Published online by Cambridge University Press: 25 February 2011
The polymerization of ethylene on surfaces sequentially dosed with TiC14 and trimethylaluminum was studied by Fourier transform infrared spectroscopy. The polymer film was observed in situ as a function of time and under the influence of 254-nm cw radiation. The rate of polymerization and the saturation thickness of the polyethylene are strongly dependent on the order of dosing and the partial pressures of the reactants that form the catalyst. UV enhancement of polymerization was demonstrated to occur through two separate photochemical channels: gas-phase photolysis of the reactants and solid-phase chemical transformation of a noncatalytic thin film.