Electron spin resonance spectra of polymers during fluorination

ESR spectra characteristic of peroxy radicals appeared rapidly in all of eleven hydrogen-containing polymers examined when treated with dilute fluorine. These radicals presumably result from the reaction of hydrocarbon and fluorocarbon radicals, existing at undetectably low steady-state concentrations, with the oxygen impurity content of commercial fluorine. In poly(vinylidene fluoride) films of thickness 11 and 58 μm the radical contents were nearly proportional to surface area rather than volume, in agreement with earlier reports of a shallow depth of penetration. Some polymers exhibited also or exclusively a broad spectral component, varying in character with the polymer; examples are polystyrene, polyethylene, poly (vinyl chloride), poly(vinylidene chloride), polyoctafluoropentadiene, polyhexafluoropropene, and a fluorinated graphite. The broad spectral component did not react with ordinary radical scavengers such as propylene and oxygen, and is probably not due to a fluorocarbon radical but to unknown transition metal fluorides.