Effects of photointensity gradient on directional crystal growth in blends of crystalline polymer and photoreactive monomer undergoing photopolymerization-induced phase transformation.

Effects of light intensity gradient on development of intricate hierarchical morphology of semicrystalline polyethylene oxide (PEO) and photoreactive diacrylate (DA) blends undergoing photopolymerization-induced crystallization have been demonstrated experimentally and theoretically. The melting temperature of PEO was found to decline upon addition of DA monomer. A solid-liquid phase diagram has been established by self-consistently solving the combined phase field free energy of crystal solidification and Flory-Huggins (FH) free energy of liquid-liquid demixing. Dynamic calculations were performed using time-dependent Ginzburg-Landau (model C) equations by incorporating the combined phase field and FH free energy densities coupled with the photopolymerization kinetics. The spatiotemporal development of gradient morphology was computed under various intensity gradient profiles including linear, cylindrical, and Gaussian profiles. The observed seaweed or dense lamellar branching morphology of the PEO/DA blend is strikingly similar to the directionally grown interface structures observed in metals driven by external thermal gradients.