Controlling frontal photopolymerization with optical attenuation and mass diffusion

Frontal photopolymerization (FPP) is a versatile directional solidification process that can be used to rapidly fabricate polymer network materials by selectively exposing a photosensitive monomer bath to light. A characteristic feature of FPP is that the monomer-to-polymer conversion profiles take on the form of traveling waves that propagate into the unpolymerized bulk from the illuminated surface. Practical implementations of FPP require detailed knowledge about the conversion profile and speed of these traveling waves. The purpose of this theoretical study is to (i) determine the conditions under which FPP occurs and (ii) explore how optical attenuation and mass transport can be used to finely tune the conversion profile and propagation kinetics. Our findings quantify the strong optical attenuation and slow mass transport relative to the rate of polymerization required for FPP. The shape of the traveling wave is primarily controlled by the magnitude of the optical attenuation coefficients of the neat and polymerized material. Unexpectedly, we find that mass diffusion can increase the net extent of polymerization and accelerate the growth of the solid network. The theoretical predictions are found to be in excellent agreement with experimental data acquired for representative systems.