Functionalization of Single-Wall Carbon Nanotubes

Carbon nanotubes (CNTs) show promise for multifunctional materials for a range of applications due to their outstanding combination of mechanical, electrical and thermal properties. However, these promising mechanical properties have not translated well to CNT nanocomposites fabricated by conventional methods due to the weak load transfer between tubes or tube bundles. In this invention, the carbon nanotube forms such as sheets and yarns were modified by in-situ polymerization with polyaniline, a -conjugated conductive polymer. The resulting CNT nanocomposites were subsequently post-processed to improve mechanical properties by hot pressing and carbonization. A significant improvement of mechanical properties of the polyaniline/carbon nanotube nanocomposites was achieved through a combination of stretching, polymerization, hot pressing, and carbonization.

The technology portfolio spans several methods for dispersion and processing of CNTs in polymer resins and composites. CNT/resin systems with high dispersion and long-term stability are provided by three general approaches. One method relies on mechanical dispersion by sonication simultaneous with partial polymerization to increase the resin viscosity to maintain dispersion and enable further polymer processing of the CNT blend into films and other articles. Another approach relies on what is termed donor acceptor bonding, which essentially is a dipole bond created on the CNT/resin interface to maintain dispersion and stability of the CNT/resin blend. This dispersion method also provides advantages in mechanical properties of processed composites due to the interface characteristics. A range of polymer types can be used, including polymethyl methacrylate, polyimide, polyethylene, and others. An additional dry blending approach provides advantages for a variety of thermoplastic and thermoset systems. Use of ball mill mixing achieves effective blending and dispersion of the CNT, even at high loadings. Further processing steps using injection molding or similar melt processing methods have yielded CNT/ polymer composites with a range of useful electronic, optical, and mechanical properties.

The new composite developed by NASA incorporates PGS and CNTs to enhance its thermal conductivity while preserving the mechanical properties of the underlying carbon fiber polymer composite. NASA has also improved the composite manufacturing process to ensure better thermal conductivity not only on the surface, but also through the thickness of the material. This was achieved by adding perforations that enable the additives to spread through the composite. The process for developing this innovative, highly thermally conductive hybrid carbon fiber polymer composite involves several steps. Firstly, a CNT-doped polymer resin is prepared to improve the matrix's thermal conductivity, which is then infused into a carbon fiber fabric. Secondly, PGS is treated to enhance its mechanical interface with the composite. Thirdly, perforation is done on the pyrolytic graphite sheet to improve the thermal conductivity through the thickness of the material by allowing CNT-doped resin to flow and better interlaminar mechanical strength. Finally, the layup of PGS and CNT-CF polymer is optimized. Initial testing of the composite has shown significant increases in thermal conductivity compared to typical carbon fiber composites, with a more than tenfold increase. The composite also has higher thermal conductivity than aluminum alloys, with more than twice the thermal conductivity of the Aluminum 6061 typically used in the aerospace industry. For this new material, NASA has completed a proof-of-concept demonstration and work continues to use the material in a heat exchanger system and further characterize the properties including longevity and radiation impact analysis.

A typical sensor device includes a set of interdigitated microelectrodes fabricated by photolithography on silicon wafer or an electrically insulating substrate. In preparation for fabricating the SWCNT portion of such a sensor, a batch of treated (coated or doped) SWCNTs is dispersed in a solvent. The resulting suspension of SWCNTs is drop-deposited or injected onto the area containing the interdigitated electrodes. As the solvent evaporates, the SWCNTs form a mesh that connects the electrodes. The density of the SWCNTs in the mesh can be changed by varying the concentration of SWCNTs in the suspension and/or the amount of suspension dropped on the electrode area. To enable acquisition of measurements for comparison and to gain orthogonality in the sensor array, undoped SWCNTs can be similarly formed on another, identical set of interdigitated electrodes. Coating materials tested so far include chlorosulfonated polyethylene. Dopants that have been tested include Pd, Pt, Au, Cu and Rh nanoparticle clusters. To date, the sensor has been tested for NO2, NH3, CH4, Cl2, HCl, toluene, benzene, acetone, formaldehyde and nitrotoulene.

A resistor-type sensor was fabricated which has a network of cross-linked SWCNTs with purity over 99%. An ordinary cellulose paper used for filtration was employed as the substrate. The filter paper exhibits medium porosity with a flow rate of 60 mL/min and particle retention of 5-10m. The roughness and porosity of the papers are attractive because they increase the contact area with the ambient air and promote the adhesion to carbon nanotubes. The SWCNTs were functionalized with carboxylic acid (COOH) to render them hydrophilic, thus increasing the adhesion with the substrate. The functionalized SWCNTs were dispersed in dimethylformamide solution. The film composed of networks of cross-linked CNTs was formed using drop-cast coating followed by evaporation of the solvent. Adhesive copper foil tape was used for contact electrodes. Our sensors outperformed the oxide nanowire-based humidity sensors in terms of sensitivity and response/recovery times.