Jocelyn Alice Peach

Supercritical carbon dioxide: a solvent like no other

Summary Supercritical carbon dioxide (scCO2) could be one aspect of a significant and necessary movement towards green chemistry, being a potential replacement for volatile organic compounds (VOCs). Unfortunately, carbon dioxide has a notoriously poor solubilising power and is famously difficult to handle. This review examines attempts and breakthroughs in enhancing the physicochemical properties of carbon dioxide, focusing primarily on factors that impact solubility of polar and ionic species and attempts to enhance scCO2 viscosity.

Shape Modification of Water-in-CO2 Microemulsion Droplets through Mixing of Hydrocarbon and Fluorocarbon Amphiphiles

An oxygen-rich hydrocarbon (HC) amphiphile has been developed as an additive for supercritical CO2 (scCO2). The effects of this custom-designed amphiphile have been studied in water-in-CO2 (w/c) microemulsions stabilized by analogous fluorocarbon (FC) surfactants, nFG(EO)2, which are known to form spherical w/c microemulsion droplets. By applying contrast-variation small-angle neutron scattering (CV-SANS), evidence has been obtained for anisotropic structures in the mixed systems. The shape transition is attributed to the hydrocarbon additive, which modifies the curvature of the mixed surfactant films. This can be considered as a potential method to enhance physicochemical properties of scCO2 through elongation of w/c microemulsion droplets. More importantly, by studying self-assembly in these mixed systems, fundamental understanding can be developed on the packing of HC and FC amphiphiles at water/CO2 interfaces. This provides guidelines for the design of fluorine-free CO2 active surfactants, and therefore, practical industrial scale applications of scCO2 could be achieved.

Alternative Route to Nanoscale Aggregates with a pH-Responsive Random Copolymer

A random copolymer, poly(methyl methacrylate-co-2-dimethylaminoethyl methacrylate) (poly(MMA-co-DMAEMA)) is shown to form nanoscale aggregates (NAs) (∼20 nm) at copolymer concentrations ≥10% w/w, directly from the preformed surfactant-stabilized latex (∼120 nm) in aqueous solution. The copolymer is prepared by conventional emulsion polymerization. Introducing a small mole fraction of DMAEMA (∼10%) allows the copolymer hydrophilicity to be adjusted by the pH and external temperature, generating NAs with tuneable sizes and a defined weight-average aggregation number, as observed by dynamic light scattering (DLS) and small-angle neutron scattering (SANS). These NAs are different from the so-called mesoglobular systems and are insensitive to temperature at fixed pH. The relatively broad chemical composition distribution of the copolymer and lumpy (or blocky but not diblock) incorporation of DMAEMA mean that the NAs cannot be simply thought of as conventional polymer micelles. In the acidic pH regime, the amphiphilic copolymer exhibits a defined critical assembly concentration (CAC) and a minimum air-water surface tension of 45.2 mN m-1. This copolymer represents a convenient route to self-assembled NAs, which form directly in aqueous dispersions after pH and temperature triggers, rather than the typically applied (and time-consuming) water-induced micellization approach for common polymer micelles.

The internal structure of poly(methyl methacrylate) latexes in nonpolar solvents

HYPOTHESIS Poly(methyl methacrylate) (PMMA) latexes in nonpolar solvents are an excellent model system to understand phenomena in low dielectric media, and understanding their internal structure is critical to characterizing their performance in both fundamental studies of colloidal interactions and in potential industrial applications. Both the PMMA cores and the poly(12-hydroxystearic acid) (PHSA) shells of the latexes are known to be penetrable by solvent and small molecules, but the relevance of this for the properties of these particles is unknown. EXPERIMENTS These particles can be prepared in a broad range of sizes, and two PMMA latexes dispersed in n-dodecane (76 and 685nm in diameter) were studied using techniques appropriate to their size. Small-angle scattering (using both neutrons and X-rays) was used to study the small latexes, and analytical centrifugation was used to study the large latexes. These studies enabled the calculation of the core densities and the amount of solvent in the stabilizer shells for both latexes. Both have consequences on interpreting measurements using these latexes. FINDINGS The PHSA shells are highly solvated (∼85% solvent by volume), as expected for effective steric stabilizers. However, the PHSA chains do contribute to the intensity of neutron scattering measurements on concentrated dispersions and cannot be ignored. The PMMA cores have a slightly lower density than PMMA homopolymer, which shows that only a small free volume is required to allow small molecules to penetrate into the cores. Interestingly, the observations are essentially the same, regardless of the size of the particle; these are general features of these polymer latexes. Despite the latexes being used as a model physical system, the internal chemical structure is complex and must be fully considered when characterizing them.

Charging poly(methyl methacrylate) latexes in nonpolar solvents: Effect of particle concentration

The electrophoresis of a well-established model system of charged colloids in nonpolar solvents has been studied as a function of particle volume fraction at constant surfactant concentration. Dispersions of poly(12-hydroxystearic acid)-stabilized poly(methyl methacrylate) (PMMA) latexes in dodecane were prepared with added Aerosol OT surfactant as the charging agent. The electrophoretic mobility (μ) of the PMMA latexes is found to decrease with particle concentration. The particles are charged by a small molecule charging agent (AOT) at finite concentration, and this makes the origin of this decrease in μ unclear. There are two suggested explanations. The decrease could either be due to the reservoir of available surfactant being exhausted at high particle concentrations or the interactions between the charged particles at high particle number concentrations. Contrast-variation small-angle neutron scattering measurements of PMMA latexes and deuterated AOT-d34 surfactant in latex core contrast-matched solvent were used to study the former, and electrokinetic modeling was used to study the latter. As the same amount of AOT-d34 is found to be incorporated with the latexes at all volume fractions, the solvodynamic and electrical interactions between particles are determined to be the explanation for the decrease in mobility. These measurements show that, for small latexes, there are interactions between the charged particles at all accessible particle volume fractions and that it is necessary to account for this to accurately determine the electrokinetic ζ potential.