RESUMEN
The dynamic behaviors of polyzwitterions, poly(4-((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate) (PSBP), are investigated using dynamic light scattering, small angle X-ray scattering, and rheology. The findings reveal two relaxation modes, including a fast and a slow mode, which are observed in both solution state and gel-like state, with varying polyzwitterion concentration (CP ) and NaCl concentration (CNaCl ). As CP and CNaCl increasing, a slower slow mode and a faster fast mode are observed. The fast mode corresponds to the diffusion of chains, while the slow mode arises from chain aggregations. In solutions, the slow mode is dominated by the diffusion of chain aggregations. However, in the gel-like state, the "cage network" traps aggregations more densely, leading to their dynamic behavior being dominated by enhanced topological entanglements and ionic interactions. This difference highlights the unique nature of the slow relaxation mode between concentrated solution and gel-like state, arising from changes in the average distance between chain aggregations resulting from increased CP and CNaCl concentrations.
Asunto(s)
Cloruro de Sodio , Dispersión Dinámica de Luz , Difusión , ReologíaRESUMEN
In this work, we investigated the dynamics of hydrogels from the polyelectrolyte complexation of sodium hyaluronate (HA) and chitosan under various temperature and salt concentration. Raising temperature and adding salt remarkably reduce the mechanical behavior of hydrogels. The stress relaxation of semi-flexible chain segments is accelerated at high temperature and salt concentration, which is controlled by thermally activated bond disassociation process. The flow activation energy determined from temperature-dependent dynamic light scattering decorrelation and rheological relaxation are in very good agreement. Our results suggest that the chain aggregations are physical crosslinked by surrounded semi-flexible chains, and their diffusion is highly hindered by the topological entanglements and ionic associations. The synergistic effect of aggregations diffusion and chain dynamics causes the slow macroscopic stress relaxation behavior of hydrogels before yield, independent of applied strain. Above yield, the amplitude of strain accelerates the stress relaxation, resulting in chain disentanglements and slipping.