Autocatalytic phase separation and graded co-continuous morphology generated by photocuring.

Interpenetrating polymer networks (IPNs) with spatially graded co-continuous structures were constructed by photo-cross-linking a homogeneous mixture of photo-reactive polystyrene and methyl methacrylate monomer. For a given thickness, irradiation with weak ultraviolet (UV) light results in a co-continuous morphology uniform throughout the sample. However, as the irradiation intensity increases to some certain extent, spatially graded co-continuous morphology in the micrometre scales emerges due to the significant effect of the gradient of the light intensity along the irradiation direction. These 3-dimensional graded structures were observed by using laser scanning confocal microscopy (LSCM) and were analyzed by digital image analysis. The depth dependence of these graded structures can be well expressed by a power law with an exponent depending strongly on the irradiation intensity. The time-evolution of the graded morphology was monitored at different depths of the same irradiated sample. It was found that the phase separation does not follow conventional laws of kinetics, but instead exhibits the autocatalytic behavior, reflecting the effects of the heat produced by the photopolymerization of MMA monomer on the phase separation process. The experimental data obtained in this study suggest a method of producing polymeric materials with spatially graded structures in the micrometer scales by solely changing the irradiation intensity.