Rheo-optics of giant micelles: SALS patterns of cetyltrimethylammonium tosylate solutions in presence of sodium bromide

Abstract

In this work, we present a systematic study based on Small-Angle Light Scattering (SALS) patterns of the simple shear flow response of semi-diluted solutions of cetyltrimethylammonium tosylate (CTAT; 5.5 $wt.\text{\%}$ - 0.12 M) in the presence of sodium bromide (NaBr) at different $\left[NaBr\right]=\{0,0.12,0.19,0.25,0.3\}$ M concentrations. We evidence a relationship between rheological and light scattering data that reveals a transition into a fast-breaking regime in the dynamics of wormlike micelles formed by the CTAT/NaBr system (Macías et al., 2011; Fierro et al., 2021). This transition into a micellar fast-breaking regime with salt addition ($\left[NaBr\right]\ge 0$) appears marked by the following features: (i) a decrease in the relaxation time of the material ${\lambda }_0$, accompanied by (ii) a decrease of the viscosity level at low shear rates ${\eta }_0$ (Macías et al., 2011; Fierro et al., 2021; Schubert et al., 2003; Alkschbirs et al., 2015; Bandyopadhyay et al., 2003). With these, (iii) the formation of butterfly-like patterns is recorded originating from concentration fluctuations, evolution that is accompanied by: (iv) shear banding in the form of non-monotonic flow curves and (v) slow oscillatory transient responses in start-up flow tests captured theoretically with the Bautista–Manero–Puig (BMP) model. In addition, the Cox–Merz rule is fulfilled at molar salt-to-surfactant ratios of $R\ge 1.5$. This results in shorter structure-recovery time-scales than the characteristic-time of the flow (Macías et al., 2011; Fierro et al., 2021; Manero et al., 2002). In the case of the elastic modulus $G_0$, the variation was small, which suggests a transition from an entangled to a multiconnected network, as suggested by Kadoma & van Egmond (1997), Kadoma et al. (1997) and Fierro et al. (2021). From a theoretical perspective, we provide predictions for the shear–stress and the first normal-stress growth coefficients in transient start-up simple shear flow using the BMP model. Here, banding $R$=1.5 solutions display overshot responses at relatively high shear rates ($\dot{\gamma }=10-30$ $s^{-1}$), in-line with experimental findings on the start-up flow of wormlike micellar solutions (Soltero et al., 1999; Lerouge et al., 2004; Hu & Lips 2005; Pipe et al., 2010; Mohammadigoushki et al., 2019). Our results are consistent with those reported in other investigations (Macías et al., 2011; Fierro et al., 2021; Schubert et al., 2003; Alkschbirs et al., 2015; Bandyopadhyay et al., 2003; Kadoma et al., 1997; Soltero et al., 1999; Lerouge et al., 2004; Hu & Lips 2005; López-Barrón et al., 2014) and reveal the influence of the Br${}^{-}$-ion used on the mechanical and optical response of the CTAT-NaBr system.