Behnam Ashrafi

3D chemically cross-linked single-walled carbon nanotube buckypapers

Single-walled carbon nanotubes (SWCNTs) covalently modified with OH functional groups were assembled into buckypapers through solvent dispersion and vacuum filtration. These SWCNT-OH buckypaper sheets were subsequently crosslinked by wetting with bifunctional linkers followed by hot compression causing reaction between the functional groups of the reagent and OH functional groups on the side-walls of SWCNTs to create three-dimensional (3D) covalently cross-linked buckypapers. Cross-linking also was performed using SWCNTs encapsulated with a functionalized polymer wrapping in a core–shell structure, where OH or/and NH2 groups are available on the surface of the polymeric shell for reaction. The 3D cross-linked SWCNT buckypapers retain the porous character typical of buckypaper, and were characterized for their tensile properties and thermal and electrical conductivities. Several cross-linking approaches dramatically improved the mechanical properties. The strongest and stiffest papers (32 MPa, E = 3.1 GPa), which approach 10× stronger and stiffer than the pristine non-crosslinked buckypaper, were obtained at the expense of a loss of electrical conductivity. In other cases, such as cross-linking using a high-performance epoxy resin monomer, improvements in strength and stiffness of ∼5× were obtained while retaining electrical and thermal conductivity. Therefore, the optimal cross-linking approach would be determined by the desired, multifunctional properties. Additionally, the approach can be used in the preparation buckypaper composites and it is demonstrated that cross-linking using a multifunctional epoxy resin prior to impregnation with the same epoxy resin results in substantially better mechanical properties in comparison to just epoxy-impregnation of pristine buckypaper.

Polymer nanocomposites from free-standing, macroscopic boron nitride nanotube assemblies†

Here we report the fabrication of free-standing boron nitride nanotube (BNNT) sheets by direct deposition and by vacuum filtration methods, including novel hybrid assemblies with BNNT and carbon nanotubes. Such sheets have enabled production of polymer nanocomposites with high nanotube content. Two example cases, BNNT–epoxy nanocomposites (>30 wt% BNNTs) produced by impregnation of dry sheets and BNNT sheets modified by integration of a thermoplastic polyurethane are described. Related methods have proven advantageous for carbon nanotube composites and, enabled by new technology for large scale BNNT production, such composites have now been realized with BNNTs. This represents an important milestone towards the development of BNNT-based multifunctional composites.

Influence of the reaction stoichiometry on the mechanical and thermal properties of SWCNT-modified epoxy composites

Previous studies suggest that carbon nanotubes (CNTs) have a considerable influence on the curing behavior and crosslink density of epoxy resins. This invariably has an important effect on different thermal and mechanical properties of the epoxy network. This work focuses on the important role of the epoxy/hardener mixing ratio on the mechanical and thermal properties of a high temperature aerospace-grade epoxy (MY0510 Araldite as an epoxy and 4,4-diaminodiphenylsulfone as an aromatic hardener) modified with single-walled carbon nanotubes (SWCNTs). The effects of three different stoichiometries (stoichiometric and off-stoichiometric) on various mechanical and thermal properties (fracture toughness, tensile properties, glass transition temperature) of the epoxy resin and its SWCNT-modified composites were obtained. The results were also supported by Raman spectroscopy and scanning electron microscopy (SEM). For the neat resin, it was found that an epoxy/hardener molar ratio of 1:0.8 provides the best overall properties. In contrast, the pattern in property changes with the reaction stoichiometry was considerably different for composites reinforced with unfunctionalized SWCNTs and reduced SWCNTs. A comparison among composites suggests that a 1:1 molar ratio considerably outperforms the other two ratios examined in this work (1:0.8 and 1:1.1). This composition at 0.2xa0wt% SWCNT loading provides the highest overall mechanical properties by improving fracture toughness, ultimate tensile strength and ultimate tensile strain of the epoxy resin by 40%, 34%, 54%, respectively.

Single-walled carbon nanotube–modified epoxy thin films for continuous crack monitoring of metallic structures

Cracks are one of the primary forms of damage that can lead to the catastrophic failure of metallic structures. This study focuses on the application of epoxy nanocomposite thin film sensors for continuous monitoring of crack evolution in metallic structures. The core approach was to monitor the current (or resistance) change in these nanocomposite films, as cracks develop and propagate in the metallic host structure. Based on optical, electrical, and mechanical properties of epoxy resins modified with different contents of single-walled carbon nanotubes, two different nanocomposites (with 0.3 and 1.0 wt%) were chosen for the development of a crack sensor. The performance of the nanocomposite sensors was evaluated under tension–tension fatigue tests, on aluminum coupons with centrally located through thickness electrical discharge machining notches. Crack growth in the aluminum was found to transfer to the nanocomposite films in a stable mode. Once the crack was established, a linear correlation was found between the measured current and crack length with a slope of −10−11 and −10−8 A/mm for 0.3 and 1.0 wt% nanocomposites, respectively. Contact between the asperities formed on the crack surfaces in the nanocomposite film while the crack was closed at small loads (<30% of maximum load) was found to be an important limiting factor causing a large variation in measured currents during each fatigue cycle. Hence, a normalized variable based upon current change during each cycle was defined, providing a more accurate measurement of the crack size, with a crack gauge factor of ∼0.04 mm−1. In summary, the nanocomposite thin film sensor developed in this study offers both continuous crack growth monitoring and the possibility of strain sensing. The sensor is also suitable for visual inspection of the host structure due to the transparency of the developed nanocomposite film.

Effects of SWCNTs on mechanical and thermal performance of epoxy at elevated temperatures

A property which limits the breadth of application of thermoset polymers and their composites is their relatively low maximum operating temperatures. This work investigates the potential application of both functionalized single-walled carbon nanotubes (f-SWCNTs) based on negative charging, and unfunctionalized SWCNTs (u-SWCNTs) to increase the mechanical and thermal performance of a high-temperature aerospace-grade epoxy with a glass transition temperature of approximately 270xa0°C. Thermal and mechanical properties of the baseline epoxy and nanocomposites containing a low content of SWCNTs (0.2xa0% by weight) were characterized through thermogravimetric analyses, tensile tests, and dynamic mechanical analyses. Tensile tests were performed both at room temperature and at 80xa0°C. Further, room temperature tensile tests were performed on untreated and heat-treated specimens. The heat treatment was performed at 300xa0°C, slightly above the resin glass transition temperature. Results demonstrate that f-SWCNTs are effective in improving the mechanical and thermal performance of the epoxy. No significant improvement was observed for u-SWCNT nanocomposites. For the nanocomposite with f-SWCNTs, the ultimate tensile strength and strain to failure at room temperature (80xa0°C) increased by 20xa0% (8xa0%) and 71xa0% (77xa0%), respectively, as compared to the baseline epoxy. The f-SWCNT nanocomposite, unlike other examined materials, exhibited a stress–strain necking behavior at 80xa0°C, an indication of increased ductility. After heat treatment, these properties further improved relative to the neat epoxy (160xa0% increase in ultimate tensile strength and 270xa0% increase in strain to failure). This work suggests the potential to utilize f-SWCNTs based on negative charging to enhance high-temperature thermoset performance.

Integration of Single-Walled Carbon Nanotubes into a Single Component Epoxy Resin and an Industrial Epoxy Resin System

Single-walled carbon nanotubes (SWCNT) exhibit amongst the best mechanical, thermal and electrical properties of any known material. With their very high aspect ratios, SWCNT are well-suited to making ultra-light multifunctional structural composites. In this work, covalent chemistry is used to integrate SWCNT into a single component epoxy resin (aerospace grade MY0510) as well as an industrialized epoxy resin system for sporting goods. In particular, reduced SWCNT react directly with epoxide groups to create direct connections to the resin backbone. As the reduction process naturally exfoliates the SWCNT bundles, excellent dispersion is readily obtained. Substantial mechanical property improvements of the modified resin and carbon fibre composites have been observed through well-controlled processing. Their mechanical properties, specifically impact resistance, compression after impact strength and fracture toughness of the modified resin and fibre composites are discussed.

Covalent derivatization of boron nitride nanotubes with peroxides and their application in polycarbonate composites

The novel derivatization of boron nitride nanotubes (BNNTs) with two organic peroxides (lauroyl peroxide and dicumyl peroxide) is presented. The functionalized-BNNTs (f-BNNTs) were characterized by FTIR, 1H NMR, TGA, and SEM. These thermally labile peroxides can decompose to generate an alkoxyl radical, or an alkyl radical (with the loss of CO2), which then acts as a Lewis base to attack the electron-deficient boron sites of BNNTs. This results in the covalent formation of R-O-BNNT or R-BNNT bonds. Thin films (15 to 35 μm thickness) of 0.5 to 1.0 wt% lauryl-BNNT/polycarbonate and 1 wt% BNNT-OH/polycarboante composites were fabricated, and their transparency was demonstrated. Semi-transparent, hot-pressed disks (200 μm thickness) of 1.0 wt% cumyloxy-BNNT/polycarbonate and 1.0 wt% lauryl-BNNT/polycarbonate composites were also fabricated and mechanically tested. The Youngs modulus and the maximum tensile stress were increased by 12% and 8%, respectively, compared to the corresponding properties of BNNT-free polycarbonate samples.

Epoxy resin nanocomposites with hydroxyl (OH) and amino (NH2) functionalized boron nitride nanotubes

Abstract Hydroxyl (OH) and amino (NH2) functionalized boron nitride nanotubes (f-BNNTs) were integrated into an epoxy resin (Epon828) to achieve improved mechanical properties. While raw BNNT-composites yielded the largest values for Young’s modulus and appeared to be well mixed, f-BNNTs were found to provide a superior combination of mechanical properties yielding improvements in strain at failure, tensile strength and toughness that were not observed using raw BNNTs. In particular, an increase of 21% in Young’s modulus is observed with 5 wt% of f-BNNT, and increases of 12, 21, and 49% are observed in tensile strength, failure strain, and toughness, respectively, with 2 wt% f-BNNT while a 34% increase in fracture toughness is observed with 3 wt% f-BNNT.