Curvature Dynamics of PEGDA Asymmetric Networks via Frontal Photopolymerization: Effect of Chain Length and Optical Attenuation

We investigate how the oligomer molecular mass, chain length, and optical attenuation affect both polymerization kinetics and the spatiotemporal response of materials patterned via frontal photopolymerization (FPP). We employ model poly(ethylene glycol) diacrylate (PEGDA) oligomers of different chain lengths and investigate their FPP kinetics and response following solvent development, focusing on the emergence and evolution of the material curvature. We find that longer precursors yield a lower dose (or time) threshold for solidification, effectively benefiting from an “early start,” while the front velocity remains unchanged with chain length; by contrast, photoinitiator concentration leads to a nonmonotonic impact on kinetics due to the combined effects on rate and optical attenuation, which we collapse on a master curve. FPP networks can exhibit nonmonotonic, spontaneous curvature fluctuations, from flat or convex, to concave, and back to convex, that we show to depend on PEGDA chain length and describe by a minimal evaporation–diffusion model. These findings demonstrate how the interplay between molecular structure, soft mechanics, and solvent transport can be harnessed to program the response of asymmetric polymer networks.