Mechanisms of triple-shape polymeric composites due to dual thermal transitions

Abstract

Shape memory polymers (SMPs) are a class of smart materials capable of fixing a temporary shape and recovering the permanent shape in response to environmental stimuli such as heat, electricity, irradiation, moisture, or magnetic field, among others. Recently, multi-shape SMPs, which are capable of fixing more than one temporary shape and recovering sequentially from one temporary shape to another and eventually to the permanent shape, have attracted increasing attention. In general, there are two approaches to achieve a multi-shape memory effect (m-SME): the first one requires the SMP to have a broad temperature range of thermomechanical transition, such as a broad glass transition. The second approach uses multiple transitions to achieve m-SME, most notably, using two distinct transition temperatures to obtain a triple-shape memory effect (t-SME). The recently reported approach for designing and fabricating triple-shape polymeric composites (TSPCs) provides a much larger degree of design flexibility by separately tuning the two functional components (matrix and fiber network) to achieve optimum control of properties. The triple-shape memory behavior demonstrated by a TSPC is studied in this paper. This composite is composed of an epoxy matrix, providing a rubber–glass transition to fix one temporary shape, and an interpenetrating crystallizable PCL fiber network providing the system the melt–crystal transition to fix a second temporary shape. A one-dimension (1D) model that combines viscoelasticity for amorphous shape memory polymers (the matrix) with a constitutive model for crystallizable shape memory polymers (the fiber network) is developed to describe t-SME. The model includes the WLF and Arrhenius equations to describe the glass transition of the matrix, and the kinetics of crystallization and melting of the fiber network. The assumption that the newly formed crystalline phase of the fiber network is initially in a stress-free state is used to model the mechanics of evolving crystallizable phases. Experiments including uniaxial tension, stress relaxation, and triple-shape memory testing were carried out for parameter identification. The model accurately captures t-SME exhibited in experiments. The stress and stored energy analysis during the shape memory cycle provides insight into the mechanisms of shape fixing for the two different temporary shapes, the nature of both recovery events, as well as a guidance on how to design transitions to achieve the desired behavior.