Effect of Chain Orientation on Coupling of Optical and Mechanical Anisotropies of Polymer Films

Polymer films have broad applications in different industries with specific requirements for their optical and mechanical properties. In mass production, processing conditions during film formation that apply forces and motions in various directions to the film tend to manifest preferred molecular chain orientation in the film microstructure, which unavoidably produces optical and mechanical anisotropies. In this paper, we investigate the effect of such macromolecular orientations on the optical and mechanical anisotropies of several polymer films, including polystyrene, poly(methyl methacrylate), poly(ethylene terephthalate), poly(ethylene naphthalate), poly(ether ether ketone), poly(ether sulfones), poly(ethylene chlorotrifluoroethylene), poly(phenylsulfone), and polycarbonate, at temperatures well below their respective glass transitions (Tg). The film mechanical responses, including elasticity, yielding, and post-yield behaviors, were obtained for the in- and out-of-plane directions utilizing tensile and nanoindentation testing methods, respectively. In addition, the net chain orientation within the films was evaluated by birefringence through analyzing the film optical refractive indices, which were verified and complemented by wide-angle X-ray scattering (WAXS) measurements. The results reveal a considerable quantitative correlation between the birefringence and the degree of elastic anisotropy and a qualitative correlation between the chain orientation and the film post-yield tensile instability (necking). These observations corroborate the interrelationship between the microstructure of polymer films and their optical and mechanical properties. In addition, they emphasize that process conditions can be selected to tune the optical and mechanical anisotropies to best serve the material performance in specific devices. We also propose an empirical equation to approximate the out-of-plane film stiffness based upon the optical and in-plane mechanical properties.