Control of wettability of carbon nanotube array by reversible dry oxidation for superhydrophobic coating and supercapacitor applications

In this thesis, dry chemical modification methods involving UV/ozone, oxygen plasma, and vacuum annealing treatments are explored to precisely control the wettability of CNT arrays. By varying the exposure time of these treatments the surface concentration of oxygenated groups adsorbed on the CNT arrays can be controlled. CNT arrays with very low amount of oxygenated groups exhibit a superhydrophobic behavior. In addition to their extremely high static contact angle, they cannot be dispersed in DI water and their impedance in aqueous electrolytes is extremely high. These arrays have an extreme water repellency capability such that a water droplet will bounce off of their surface upon impact and a thin film of air is formed on their surface as they are immersed in a deep pool of water. In contrast, CNT arrays with very high surface concentration of oxygenated functional groups exhibit an extreme hydrophilic behavior. In addition to their extremely low static contact angle, they can be dispersed easily in DI water and their impedance in aqueous electrolytes is tremendously low. Since the bulk structure of the CNT arrays are preserved during the UV/ozone, oxygen plasma, and vacuum annealing treatments, all CNT arrays can be repeatedly switched between superhydrophilic and superhydrophobic, as long as their O/C ratio is kept below 18%.

The effect of oxidation using UV/ozone and oxygen plasma treatments is highly reversible as long as the O/C ratio of the CNT arrays is kept below 18%. At O/C ratios higher than 18%, the effect of oxidation is no longer reversible. This irreversible oxidation is caused by irreversible changes to the CNT atomic structure during the oxidation process. During the oxidation process, CNT arrays undergo three different processes. For CNT arrays with O/C ratios lower than 40%, the oxidation process results in the functionalization of CNT outer walls by oxygenated groups. Although this functionalization process introduces defects, vacancies and micropores opening, the graphitic structure of the CNT is still largely intact. For CNT arrays with O/C ratios between 40% and 45%, the oxidation process results in the etching of CNT outer walls. This etching process introduces large scale defects and holes that can be obviously seen under TEM at high magnification. Most of these holes are found to be several layers deep and, in some cases, a large portion of the CNT side walls are cut open. For CNT arrays with O/C ratios higher than 45%, the oxidation process results in the exfoliation of the CNT walls and amorphization of the remaining CNT structure. This amorphization process can be implied from the disappearance of C-C sp2 peak in the XPS spectra associated with the pi-bond network.

The impact behavior of water droplet impinging on superhydrophobic CNT arrays in a low viscosity regime is investigated for the first time. Here, the experimental data are presented in the form of several important impact behavior characteristics including critical Weber number, volume ratio, restitution coefficient, and maximum spreading diameter. As observed experimentally, three different impact regimes are identified while another impact regime is proposed. These regimes are partitioned by three critical Weber numbers, two of which are experimentally observed. The volume ratio between the primary and the secondary droplets is found to decrease with the increase of Weber number in all impact regimes other than the first one. In the first impact regime, this is found to be independent of Weber number since the droplet remains intact during and subsequent to the impingement. Experimental data show that the coefficient of restitution decreases with the increase of Weber number in all impact regimes. The rate of decrease of the coefficient of restitution in the high Weber number regime is found to be higher than that in the low and moderate Weber number. Experimental data also show that the maximum spreading factor increases with the increase of Weber number in all impact regimes. The rate of increase of the maximum spreading factor in the high Weber number regime is found to be higher than that in the low and moderate Weber number. Phenomenological approximations and interpretations of the experimental data, as well as brief comparisons to the previously proposed scaling laws, are shown here.

Dry oxidation methods are used for the first time to characterize the influence of oxidation on the capacitive behavior of CNT array EDLCs. The capacitive behavior of CNT array EDLCs can be tailored by varying their oxygen content, represented by their O/C ratio. The specific capacitance of these CNT arrays increases with the increase of their oxygen content in both KOH and Et4NBF4/PC electrolytes. As a result, their gravimetric energy density increases with the increase of their oxygen content. However, their gravimetric power density decreases with the increase of their oxygen content. The optimally oxidized CNT arrays are able to withstand more than 35,000 charge/discharge cycles in Et4NBF4/PC at a current density of 5 A/g while only losing 10% of their original capacitance.

Large-eddy simulations of fully developed turbulent channel and pipe flows with smooth and rough walls

Studies in turbulence often focus on two flow conditions, both of which occur frequently in real-world flows and are sought-after for their value in advancing turbulence theory. These are the high Reynolds number regime and the effect of wall surface roughness. In this dissertation, a Large-Eddy Simulation (LES) recreates both conditions over a wide range of Reynolds numbers Re_τ = O(10²)-O(10⁸) and accounts for roughness by locally modeling the statistical effects of near-wall anisotropic fine scales in a thin layer immediately above the rough surface. A subgrid, roughness-corrected wall model is introduced to dynamically transmit this modeled information from the wall to the outer LES, which uses a stretched-vortex subgrid-scale model operating in the bulk of the flow. Of primary interest is the Reynolds number and roughness dependence of these flows in terms of first and second order statistics. The LES is first applied to a fully turbulent uniformly-smooth/rough channel flow to capture the flow dynamics over smooth, transitionally rough and fully rough regimes. Results include a Moody-like diagram for the wall averaged friction factor, believed to be the first of its kind obtained from LES. Confirmation is found for experimentally observed logarithmic behavior in the normalized stream-wise turbulent intensities. Tight logarithmic collapse, scaled on the wall friction velocity, is found for smooth-wall flows when Re_τ ≥ O(10⁶) and in fully rough cases. Since the wall model operates locally and dynamically, the framework is used to investigate non-uniform roughness distribution cases in a channel, where the flow adjustments to sudden surface changes are investigated. Recovery of mean quantities and turbulent statistics after transitions are discussed qualitatively and quantitatively at various roughness and Reynolds number levels. The internal boundary layer, which is defined as the border between the flow affected by the new surface condition and the unaffected part, is computed, and a collapse of the profiles on a length scale containing the logarithm of friction Reynolds number is presented. Finally, we turn to the possibility of expanding the present framework to accommodate more general geometries. As a first step, the whole LES framework is modified for use in the curvilinear geometry of a fully-developed turbulent pipe flow, with implementation carried out in a spectral element solver capable of handling complex wall profiles. The friction factors have shown favorable agreement with the superpipe data, and the LES estimates of the Karman constant and additive constant of the log-law closely match values obtained from experiment.