Programmable materials that can reversibly transform between distinct shapes represent a promising technology for applications spanning biomedicine, robotics, and aerospace engineering. Although shape memory polymers offer promising stimuli-responsive behavior, current manufacturing approaches limit geometric complexity and performance optimization. Here, we demonstrate a manufacturing strategy that combines radiation-induced crosslinking with additive manufacturing to create programmable shape memory materials with superior performance and architectural control. This study examines radiation crosslinking of 3D printed polycaprolactone-trimetylolpropane triacrylate (PCL–TMPTA) composites comprised of two different concentrations of TMPTA (2.5% and 5%), revealing fundamental structure–property relationships that enable rational material design.
