Thermal desorption mass spectrometric and x-ray photoelectron studies of etched surfaces of polytetrafluoroethylene

The etching of polytetrafluoroethylene (PTFE) with Na solutions is known to lead to a loss of F, a loss which is correlated with enhanced adhesion. Subsequent heating partially restores surface F with a concurrent loss of adhesion strength. We have combined X-ray photoelectron spectroscopy (XPS) and gas phase mass spectroscopy for in situ measurements of the processes that occur as the fluorocarbon is heated. An array of volatile products, which vary with the specific treatment, desorb from etched PTFE. Among these are: N₂ and low molecular weight fluorocarbons, the amounts of which monotonically decrease with increasing exposure to the etching solution (and probably result from the bulk); species such as CO and CO₂, which in part result from surface impurities; and water and acetone which result from the rinse steps following the etching process. XPS measurements show that etching produces a major loss of surface F and a gain of surface O. The latter probably results from the subsequent rinse steps. Heating produces a substantial recovery in surface F with only a small decrease in the surface O, and the gain in surface F is shown to occur at a higher temperature than the desorption of any species from the surface. Thus, desorption of products from the surface is decoupled, in terms of both the distribution of products and their relative temperatures, from the surface changes as monitored by XPS. This decoupling suggests that the increase in surface F results from diffusion of low molecular weight fluorocarbons from the bulk or a transition region, or from a rearrangement of the sponge-like surface region produced in the etching process.