Carbon nanotube survivability in marine environments and method for biofouling removal.

The deep sea survivability and biofouling characteristics of corrosion-resistant bulk carbon nanotubes (CNTs) have been studied after deployment in the Atlantic Ocean over the course of 12 months. Quantification of barnacle count, biofouling density, and non-combustible residue shows cyanoacrylate coatings increase durability and reduce the colonization of biofouling compared to as-received CNTs. Scanning electron microscopy was performed on the biofouled CNTs, and the majority of species were identified as diatoms, consisting of an ordered silica cell wall. Both the as-received and cyanoacrylate-treated CNTs were successfully acid purified to remove biogrowth, leading to complete recovery of tensile strength and electrical transport properties. Thermogravimetric analysis, scanning electron microscopy, contact angle, dynamic mechanical analysis, and current carrying capacity measurements validated the refunctionalization results. Thus, the multifunctional property recovery and enhanced durability confirms that CNTs are electrochemically stable in saltwater environments and are resilient to biofouling conditions in real-world environments after extended exposure.

Removal of sodium dodecyl sulfate surfactant from aqueous dispersions of single-wall carbon nanotubes.

A reagent-based treatment method was developed for the removal of sodium dodecyl sulfate (SDS) from aqueous dispersions of single-wall carbon nanotubes (SWCNTs). Based on a survey of various reagents, organic solvents emerged as the most effective at interrupting the SDS:SWCNT interaction without producing deleterious side reactions or causing precipitation of the surfactant. Specifically, treatment with acetone or acetonitrile allows for the facile isolation of SWCNTs with near complete removal of SDS through vacuum filtration, resulting in a 100x reduction in processing time. These findings were validated via quantitative analysis using thermogravimetric analysis, Raman spectroscopy, 4-point probe electrical measurement, and X-ray photoelectron spectroscopy. Subsequent thermal oxidation further enhances the purity of the reagent treated samples and yields bulk SWCNT samples with >95% carbonaceous purity. The proposed reagent treatment method thus demonstrates potential for large volume SWCNT processing.

Modification of Silver/Single-Wall Carbon Nanotube Electrical Contact Interfaces via Ion Irradiation.

Introduction of defects via ion irradiation ex situ to modify silver/single-wall carbon nanotube (Ag-SWCNT) electrical contacts and the resulting changes in the electrical properties were studied. Two test samples were fabricated by depositing 0.1 µm Ag onto SWCNT thin films with average thicknesses of 10 and 60 nm, followed by ion irradiation (150 keV 11B+ at 5 × 1014 ions/cm2). The contact resistance (Rc) between the Ag and SWCNT thin films was determined using transfer length method (TLM) measurements before and after ion irradiation. Rc increases for both test samples after irradiation, while there is no change in Rc for control structures with thick Ag contacts (1.5 µm), indicating that changes in Rc originate from changes in the SWCNT films and at the Ag-SWCNT interface caused by ion penetration through the Ag contact electrodes. Rc increases by ∼4× for the 60 nm SWCNT structure and increases by ∼2.4× for the 10 nm SWCNT structure. Raman spectroscopy measurements of the SWCNTs under the contacts compared to the starting SWCNT film show that the degradation of the 10 nm SWCNT structure was less significant than that of the 60 nm SWCNT structure, suggesting that the smaller change in Rc for the 10 nm SWCNT structure is a result of the thickness-dependent damage profile in the SWCNTs. Despite the increase in overall contact resistance, further TLM analysis reveals that the specific contact resistance actually decreases by ∼3.5-4× for both test samples, suggesting an enhancement of the electrical properties at the Ag-SWCNT interface. Irradiation simulations provide a physical description of the underlying mechanism, revealing that Ag atoms are forward-scattered into the SWCNTs, creating an Ag/C interfacial layer several nanometers in depth. The collective results indicate competing effects of improvement of the Ag-SWCNT interface versus degradation of the bulk SWCNT films, which has implications for scaled high-performance devices employing thinner SWCNT films.

Carbon Nanotube Thin-Film Antennas.

Multiwalled carbon nanotube (MWCNT) and single-walled carbon nanotube (SWCNT) dipole antennas have been successfully designed, fabricated, and tested. Antennas of varying lengths were fabricated using flexible bulk MWCNT sheet material and evaluated to confirm the validity of a full-wave antenna design equation. The ∼20× improvement in electrical conductivity provided by chemically doped SWCNT thin films over MWCNT sheets presents an opportunity for the fabrication of thin-film antennas, leading to potentially simplified system integration and optical transparency. The resonance characteristics of a fabricated chlorosulfonic acid-doped SWCNT thin-film antenna demonstrate the feasibility of the technology and indicate that when the sheet resistance of the thin film is >40 ohm/sq no power is absorbed by the antenna and that a sheet resistance of <10 ohm/sq is needed to achieve a 10 dB return loss in the unbalanced antenna. The dependence of the return loss performance on the SWCNT sheet resistance is consistent with unbalanced metal, metal oxide, and other CNT-based thin-film antennas, and it provides a framework for which other thin-film antennas can be designed.

Enhanced Electrical Conductivity in Extruded Single-Wall Carbon Nanotube Wires from Modified Coagulation Parameters and Mechanical Processing.

Single-wall carbon nanotubes (SWCNTs) synthesized via laser vaporization have been dispersed using chlorosulfonic acid (CSA) and extruded under varying coagulation conditions to fabricate multifunctional wires. The use of high purity SWCNT material based upon established purification methods yields wires with highly aligned nanoscale morphology and an over 4× improvement in electrical conductivity over as-produced SWCNT material. A series of eight liquids have been evaluated for use as a coagulant bath, and each coagulant yielded unique wire morphology based on its interaction with the SWCNT-CSA dispersion. In particular, dimethylacetamide as a coagulant bath is shown to fabricate highly uniform SWCNT wires, and acetone coagulant baths result in the highest specific conductivity and tensile strength. A 2× improvement in specific conductivity has been measured for SWCNT wires following tensioning induced both during extrusion via increased coagulant bath depth and during solvent evaporation via mechanical strain, over that of as-extruded wires from shallower coagulant baths. Overall, combination of the optimized coagulation parameters has yielded acid-doped wires with the highest reported room temperature electrical conductivities to date of 4.1-5.0 MS/m and tensile strengths of 210-250 MPa. Such improvements in bulk electrical conductivity can impact the adoption of metal-free, multifunctional SWCNT materials for advanced cabling architectures.