Beatrice Muriithi

Strong, Low-Density Nanocomposites by Chemical Vapor Deposition and Polymerization of Cyanoacrylates on Aminated Silica Aerogels

Strong polymer-silica aerogel composites were prepared by chemical vapor deposition of cyanoacrylate monomers onto amine-modified aerogels. Amine-modified silica aerogels were prepared by copolymerizing small amounts of (aminopropyl)triethoxysilane with tetraethoxysilane. After silation of the aminated gels with hexamethyldisilazane, they were dried as aerogels using supercritical carbon dioxide processing. The resulting aerogels had only the amine groups as initiators for the cyanoacrylate polymerizations, resulting in cyanoacrylate macromolecules that were higher in molecular weight than those observed with unmodified silica and that were covalently attached to the silica surface. Starting with aminated silica aerogels that were 0.075 g/cm(3) density, composite aerogels were made with densities up to 0.220 g/cm(3) and up to 31 times stronger (flexural strength) than the precursor aerogel and about 2.3 times stronger than an unmodified silica aerogel of the same density.

Mechanically reinforced silica aerogel nanocomposites via surface initiated atom transfer radical polymerizations

Here we report the preparation of mechanically robust silica aerogel polymer nanocomposites using surface-initiated atom transfer radical polymerization. This approach was used to grow poly(methyl methacrylate) (PMMA) with low polydispersities and establish the first structure–property relationship between the grafted PMMA molecular weight and bulk physical properties of the hybrid aerogel.

Processing, morphology, and water uptake of Nafion/ex situ Stöber silica nanocomposite membranes as a function of particle size.

Because of the bicontinuous phase structure of Nafion with small hydrophilic channels, formation of composites with silica colloids to improve thermal stability, hydration, and proton conductivity should be influenced by size and surface functionality of the colloids. To test this hypothesis, we prepared batches of silica particles between 20 and 400 nm in diameter with narrow polydispersities using a modified Stöber procedure. Some particles were subsequently surface-modified using mercaptopropyltriethoxysilane. Enough particles were mixed with Nafion in alcohols to achieve 5 wt % silica in the final membranes, which were made by casting and drying. Membrane top and bottom surface and cross-section morphologies were examined with AFM and SEM to determine how the particles were dispersed. We discovered that casting the membranes from dispersions with viscosities less than 65 cPs led to larger particles floating to the top surface of the membrane where they were easily dislodged from the dry membrane. Membranes cast from more viscous solutions exhibited homogeneous distributions of particles. Water uptake was over 60% higher in nanocomposites with unmodified silica particles than for Nafion and about 15% higher than for Nafion with in situ generated silica particles, but showed no trend in water uptake correlating with particle size. Surface silated particles of all sizes appeared to have reduced water uptake relative to Nafion alone.

Mechanical properties of hexylene- and phenylene-bridged polysilsesquioxane aerogels and xerogels

Bridged polysilsesquioxanes are increasingly used to prepare protective coatings, particulate chromatographic materials, and adsorbents. However, little is known about the mechanical properties of the materials and how they are influenced by the nature of the bridging group. In this paper, we have prepared monolithic xerogels and aerogels of hexylene- and phenylene-bridged polysilsesquioxanes and have measured their flexural strength and modulus. Consistent with their compact structure, the porous, glassy phenylene- and hexylene-bridged xerogels were hundreds of stronger than the analogous aerogels. The nature of the bridging group did not appear to affect the mechanical properties of the xerogels, in contrast, it presented a profound effect on the mechanical properties of the aerogels. Phenylene-bridged aerogels were brittle and 30% stronger than silica aerogels of the same density. However, the opaque hexylene-bridged aerogels were found to be elastic and appreciably weaker than the phenylene-bridged or silica aerogels.

Proton conductivity of Nafion/ex-situ sulfonic acid-modified Stöber silica nanocomposite membranes as a function of temperature, silica particles size and surface modification

The introduction of sulfonic acid modified silica in Nafion nanocomposite membranes is a good method of improving the Nafion performance at high temperature and low relative humidity. Sulfonic acid-modified silica is bifunctional, with silica phase expected to offer an improvement in membranes hydration while sulfonic groups enhance proton conductivity. However, as discussed in this paper, this may not always be the case. Proton conductivity enhancement of Nafion nanocomposite membranes is very dependent on silica particle size, sometimes depending on experimental conditions, and by surface modification. In this study, Sulfonated Preconcentrated Nafion Stober Silica composites (SPNSS) were prepared by modification of Stober silica particles with mercaptopropyltriethoxysilane, dispersing the particles into a preconcentrated solution of Nafion, then casting the membranes. The mercapto groups were oxidized to sulfonic acids by heating the membranes in 10 wt % hydrogen peroxide for 1 h. At 80 °C and 100% relative humidity, a 20%–30% enhancement of proton conductivity was only observed when sulfonic acid modified particle less than 50 nm in diameter were used. At 120 °C, and 100% humidity, proton conductivity increased by 22%–42% with sulfonated particles with small particles showing the greatest enhancement. At 120 °C and 50% humidity, the sulfonated particles are less efficient at keeping the membranes hydrated, and the composites underperform Nafion and silica-Nafion nanocomposite membranes.