Micro-fabrications of various perfluorinated polymers were carried out by the synchrotron radiation (SR) direct photo etching, and the SR-induced surface modifications were studied by DSC and 19F solid-state NMR spectroscopy. The etching depth measurements of perfluorinated polymers were carried out by optical microscope. Although ETFE could be hardly etched, it was confirmed that the microstructures of PFA and FEP could be fabricated by SR direct photo etching. It was found that the etching rate of FEP at 140 °C was highest and those of PTFE and PFA at 140 °C were lower. It was found that crosslinking reactions were induced by the SR-irradiation at the region within 50 μm from the irradiated surface.
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