Siliceous mesostructured cellular foams (MCFs) with well-defined ultralarge mesopores and hydrothermally robust frameworks are described. The MCFs are templated by oil-inwater microemulsions and are characterized by small-angle X-ray scattering, nitrogen sorption, transmission electron microscopy, scanning electron microscopy, thermogravimetry, and differential thermal analysis. The MCFs consist of uniform spherical cells measuring 24-42 nm in diameter, possess BET surface areas up to 1000 m 2 /g and porosities of 80-84%, and give, because of their pores with small size distributions, higher-order scattering peaks even in the absence of long-range order. Windows with diameters of 9-22 nm and narrow size distribution interconnect the cells. The pore size can be controlled by adjusting the amount of the organic swelling agent that is added and by varying the aging temperature. Adding ammonium fluoride selectively enlarges the windows by 50-80%. In addition, the windows can be enlarged by postsynthesis treatment in hot water. The MCF materials resemble aerogels, but offer the benefits of a facilitated synthesis in combination with welldefined pore and wall structure, thick walls, and high hydrothermal stability. The open system of large pores give MCFs unique advantages as catalyst supports and separation media for processes involving large molecules, and the high porosities make them of interest for electrical and thermal insulation applications.
We have investigated the phase transition between two distinct mesoporous silicas: SBA-15, comprising a hexagonally packed arrangement of cylindrical pores (6−12 nm in diameter), and mesocellular silica foams (MCF), consisting of spherical voids (22−42 nm in diameter) interconnected by “windows” of ∼10 nm. Both SBA-15 and MCF are formed using an amphiphilic triblock copolymer (Pluronic P123) as a template. The synthesis conditions for the two materials are identical, except substantial trimethylbenzene is added to form MCF. We find that the phase transition occurs at an oil−polymer mass ratio of 0.2−0.3. Although the pore structures and pore sizes change dramatically, the mean surface curvature of the system remains essentially the same throughout the transition.
The aim of this study is to determine the effects of oil solutes and alcohol cosolvents on the structure of oil-in-water microemulsions stabilized by poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers. The systems investigated involved the solubilization of 1,3,5-trimethylbenzene or 1,2-dichlorobenzene by P123 (EO(20)-PO(70)-EO(20)) pluronic surfactant micelles in water and water + ethanol solvents. The structures of these swollen micelles were determined by small-angle neutron scattering (SANS). A thermodynamic model was employed to interpret the characterization data. The results of the thermodynamic model for micellization agreed well with the SANS data from samples of micelles swollen by both oils. The model predicted the size of the micelles within 5% accuracy using only one fitting parameter, the micelle polydispersity. Ethanol had significantly different effects on the polymer micelles that contained solubilized oil compared to pure polymer micelles. For pure polymer micelles, the addition of ethanol increased the solubility of the polymer and, therefore, decreased the total volume fraction of micelles, while for polymer-oil aggregates, ethanol tended to have a positive effect on the volume fraction of micelles. SANS results showed that the greatest divergence from pure aqueous solvent results occurred at oil concentrations above the microemulsion stability limit.
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