Baochau N. Nguyen

Tailoring Elastic Properties of Silica Aerogels Cross-Linked with Polystyrene

The effect of incorporating an organic linking group, 1,6-bis(trimethoxysilyl)hexane (BTMSH), into the underlying silica structure of a styrene cross-linked silica aerogel is examined. Vinyltrimethoxysilane (VTMS) is used to provide a reactive site on the silica backbone for styrene polymerization. Replacement of up to 88 mol % of the silicon from tetramethoxyorthosilicate with silicon derived from BTMSH and VTMS during the making of silica gels improves the elastic behavior in some formulations of the cross-linked aerogels, as evidenced by measurement of the recovered length after compression of samples to 25% strain. This is especially true for some higher density formulations, which recover nearly 100% of their length after compression to 25% strain twice. The compressive modulus of the more elastic monoliths ranged from 0.2 to 3 MPa. Although some of these monoliths had greatly reduced surface areas, changing the solvent used to produce the gels from methanol to ethanol increased the surface area in one instance from 6 to 220 m(2)/g with little affect on the modulus, elastic recovery, porosity, or density.

Flexible Nanofiber-Reinforced Aerogel (Xerogel) Synthesis, Manufacture, and Characterization

Silica aerogels are sol-gel-derived materials consisting of interconnected nanoparticle building blocks that form an open and highly porous three-dimensional silica network. Flexible aerogel films could have wide applications in various thermal insulation systems. However, aerogel thin films produced with a pure sol-gel process have inherent disadvantages, such as high fragility and moisture sensitivity, that hinder wider applications of these materials. We have developed synthesis and manufacturing methods to incorporate electrospun polyurethane nanofibers into the cast sol film prior to gelation of the silica-based gel in order to reinforce the structure and overcome disadvantages such as high fragility and poor mechanical strength. In this method, a two-stage sol-gel process was employed: (1) acid-catalyzed tetraethyl orthosilicate hydrolysis and (2) base-catalyzed gelation. By precisely controlling the sol gelation kinetics with the amount of base present in the formulation, nanofibers were electrospun into the sol before the onset of the gelation process and uniformly embedded in the silica network. Nanofiber reinforcement did not alter the thermal conductivity and rendered the final composite film bendable and flexible.

Elastic Behavior of Methyltrimethoxysilane Based Aerogels Reinforced with Tri-Isocyanate

The elastic properties and/or flexibility of polymer reinforced silica aerogels having methyltrimethoxysilane (MTMS) and bis(trimethoxysilylpropyl)amine (BTMSPA) making up the silica structure are examined. The dipropylamine spacer from BTMSPA is used both to provide a flexible linking group in the silica structure, and as a reactive site via its secondary amine for reaction with a tri-isocyanate, Desmodur N3300A. The tri-isocyanate provides an extended degree of branching or reinforcement, resulting in increased compressive strength of the aerogel monoliths while the overall flexibility arising from the underlying silica structure is maintained. The compressive moduli of the reinforced aerogel monoliths in this study range from 0.001 to 158 MPa. Interestingly, formulations across this entire range of modulus recover nearly all of their length after two compressions to 25% strain. Differences in pore structure of the aerogels due to processing conditions and solvent are also discussed.

Elastic low density aerogels derived from bis[3-(triethoxysilyl)propyl]disulfide, tetramethylorthosilicate and vinyltrimethoxysilane via a two-step process

A series of low density, porous structures were prepared using bis[3-(triethoxysilyl)propyl]disulfide (BTSPD), tetramethylorthosilicate (TMOS) and vinyltrimethoxysilane (VTMS) as precursors via a two-step (acid–base) sol-gel process followed by supercritical CO2 extraction. Using statistical experimental design methodology and empirical modelling, the concentrations of BTSPD, TMOS and VTMS were varied in the production of the monoliths and found to have a significant effect on their bulk density, porosity, BET surface areas, hydrophobicity and mechanical properties. Increasing the TMOS concentration significantly increases the surface area and Youngs modulus while higher VTMS concentration improves hydrophobicity and higher BTSPD concentration leads to increased elastic recovery after compression. Optimized aerogels produced in the study have a combination of high Youngs modulus, good hydrophobicity and near complete recovery after compression in agreement with model predictions.

Clay reinforced polyimide/silica hybrid aerogel

Silica aerogels are comprised of highly porous three-dimensional networks. They typically are very fragile and brittle due to the inter-particle connections in the pearl-necklace-like fractal network. This behavior prevents their wider utility. The present study aims to reinforce the silica-based gel to improve the poor mechanical strength through crosslinking the silica particles with polyimide and incorporating Lucentite STN clay into the skeletal silica–polyimide network. 3-Aminopropyltriethoxysilane (APTES) end-capped polyamic acid oligomers were first formed followed by gelation with TMOS at a range of clay concentrations to generate a silica network. The incorporation of clay leads to slightly lower BET surface area with little effect on shrinkage, porosity and density. Microscopy revealed that the aerogel preferentially grows from the edges of well dispersed clay particles while minimal growth occurs from clay surfaces. The formation of covalent bonds and hydrogen bonding through the OH functionalized clay edges is thought to enhance the connectivity with silica network and clay, leading to a substantial reinforcement effect as evidenced by an increase in modulus.

Highly Porous, Rigid-Rod Polyamide Aerogels with Superior Mechanical Properties and Unusually High Thermal Conductivity

We report here the fabrication of polyamide aerogels composed of poly-p-phenylene-terephthalamide, the same backbone chemistry as DuPonts Kevlar. The all-para-substituted polymers gel without the use of cross-linker and maintain their shape during processing-an improvement over the meta-substituted cross-linked polyamide aerogels reported previously. Solutions containing calcium chloride (CaCl2) and para-phenylenediamine (pPDA) in N-methylpyrrolidinone (NMP) at low temperature are reacted with terephthaloyl chloride (TPC). Polymerization proceeds over the course of 5 min resulting in gelation. Removal of the reaction solvent via solvent exchange followed by extraction with supercritical carbon dioxide provides aerogels with densities ranging from 0.1 to 0.3 g/cm3, depending on the concentration of calcium chloride, the formulated number of repeat units, n, and the concentration of polymer in the reaction mixture. These variables were assessed in a statistical experimental study to understand their effects on the properties of the aerogels. Aerogels made using at least 30 wt % CaCl2 had the best strength when compared to aerogels of similar density. Furthermore, aerogels made using 30 wt % CaCl2 exhibited the lowest shrinkage when aged at elevated temperatures. Notably, whereas most aerogel materials are highly insulating (thermal conductivities of 10-30 mW/m K), the polyamide aerogels produced here exhibit remarkably high thermal conductivities (50-80 mW/(m K)) at the same densities as other inorganic and polymer aerogels. These high thermal conductivities are attributed to efficient phonon transport by the rigid-rod polymer backbone. In conjunction with their low cost, ease of fabrication with respect to other polymer aerogels, low densities, and high mass-normalized strength and stiffness properties, these aerogels are uniquely valuable for applications such as lightweighting in consumer electronics, automobiles, and aerospace where weight reduction is desirable but trapping of heat may be undesirable-applications where other polymer aerogels have to date otherwise been unsuitable-creating new opportunities for commercialization of aerogels.