ABSTRACTSilicone rubber (SIR) samples are fluorinated using a F2/N2 mixture at different temperatures. Physicochemical characteristics are analyzed by attenuated total reflection infrared spectroscopy, X‐ray photoelectron spectroscopy, and scanning electron microscopy. Basic properties of the fluorinated surface layers are investigated, and the intrinsic alternating current (AC) flashover performance and tracking resistance of the surface fluorinated samples are evaluated. The flashover test results indicate that the fluorination leads to an improvement in AC flashover performance of the SIR material, as a result of the competition between the favorable effect of the increase in surface conduction and the adverse effect of a likely increase in surface layer permittivity. The increase in AC flashover voltage is associated with the voltage‐increasing mode of the flashover test. The flashover test results also show an improved tracking resistance of the SIR material by the fluorination, and the improvement is especially significant for the fluorinated surface layer that has less cleavage of SiC bonds or a good compactness as well as a large thickness. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48556.
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