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.

Magnetic alignment of high-aspect ratio microwires into vertical arrays

Fundamental studies of magnetic alignment of highly anisotropic mesostructures can enable the clean-room-free fabrication of flexible, array-based solar and electronic devices, in which preferential orientation of nano- or microwire-type objects is desired. In this study, ensembles of 100 micron long Si microwires with ferromagnetic Ni and Co coatings are oriented vertically in the presence of magnetic fields. The degree of vertical alignment and threshold field strength depend on geometric factors, such as microwire length and ferromagnetic coating thickness, as well as interfacial interactions, which are modulated by varying solvent and substrate surface chemistry. Microwire ensembles with vertical alignment over 97% within 10 degrees of normal, as measured by X-ray diffraction, are achieved over square cm scale areas and set into flexible polymer films. A force balance model has been developed as a predictive tool for magnetic alignment, incorporating magnetic torque and empirically derived surface adhesion parameters. As supported by these calculations, microwires are shown to detach from the surface and align vertically in the presence of magnetic fields on the order of 100 gauss. Microwires aligned in this manner are set into a polydimethylsiloxane film where they retain their vertical alignment after the field has been removed and can subsequently be used as a flexible solar absorber layer. Finally, these microwires arrays can be protected for use in electrochemical cells by the conformal deposition of a graphene layer.

Synthesis of nickel(II) complexes of alpha-isoxazolylazo-beta-diketones and their absorption of spin-coating films and thermal properties for HD-DVD-R

Three kinds of new nickel(II) complexes of alpha-isoxazolylazo-beta-diketones with blue-violet light absorption were synthesized. Their structures were postulated based on elemental analysis, MS and FT-IR spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. The absorption properties and thermal stability of these complexes were discussed. The static optical recording test for high density digital versatile disc-recordable (HD-DVD-R) system was also studied. (c) 2005 Elsevier B.V. All rights reserved.

Determination and analysis of the optical constants of thin films of nickel(II) and copper(II) hydrazone complexes by spectroscopic ellipsometry

Thin films of four nickel(II) and copper(II) hydrazone complexes, which will hopefully be used as recording layers for the next-generation of high-density recordable disks, were prepared by using the spin-coating method. Absorption spectra of the thin films on K9 optical glass substrates in the 300-700 nm wavelength region were measured. Optical constants (complex refractive indices N) and thickness d of the thin films prepared on single-crystal silicon substrates in the 275-675 nm wavelength region were investigated on a rotating analyzer-polarizer scanning ellipsometer by fitting the measured ellipsometric angles (Psi(lambda) and Delta(lambda)) with a 3-layer model (Si/dye film/air). The dielectric functions epsilon and absorption coefficients alpha as a function of the wavelength were then calculated. Additionally, a design to achieve high reflectivity and optimum dye film thickness with an appropriate reflective layer was performed with the Film Wizard software using a multilayered model (PC substrate/reflective layer/dye film/air) at 405 nm wavelength.

Preparation, characterization and gas sensing properties of nickel octa-iso-pentyloxynaphthalocyanine spin-coating films

Spin-coated films of nickel 1,6,10,15,19,24,28,33-octa-iso-pentyloxy-2,3-naphthalocyanine complex were obtained and characterized by UV-vis absorption spectroscopy. A linear relationship between the absorbance and solution concentration was observed. Low concentration solutions could afford smooth and homogeneous film surfaces as indicated by atomic force microscopy. The film structure was studied by small angle X-ray diffraction. The films were used for NO2 sensing experiments. The results indicate that the elevation of sensing temperature can shorten the response time and increase recovery ratio and response magnitude of the sensing films. High NO2 concentration can also shorten response time. (C) 2008 Elsevier B.V. All rights reserved.

Rare earth dibenzoylmethane complexes for potential application as high-density recordable optical recording materials

Three kinds of rare earth complexes derived from dibenzoylmethane (DBM) ligand were synthesized by reacting free ligand and different rare earth ions(La (3+), Sm3+ and Gd3+). Their contents and structures were postulated based on elemental analysis, LDI-TOF-MS, FT-IR spectra and UV-Vis spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. Their solubility in organic solvents, absorption and reflection properties of thin film and thermal stability of these complexes were evaluated. These complexes would be a promising recording material for high-density digital versatile disc-recordable (HD-DVD-R) system. (c) 2007 Elsevier B.V. All rights reserved.

Bimesogenic liquid crystals: New materials for high performance flexoelectric and blue phase displays

In this paper we will describe new bimesogenic nematic liquid crystals that have high flexoelectro-optic coefficients (e/K),of the order of 1.5 CN 1 m-1, high switching angles, up to 100° and fast response times, of the order of 100μs or less. We will describe devices constructed, using the ULH texture that may be switched to the optimum angle of 45° for a birefringence based device with the fields of 4Vμm-1 over a wide temperature range. Such devices use an "in plane" optical switching mode, have gray scale capability and a wide viewing angle. We will describe devices using the USH or Grandjean texture that have an optically isotropic "field off" black state, uses "in plane" switching E fields, to give an induced birefringence phase device, with switching times of the order of 20μs. We will briefly describe new highly reflective Blue Phase devices stable over a 50V temperature range in which an electric field is used to switch the reflection from red to green, for example. Full RGB reflections may be obtained with switching times of a few milliseconds. Finally we will briefly mention potential applications including high efficiency RGB liquid crystal laser sources. © 2006 SID.

Ultrafast switching liquid crystals for electro-optic transmissive and reflective displays and microscopic lasers

We have used novel liquid crystals with extremely large flexoelectric coefficients in a range of ultra-fast photonic/display modes, namely 1) the uniform lying helix, that leads to in-plain switching, birefringence based displays with 100 μs switching times at low fields, i.e.2-5 V/μm, wide viewing angle and analogue or grey scale capability, 2) the uniform standing helix, using planar surface alignment and in-plane fields, with sub ms response times and optical contrasts in excess of 5000:1 with a perfect black "off state", 3) the wide temperature range blue phase that leads to field controlled reflective color and 4) high slope efficiency, wide wavelength range tunable narrow linewidth microscopic liquid crystal lasers.

High speed titanium coatings by supersonic laser deposition

The importance of metal coating technologies drives the continuous improvement of metal deposition techniques for application in a wide range of industrial sectors. This work presents the foundations of a new process technology for the deposition of titanium coatings on steel tube substrates using supersonic powder streams and impact site laser heating, known as Supersonic Laser Deposition (SLD). Metallic deposits are obtained under appropriate impact conditions without the need for exceeding the melting point of the deposited material or substrate leading to improved coating quality. Details of the experimental approach are presented along with the general characteristics of the titanium coating produced using this novel coatings method. © 2011 Elsevier B.V. All rights reserved.

Ultrafast switching liquid crystals for electro-optic transmissive and reflective displays and microscopic lasers

We report on novel liquid crystals with extremely large flexoelectric coefficients in a range of ultra-fast photonic modes, namely 1) the uniform lying helix, that leads to in-plain switching, birefringence phase devices with 100 μs switching times at low fields, i.e.2-5 V/μm, and analogue or grey scale capability, 2) the uniform standing helix, using planar surface alignment and in-plane fields, with sub ms response times and optical contrasts in excess of 5000:1 with a perfect optically isotropic or black "off state", 3) the wide temperature range blue phase that leads to field controlled reflective color, 4) chiral nematic optical reflectors electric field tunable over a wide wavelength range and 5) high slope efficiency, wide wavelength range tunable narrow linewidth microscopic liquid crystal lasers. © 2011 Materials Research Society.

Effect of laser heating temperature on coating characteristics of Stellite 6 deposited by cold spray

Laser-assisted cold spray (LCS) is a new coating and fabrication process which combines some advantages of CS: solid-state deposition, retain their initial composition and high build rate with the ability to deposit materials which are either difficult or impossible to deposit using cold spray alone. Stellite 6 powder is deposited on medium carbon steels by LCS using N 2 as carrier gas pressure. The topography, cross section thickness, structure of the coatings is examined by SEM, optical microscopy, EDX. The results show that thickness and fluctuation of coating are improved with increased deposition site temperature. Porosity of coating is affected by N 2 and deposition site temperature. In this paper, it presents optimal coating using N 2 at a pressure of 3 MPa and temperature of 450°C and deposition site temperature of 1100°C.

UV durable colour pigment doped SmA liquid crystal composites for outdoor trans-reflective bi-stable displays

High brightness trans-reflective bi-stable displays based on smectic A (SmA) liquid crystals (LCs) can have nearly perfect transparency in the clear state and very high reflection in the scattered state. Because the LC material in use is stable under UV radiation, this kind of displays can stand for strong day-light and therefore be ideal for outdoor applications from e-books to public signage and advertisement. However, the colour application has been limited because the traditional colourants in use are conventional dyes which are lack of UV stability and that their colours are easily photo bleached. Here we present a colour SmA display demonstrator using pigments as colourant. Mixing pigments with SmA LCs and maintain the desirable optical switching performance is not straightforward. We show here how it can be done, including how to obtain fine sized pigment nano-particles, the effects of particle size and size distribution on the display performance. Our optimized pigments/SmA compositions can be driven by a low frequency waveform (∼101Hz) to a scattered state to exhibit colour while by a high frequency waveform (∼103Hz) to a cleared state showing no colour. Finally, we will present its excellent UV life-time (at least >7.2 years) in comparison with that of dye composition (∼2.4 years). The complex interaction of pigment nano-particles with LC molecules and the resulting effects on the LC electro-optical performances are still to be fully understood. We hope this work will not only demonstrate a new and practical approach for outdoor reflective colour displays but also provide a new material system for fundamental liquid crystal colloid research work. © 2012 SPIE.

Core design options for high conversion BWRs operating in Th- 233U fuel cycle

Several options of fuel assembly design are investigated for a BWR core operating in a closed self-sustainable Th-233U fuel cycle. The designs rely on an axially heterogeneous fuel assembly structure consisting of a single axial fissile zone "sandwiched" between two fertile blanket zones, in order to improve fertile to fissile conversion ratio. The main objective of the study was to identify the most promising assembly design parameters, dimensions of fissile and fertile zones, for achieving net breeding of 233U. The design challenge, in this respect, is that the fuel breeding potential is at odds with axial power peaking and the core minimum critical power ratio (CPR), hence limiting the maximum achievable core power rating. Calculations were performed with the BGCore system, which consists of the MCNP code coupled with fuel depletion and thermo-hydraulic feedback modules. A single 3-dimensional fuel assembly having reflective radial boundaries was modeled applying simplified restrictions on the maximum centerline fuel temperature and the CPR. It was found that axially heterogeneous fuel assembly design with a single fissile zone can potentially achieve net breeding, while matching conventional BWR core power rating under certain restrictions to the core loading pattern design. © 2013 Elsevier B.V. All rights reserved.

A solid-phase microextraction fiber coated with diglycidyloxycalix[4]arene yields very high extraction selectivity and sensitivity during the analysis of chlorobenzenes in soil

A novel fiber coated with novel sol-gel (5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-diglycidyloxycalix[4]arene/hydroxy-terminated silicone oil; diglycidyloxy-C[4]/OH-TSO) was prepared for use with headspace solid-phase microextraction (HS-SPME) combined with gas chromatography (GC) and electron capture detection (ECD), which was applied in order to determine nine chlorobenzenes in soil matrices. Due to the improved fiber preparation, which increases the percentage of calixarene in the coating, the new calixarene fiber exhibits very high extraction selectivity and sensitivity to chlorine-substituted compounds. Various parameters affecting the extraction efficiency were optimized in order to maximize the sensitivity during the chlorobenzene analysis. Interferences from different soil matrices with different characteristics were investigated, and the amount extracted was strongly influenced by the matrix. Therefore, a standard addition protocol was performed on the real soil samples. The linear ranges of detection for the chlorobenzenes tested covered three orders of magnitude, and correlation coefficients > 0.9976 and relative standard deviations (RSD) < 8% were observed. The detection limits were found at sub-ng/g of soil levels, which were about an order of magnitude lower than those given by the commercial poly(dimethylsiloxane) (PDMS) coating for most of the compounds. The recoveries ranged from 64 to 109.6% for each analyte in the real kaleyard soil matrix when different concentration levels were determined over the linear range, which confirmed the reliability and feasibility of the HS-SPME/GC-ECD approach using the fiber coated with diglycidyloxy-C[4]/OH-TSO for the ultratrace analysis of chlorobenzenes in complex matrices.

High performance transistors based on the controlled growth of triisopropylsilylethynyl-pentacene crystals via non-isotropic solvent evaporation

Triisopropylsilylethynyl-pentacene (TIPS-PEN) has proven to be one of the most promising small molecules in the field of molecular electronics, due to its unique features in terms of stability, performance and ease of processing. Among a wide variety of well-established techniques for the deposition of TIPS-PEN, blade-metered methods have recently gained great interest towards the formation of uniform crystalline films over a large area. Following this rationale, we herein designed a versatile approach based on blade-coating, which overcomes the problem of anisotropic crystal formation by manipulating the solvent evaporation behaviour, in a way that brings about a preferential degree of crystal orientation. The applicability of this method was evaluated by fabricating field-effect transistors on glass as well as on silicon dioxide/silicon (SiO2/Si) substrates. Interestingly, in an attempt to improve the rheological and wetting behaviour of the liquid films on the SiO2/Si substrates, we introduced a polymeric interlayer of polystyrene (PS) or polymethylmethacrylate (PMMA) which concurrently acts as passivation and crystallization assisting layer. In this case, the synergistic effects of the highly-ordered crystalline structure and the oxide surface modification were thoroughly investigated. The overall performance of the fabricated devices revealed excellent electrical characteristics, with high saturation mobilities up to 0.72 cm2 V-1 s-1 (on glass with polymeric dielectric), on/off current ratio >104 and low threshold voltage values (<-5 V). This journal is © the Partner Organisations 2014.