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Langmuir Article Figure 5. Bright field image (BF), carbon map (C map), oxygen map (O map), and fluorine map (F map) of the dry extract of the PTFE tribocharged surface. Table 2. ΔG for the Formation of Ions from the Corresponding Hydrocarbon and Fluorocarbon Radicals roughness down to the atomic size range. The simple but effective model for tribocharging described in this work will certainly speed up the development of functional tribocharged materials and devices. To sum up, electrostatic charge patterns deriving from contact and tribocharging events are presented here for the first time with a model to explain their appearance, based on their stability and on the effect of simple liquids, together with well- established knowledge on polymer surface behavior and polymer chemistry. species formed CH3(CH2)8CH2− CH3(CH2)8CH2+ CF3(CF2)8CF2− CF3(CF2)8CF2+ species charge −1 +1 −1 +1 ΔG/(kJ/mol) 9.43 627.51 −216.91 902.16 previously demonstrated or even hinted at but it could have been predicted, considering current knowledge on polymer chain mechanochemistry and on the widespread polymer immiscibility44 that counters electrostatic repulsion. This also explains why charge or potential nanopatterns have been found in any polymer surface that was previously examined: simple handling and contact of surfaces that are not atomically smooth concentrates mechanical energy in protruding areas, thus triggering a host of mechanochemical events followed by product segregation. Using the techniques for charge build-up and dissipation described in this paper, we can make macroscopic electrostatic lithography on plain PTFE sheets, as shown in Figure 7. Finally, we can now easily understand the great difficulty in establishing a tribochemical series that is abundantly described in the literature, because polymer tribocharging depends not only on a complex series of chemical events, but also on surface characteristics that were hardly accounted for, like surface ■ CONCLUSIONS 7413 dx.doi.org/10.1021/la301228j | Langmuir 2012, 28, 7407−7416 Polymer tribocharging produces macroscopic charge mosaics presenting large islands carrying either positive or negative net charge, including macroscopic electric dipoles. This confirms the fractal nature of electrostatic patterns on polymer surfaces, previously observed using scanning electric probe microscopy techniques. Tribocharges are identified for the first time, using suitably sensitive techniques, as polymer ions formed by polymer chain scission followed by electron transfer according to the polymer chain electronegativity, e.g., fluorinated alkyl residues acquire predominantly negative charge, while alkyl residues are predominantly positive. Cation and anion chain fragments further segregate according to their chemical nature, following Flory−Huggins theory and thus forming the charge islands.PDF Image | Triboelectricity: Macroscopic Charge Patterns Formed by Self- Arraying Ions on Polymer Surfaces
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