Wormlike micelles (WLMs) of surfactants are widely used as smart thickeners in various applications, including enhanced oil recovery. However, their thickening ability needs to be improved both at ambient and elevated temperatures. In the present paper, we propose to enhance the viscoelastic properties of surfactant solutions by incorporating carboxymethylated cellulose nanocrystals (CNCs). Upon addition of CNCs, dilute solutions of short WLMs acquire viscoelasticity and then transition into a viscoelastic solid state. This process is accompanied by an increase in the viscosity and storage modulus by up to five and four orders of magnitude, respectively. The observed effect of CNCs on the storage modulus and viscosity is greater than that of any of the previously studied WLM-CNC systems. It is attributed to the formation of a network of fibrillar-like aggregates composed of WLMs and CNCs, which was confirmed by cryo-TEM data. To our knowledge, such kind of aggregates have not been observed before. When CNCs are added to a transient network of long entangled WLMs, the viscoelastic solution transitions into a viscoelastic solid state, which results in an increase in the viscosity and storage modulus by up to two orders of magnitude. CNCs provide the WLM solution with greater resistance to heating, such that the storage modulus remains almost unchanged when the temperature increases from 20 to 70 °C. Moreover, a heat-induced gelation was observed. It was shown that higher concentrations of nanocrystals lower the critical gel temperature, indicating that they promote the gelation of the mixture. SANS data revealed that the local structures of both micelles and nanocrystals are preserved in the mixed system upon heating. According to ITC data, at room temperature, the interaction between surfactant ions and similarly charged nanocrystals is governed by both enthalpy and entropy, which suggests that hydrogen bonding plays a major role in this process, although hydrophobic interactions may also be involved. When the temperature increases to 60 °C, the aggregation becomes entropy-driven, indicating that hydrophobic interactions begin to dominate. The results obtained can expand the range of practical applications of WLMs as thickening agents, in particular, to higher-temperature conditions in deeper oil wells.
Avdeev et al. (Sun,) studied this question.