4D Printing of Body Temperature-Responsive Hydrogels Based on Poly(acrylic acid) with Shape-Memory and Self-Healing Abilities.

Abstract

Additive manufacturing of smart materials that can be dynamically programmed with external stimuli is known as 4D printing. Among the 4D printable materials, hydrogels are the most extensively studied materials in various biomedical areas because of their hierarchical structure, similarity to native human tissues, and supreme bioactivity. However, conventional smart hydrogels suffer from poor mechanical properties, slow actuation speed, and instability of actuated shape. Herein, we present 4D-printed hydrogels based on poly(acrylic acid) that can concurrently possess shape-memory and self-healing properties. The printing of the hydrogels is achieved by solvent-free copolymerization of the hydrophilic acrylic acid (AAc) and hydrophobic hexadecyl acrylate (C16A) monomers in the presence of TPO photoinitiator using a stereolithography-based commercial resin printer followed by swelling in water. The printed hydrogels undergo a reversible strong-to-weak gel transition below and above human body temperature due to the melting and crystallization of the hydrophobic C16A domains. In this way, the shape-memory and self-healing properties of the hydrogels can be magically actuated near the body temperature by adjusting the molar ratio of the monomers. Furthermore, the printed hydrogels display a high Young's modulus (up to ∼215 MPa) and high toughness (up to ∼7 MJ/m3), and their mechanical properties can be tuned from brittle to ductile by reducing the molar fraction of C16A, or the deformation speed. Overall, the developed 4D printable hydrogels have great potential for various biomedical applications.