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Fulltext Properties of the micelles of sulfonated methyl esters determined from the stepwise thinning of foam films and by rheological measurements

Basheva ES, Danov KD, Radulova GM, Kralchevsky PA, Xu H, Ung YW, et al.

J Colloid Interface Sci, 2019 Mar 07;538:660-670.
PMID: 30572230 DOI: 10.1016/j.jcis.2018.12.034

HYPOTHESES: The micellar solutions of sulfonated methyl esters (SME) are expected to form stratifying foam films that exhibit stepwise thinning. From the height of the steps, which are engendered by micellar layers confined in the films, we could determine the micelle aggregation number, surface electric potential, and ionization degree. Moreover, addition of the zwitterionic surfactant cocamidopropyl betaine (CAPB) is expected to transform the small spherical micelles of SME into giant wormlike aggregates.
EXPERIMENTS: Stratifying films from SME solutions are formed and the heights of the steps are recorded. The viscosity of mixed SME + CAPB solutions is measured at various concentrations and weight ratios of the two surfactants.
FINDINGS: By theoretical analysis of the foam film data, we established that at 30-100 mM SME spherical micelles are formed and their aggregation number was determined. The addition of calcium ions, as in hard water, does not produce significant effect. However, SME and CAPB exhibit a strong synergism with respect to micelle growth as indicated by the high solution's viscosity. For this reason, the SME + CAPB mixtures represent a promising system for formulations in personal-care and house-hold detergency, having in mind also other useful properties of SME, such as high hard water tolerance, biodegradability and skin compatibility.
Rheology of mixed solutions of sulfonated methyl esters and betaine in relation to the growth of giant micelles and shampoo applications

Yavrukova VI, Radulova GM, Danov KD, Kralchevsky PA, Xu H, Ung YW, et al.

Adv Colloid Interface Sci, 2020 Jan;275:102062.
PMID: 31718784 DOI: 10.1016/j.cis.2019.102062

This is a review article on the rheological properties of mixed solutions of sulfonated methyl esters (SME) and cocamidopropyl betaine (CAPB), which are related to the synergistic growth of giant micelles. Effects of additives, such as fatty alcohols, cocamide monoethanolamine (CMEA) and salt, which are expected to boost the growth of wormlike micelles, are studied. We report and systematize the most significant observed effects with an emphasis on the interpretation at molecular level and understanding the rheological behavior of these systems. The experiments show that the mixing of SME and CAPB produces a significant rise of viscosity, which is greater than in the mixed solutions of sodium dodecyl sulfate and CAPB. The addition of fatty alcohols, CMEA and cationic polymer, leads to broadening of the synergistic peak in viscosity without any pronounced effect on its height. The addition of NaCl leads to a typical salt curve with high maximum, but in the presence of dodecanol this maximum is much lower. At lower salt concentrations, the fatty alcohol acts as a thickener, whereas at higher salt concentrations - as a thinning agent. Depending on the shape of the frequency dependences of the measured storage and loss moduli, G' and G", the investigated micellar solutions behave as systems of standard or nonstandard rheological behavior. The systems with standard behavior obey the Maxwell viscoelastic model (at least) up to the crossover point (G' = G") and can be analyzed in terms of the Cates reptation-reaction model. The systems with nonstandard rheological behavior obey the Maxwell model only in a restricted domain below the crossover frequency; they can be analyzed in the framework of an augmented version of the Maxwell model. The methodology for data analysis and interpretation could be applied to any other viscoelastic micellar system.

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