Relative Rates for Plasma Homo-; and Copolymerizations of a Homologous Series of Fluorinated Ethylenes

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Abstract

The relative rates of plasma homo- and Copolymerizations of ethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene and tetrafluoroethylene (VFx, x = 0–4, respectively) were determined in an rf, capacitively coupled, tubular reactor with external electrodes using identical plasma parameters. The deposition rates for VFx (x = 1–3) and 20 different monomer blends, when plotted versus the F/C ratios of the monomers or monomer blends, followed a concave-downward curve situated above the straight-line joining the rates for VF0 and VF4. The deposition rates for VFm/VFn blends (m = 3 or 4; n = 0–2) likewise yielded concave-downward curves situated above the straight lines joining the rates for the respective monomers; the rates for VFm/VFn blends (m = 0 or 1; n = 1 or 2) yielded concave-upward curves situated below the straight lines joining the rates for the respective monomers; while the rates for VF3/VF4 blends fell along the straight line joining the rates for VF3 and VF4. The mechanisms for plasma (co) polymerizations of VFx monomers responsible for the wide range of relative deposition rates remain to be elucidated.

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