Thermosensitive P(AAc‐co‐NIPAm) Hydrogels Display Enhanced Toughness and Self‐Healing via Ion–Ligand Interactions

Hydrogels containing thermosensitive polymers such as poly(N-isopropylacrylamide) (P(NIPAm)) may contract during heating and show great promise in fields ranging from soft robotics to thermosensitive biosensors. However, these gels often exhibit low stiffness, tensile strength, and mechanical toughness, limiting their applicability. Through copolymerization of P(NIPAm) with poly(Acrylic acid) (P(AAc)) and introduction of ferric ions (Fe3+ ) that coordinate with functional groups along the P(AAc) chains, here a thermoresponsive hydrogel with enhanced mechanical extensibility, strength, and toughness is introduced. Using both experimentation and constitutive modeling, it is found that increasing the ratio of m(AAc):m(NIPAm) in the prepolymer decreases strength and toughness but improves extensibility. In contrast, increasing Fe3+ concentration generally improves strength and toughness with little decrease in extensibility. Due to reversible coordination of the Fe3+ bonds, these gels display excellent recovery of mechanical strength during cyclic loading and self-healing ability. While thermosensitive contraction imbued by the underlying P(NIPAm) decreases slightly with increased Fe3+ concentration, the temperature transition range is widened and shifted upward toward that of human body temperature (between 30 and 40 °C), perhaps rendering these gels suitable as in vivo biosensors. Finally, these gels display excellent adsorptive properties with a variety of materials, rendering them possible candidates in adhesive applications.