We report experiments on two series of wormlike micellar solutions that comprise octyl trimethylammonium bromide/sodium oleate (OTAB/NaOA) and cetylpyridinium chloride/sodium salicylate (CPCl/NaSal) using a capillary breakup extensional rheometer (CaBER) and a dripping onto substrate (DoS) technique. These wormlike micellar systems show a peak in zero shear viscosity or in the shear relaxation time beyond a critical surfactant or salt concentration. Prior cryogenic transmission electron microscopy imaging has indicated that the system based on OTAB/NaOA experiences a transition from linear to shorter linear micelles (L-L) beyond the viscosity peak. However, the linear wormlike micelles based on CPCl/NaSal form branched networks beyond the viscosity peak (L-B). In this work, we investigate whether the extensional rheology is sensitive to these two different microstructural transitions. In particular, we attempt to develop a criterion based on the extensional flow parameters in order to distinguish these two systems from each other. In addition, we probe the possibility of flow-induced micellar breakage imposed by capillary breakup extensional experiments. Our results indicate that at a given zero shear viscosity, the branched wormlike micelles based on CPCl/NaSal exhibit a longer filament lifetime tfil than the linear wormlike micelles. However, beyond the critical concentration, the linear wormlike micelles based on OTAB/NaOA exhibit significantly shorter filament lifetimes than their linear counterparts at concentrations below the viscosity peak. More importantly, we show that the filament lifetime scales differently with zero shear viscosity η0 in these two systems. For L-B transition, tfil∝η01.1 below the viscosity peak and tfil∝η00.76 above the viscosity peak. However, for L-L transition, this scaling remains the same for concentrations below and above the viscosity peak and reads as tfil∝η00.5. These findings provide a novel criterion to distinguish these two types of microstructural transitions in wormlike micelles. On the other hand, we demonstrate that the Trouton ratio, filament lifetime, and the extensional relaxation time measured by CaBER technique are all lower than the ones obtained by DoS method. The latter result provides the first evidence for strong nonlinear effects (e.g., flow-induced micellar breakage) in capillary breakup extensional flows of wormlike micelles.

The design and synthesis of a new class of thermally-labile poly­(β-thioester)­s is reported. Aliphatic azo linkages were incorporated into the main chain of the polymers to allow for degradation to lower molecular weights upon heating. These polymers displayed a temperature-dependent degradation profile with a significant increase in decomposition rate as the temperature was raised from 60 to 95 °C. This approach was further extended to prepare amphiphilic triblock copolymers containing poly­(β-thioester)­s and poly­(ethylene glycol) (PEG). The resulting block copolymers were capable of self-assembly into micelles in water. Moreover, the assembled nanoparticles underwent dissociation as a result of exposure to heat.

We report experiments on the flow of wormlike micellar solutions based on cetylpyridinium chloride/sodium salicylate past a falling sphere via a combination of particle tracking velocimetry, particle image velocimetry, rheology, and flow induced birefringence (FIB). Recent studies have shown that beyond a critical extensional Deborah number, a falling sphere in wormlike micelles never reaches a constant terminal velocity; instead, it settles with an unsteady velocity. This behavior is linked to the wormlike micellar chain scission in the wake of the sphere. Similar instabilities in viscoelastic polymer solutions, where polymer chain scission is highly unlikely, are thought to be the results of a single-mode relaxation spectrum of the polymer chains or the asymmetry in the polymer chain extensions on the flanks of the falling sphere. In this paper, we examine the effect of micellar relaxation spectrum and gradients in micellar extensions on sphere instability in wormlike micelles over a wide range of flow parameters (10−2 < DeE < 40.7 and 10−6 < Re < 10). In wormlike micelles with a single-mode relaxation spectrum, the sphere instability occurs for DeE ≥ 2.6. However, for similar conditions (2.5 ≤ DeE ≤ 40.7 and 10−2 < Re < 10), spheres never exhibit unsteady motion in the wormlike micelles with a broad spectrum of relaxation times. This indicates the importance of the micellar relaxation spectrum on dynamics of sphere sedimentation in wormlike micelles. We show that a criterion based on the ratio of dissipated energy to the stored elastic energy of micelles can successfully describe the effect of micellar relaxation spectrum on sphere sedimentation dynamics. In addition, for conditions that give rise to sphere instability, FIB indicates that micellar extensions on sphere sideways are perfectly symmetric.

We report experiments on flow of wormlike micellar solutions past a falling sphere. By increasing the salt-to-surfactant concentration ratio, and beyond a viscosity peak, wormlike micelles experience a transition from...