Hypothesis: Aqueous solutions of long-chain water-soluble sucrose ester surfactants exhibit non-trivial response to temperature variations, revealing a peak in viscosity around 40–50 ◦C. While previous investigations have explored the structures within sucrose stearate systems at various constant temperatures, a comprehensive understanding of the entire temperature dependence and the underlying molecular factors, contributing to this phenomenon is currently missing. Experiments: Temperature dependent properties and supramolecular structures formed in aqueous solutions of commercial sucrose palmitate were examined using SAXS/WAXS, DSC, optical microscopy, rheological measurements, NMR, and cryo-TEM. Findings: The underlying mechanism governing this unusual behavior is revealed and is shown to relate to the mono- to di-esters ratio in the solutions. Solutions primarily containing sucrose monoesters (monoesters molecules ≳ 98% of all surfactant molecules) exhibit behavior typical of nonionic surfactants, with minimal changes with temperature. In contrast, the coexistence of mono- and di-esters results in the formation of discrete monodisperse diester particles and a network of partially fused diester particles at low temperature. As the temperature approaches the diesters’ melting point, wormlike mixed micelles form, causing a viscosity peak. The height of this peak increases significantly with the diester concentration. Further temperature increase leads to fluidization of surfactant tails and formation of branched micelles, while excess diester molecules phase separate into distinct droplets.

The effects of antifoam and surfactant concentration on the foamability of solutions of an anionic (SLES) and nonionic (Brij 35) surfactants and a series of polyvinyl alcohols with 88% and 98% degree of hydrolysis and molecular masses between 31 and 205 kDa, were studied. Three methods which differ in the way of air incorporation were used for foaming – Bartsch test, shake test and Ultra Turrax. Mixed silicone oil-silica particles antifoam was studied. The antifoam was introduced in the foaming solution as pre-dispersed in organic solvent or as antifoam-in-water emulsion. It was shown that the antifoam is very active in the fast foaming methods (Bartsch and shake tests) for the slow adsorbing polymers PVA and has no any activity in the slow foaming method (Ultra Turrax) for the fast adsorbing surfactants with electrostatic stabilization (SLES). The efficiency of pre-dispersed in organic solvent antifoam is much higher as compared to that of emulsified antifoam, due to the faster segregation of the silica particles and silicone oil in the emulsified antifoam. The antifoam efficiency increases with antifoam concentration and with lowering the surfactant concentration. In a given foaming method, the antifoam efficiency is the highest in PVA solutions with 98% DH, intermediate for PVA with 88% DH and Brij 35, and the lowest for SLES solutions. At a certain degree of hydrolysis, the molecular mass of PVA has no significant effect on the antifoam activity. Good correlation between the antifoam efficiency and the stability of the pseudo emulsion film formed between the antifoam globule and the bubble surface is established, showing that the electrostatic repulsion is more efficient to prevent the entering of the antifoam globules on the air-water interface, as compared to the steric repulsion.

The surface, film, and foam properties of six polyvinyl alcohols (PVA) with different degrees of hydrolysis (DH) and molecular weights were studied and compared with the properties of nonionic Brij 35 and anionic SLES. Four different foaming methods were employed: the fast foaming method (Bartsch test), intermediate tests (shake test and Ultra Turrax), and slow foaming method (foam rise method) to assess the foamability at various bulk concentrations. The foamability data obtained from different foaming tests, utilizing various surfactant and polymeric concentrations, and differing foaming times, were shown to follow a universal master curve when plotted as relative foamability vs. scaled concentration. A new simple theoretical equation was derived to describe this universal curve, allowing for foamability prediction. The threshold surfactant concentration required to achieve 50% of the maximal foam volume under given conditions (used for scaling the bulk concentration) was found to decrease with foaming time and increase from slow foaming methods to fast foaming methods. When the experimental data are plotted against surface coverage, the results for PVA solutions exhibit intermediate behavior between nonionic surfactants, where a threshold surface coverage of 95% is required to achieve 50% of maximal foamability and anionic surfactants, where 30% surface coverage is sufficient to reach 50% of maximal foamability due to the action of electrostatic repulsion. This intermediate behavior observed in PVA solutions is attributed to the presence of a long-range steric repulsion arising from the adsorption of PVA molecules onto the bubble surfaces. This work advances the foam field by showing that the approach developed in Petkova et al. 2020 can be used for polymeric molecules and by deriving a new equation for foamability which is expected to be applicable for wide range of systems.

The effect of the fatty alcohols (CnOH), fatty acids (CnAc), alkyltrimethyl ammonium bromides (CnTAB), alkyl sulfates (CnSO4Na) and alkyl acetates (CnAcet), with n varied between 6 and 12 C-atoms, on the surface properties of 0.5 wt% mixed solutions of sodium laurylether sulfate (SLES) and cocoamidopropyl betaine (CAPB) was studied. It was shown that the equilibrium surface tension decreases with increasing the cosurfactant chain-length. For example, the addition of C12OH to SLES+CAPB solution decreases its surface tension from 29 down to 22 mN/m. Both the dynamic surface tension and the characteristic adsorption time pass through a deep minimum when cationic or nonionic cosurfactants with 8 or 10 C-atoms are added. The minimum is particularly deep for nonionic surfactants with small head group (acids and alcohols) which destabilize the micelles and increase the rate of surfactant adsorption. The addition of anionic cosurfactants does not change the dynamic and equilibrium surface tensions of SLES+CAPB system. A strong correlation between the dynamic surface tension of diluted surfactant solutions (0.5 wt%) and the viscosity of the respective concentrated solutions (10 wt%) is established and explained for nonionic cosurfactants.

The effects of the charge, size and concentration of counter-ions (Na+, NH4+, K+, Mg2+, Ca2+ and Al3+) on the rheological properties of 300 mM SLES+CAPB surfactant solutions are studied and compared with results available in the literature for the effects of Na+ and K+ on SLES solution. The results show that all counter-ions studied are able to induce formation of wormlike micelles in a certain concentration range – as a consequence, the solution viscosity passes through a high maximum as a function of salt concentration. The salt concentration leading to maximum in the solution viscosity decreases with increasing the charge density of the counter-ion, defined as the ratio of the charge of the counterion and its hydrated radius, Z/R. The maximum viscosity in the salt curve decreases with increasing the hydrated radius of the counter-ion. The addition of CAPB to SLES leads to about 10-fold higher viscosity and to higher maximum viscosity in the presence of K+ as compared to Na+, whereas the opposite trend was observed for SLES alone. These effects are attributed to the interplay between the anionic and zwitterionic surfactants, and the electrolyte in the mixed SLES+CAPB system.