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.

Trimethylsilyl hedgehogs - a novel class of super-efficient hydrocarbon surfactants.

Presented here are the results for a novel class of hydrocarbon surfactants, termed trimethylsilyl hedgehogs (TMS-hedgehogs), due to the presence of silicon in the tails. By comparing the surface properties of these hybrid hedgehogs to purely hydrocarbon equivalents, links between performance and the structure are made. Namely, by controlling the molecular volume of the surfactant fragments, improvements can be made in surface coverage, generating lower surface energy monolayers. Small-angle neutron scattering (SANS) data have been collected showing that these novel surfactants aggregate to form ellipsoidal micelles which grow with increasing concentration. This study highlights the sensitive relationship between surface tension and the surfactant chain, for designing new super-efficient surfactants close to the limit of the lowest surface tensions possible.

Solubilisation of oils in aqueous solutions of a random cationic copolymer.

HYPOTHESIS: Reports of random copolymers capable of solubilising hydrophobic oils are rare. This is primarily because random copolymers are unlikely to self-assemble into suitable aggregates (or micelles) in water. A random copolymer with a "blocky" (or lumpy) microstructure may have potential to solubilise hydrophobic oils in water. This type of polymer would have advantages over block copolymers which are more laborious and costly to synthesise. EXPERIMENTS: The solubilising capacity of a blocky random copolymer, namely poly(methyl methacrylate-co-2-dimethylaminoethyl methacrylate) (PMMA-co-PDMAEMA) is assessed by UV-visible spectroscopy and compared with common reference surfactants. The relative solubilising performance of random copolymers (across a narrow range of DMAEMA mol % fraction) for aromatic and aliphatic oils was also studied. The morphology of the aggregates was monitored as a function of the solubilisation capacity by small-angle neutron scattering (SANS) and dynamic-light scattering (DLS). FINDINGS: Similarly to well-defined block copolymers, these random copolymers have a specific preference for solubilising aromatic over aliphatic oils. Increasing hydrophobicity of the copolymer enhances the solubilisation capacity. SANS has highlighted that aggregates become swollen and more uniform/spherical with increasing concentration of aromatic solubilisate, and that the aromatic solubilisate partitions throughout the random copolymer aggregates.

Tuning Micellar Structures in Supercritical CO2 Using Surfactant and Amphiphile Mixtures.

For equivalent micellar volume fraction (ϕ), systems containing anisotropic micelles are generally more viscous than those comprising spherical micelles. Many surfactants used in water-in-CO2 (w/c) microemulsions are fluorinated analogues of sodium bis(2-ethylhexyl) sulfosuccinate (AOT): here it is proposed that mixtures of CO2-philic surfactants with hydrotropes and cosurfactants may generate elongated micelles in w/c systems at high-pressures (e.g., 100-400 bar). A range of novel w/c microemulsions, stabilized by new custom-synthesized CO2-phillic, partially fluorinated surfactants, were formulated with hydrotropes and cosurfactant. The effects of water content (w = [water]/[surfactant]), surfactant structure, and hydrotrope tail length were all investigated. Dispersed water domains were probed using high pressure small-angle neutron scattering (HP-SANS), which provided evidence for elongated reversed micelles in supercritical CO2. These new micelles have significantly lower fluorination levels than previously reported (6-29 wt % cf. 14-52 wt %), and furthermore, they support higher water dispersion levels than other related systems (w = 15 cf. w = 5). The intrinsic viscosities of these w/c microemulsions were estimated based on micelle aspect ratio; from this value a relative viscosity value can be estimated through combination with the micellar volume fraction (ϕ). Combining these new results with those for all other reported systems, it has been possible to "map" predicted viscosity increases in CO2 arising from elongated reversed micelles, as a function of surfactant fluorination and micellar aspect ratio.

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.

Sulfosuccinate and Sulfocarballylate Surfactants As Charge Control Additives in Nonpolar Solvents.

A series of eight sodium sulfonic acid surfactants with differently branched tails (four double-chain sulfosuccinates and four triple-chain sulfocarballylates) were studied as charging agents for sterically stabilized poly(methyl methacrylate) (PMMA) latexes in dodecane. Tail branching was found to have no significant effect on the electrophoretic mobility of the latexes, but the number of tails was found to influence the electrophoretic mobility. Triple-chain, sulfocarballylate surfactants were found to be more effective. Several possible origins of this observation were explored by comparing sodium dioctylsulfosuccinate (AOT1) and sodium trioctylsulfocarballylate (TC1) using identical approaches: the inverse micelle size, the propensity for ion dissociation, the electrical conductivity, the electrokinetic or ζ potential, and contrast-variation small-angle neutron scattering. The most likely origin of the increased ability of TC1 to charge PMMA latexes is a larger number of inverse micelles. These experiments demonstrate a small molecular variation that can be made to influence the ability of surfactants to charge particles in nonpolar solvents, and modifying molecular structure is a promising approach to developing more effective charging agents.

Solid mesostructured polymer-surfactant films at the air-liquid interface.

Pioneering work by Edler et al. has spawned a new sub-set of mesostructured materials. These are solid, self-supporting films comprising surfactant micelles encased within polymer hydrogel; composite polymer-surfactant films can be grown spontaneously at the air-liquid interface and have defined and controllable mesostructures. Addition of siliconalkoxide to polymer-surfactant mixtures allows for the growth of mesostructured hybrid polymer-surfactant silica films that retain film geometry after calcinations and exhibit superior mechanical properties to typically brittle inorganic films. Growing films at the air-liquid interface provides a rapid and simple means to prepare ordered solid inorganic films, and to date the only method for generating mesostructured films thick enough (up to several hundred microns) to be removed from the interface. Applications of these films could range from catalysis to encapsulation of hydrophobic species and drug delivery. Film properties and mesostructures are sensitive to surfactant structure, polymer properties and polymer-surfactant phase behaviour: herein it will be shown how film mesostructure can be tailored by directing these parameters, and some interesting analogies will be drawn with more familiar mesostructured silica materials.