4D printable maleated poly(styrene-b-ethylene/butylene-b-styrene) / Poly(ethylene-co-vinyl acetate) thermoplastic elastomer blends; effects of blend composition on shape memory and mechanical properties

Abstract

Shape memory polymers are attracting attention in materials science with their responsive properties and their application areas are gradually developing. By adapting these materials to the additive manufacturing process, four-dimensional (4D) printing technology has been developed. In this study, novel thermo-responsive shape memory polymer blends were prepared for high temperature applications from commercially available polymers using maleated poly(styrene-b-ethylene/butylene-b-styrene) (SEBS-g-MA) and poly(ethylene-co-vinyl acetate) (EVA) and their applicability in three-dimensional (3D) printing was explored. The presence of SEBS-g-MA led to an increase in the degree of crystallization and glass transition temperature of EVA, accompanied by a decrease in crystallization temperature. As the EVA content increased, the blend morphology transitioned from droplet to co-continuous structure. Higher EVA content resulted in an increase in Young's modulus, but a decrease in tensile strength. Nevertheless, these blends exhibited exceptional elongation at break, surpassing 1200%. The blend comprising 70 wt% SEBS-g-MA and 30 wt% EVA demonstrated a synergistic effect, yielding the highest values for elastic modulus, creep resistance, and storage modulus. Furthermore, the blend with 60 wt% SEBS-g-MA and 40 wt% EVA exhibited optimal shape memory performance, achieving a shape fixing ratio of 93.1% and a shape recovery ratio of 98.7%. The conducted analyses demonstrated that the shape recovery of the produced blends could be adjusted according to temperature, and the blends were able to consistently replicate the shape memory effect across multiple cycles. A filament was manufactured for a 3D printer from the blend of 60 wt% SEBS-g-MA and 40 wt% EVA. Using this filament, 4D models having complex geometries were successfully printed. The produced models were able to maintain their temporary shapes to a significant degree. When triggered by heat, these models rapidly returned to their original shapes within a very short period.