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Polyampholyte (PA) hydrogels are a new class of tough and self-healing supramolecular hydrogels that have a potential as load-bearing soft materials. Studying on the creep behavior of these hydrogels and understanding the molecular mechanism are important for prediction of lifetime of the materials. In the present work, we study the creep rupture dynamics of the PA hydrogels with and without chemical cross-linking, in a certain observation time window. We have found that above some critical loading stress both physical and lightly chemically cross-linked hydrogels undergo creep rupture while moderately chemically cross-linked hydrogel resists creep flow. To elucidate the molecular mechanism, we have further compared the creep behaviors of the physical and lightly chemically cross-linked samples. The creep rate of the samples decreases with the creep time, following a power law relation, regardless of the loading stress variation. The fracture time of both of these hydrogels exponentially decreases with the increase of the loading stress, following the same master curve at high loading stress region, while the behavior of the two samples becomes different in the low loading stress region. We have explained the delayed fracture dynamics at high loading stress region in terms of a relatively weak strong bond rupture mechanism. [ABSTRACT FROM AUTHOR]

Recently, polyampolytes have been discovered to form hydrogels that possess high toughness, full resilience, and self-healing between two cut surfaces. The self-healing of this class of hydrogels is based on the re-forming of the multiple ionic bonds at the fractured surfaces, in which the mobility of the polymer segments and strength of the ionic bonds play an important role. In this work, we study the effects of healing temperature and chemistry of the polyampholyte hydrogels (chemical cross-linker density and chemical structure of the monomers) on the healing kinetics and healing efficiency. The high healing temperature substantially accelerates the self-healing kinetics. Chemical cross-linking reduces the self-healing efficiency. Monomers with more hydrophobic feature give a low self-healing efficiency. For polyampholyte physical hydrogels with a softening temperature below the room temperature, excellent healing efficiency (∼84% on average and maximum 99%) was observed without any external stimuli. We found a correlation between the self-healing efficiency and the fraction of dynamic bonds in the total bonds for relatively soft samples, which is an evidence that the self-healing is due to the re-forming of dynamic bonds. [ABSTRACT FROM AUTHOR]

Recently, we have reported that polyampholytes,synthesized fromfree radical copolymerization of anionic monomer and cationic monomer,form physical hydrogels of high toughness and self-healing. The randomdistribution of the opposite charges forms ionic bonds of a wide distributionof strength. The strong bonds serve as permanent cross-links, impartingelasticity, whereas the weak bonds serves as reversible sacrificialbonds by breaking and reforming to dissipate energy. In this work,we focus on the rupture behaviors of the polyampholyte physical hydrogel,P(NaSS-co-MPTC), copolymerized from sodium p-styrenesulfonate (NaSS) and 3-(methacryloylamino)propyltrimethylammoniumchloride (MPTC). Tensile test and pure shear test were performed atvarious stretch rates in the viscoelastic responses region of thematerial. Tensile test showed yielding, strain softening, and strainhardening, revealing the dually cross-linked feature of the gel. Pureshear test showed crack blunting at the notched tip and a large yieldingzone with butterfly shaped birefringence pattern ahead of the cracktip. After blunting, crack advanced at steady-state velocity witha constant angle. The conditions for the occurrence of crack bluntingand variables governing the crack advancing angle are discussed. Wefound that even for these highly stretchable samples, significantblunting only occurs when the tensile fracture stress σfis larger than modulus Eby a factor of about 2, in consistent with Hui’s theoreticalprediction for elastic materials. The crack advancing angle θwas found to be proportional to σy/Eover a wide stretch rate range, where σyis the yielding stress. In addition, thefracture energy was correlated to small strain modulus by a powerlaw in the viscoelastic response region. This systematic study willmerit revealing the fracture mechanism of tough viscoelastic materialsincluding biological tissues and recently developed tough and highlystretchable hydrogels. [ABSTRACT FROM AUTHOR]