Tailoring Physical Properties of Dual-Network Acrylamide Hydrogel Composites by Engineering Molecular Structures of the Cross-linked Network

We demonstrate the impact of engineering molecular structures of poly(acrylamide) (PAAm) and poly(N-isopropylacrylamide) (PNIPAm) hydrogel composites on several physical properties. The network structure was systematically varied by (i) the type and the concentration of difunctional cross linkers and (ii) the type of native or chemically modified natural polymers, including sodium alginate, methacrylate/dopamine-incorporated porcine skin gelatin and fish skin gelatin, and thiolincorporated lignosulfonate, which are attractive biopolymers generated in pulp and food industries because of their abundance, rich chemical functionalities, and environmental friendliness. First, we added cross-linking agents of varying lengths at different concentrations to assess how the cross-linking agent modulates the mechanical properties of acrylamide-based composites with alginate. After chemically modifying gelatins from fish or porcine skin with methacrylate and/or dopamine, the acrylamide-based composites were fabricated with the chemically modified gelatins and thiolated lignosulfonate to assess the stress-strain behavior. Furthermore, swelling ratios were measured with respect to temperature change. The mechanical properties were systematically modulated by the changes in the molecular structure, that is, the length of the chemical unit between two end alkene groups in the difunctional cross-linker and the types of the additive natural polymers. Overall, PAAm hydrogel composites exhibit a significant, negative correlation between toughness and the volume fraction of the swollen state and between strain at fracture and the volume fraction of the swollen state. In contrast, PNIPAm hydrogel composites showed positive, but only moderate correlations, which is attributed to the difference in the network polymer structure.