RESUMEN

A new series of flexible polyamide (PA) aerogels was synthesized using terephthaloyl chloride (TPC), 2,2'-dimethylbenzidine (DMBZ) and cross-linked with an inexpensive, commercially available tri-isocyanate (Desmodur N3300A) at polymer concentrations of 6-8 wt.% total solids and repeating units, n, from 30 to 60. The cross-linked DMBZ-based polyamide aerogels obtained, after supercritically drying using liquid CO2, had shrinkages of 19-27% with densities ranging from 0.12 g/cm3 to 0.22 g/cm3, porosity and surface areas up to 91% and 309 m2/g, respectively, and modulus values ranging from 20.6 to 109 MPa. Evidence suggests that a higher flexibility could be achieved using DMBZ in the polyamide backbone with N3300A as a cross-linker, when compared to previously reported TPC-mPDA-BTC PA aerogels, N3300A-polyimide aerogels, and N3300-reinforced silica aerogels.

RESUMEN

Aerogels are promising materials for many aerospace applications, including high-performance antennae and flexible insulation, because of their inherent low density and high surface areas. Polymer aerogels, especially polyimide aerogels, provide excellent mechanical properties beyond traditional silica aerogels while maintaining the required thermal stability. Polyimide aerogel surface area, porosity, and pore volume are important properties; however, these measurements are traditionally conducted on the aerogel after removal of the solvent. Because of this, the impact of synthetic control and solvent presence on the nanoscale to mesoscale structure of polyimide aerogels in functional applications is unclear. In this report, we use small-angle neutron scattering to determine the dry and solvated skeletal strut size and composition of polyimide aerogels to deduce the impact of solvation on the structure of complex aerogel struts. Our results show that the aerogel contains a hierarchical assembly of pores, with pores present both within and between the supporting struts. This translates to a material with solvent in the larger pores, as well as absorbed in the supporting polyimide skeleton. The amount of solvent uptake in the struts varies with the solvent and polyimide properties. The insight from these results provides pathways to determine the correlations between aerogel nano- and mesoscale structural characteristics, fabrication processes, and their performance in functional applications such as polymeric battery separators. These results also broaden the characterization tools of polymeric aerogels that differentiate between dry and solvated nano- and mesoscale structures that exist in common operating conditions.

RESUMEN

A family of polyimide (PI)-based aerogels is produced using Desmodur N3300A, an inexpensive triisocyanate, as the cross-linker. The aerogels are prepared by cross-linking amine end-capped polyimide oligomers with the triisocyanate. The polyimide oligomers are formulated using 2,2'-dimethylbenzidine, 4,4'-oxydianiline, or mixtures of both diamines, combined with 3,3',4,4'-biphenyltetracarboxylic dianhydride, and are chemically imidized at room temperature. Depending on the backbone chemistry, chain length, and polymer concentration, density of the aerogels ranged from 0.06 to 0.14 g/cm3 and Brunauer-Emmett-Teller surface areas ranged from 350 to 600 m2/g. Compressive moduli of these aerogels were as high as 225 MPa, which are comparable to, or higher than, those previously reported prepared with similar backbone structures but with other cross-linkers. Because of their lower cost and commercial availability as cross-linker, the aerogels may have further potential as insulation for building and construction, clothing, sporting goods, and automotive applications, although lower-temperature stability may limit their use in some aerospace applications.

RESUMEN

We report here the fabrication of polyamide aerogels composed of poly-p-phenylene-terephthalamide, the same backbone chemistry as DuPont's 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.

RESUMEN

The dielectric properties and loss tangents of low-density polyimide aerogels have been characterized at various frequencies. Relative dielectric constants as low as 1.16 were measured for polyimide aerogels made from 2,2'-dimethylbenzidine (DMBZ) and biphenyl 3,3',4,4'-tetracarbozylic dianhydride (BPDA) cross-linked with 1,3,5-triaminophenoxybenzene (TAB). This formulation was used as the substrate to fabricate and test prototype microstrip patch antennas and benchmark against state of practice commercial antenna substrates. The polyimide aerogel antennas exhibited broader bandwidth, higher gain, and lower mass than the antennas made using commercial substrates. These are very encouraging results, which support the potential advantages of the polyimide aerogel-based antennas for aerospace applications.

Asunto(s)

RESUMEN

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.

RESUMEN

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.