circular holes was mounted on top of spacers, 1 mm above the PTFE surface. 2-mm-diameter washed glass spheres were placed on each hole and the whole setup was shaken on a reciprocating platform for 60 min, after which the PTFE was placed on the x−y scanner for potential mapping. Tribocharge is extracted with both nonpolar and polar liquids but shows some solvent specificity, and the analysis of the extracts by analytical TEM confirms that fluorocarbanions are the negative tribocharge species. Charge stability at the polymer surfaces under air is explained by the tendency of ions bound to apolar chains to occupy subsurface layers, to minimize surface tension. Positive and negative domains can be cut and mounted, and they can be produced forming regular patterns, as a new and simple potential alternative for electrolithography. 7414 dx.doi.org/10.1021/la301228j | Langmuir 2012, 28, 7407−7416PDF Image | Triboelectricity: Macroscopic Charge Patterns Formed by Self- Arraying Ions on Polymer Surfaces
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