Shape memory polymer foams from emulsion templating

Shape memory polymers (SMPs) change their shape under a stimulus (thermal, chemical, light) and return from an imposed temporary shape to their permanent, original shape. SMPs usually contain permanent domains that determine the permanent shape (chemical or physical crosslinks) and reversible domains that determine the temporary shape, usually by heating above a glass transition temperature or a melting point (T-m). Compared to fully dense SMPs, SMP foams can undergo higher temporary deformations and can exhibit higher deformations when they recover. In this paper, SMP foams based upon (meth)acrylates with crystallizable long side-chains were synthesized through emulsion-templating within nanoparticle-stabilized high internal phase Pickering emulsions where the nanoparticles also served as crosslinking centers. The nature of the polymer backbone affected the nature of the crystalline phase for identical side chains. The SMP foams at room temperature maintained the temporary shape (a strain of 0.7) imposed above the T-m and exhibited good recovery upon reheating for all four compression-recovery cycles. While the methacrylate-based SMP exhibited a single-stage recovery, the acrylate-based SMP, with identical side-chains, exhibited a two-stage recovery that can be associated with the existence of two crystalline phases. The recovery behavior was described using Kelvin-Voigt units in series with the dependence of viscosity on temperature described using a WLF-like relationship.