Anil Kumar Karumuri

Hierarchical nanostructures by nanotube grafting on porous cellular surfaces

Natural biological systems make use of capillary-type hierarchical structures in order to enhance surface functionality within limited size. This paper discusses fabrication of similar synthetic structures by grafting carbon nanotubes (CNTs) on microcellular substrates such as graphitic foam. A major hurdle so far had been deposition of dense CNT layers inside uneven pores. This has been overcome in this study by pre-coating the porous surface with plasma-derived silica molecules. It is seen that the pre-coating not only increases the density of nanocatalyst attachment on the surface but also makes each nanocatalyst more effective in nucleation and growth of nanotubes. The CNT layers formed are strongly attached to the substrate, which makes them particularly suitable for use in robust hierarchical devices in the future.

Silver Nanoparticles Supported on Carbon Nanotube Carpets: Influence of Surface Functionalization

The effectiveness of nanoparticle-based functional devices depends strongly on the surface morphology and area of the support. An emerging powerful approach of increasing the available surface area without decreasing strength or increasing bulk is to attach arrays of suitable nanotubes on the surface, and to attach the necessary nanoparticles to them. Earlier publications by this team have shown that carpet-like arrays of carbon nanotubes (CNTs) can be successfully grown on a variety of larger carbon substrates such as graphite, foams and fabric, which offer hierarchical multiscale supporting architecture suitable for the attachment of silver nanoparticles (AgNPs). A limiting factor of pure CNT arrays in fluid-based applications is their hydrophobicity, which can reduce the percolation of an aqueous medium through individual nanotubes. Previous studies have demonstrated that the treatment of CNT carpets with dry (oxygen) plasma can induce reversible wettability, and treatment with wet (sol-gel) coating can impart permanent wettability. In this paper, we report the influence of such treatments on the attachment of AgNPs, and their effectiveness in water disinfection treatments. Both types of hydrophilic surface treatment show an increase in silver loading on the CNT carpets. Oxygen-plasma treated surfaces (O-CNT) show fine and densely packed AgNPs, whereas silica-coated nanotubes (silica-CNT) show uneven clusters of AgNPs. However, O-CNT surfaces lose their hydrophilicity during AgNP deposition, whereas silica-CNT surfaces remain hydrophilic. This difference significantly impacts the antibacterial effectiveness of these materials, as tested in simulated water containing Gram negative Escherichia coli (E. coli, JM109). AgNPs on silica-coated CNT substrates showed significantly higher reduction rates of E. coli compared to AgNPs on plasma-treated CNT substrates, despite the finer and better dispersed AgNP distribution in the latter. These results provide important insights into different aspects of surface modification approaches that can control the wettability of CNT carpets, and their applicability in water treatment applications.

Wettability tailoring of nanotube carpets: morphology-chemistry synergy for hydrophobic–hydrophilic cycling

Carpet-like arrays of carbon nanotubes (CNTs) on graphitic carbon materials have been investigated in order to understand all-carbon hierarchical structures for multifunctional surface-active devices. Pure CNT carpets are seen to be super-hydrophobic as long as they are well aligned. For future applications involving aqueous environments, the ability to tailor the surface wettability and switch it on demand can be very useful, and enable unprecedented devices related to microfluidics, catalysis and sensing/detection systems. In this study, microwave plasma treatments were used to functionalize CNT carpets for a progressive increase in wettability so that they could eventually become super-hydrophilic. This change could be reversed by heating. Alternating between microwave plasma treatment and heating enabled repeated cycling of the CNT carpets between super-hydrophobic and super-hydrophilic states. This paper focuses on the influence of these two treatments on surface chemical states and multiscale morphology of CNT carpets, and their relation to wettability. It was shown by X-ray Photoelectron Spectroscopy (XPS) that oxygen-containing groups attached to surface carbon atoms are created during plasma treatment. These species desorb at temperatures of about 110 °C. The strength of C 1s and O 1s XPS signals from these radicals were seen to have direct correlation with water contact angles. In addition to surface chemistry, carpet morphology plays an important role in contact angle variations. Extreme surface roughness caused by high aspect-ratio of nanotubes would strongly accentuate both hydrophobic and hydrophilic behavior compared to flat surfaces. Classical geometric models of liquid droplets on uneven solids have been considered. Topological image analysis combined with intrinsic contact angle on flat graphene is used to predict the contact angle of these carpets, which matches well with experimental results. This analysis further explains why observed contact angles change if the vertical alignment of CNT is disturbed.