Linda McCorkle

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.

Hydrophobic monolithic aerogels by nanocasting polystyrene on amine-modified silica

We describe a three-dimensional core–shell structure where the core is the assembly of nanoparticles that comprises the skeletal framework of a typical silica aerogel, and the shell is polystyrene. Specifically, the mesoporous surfaces of silica were first modified with amines by co-gelation of tetramethylorthosilicate (TMOS) and 3-aminopropyltriethoxysilane (APTES). Next, styrene moieties were attached to the amines by reaction with p-chloromethylstyrene. Finally, dangling styrene moieties were crosslinked by a free-radical polymerization process initiated by AIBN and styrene, p-chloromethylstyrene or 2,3,4,5-pentafluorostyerene introduced in the mesopores. Polystyrene crosslinked aerogels are mechanically strong, lightweight (0.41–0.77 g cm−3), highly porous materials (they consist of ca. 63% empty space, with a BET surface areas in the range of 213–393 m2 g−1). Their thermal conductivity (0.041 W m−1 K−1) is comparable to that of glass wool. Hydrophobicity, however, is the property that sets the new material apart from analogous polyurea and epoxy crosslinked aerogels. The contact angles of water droplets on disks cut from larger monoliths are >120°. (By comparison, the contact angle with polyurea crosslinked aerogels is only ca. 60°.) Polystyrene crosslinked aerogel monoliths float on water indefinitely, while their polyurea counterparts absorb water and sink within minutes.

Structure−Property Relationships in Porous 3D Nanostructures: Epoxy-Cross-Linked Silica Aerogels Produced Using Ethanol as the Solvent

Cross-linking silica aerogels with organic groups has been shown to improve the strength over un-cross-linked aerogels by as much as 2 orders of magnitude. Previous cross-linking chemistry has been developed using solvents specifically chosen to dissolve the monomers and accommodate the reaction temperature. Because the process of making the aerogels requires so much solvent, it is of interest to consider less toxic solvents such as ethanol to increase safety and enhance scale up. To this end, two different epoxy precursors with suitable solubility in ethanol were evaluated as cross-linkers for silica gels prepared from (3-aminopropyl)triethoxysilane and tetraethylorthosilicate. In addition, 1,6-bis(trimethoxysilyl)hexane (BTMSH) was used as an additive in the underlying silica structure to add flexibility to the aerogels. It was found that the ethanol-derived aerogels exhibited more shrinkage than those prepared from other solvents but that including BTMSH in the aerogels significantly reduced this shrinkage. Inclusion of BTMSH also imparted the ability of the aerogel monoliths to recover elastically when compressed up to 50% strain. In addition, optimized cross-linked aerogels prepared in this study have mechanical properties comparable to those using other more undesirable solvents and cross-linkers.

Reinforcing polymer cross-linked aerogels with carbon nanofibers

We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacted with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Herein, we examine the effect of including up to 5% (w/w) carbon nanofibers in the silica backbone before cross-linking. The addition of 5% carbon nanofibers to the lowest density aerogels studied triples the compressive modulus and the tensile stress at break is increased five-fold with no density penalty. The carbon fiber also improves the strength of the initial hydrogels before cross-linking, which may have implications in manufacturing.

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.

Increased Tensile Strength of Carbon Nanotube Yarns and Sheets through Chemical Modification and Electron Beam Irradiation

The inherent strength of individual carbon nanotubes (CNTs) offers considerable opportunity for the development of advanced, lightweight composite structures. Recent work in the fabrication and application of CNT forms such as yarns and sheets has addressed early nanocomposite limitations with respect to nanotube dispersion and loading and has pushed the technology toward structural composite applications. However, the high tensile strength of an individual CNT has not directly translated into that of sheets and yarns, where the bulk material strength is limited by intertube electrostatic attractions and slippage. The focus of this work was to assess postprocessing of CNT sheets and yarns to improve the macro-scale strength of these material forms. Both small-molecule functionalization and electron-beam irradiation were evaluated as means to enhance the tensile strength and Youngs modulus of the bulk CNT materials. Mechanical testing revealed a 57% increase in tensile strength of CNT sheets upon functionalization compared with unfunctionalized sheets, while an additional 48% increase in tensile strength was observed when functionalized sheets were irradiated. Similarly, small-molecule functionalization increased tensile strength of yarn by up to 25%, whereas irradiation of the functionalized yarns pushed the tensile strength to 88% beyond that of the baseline yarn.

The Effects of Fiber Surface Modification and Thermal Aging on Composite Toughness and Its Measurement

A detailed experimental study was conducted to establish the structure-property relationships between elevated temperature aging and (1) fiber-matrix bonding, (2) Mode II interlaminar fracture toughness, and (3) failure modes of carbon fiber/PMR-15 composites. The fiber-matrix adhesion was varied by using carbon fibers with different surface treatments. Short beam shear tests were used to quantify the interfacial shear strength afforded by the use of the different fiber surface treatments. The results of the short beam shear tests definitely showed that, for aging times up to 1000 hr, the aging process caused no observable changes in the bulk of the three composite materials that would degrade the shear properties of the material. Comparisons between the interlaminar shear strength (ILSS) measured by the short beam shear tests and the G,,, test results, as measured by the ENF test, indicated that the differences in the surface treatments significantly affected the fracture properties while the effect of the aging process was probably limited to changes at the starter crack tip. The fracture properties changed due to a shift in the fracture from an interfacial failure to a failure within the matrix when the fiber was changed from AU-4 to AS-4 or AS-4G. There appears to be an effect of the fiber/matrix bonding on the thermo-oxidative stability of the composites that were tested. The low bonding afforded by the AU-4 fiber resulted in weight losses about twice those experienced by the AS-4 reinforced composites, the ones with the best TOS. The results are in agreement with those of previous work completed by the authors.

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.

Poly(maleic anhydride) cross-linked polyimide aerogels: synthesis and properties

A series of aerogels was fabricated by cross-linking amine end-capped polyimide oligomers with poly(maleic anhydride)s. Poly(maleic anhydride)s are commercially available with various aliphatic side groups and are less costly than other cross-linkers used for polyimide aerogels. Thus they are used here as possible substitutes to form cross-linked polyimide aerogels at a lower cost. The effects of the different side groups of the cross-linkers and oligomer backbone structures on the density, porosity, shrinkage, surface area, morphology, and mechanical properties of the aerogels are discussed. Aerogels with low density (0.12–0.17 g cm−3), high porosity (>88%), high surface area (360–550 m2 g−1), and Youngs modulus (2–60 MPa) were produced in the study. The thermal stability and water uptake of the samples were also studied. The aerogels may be potential candidates in a variety of aeronautic and space applications, such as space suit insulation for planetary surface missions, insulation for inflatable structures for habitats, and cryotank insulation for advanced space propulsion systems.