<p>Polyampholyte (PA) gels possess tunable mechanical properties governed by chemical crosslinking and noncovalent interactions. However, the mechanisms by which topological constraints dictate network deformation remain poorly understood. Here, small-angle neutron scattering (SANS) with deuterium substitution was employed to characterize the chain network deformation of PA gels under uniaxial stretching. In systems with lower crosslinker concentrations, the chain network undergoes uneven deformation originating from heterogeneous crosslinking with local microdomains, leading to nonaffine deformation. As the crosslinker concentration increases, the introduced permanent crosslinks partition the network into more uniform segments, effectively suppressing localized inhomogeneous deformation and driving chain network deformation to align with the affine prediction. Furthermore, increasing the monomer concentration is expected to introduce a higher density of physical entanglements, producing a similar effect. Importantly, the relationship between structural inhomogeneity and extensibility in PA gels is opposite to that in conventional chemical gels: the more inhomogeneous network exhibits the greatest elongation at break. This reversed relationship is enabled by dynamic ionic bonds, which dissipate energy through progressive rupture, accommodating local strain mismatch. This study quantifies the transition from inhomogeneous deformation to affine deformation, clarifying the relationship between microstructural uniformity and the deformation behavior of crosslinked tough hydrogels.</p>

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Chain network deformation of tough and self-healing polyampholyte gels revealed by small-angle neutron scattering

  • Kaining He,
  • Siqi Huang,
  • Yike Li,
  • Kunpeng Cui

摘要

Polyampholyte (PA) gels possess tunable mechanical properties governed by chemical crosslinking and noncovalent interactions. However, the mechanisms by which topological constraints dictate network deformation remain poorly understood. Here, small-angle neutron scattering (SANS) with deuterium substitution was employed to characterize the chain network deformation of PA gels under uniaxial stretching. In systems with lower crosslinker concentrations, the chain network undergoes uneven deformation originating from heterogeneous crosslinking with local microdomains, leading to nonaffine deformation. As the crosslinker concentration increases, the introduced permanent crosslinks partition the network into more uniform segments, effectively suppressing localized inhomogeneous deformation and driving chain network deformation to align with the affine prediction. Furthermore, increasing the monomer concentration is expected to introduce a higher density of physical entanglements, producing a similar effect. Importantly, the relationship between structural inhomogeneity and extensibility in PA gels is opposite to that in conventional chemical gels: the more inhomogeneous network exhibits the greatest elongation at break. This reversed relationship is enabled by dynamic ionic bonds, which dissipate energy through progressive rupture, accommodating local strain mismatch. This study quantifies the transition from inhomogeneous deformation to affine deformation, clarifying the relationship between microstructural uniformity and the deformation behavior of crosslinked tough hydrogels.