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Abstract Double-network (DN) hydrogels, consisting of two contrasting and interpenetrating polymer networks, are considered as perhaps the toughest soft-wet materials. Current knowledge of DN gels from synthesis methods to toughening mechanisms almost exclusively comes from chemically-linked DN hydrogels by experiments. Molecular modeling and simulations of inhomogeneous DN structure in hydrogels have proved to be extremely challenging. Herein, we developed a new multiscale simulation platform to computationally investigate the early fracture of physically-chemically linked agar/polyacrylamide (agar/PAM) DN hydrogels at a long timescale. A “random walk reactive polymerization” (RWRP) was developed to mimic a radical polymerization process, which enables to construct a physically-chemically linked agar/PAM DN hydrogel from monomers, while conventional and steered MD simulations were conducted to examine the structural-dependent energy dissipation and fracture behaviors at the relax and deformation states. Collective simulation results revealed that energy dissipation of agar/PAM hydrogels was attributed to a combination of the pulling out of agar chains from the DNs, the disruption of massive hydrogen bonds between and within DN structures, and the strong association of water molecules with both networks, thus explaining a different mechanical enhancement of agar/PAM hydrogels. This computational work provided atomic details of network structure, dynamics, solvation, and interactions of a hybrid DN hydrogel, and a different structural-dependent energy dissipation mode and fracture behavior of a hybrid DN hydrogel, which help to design tough hydrogels with new network structures and efficient energy dissipation modes. Additionally, the RWRP algorithm can be generally applied to construct the radical polymerization-produced hydrogels, elastomers, and polymers.
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Responsiveness of Charged Double Network Hydrogels to Ionic Environment
Abstract Charged double network (DN) hydrogels are widely studied for their desirable mechanical strength and tunable properties. In this work, the influence of polymer concentration on microstructure and properties of agarose/polyacrylic acid DN hydrogels is studied. Agarose, the first network, is a brittle biopolymer, while polyacrylic acid (PAAc) is a weak polyelectrolyte. The microstructure, visualized in liquid environment, displays an agarose scaffold coated and interconnected by PAAc, deviating from the common assumption of an entangled double network. Importantly, the charging of PAAc in the hydrogel is regulated not only by the pH and weak polyelectrolyte effects, but also by the restricted swelling of the double network, and hence, it is an inherent regulation mechanism of charged hydrogels. The interactions between the hydrogel and the ionic environment induce microstructural changes and charging of the double network, impacting surface properties such as topography, stiffness, and adhesion, which are spatially resolved by liquid‐environment atomic force microscopy. The responsiveness of the DN hydrogels significantly depends on both polymer concentrations and ion concentrations. These findings provide insights into the responsive behavior of double network hydrogels and reveal universal mechanisms for charged hydrogels, which can guide the future development of functional soft materials.
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- Award ID(s):
- 2154530
- PAR ID:
- 10500338
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 34
- Issue:
- 37
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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