Photomechanics of light-activated polymers

Abstract

Light-activated polymers are an exciting class of modern materials that respond mechanically when irradiated by light at particular wavelengths. While details of the mechanisms that connect the optical excitation to mechanical behavior are complex and differ from material to material, there is sufficient commonality among them to permit the development of a generalized modeling framework to describe the photomechanics. The features shared by light-activated polymers involve light interacting with the material, which triggers photochemical reactions that alter the structure of the crosslinked polymer network. Many such structural alterations result in an evolution of the polymer network, and subsequent macroscopic deformation. When this process is appropriately executed it can enable a photomechanical shape-memory effect. In this paper, we develop a three-dimensional finite-deformation modeling framework to describe the photomechanical response of light-activated polymer systems. This framework integrates four coupled phenomena that contribute to macroscopic photomechanical behavior: photophysics, photochemistry, chemomechanical coupling, and mechanical deformation. The chemomechanical coupling consists of chemically induced structural alterations of the crosslinked network that result in subsequent deformation. We describe this behavior through a decomposition of the crosslinked network into two components consisting of an original network and a photochemically altered network; both evolve during photomechanical deformation. The modeling framework presented in this paper is sufficiently general that it is applicable to light-activated polymer systems that operate with various mechanisms in each of the four areas. Using this modeling approach, we develop constitutive models for two recently developed light-activated polymer systems [Lendlein, A., Hongyan, J., Junger, O., Langer, R., 2005. Light-induced shape-memory polymers. Nature 434 (7035) 879; Scott, T.F., Schneider, A.D., Cook, W.D., Bowman, C.N., 2005. Photoinduced plasticity in crosslinked polymers. Science 308 (5728) 1615]. For the material developed by Scott and his co-workers we validate our model by measuring and numerically simulating photo-induced stress relaxation and bending deformation and obtain good agreement between measurements and predictions. Finally, we use the model to study the effects of photomechanical parameters (applied strain magnitude, irradiation time and intensity, and photoabsorber concentration) and the behavior of the network evolution rule on the material response.