Wormlike micelles (WLMs) formed from surfactants have attracted much attention for their ability to thicken water in a manner similar to water-soluble polymers. It is known that WLMs are cylindrical filaments that can attain very long contour lengths (∼few μm), akin to chains of polymers with ultra-high molecular weights (UHMWs). In this study, we aim to make a direct comparison between the thickening capabilities of WLMs and UHMW polymers. The chosen surfactant is erucyl dimethyl amidopropyl betaine (EDAB), a C-tailed zwitterionic surfactant known to form particularly long WLMs independent of salt. The chosen polymer is nonionic polyacrylamide (PAM) having an UHMW of 12 MDa. Both EDAB WLMs and the PAM show strong thickening capability in saline water at 25 °C, but the WLMs are more efficient. For example, a 1.0 wt% EDAB WLM sample has a similar zero-shear viscosity η (∼40 000 mPa s) to a 2.5 wt% PAM solution. When temperature is increased, both samples show an exponential reduction in viscosity, but the WLMs are more sensitive to temperature. Microstructural differences between the two systems are confirmed by data from small-angle neutron scattering (SANS) and cryo-transmission electron microscopy (cryo-TEM). As expected, the key differences are that the WLM chains have a larger core radius (R) and in turn, a longer persistence length (l) than the PAM chains.

Wormlike micelles (WLMs) are long, flexible cylindrical chains formed by the self-assembly of surfactants in semidilute solutions. Scientists have been fascinated by WLMs because of their similarities to polymers, while at the same time, the viscoelastic properties of WLM solutions have made them useful in a variety of industrial applications. To date, most studies on WLMs have been performed in water (i.e., a highly polar liquid), while there are a few examples of "reverse" WLMs in oils (i.e., highly nonpolar liquids). However, in organic solvents with lower polarity than water such as glycerol, formamide, and ethylene glycol, there have been no reports of WLMs thus far. Here, we show that it is indeed possible to induce a long-tailed cationic surfactant to assemble into WLMs in several of these solvents. To form WLMs, the surfactant is combined with a "binding" salt, i.e., one with a large organic counterion that is capable of binding to the micelles. Examples of such salts include sodium salicylate and sodium tosylate, and we find self-assembly to be maximized when the surfactant and salt concentrations are near-equimolar. Interestingly, the addition of a simple, inorganic salt such as sodium chloride (NaCl) to the same surfactant does not induce WLMs in polar solvents (although it does so in water). Thus, the design rules for WLM formation in polar solvents are distinct from those in water. Aqueous WLMs have been characterized at temperatures from 25 °C and above, but few studies have examined WLMs at much lower (e.g., subzero) temperatures. Here, we have selected a surfactant with a very low Krafft point (i.e., the surfactant does not crystallize out of solution upon cooling due to a cis-unsaturation in its tail) and a low-freezing solvent, viz. a 90/10 mixture of glycerol and ethylene glycol. In these mixtures, we find evidence for WLMs that persist down to temperatures as low as −20 °C. Rheological techniques as well as small-angle neutron scattering (SANS) have been used to characterize the WLMs under these conditions. Much like their aqueous counterparts, WLMs in polar solvents show viscoelastic properties, and accordingly, these fluids could find applications as synthetic lubricants or as improved antifreezing fluids.

The additive manufacturing of energetic materials has received worldwide attention. Here, an ink formulation is developed with only 10 wt% of polymers, which can bind a 90 wt% nanothermite using a simple direct‐writing approach. The key additive in the ink is a hybrid polymer of poly(vinylidene fluoride) (PVDF) and hydroxy propyl methyl cellulose (HPMC) in which the former serves as an energetic initiator and a binder, and the latter is a thickening agent and the other binder, which can form a gel. The rheological shear‐thinning properties of the ink are critical to making the formulation at such high loadings printable. The Young's modulus of the printed stick is found to compare favorably with that of poly(tetrafluoroethylene) (PTFE), with a particle packing density at the theoretical maximum. The linear burn rate, mass burn rate, flame temperature, and heat flux are found to be easily adjusted by varying the fuel/oxidizer ratio. The average flame temperatures are as high as ≈2800 K with near‐complete combustion being evident upon examination of the postcombustion products.