RESUMO
Depending on how they form their linkages, biopolymer gelatin gels are commonly classified as physical, chemical, or hybrid; in gelatin hybrid gels, the physical and chemical crosslinking mechanisms occur simultaneously. The viscoelastic behavior of gels following different gelation processes was determined around the gel point. Their gel fractal dimensions were obtained using the BST-scaling model from large amplitude oscillatory shear results. The fractal dimension of hybrid gels is between 1.46 and 1.60, depending on the dominant crosslinking process. The main features of the Lissajous-Bowditch curves were determined for maturated gels that follow different gelation processes, and it is possible to observe the dominant gelation mechanism. The gelation kinetics process is followed by measuring the mean squared displacement (MSD) of microspheres embedded in gelatin solutions using diffusion wave spectroscopy, which in turn allows evaluating G'(ω) and G''(ω), the persistence length, and the mesh size as a function of time throughout the gelation process. The MSD, as a function of elapsed time from the start of the gelation process, follows a behavior that depends on the gelation processes. As time elapses after gelation starts, the persistence length of the unstructured, non-bonded flexible polymer sections decreases due to the formation of bonds. In the hybrid case, it is not a mixture of both processes; they are not independent when occurring simultaneously. The time evolution of the gel network's mesh size roughly follows an exponential decay.
RESUMO
HYPOTHESIS: The elastic contribution to the fluid dynamics of wormlike micellar solutions makes these fluids unique due to the distinctive self-assembled micellar network formed by tubular micelles. Measured mesoscopic scales of the micellar network related to the degree of entanglement can give guidelines for understanding the origin of elastic forces and their effect on rheological response. EXPERIMENTS: Different experiments were made as flow curves, rotating the internal or external cylinder in a Couette geometry, small and large oscillatory shear tests, and linear shear banding observations, all of them to determine how elastic forces modify the rheological behavior in systems made of different ratios of hexadecyltrimethylammonium bromide (CTAB)/sodium salicylate (NaSal) and different ratios of CTAB/NaNO3. Diffusive wave spectroscopy micro-rheology was also performed to measure the mean square displacements of microspheres embedded in the micellar fluids to obtain their high-frequency viscoelastic spectra. With this information, the entanglement index κ, the ratio of the total contour of the micelles to the entanglement length, was estimated and correlated with the rheological behavior. FINDINGS: The entanglement index is a valuable piece of information to understand the origin of the contribution of the elastic forces from a molecular point of view on the fluid dynamics of wormlike micelle solutions.