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With high-pressure pendant-drop tensiometry, the interfacial tension (γ) and surface excess (Γ∞) for a family of ionic surfactants with identical phosphate headgroups and varying fluorocarbon and hydrocarbon tail structures were examined at the water−CO2 interface. To compensate for the unusually weak CO2−surfactant tail interactions, we designed hydrocarbon tails with weak tail−tail interactions to achieve a more favorable hydrophilic−CO2-philic balance. Branching of hydrocarbon surfactant tails is shown to lead to more favorable adsorption at the interface, closer to that of fluorocarbon surfactants. γ for a double-tail hydrocarbon phosphate surfactant with a relatively high degree of tail branching was lowered from the water−CO2 binary interface value of about 20 mN/m at 25 °C and 340 bar to 3.7 mN/m. This reduction in γ is attributed to both a decrease in the free volume between tails at the interface and reduced tail−tail interactions. In addition to tail structure, the effects of surfactant counterion, salt concentration, temperature, and CO2 density on γ and Γ∞ were investigated. The hydrophilic−CO2-philic balances of these surfactants are mapped by investigating changes in interfacial tension with these formulation variables. Low-molecular-weight branched hydrocarbon ionic surfactants are shown to stabilize concentrated CO2-in-water emulsions for greater than 1 h.

Anionic phosphodiester surfactants, possessing either two fluorinated chains (F/F) or one hydrocarbon chain and one fluorinated chain (H/F), were synthesized and evaluated for solubility and self-assembly in liquid and supercritical carbon dioxide. Several surfactants, of both F/F and H/F types and having varied counterions, were found to be capable of solubilizing water-in-CO2 (W/C), via the formation of microemulsions, expanding upon the family of phosphate fluorosurfactants already found to stabilize W/C microemulsions. Small-angle neutron scattering was used to directly characterize the microemulsion particles at varied temperatures, pressures, and water loadings, revealing behavior consistent with previous results on W/C microemulsions.

The existence of microemulsions in the system composed of phosphate-based fluorosurfactant, water, and supercritical CO2 is demonstrated by small-angle neutron scattering experiments. A computer simulation study performed on a reverse micelle created in this system shows that the micelle remains stable over a 4 ns time period of the simulation. While the data obtained from the experiments provide information about the size of the reverse micelle, the data obtained from the simulations provide additional information about the shape and structure of such a micelle.

The foreseeable future should find carbon dioxide used in an ever-increasing number of industrial applications, from materials production to lithography. Many such processes will involve the use of amphiphilic compounds, which have greatly enhanced the versatility and potential of CO2 as a solvent. In a relatively short period of time, research on the self-assembly of amphiphilic polymers in CO2 has undergone remarkable maturation. The growth is largely due to strong fundamental and practical interest, as well as a cache of techniques available to characterize the self-assembly process. This article serves to summarize what has thus far been discovered about polymer self-assembly in CO2, what needs further examination, and where the field is headed.

A total of 24 dicationic geminis surfactants were synthesized, having a 2-butynyl spacer and chain lengths varying from 8 to 18 carbons. Geminis with more flexible butyl spacers were also synthesized for comparison purposes. Tensiometry gave critical micelle concentration (cmc) values, surface activity, and Gibbs areas. Film studies on the C18 geminis gave liftoff and collapse areas. The acetylenic geminis behave normally with the log cmc values decreasing linearly with chain length for all the dibromide salts. Anomalous behavior occurred, however, with the C18 gemini having a butyl spacer. It was found that cmc data correlate with spacer area, a relationship ascribed to packing constraints on curved surfaces and, possibly, to steric inhibition of ion binding. The effects are accentuated with the C18 surfactants. Geminis with heterocyclic headgroups were examined.

Product yields measured by high-performance liquid chromatography from chemical trapping of Cl^-, Br^-, and H2O by an aggregate-bound arenediazonium ion in cetyltrialkylammonium halide {(CTRA)X, R = Me, Et, n-Pr, and n-Bu; X = Cl, Br}, micelles are used to estimate, simultaneously, interfacial counterion, Xm, and water, H2Om, concentrations as a function of [(CTRA)X] and tetramethylammonium halide concentrations, [(TMA)X]. The results are interpreted by using a two-site pseudophase model. Values of Xm and H2Om are estimated by assuming that when the product yields from reaction of a long-tail aggregate-bound arenediazonium ion in micelles are the same as the product yields from reaction of its short chain analogue in an aqueous quaternary ammonium ion salt solution, then Xm = [Xw] and H2Om = [H2Ow] in those solutions. The results show that Xm and H2Om are functions of headgroup size, surfactant concentration, and aqueous counterion concentration and type. Plots of Xm against [(CTRA)X] at a series of salt concentrations fall on separate curves. Xm increases gradually with added (CTRA)X and almost incrementally with added (TMA)X. However, plots of Xm and H2Om are essentially continuous functions of the aqueous counterion concentration, [Xw], at constant degree of micelle ionization, α. Three factors affect the shapes of these profiles. (a) An initial rapid increase in Xm is attributed to a salt-induced contraction of the micellar interfacial volume. (b) Above ca. 0.1 M [Xw], an incremental (slope of 1) increase in Xm with added counterion for (CTEA)Br, (CTPA)Br, and (CTBA)Br micelles is attributed to free movement counterions and co-ions between the interfacial region of the micelles (up to the micellar core) and the aqueous pseudophase. (c) Xm increases markedly for (CTMA)Br and (CTMA)Cl at their respective sphere-to-rod transitions ca. 0.1 M [Brw] and ca. 1.2 M [Clw]. The increases in Xm are accompanied by concomitant decreases in H2Om. Specific salt-induced rod formation is attributed to dehydration (partial) and tight ion pair formation between surfactant headgroups and counterions. Phase separation of (CTBA)Br micelles in 0.5 M (TMA)Br occurs when the interfacial water concentration is too low to maintain micelle stability. The dependence of Xm on [Xw] contradicts assumptions in the original pseudophase ion exchange model for aggregate effects on chemical reactivity that can be corrected, in part, by setting Xm equal to the sum the aqueous and interfacial counterion concentrations.