Three-Dimensional Printed Shape Memory Objects Based on an Olefin Ionomer of Zinc-Neutralized Poly(ethylene-co-methacrylic acid)

Three-dimensional printing enables the net shape manufacturing of objects with minimal material waste and low tooling costs, but the functionality is generally limited by available materials, especially for extrusion-based printing, such as fused deposition modeling (FDM). Here, we demonstrate shape memory behavior of 3D printed objects with FDM using a commercially available olefin ionomer, Surlyn 9520, which is zinc-neutralized poly(ethylene-co-methacrylic acid). The initial fixity for 3D printed and compression-molded samples was similar, but the initial recovery was much lower for the 3D printed sample (R = 58%) than that for the compression-molded sample (R = 83%). The poor recovery in the first cycle is attributed to polyethylene crystals formed during programming that act to resist the permanent network recovery. This effect is magnified in the 3D printed part due to the higher strain (lower modulus in the 3D printed part) at a fixed programming stress. The fixity and recovery in subsequent shape memory cycles are greater for the 3D printed part than for the compression-molded part. Moreover, the programmed strain can be systematically modulated by inclusion of porosity in the printed part without adversely impacting the fixity or recovery. These characteristics enable the direct formation of complex shapes of thermoplastic shape memory polymers that can be recovered in three dimensions with the appropriate trigger, such as heat, through the use of FDM as a 3D printing technology.