Sol/gel transition of oil/water microemulsions controlled by surface grafted triblock copolymer dodecyl–PEO(227)–dodecyl: molecular dynamics simulations with experimentally validated interaction potential

We studied a large range of identical spherical oil/water microemulsion (O/W-MI) volume fractions. The O/W-MIs are stabilized by cetylpyridinium chloride ionic surfactant (CpCl) and octanol cosurfactant and dispersed in salt water. We grafted different numbers of dodecyl–(polyEthylene oxide)(227)–dodecyl triblock copolymer that we note (n(D–PEO(227)–D)), where n varies from 0 to 12. We accomplished the grafting process by replacing a small amount of CpCl and octanol with the appropriate n(D–PEO(227)–D). The aim is to determine the interaction/structure relationship of the covered microemulsions. Precisely, we are interested in a quantitative investigation of the influence of volume fraction Φ, temperature (T), and n(D–PEO(227)–D) on the microemulsion sol/gel transition. To this end, we first study the uncoated microemulsion structure depending only on Φ. Second, we determine the coated microemulsions structure as a function of n(D–PEO(227)–D) for different Φ. Third, we examine the effect of temperature on the uncoated and coated microemulsion. We show that the sol/gel transition is controlled by the three main parameters, Φ, T, and n(D–PEO(227)–D). Accordingly, the uncoated microemulsion sol/gel transition, at ambient temperature, occurred for Φ ≃ 33.65%. By increasing Φ, the O/W-MIs show a glass state, which occurs, along with the gel state, at Φ ≃ 37% and arises clearly at Φ ≃ 60%. The coated O/W-MI sol/gel transition is found to be linearly dependent on n(D–PEO(227)–D) and takes place for Φ ≃ 26.5% for n(D–PEO(227)–D) = 12. Ordinarily, the decrease in temperature leads to gel formation of microemulsions for low Φ. Additionally, in this work, we found that the gelation temperature increases linearly with n(D–PEO(227)–D). Thus, the parameter n(D–PEO(227)–D) can control the sol/gel transition of the O/W-MIs at ambient temperature and moderate Φ.