Enhancing Temperature Responsiveness of PNIPAM Through 3D‐Printed Hierarchical Porosity

Abstract Materials with ultra‐fast responsive properties are essential for various applications. Among the responsive materials, poly( N ‐isopropylacrylamide) (PNIPAM) stands out due to its well‐studied temperature‐responsive properties. Improving the kinetics of the responsive properties of PNIPAM is, however, still essential for advancing its practical use. Here, the responsive rate of PNIPAM hydrogels is enhanced by first incorporating sub‐micrometer porosity into the material through polymerization‐induced phase separation (PIPS), followed by introducing millimeter scale pores via 3D printing, thereby rendering the material with hierarchical porosity. The 3D‐printed porous PNIPAM structures show accelerated swelling and deswelling, when compared to non‐porous PNIPAM structures, due to enhanced water permeability associated with the continuous network of micrometer to millimeter‐sized pores. Additionally, thinner polymer structures result in faster temperature response rates. At the same time, the mechanical strength of PNIPAM hydrogels with high porosity and thinner polymer walls is not compromised, overcoming the common trade‐off between swelling and mechanical properties.