Mechanics of amorphous polymers and polymer gels

Abstract

Many applications of amorphous polymers require a thermo-mechanically coupled large-deformation elasto-viscoplasticity theory which models the strain rate and temperature dependent response of amorphous polymeric materials in a temperature range which spans the glass transition temperature of the material. We have formulated such a theory, and also numerically implemented our theory in a finite element program. The material parameters in the theory have been calibrated for poly(methyl methacrylate), polycarbonate, and Zeonex - a cyclo-olefin polymer. The predictive capabilities of the constitutive theory and its numerical implementation have been validated by comparing the results from a suite of validation experiments against corresponding results from numerical simulations. Amorphous chemically-crosslinked polymers form a relatively new class of thermallyactuated shape-memory polymers. Several biomedical applications for thermally-actuated shape-memory polymers have been proposed/demonstrated in the recent literature. However, actual use of such polymers and devices made from these materials is still quite limited. For the variety of proposed applications to be realized with some confidence in their performance, it is important to develop a constitutive theory for the thermo-mechanical response of these materials and a numerical simulation-based design capability which, when supported with experimental data, will allow for the prediction of the response of devices made from these materials under service conditions. We have developed such a theory and a numerical simulation capability, and demonstrated its utility for modeling the thermo-mechanical response of the shape-memory polymer tBA-PEGDMA. An elastomeric gel is a cross-linked polymer network swollen with a solvent, and certain thermally-responsive gels can undergo large reversible volume changes as they are cycled about a critical temperature. We have developed a thermodynamically-consistent continuum-level theory to describe the coupled mechanical-deformation, fluid permeation, and heat transfer of such gels. We have numerically implemented our theory in a finite element program by writing thermo-chemo-mechanically coupled elements. We show that our theory is capable of simulating swelling, squeezing of fluid by applied mechanical forces, and thermally-responsive swelling/de-swelling of such materials.