Optimal conditions for maximum efficacy of photoinitiated polymerization are theoretically presented. Analytic formulas are shown for the crosslink time, crosslink depth, and efficacy function. The roles of photoinitiator (PI) concentration, diffusion depth, and light intensity on the polymerization spatial and temporal profiles are presented for both uniform and non-uniform cases. For the type I mechanism, higher intensity may accelerate the polymer action process, but it suffers a lower steady-state efficacy. This may be overcome by a controlled re-supply of PI concentration during the light exposure. In challenging the conventional Beer⁻Lambert law (BLL), a generalized, time-dependent BLL (a Lin-law) is derived. This study, for the first time, presents analytic formulas for curing depth and crosslink time without the assumption of thin-film or spatial average. Various optimal conditions are developed for maximum efficacy based on a numerically-fit A-factor. Experimental data are analyzed for the role of PI concentration and light intensity on the gelation (crosslink) time and efficacy.
Keywords: crosslinking; kinetic; optimal efficacy; photoinitiator; polymerization modeling.