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Viscoelasticity and Structures in Chemically and Physically Dual Cross-Linked Hydrogels: Insights from Rheology and Proton Multiple-Quantum NMR Spectroscopy
作者:XT Zou, X Kui, RC Zhang*, Y Zhang, XL Wang, Q Wu, TH Chen, and PC Sun*
关键字:Dual-crosslinked hydrogel; Solid-state NMR; Rheology; Metal-coordination; Crosslinking; Proton MQ NMR
论文来源:期刊
具体来源:Macromolecules, 2017, 50, 9340–9352
发表时间:2017年
Hydrogels have received considerable attention as an innovative material due to their widespread applications in various fields. As a soft and wet material, its mechanical behavior is best understood in terms of the viscoelastic response to the periodic deformation, which is closely related to the microscopic chemically/physically cross-linked structures. Herein, a dual-cross-linked (DC) hydrogel, where a physically cross-linked network by ionic coordination (Fe3+) is imposed on a chemically cross-linked poly(acrylamide-co-acrylic acid) network, was studied in detail by rheology and proton multiple-quantum (MQ) NMR spectroscopy. Rheology experiments revealed the diverse temperature- and strain-frequency-dependent viscoelastic behaviors for DC hydrogels induced by the dynamic Fe3+ coordination interactions, in contrast to the single chemically cross-linked (SC) hydrogels. During the shear experiment, the trivalent Fe3+ complex with moderate/weak binding strength might transform to those with strong binding strength and serve as permanent-like cross-linkages to resist the periodic deformation when a large strain frequency was applied. The viscoelastic behaviors of the DC hydrogels were strongly affected by the monomer ratio (CAAc/CAAm) and Fe3+ concentrations; however, the chemically cross-linked density did not change with CAAc/CAAm, while the physically cross-linked density was greatly enhanced with increasing Fe3+ concentrations. Besides, the DC hydrogels have less contents of network defects in comparison to the SC hydrogels. The heterogeneous structural evolution with increasing the Fe3+ concentration and monomer ratio was also quantitatively determined and elucidated by proton MQ NMR spectroscopy. In addition, the moduli (G′, G″) of DC hydrogels were almost an order magnitude higher than that of the corresponding SC hydrogels, demonstrating the significant contribution of Fe3+ coordination to the mechanical properties, in consistent with the high activation energy of viscoelasticity for the physically cross-linked network as obtained from the variable-temperature shear rheology experiments. The experimental findings obtained from the rheology and proton MQ NMR experiments can be correlated with and complementary to each other. Herein, a combination of rheology and proton solid-state NMR is well demonstrated as an effective and unique way for establishing the relationship between microscopic structures and macroscopic viscoelastic properties.