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  1. Danov KD, Stanimirova RD, Kralchevsky PA, Basheva ES, Ivanova VI, Petkov JT
    J Colloid Interface Sci, 2015 Nov 1;457:307-18.
    PMID: 26196714 DOI: 10.1016/j.jcis.2015.07.020
    The interest to sulfonated methyl esters of fatty acids (SME) has been growing during the last decade, because these surfactants are considered as an environmentally friendly and renewable alternative of the linear alkyl-benzene sulfonates (LAS). Here, we present a quantitative study on the properties of aqueous SME solutions, and especially on their surface tension isotherms, critical micelle concentration (CMC) and its dependence on the concentration of added NaCl. It is demonstrated that the CMC of an ionic surfactant determined by electrical conductivity is insensitive to the presence of a small nonionic admixture, so that the CMC values determined by conductivity represent the CMC of the pure surfactant. Using SME as an example, we have demonstrated the application of a new and powerful method for determining the physicochemical parameters of the pure ionic surfactant by theoretical data analysis ("computer purification") if the used surfactant sample contains nonionic admixtures, which are present as a rule. This method involves fits of the experimental data for surface tension and conductivity by a physicochemical model based on a system of mass-balance, chemical-equilibrium and electric-double-layer equations, which allows us to determine the adsorption and micellization parameters of C12-, C14-, C16- and C18-SME, as well the fraction of nonionic admixtures (if any). Having determined these parameters, we can further predict the interfacial and micellization properties of the surfactant solutions, such as surface tension, adsorption, degree of counterion binding, and surface electric potential at every surfactant, salt and co-surfactant concentrations.
  2. Danov KD, Stanimirova RD, Kralchevsky PA, Slavova TG, Yavrukova VI, Ung YW, et al.
    J Colloid Interface Sci, 2021 Nov;601:474-485.
    PMID: 34090025 DOI: 10.1016/j.jcis.2021.05.147
    HYPOTHESIS: Many ionic surfactants with wide applications in personal-care and house-hold detergency show limited water solubility at lower temperatures (Krafft point). This drawback can be overcome by using mixed solutions, where the ionic surfactant is incorporated in mixed micelles with another surfactant, which is soluble at lower temperatures.

    EXPERIMENTS: The solubility and electrolytic conductivity for a binary surfactant mixture of anionic methyl ester sulfonates (MES) with nonionic alkyl polyglucoside and alkyl polyoxyethylene ether at 5 °C during long-term storage were measured. Phase diagrams were established; a general theoretical model for their explanation was developed and checked experimentally.

    FINDINGS: The binary and ternary phase diagrams for studied surfactant mixtures include phase domains: mixed micelles; micelles + crystallites; crystallites, and molecular solution. The proposed general methodology, which utilizes the equations of molecular thermodynamics at minimum number of experimental measurements, is convenient for construction of such phase diagrams. The results could increase the range of applicability of MES-surfactants with relatively high Krafft temperature, but with various useful properties such as excellent biodegradability and skin compatibility; stability in hard water; good wetting and cleaning performance.

  3. Yavrukova VI, Danov KD, Slavova TG, Stanimirova RD, Wei Ung Y, Tong Kim Suan A, et al.
    J Colloid Interface Sci, 2024 Jan 22;660:896-906.
    PMID: 38280282 DOI: 10.1016/j.jcis.2024.01.127
    HYPOTHESIS: Methyl ester sulfonates (MES) show limited water solubility at lower temperatures (Krafft point). One way to increase their solubility below their Krafft points is to incorporate them in anionic surfactant micelles. The electrostatic interactions between the ionic surfactant molecules and charged micelles play an important role for the degree of MES solubility.

    EXPERIMENTS: The solubility and electrolytic conductivity for binary and ternary surfactant mixtures of MES with anionic sodium alpha olefin sulfonate (AOS) and sodium lauryl ether sulfate with two ethylene oxide groups (SLES-2EO) at 5 °C during long-term storage were measured. Phase diagrams were established; a general phase separation theoretical model for their explanation was developed and checked experimentally.

    FINDINGS: The binary and ternary phase diagrams for studied surfactant mixtures include phase domains: mixed micelles; micelles + crystallites; crystallites, and molecular solution. The proposed general phase separation model for ionic surfactant mixtures is convenient for construction of such complex phase diagrams and provides information on the concentrations of all components of the complex solution and on the micellar electrostatic potential. The obtained maximal MES mole fraction of transparent micellar solutions could be of interest to increase the range of applicability of MES-surfactants.

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