Fabrication of Nanoscale Oxide Textured Surfaces on Polymers.

Nanoscale textured surfaces play an important role in creating antibacterial surfaces, broadband anti-reflective properties, and super-hydrophobicity in many technological systems. Creating nanoscale oxide textures on polymer substrates for applications such as ophthalmic lenses and flexible electronics imposes additional challenges over conventional nanofabrication processes since polymer substrates are typically temperature-sensitive and chemically reactive. In this study, we investigated and developed nanofabrication methodologies to create highly ordered oxide nanostructures on top of polymer substrates without any lithography process. We developed suitable block copolymer self-assembly, sequential infiltration synthesis (SIS), and reactive ion etching (RIE) for processes on polymer substrates. Importantly, to prevent damage to the temperature-sensitive polymer and polymer/oxide interface, we developed the process to be entirely performed at low temperatures, that is, below 80 °C, using a combination of UV crosslinking, solvent annealing, and modified SIS and RIE processes. In addition, we developed a substrate passivation process to overcome reactivity between the polymer substrate and the SIS precursors as well as a high precision RIE process to enable deep etching into the thermally insulated substrate. These methodologies widen the possibilities of nanofabrication on polymers.

Indium Oxide-Single-Walled Carbon Nanotube Composite for Ethanol Sensing at Room Temperature.

Utilizing a sol-gel synthesis, indium oxide is grown on the surface of oxidized single-walled carbon nanotubes (SWCNT) to form a hybrid material with high conductivity and sensitivity toward certain organic vapors. The room-temperature sensing of dilute ethanol and acetone vapors on the surface of indium oxide/SWCNT hybrid material is studied using electrical conductance experiments in a nonoxidizing environment. Through testing of variously calcinated materials, it was observed that the degree of annealing greatly affects the material's response to acetone and ethanol, such that the intermediate calcination condition yields the best sensitivity. DFT simulations are used to study the interface between defective SWCNT and indium oxide, as well as the interaction between ethanol and acetone molecules with the indium oxide/SWCNT hybrid material.

Exploring the radical nature of a carbon surface by electron paramagnetic resonance and a calibrated gas flow.

While the first Electron Paramagnetic Resonance (EPR) studies regarding the effects of oxidation on the structure and stability of carbon radicals date back to the early 1980s the focus of these early papers primarily characterized the changes to the structures under extremely harsh conditions (pH or temperature)(1-3). It is also known that paramagnetic molecular oxygen undergoes a Heisenberg spin exchange interaction with stable radicals that extremely broadens the EPR signal(4-6). Recently, we reported interesting results where this interaction of molecular oxygen with a certain part of the existing stable radical structure can be reversibly affected simply by flowing a diamagnetic gas through the carbon samples at STP(7). As flows of He, CO2, and N2 had a similar effect these interactions occur at the surface area of the macropore system. This manuscript highlights the experimental techniques, work-up, and analysis towards affecting the existing stable radical nature in the carbon structures. It is hoped that it will help towards further development and understanding of these interactions in the community at large.

Elucidating the role of stable carbon radicals in the low temperature oxidation of coals by coupled EPR-NMR spectroscopy - a method to characterize surfaces of porous carbon materials.

Recently, the nature of the carbon radicals stabilized in various coals was characterized using Electron Paramagnetic Resonance (EPR) spectroscopy. It was demonstrated that introducing diamagnetic gases, such as He, CO2, or N2, under STP conditions to the coal surface induces the appearance of a new type of carbon surface radical. This interesting phenomenon was not observed for all coal types, which suggests that the use of EPR measurements can provide information on functional groups that exist on the carbon surface. In the current study coupling Nuclear Magnetic Resonance (NMR) with gas flow in situ EPR measurements significantly enhances the ability to characterize the nature of these radicals and the surface functional groups of coal samples. It was observed that the oxidative reaction with aliphatic groups leads to the increase in stable carbon centered radicals. In addition, there are some species of carbon centered radicals that show reversible binding to O2. This phenomena, however, is dependent on the coal rank, sample porosity and the degree of the coal sample to undergo structural changes under the LTO process. These findings shed new light onto the complex heterogeneous low temperature oxidation reactions occurring at the coal surface.

Reducing the spin-spin interaction of stable carbon radicals.

We report the discovery that a flow of CO2, N2 or He can sufficiently reduce the spin-spin interactions of specific stable carbon centered radicals by displacing the molecular oxygen in the atmosphere enabling their detection via electron paramagnetic resonance (EPR). This finding unlike other reported effects on carbon radicals occurs under STP conditions and is reversible.

Stable radicals formation in coals undergoing weathering: effect of coal rank.

Once coal is excavated it comes into contact with atmospheric oxygen and begins to undergo low temperature oxidation. The mechanism by which the molecular oxygen interacts with the coal macromolecule is suggested to occur in several steps. These steps primarily involve O(2) diffusion to the surface where physical adsorption followed by chemical adsorption takes place. The chemical adsorption forms several types of oxides that can subsequently react to form several products, primarily CO(2). It has also been suggested that some of these oxidation mechanisms might involve radical reactions. As the previous studies were conducted under conditions where significant structural changes occur it is possible that in the low temperature range (T < 100 °C) the oxidation mechanism is different. Several different rank (lignite-subbituminous-bituminous) coals were isothermally heated at 95 °C in an air atmosphere for a period of up to 6 months and samples were collected at two week intervals. The radical concentration of each sample was measured by Continuous Wave Electron Paramagnetic Resonance (CW-EPR). It is apparent that there are distinct differences between the lower rank (lignite) and the higher rank (subbituminous, bituminous) coals. The lower rank coals exhibited only carbon centered radicals with an adjacent oxygen atom and the higher rank coals exhibited only carbon centered radicals. Interestingly, the lower rank coals exhibited no change in radical concentration due to the long term oxidation treatment while the higher rank coals showed a distinct increase in the radical concentration. These findings shed new light on the complex heterogeneous low temperature oxidation reactions occurring at the coal surface.