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

The ballistic performance of edge-clamped monolithic polyimide aerogel blocks (12 mm thickness) has been studied through a series of impact tests using a helium-filled gas gun connected to a vacuum chamber and a spherical steel projectile (approximately 3 mm diameter) with an impact velocity range of 150-1300 m s-1. The aerogels had an average bulk density of 0.17 g cm-3 with high porosity of approximately 88%. The ballistic limit velocity of the aerogels was estimated to be in the range of 175-179 m s-1. Moreover, the aerogels showed a robust ballistic energy absorption performance (e.g., at the impact velocity of 1283 m s-1 at least 18% of the impact energy was absorbed). At low impact velocities, the aerogels failed by ductile hole enlargement followed by a tensile failure. By contrast, at high impact velocities, the aerogels failed through an adiabatic shearing process. Given the substantially robust ballistic performance, the polyimide aerogels have a potential to combat multiple constraints such as cost, weight, and volume restrictions in aeronautical and aerospace applications with high blast resistance and ballistic performance requirements such as in stuffed Whipple shields for orbital debris containment application.

RESUMEN

Polyimide aerogels using 1,12-dodecyldiamine (DADD), 3,3'-dimethylbenzidine (DMBZ), and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and cross linked using 1,3,5-triaminophenoxybenzene (TAB) were synthesized. Substitution of the aromatic diamine, DMBZ, with varying amounts of the aliphatic diamine, DADD, increases the flexibility in the backbone structure of the prepared aerogel. These aerogels are also lightweight, low density, have a low dielectric constant, and high modulus. Their overall properties (density, shrinkage, porosity, dielectric constant, water uptake, and modulus) and potential use as a conformal substrate for lightweight, high-performance antennas are discussed.

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

Surface functionalization of pretreated carbon nanotubes (CNT) using aromatic, aliphatic, and aliphatic ether diamines was performed. The pretreatment of the CNT consisted of either acid- or photo-oxidation. The acid treated CNT had a higher initial oxygen content compared to the photo-oxidized CNT and this resulted in a higher density of functionalization. X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis (TGA) were used to verify the presence of the oxygenated and amine moieties on the CNT surfaces. Epoxy/0.1 wt % CNT nanocomposites were prepared using the functionalized CNT and the bulk properties of the nanocomposites were examined. Macroscale correlations between the interfacial modification and bulk dynamic mechanical and thermal properties were observed. The amine modified epoxy/CNT nanocomposites exhibited up to a 1.9-fold improvement in storage modulus (G') below the glass transition (Tg) and up to an almost 4-fold increase above the Tg. They also exhibited a 3-10 °C increase in the glass transition temperature. The aromatic diamine surface modified epoxy/CNT nanocomposites resulted in the largest increase in shear moduli below and above the Tg and the largest increase in the Tg. Surface examination of the nanocomposites with scanning electron microscopy (SEM) revealed indications of a greater adhesion of the epoxy resin matrix to the CNT, most likely due to the covalent bonding.

RESUMEN

Flexible graphene polyimide nanocomposites (0.1-4 wt %) with superior mechanical properties over those of neat polyimide resin have been prepared by solution blending. Imide moieties were grafted to amine-functionalized graphene using a step-by-step condensation and thermal imidization method. The imide-functionalized graphene exhibited excellent compatibility with N-methyl-2-pyrrolidone. The dynamic storage moduli of the graphene polyimide nanocomposites increased linearly with increasing graphene content for both unmodified graphene and imidized graphene. Moduli of the imidized graphene nanocomposites were 25-30% higher than those of unmodified graphene nanocomposites. Both neat polyimide and polyimide nanocomposites exhibited shape memory effects with a triggering temperature of 230 °C. where addition of graphene improved the recovery rate. Addition of graphene improved thermal stability of the polyimide nanocomposites for both graphene and modified graphene.

Asunto(s)

Grafito/química , Imidas/química , Nanoestructuras/química , Nanoestructuras/ultraestructura , Cristalización/métodos , Módulo de Elasticidad , Calor , Sustancias Macromoleculares/química , Ensayo de Materiales , Conformación Molecular , Tamaño de la Partícula , Propiedades de Superficie , Temperatura , Resistencia a la Tracción , Conductividad Térmica

RESUMEN

Molecular pi-complexes were formed from pristine HiPCO single- wall carbon nanotubes (SWCNTs) and 1-pyrene- N-(4-N'-(5-norbornene-2,3-dicarboxyimido)phenyl butanamide, 1. Polyimide films were prepared with these complexes as well as uncomplexed SWCNTs and the effects of nanoadditive addition on mechanical, thermal, and electrical properties of these films were evaluated. Although these properties were enhanced by both nanoadditives, larger increases in tensile strength and thermal and electrical conductivities were obtained when the SWCNT/1 complexes were used. At a loading level of 5.5 wt %, the T(g) of the polyimide increased from 169 to 197 degrees C and the storage modulus increased 20-fold (from 142 to 3045 MPa). The addition of 3.5 wt % SWCNT/1 complexes increased the tensile strength of the polyimide from 61.4 to 129 MPa; higher loading levels led to embrittlement and lower tensile strengths. The electrical conductivities (DC surface) of the polyimides increased to 1 x 10(-4) Scm(-1) (SWCNT/1 complexes loading level of 9 wt %). Details of the preparation of these complexes and their effects on polyimide film properties are discussed.

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.