Ultralight Interconnected Metal Oxide Nanotube Networks.

Record-breaking ultralow density aluminum oxide structures are prepared using a novel templating technique. The alumina structures are unique in that they are comprised by highly aligned and interconnected nanotubes yielding anisotropic behavior. Large-scale network structures with complex form-factors can easily be made using this technique. The application of the low density networks as humidity sensing materials as well as thermal insulation is demonstrated.

Photoluminescence Mechanism and Photocatalytic Activity of Organic-Inorganic Hybrid Materials Formed by Sequential Vapor Infiltration.

Organic-inorganic hybrid materials formed by sequential vapor infiltration (SVI) of trimethylaluminum into polyester fibers are demonstrated, and the photoluminescence of the fibers is evaluated using a combined UV-vis and photoluminescence excitation (PLE) spectroscopy approach. The optical activity of the modified fibers depends on infiltration thermal processing conditions and is attributed to the reaction mechanisms taking place at different temperatures. At low temperatures a single excitation band and dual emission bands are observed, while, at high temperatures, two distinct absorption bands and one emission band are observed, suggesting that the physical and chemical structure of the resulting hybrid material depends on the SVI temperature. Along with enhancing the photoluminescence intensity of the PET fibers, the internal quantum efficiency also increased to 5-fold from ∼4-5% to ∼24%. SVI processing also improved the photocatalytic activity of the fibers, as demonstrated by photodeposition of Ag and Au metal particles out of an aqueous metal salt solution onto fiber surfaces via UVA light exposure. Toward applications in flexible electronics, well-defined patterning of the metallic materials is achieved by using light masking and focused laser rastering approaches.

Ultralight anisotropic foams from layered aligned carbon nanotube sheets.

In this work, we present large scale, ultralight aligned carbon nanotube (CNT) structures which have densities an order of magnitude lower than CNT arrays, have tunable properties and exhibit resiliency after compression. By stacking aligned sheets of carbon nanotubes and then infiltrating with a pyrolytic carbon (PyC), resilient foam-like materials were produced that exhibited complete recovery from 90% compressive strain. With density as low as 3.8 mg cm(-3), the foam structure is over 500 times less dense than bulk graphite. Microscopy revealed that PyC coated the junctions among CNTs, and also increased CNT surface roughness. These changes in the morphology explain the transition from inelastic behavior to foam-like recovery of the layered CNT sheet structure. Mechanical and thermal properties of the foams were tuned for different applications through variation of PyC deposition duration while dynamic mechanical analysis showed no change in mechanical properties over a large temperature range. Observation of a large and linear electrical resistance change during compression of the aligned CNT/carbon (ACNT/C) foams makes strain/pressure sensors a relevant application. The foams have high oil absorption capacities, up to 275 times their own weight, which suggests they may be useful in water treatment and oil spill cleanup. Finally, the ACNT/C foam's high porosity, surface area and stability allow for demonstration of the foams as catalyst support structures.

Conformal atomic layer deposition of alumina on millimeter tall, vertically-aligned carbon nanotube arrays.

Atomic layer deposition (ALD) can be used to coat high aspect ratio and high surface area substrates with conformal and precisely controlled thin films. Vertically aligned arrays of multiwalled carbon nanotubes (MWCNTs) with lengths up to 1.5 mm were conformally coated with alumina from base to tip. The nucleation and growth behaviors of Al2O3 ALD precursors on the MWCNTs were studied as a function of CNT surface chemistry. CNT surfaces were modified through a series of post-treatments including pyrolytic carbon deposition, high temperature thermal annealing, and oxygen plasma functionalization. Conformal coatings were achieved where post-treatments resulted in increased defect density as well as the extent of functionalization, as characterized by X-ray photoelectron spectroscopy and Raman spectroscopy. Using thermogravimetric analysis, it was determined that MWCNTs treated with pyrolytic carbon and plasma functionalization prior to ALD coating were more stable to thermal oxidation than pristine ALD coated samples. Functionalized and ALD coated arrays had a compressive modulus more than two times higher than a pristine array coated for the same number of cycles. Cross-sectional energy dispersive X-ray spectroscopy confirmed that Al2O3 could be uniformly deposited through the entire thickness of the vertically aligned MWCNT array by manipulating sample orientation and mounting techniques. Following the ALD coating, the MWCNT arrays demonstrated hydrophilic wetting behavior and also exhibited foam-like recovery following compressive strain.

Copper-encapsulated vertically aligned carbon nanotube arrays.

A new procedure is described for the fabrication of vertically aligned carbon nanotubes (VACNTs) that are decorated, and even completely encapsulated, by a dense network of copper nanoparticles. The process involves the conformal deposition of pyrolytic carbon (Py-C) to stabilize the aligned carbon-nanotube structure during processing. The stabilized arrays are mildly functionalized using oxygen plasma treatment to improve wettability, and they are then infiltrated with an aqueous, supersaturated Cu salt solution. Once dried, the salt forms a stabilizing crystal network throughout the array. After calcination and H2 reduction, Cu nanoparticles are left decorating the CNT surfaces. Studies were carried out to determine the optimal processing parameters to maximize Cu content in the composite. These included the duration of Py-C deposition and system process pressure as well as the implementation of subsequent and multiple Cu salt solution infiltrations. The optimized procedure yielded a nanoscale hybrid material where the anisotropic alignment from the VACNT array was preserved, and the mass of the stabilized arrays was increased by over 24-fold because of the addition of Cu. The procedure has been adapted for other Cu salts and can also be used for other metal salts altogether, including Ni, Co, Fe, and Ag. The resulting composite is ideally suited for application in thermal management devices because of its low density, mechanical integrity, and potentially high thermal conductivity. Additionally, further processing of the material via pressing and sintering can yield consolidated, dense bulk composites.