Carbon nanotubes (CNTs) are a relatively new allotrope of carbon that possess very unique and exciting physical characteristics. However, much is still unknown regarding their physical structure and chemical reactivity. The focus of this dissertation is to utilize the chemical modification of these filamentous carbon structures as a probe to investigate the structure and reactivity of carbon nanotubes. Also discussed is the ability of CNTs, once chemically modified, to interact with specific polymer matrices and how the addition of modified and unmodified CNTs affects the physical properties of these matrices.

Diese Arbeit befasst sich mit der Charakterisierung einer verhältnismäßig wenig beforschten Untergruppe der hochtemperatur-supraleitenden Kuprate (HTSCs-high-temperature superconducting cuprates), den elektronendotierten HTSCs, vermittels kernmagnetischer Resonanz (NMR-nuclear magnetic resonance). Die Untersuchungen umfassen 63Cu und 17O NMR an ausgerichteten Pulverproben und Einkristallen von Pr2−xCexCuO4 (x = 0, 0.05, 0.10, 0.15, 0.20) sowie auch Nd2−xCexCuO4 (x = 0, 0.13) in externen Magnetfeldern von 2.35 bis 17.6 T und Temperaturen zwischen 8 und 400 K. Durch eine Vielzahl von Experimenten wird die erste eindeutige spektrale Analyse für beide Nuklide vorgenommen. Es wird gezeigt, dass die indirekte, homonukleare Kopplung, wie sie beim Hahn-Echo-Zerfall von planarem 63,65Cu in lochdotierten HTSCs und auch im undotierten Pr2CuO4 gefunden wird, durch Elektronendotierung weitestgehend unterdrückt wird. Eine Analyse der Quadrupolaufspaltungen zeigt, dass nicht nur die lokale Verteilung der dotierten Elektronen und Löcher in den CuO2-Schichten quantitativ gemessen werden kann, sondern, dass auch Unterschiede in den 63Cu und 17O Aufspaltungen verschiedener undotierter Kuprate auf eine variable Ladungsverteilung zurückzuführen sind. Somit ist eine quantitative Messung der lokalen Ladungsverteilung in der CuO2 -Schicht der HTSCs möglich, welche ein neues, differenziertes Bild der unterschiedlichen Materialien ergibt.

Studies have been done to determine rare-earth elements’ optical and luminescent properties using wide bandgap nitride semiconductors as suitable hosts. Research done here will contribute to the information needed to further study rare-earth elements and their unique properties. Thin films of rare-earth elements erbium, terbium, ytterbium, and both erbium and ytterbium doped into AlN are studied by laser excitation. A 532 nm Nd: YAG green laser and 783nm crystal infrared laser are used for excitation in conjunction with a spectrometer to measure photoluminescence. With the 532 nm laser, AlN: Er emits peaks at 554 nm, 561 nm, and 1552 nm, AlN: Tb emits peaks at 549 nm and 562 nm, AlN: Yb emits peaks at 966 nm, and co-doped AlN: ErYb contains peaks including both AlN: Er and AlN: Yb. Energy transfer occurred from Er to Yb resulting in an increased magnitude and peak shift. The 783 nm laser gave peaks at 1563nm for AlN: Er, 1508 nm and 1533 nm for AlN: Tb, and 1567nm for AlN: ErYb. No detectable peaks were given for AlN: Yb. A peak shift was detected in comparison of AlN: Er and AlN: ErYb. A magnetic field of 1000 G was applied to AlN: ErYb resulting in an increase in intensity of the major peak at 561nm with a splitting, creating a secondary peak at 564.5 nm. Biomedical applications can be used from the high penetration ability of lower wavelength lasers and the use of a magnetic field, which is not harmful to the human body. Enhanced green emission in erbium can be useful in future optical, photonic, and electrical devices. / Department of Physics and Astronomy

Photocatalysis is an advanced oxidation process for the purification and remediation of contaminated waters and wastewaters, and is advantageous over conventional treatment technologies due to its ability to degrade emerging and recalcitrant pollutants. In addition, photocatalytic disinfection is less chemical-intensive than other methods such as chlorination, and can inactivate even highly resistant microorganisms with good efficacy. Process sustainability and cost-effectiveness may be improved by utilizing solar irradiation as the source of necessary photons for photocatalyst excitation. However, solar-induced activity of the traditionally-used titania is poor due to its inefficient visible light absorption, and recombination of photo-excited species is problematic. Additionally, mass transfer limitations and difficulties separating the catalyst from the post-treatment slurry hinder conversions and efficiencies obtainable in practice. In this research, various strategies were explored to address these issues using novel visible light active photocatalysts. Two classes of carbon-enhanced photocatalytic materials were studied: activated carbon adsorbent photocatalyst composites, and carbon-doped TiO2. Adsorbent photocatalyst composites based on activated carbon and plasmonic silver/silver chloride structures were synthesized, characterized, and experimentally investigated for their photocatalytic activity towards the degradation of model organic pollutants (methyl orange dye, phenol) and the inactivation of a model microorganism (Escherichia coli K-12) under visible light. The adsorptive behaviour of the composites towards methyl orange dye was also studied and described according to appropriate models. Photocatalytic bacterial inactivation induced by the prepared composites was investigated, and the inactivation mechanisms and roles of incorporated antimicrobial silver on disinfection were probed and discussed. These composites were extended towards magnetic removal strategies for post-use separation through the incorporation of magnetic nanoparticles to prepare Ag/AgCl-magnetic activated carbon composites, and the effect of nanoparticles addition on the properties and photoactivities of the resulting materials was explored. Another silver/silver halide adsorbent photocatalyst composite based on activated carbon and Ag/AgBr exhibiting visible light absorption due to both localized surface plasmon resonance and optical band gap absorption was synthesized and its photocatalytic activity towards organics degradation and microbial inactivation was studied. Carbon-doped mixed-phase titania was also prepared and experimentally investigated.

<p>The primary goals of this research were to investigate the electrochemical behavior of carbon nanostructures of varying morphology, identify morphological characteristics that improve electrochemical capacitance for applications in energy storage and neural stimulation, and engineer and characterize a boron-­doped diamond (BDD) electrode based electrochemical system for disinfection of human liquid waste. </p><p>Carbon nanostructures; ranging from vertically aligned multiwalled carbon nanotubes (MWCNTs), graphenated carbon nanotubes (g-­CNTs) to carbon nanosheets (CNS); were synthesized using a MPECVD system. The nanostructures were characterized by using scanning electron microscopy (SEM) and Raman spectroscopy. In addition to employing commonly used electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), a new technique was developed to evaluate the energy and power density of individual electrodes. This facilitated comparison of a variety of electrode materials without having to first develop complex device packaging schemes. It was found that smaller pore size and higher density of carbon foliates on a three-dimensional scaffold of carbon nanotubes increased specific capacitance. A design of experiments (DOE) study was conducted to explore the parametric space of the MWCNT system. A range of carbon nanostructures of varying morphology were obtained. It was observed that the capacitance was dependent on defect density. Capacitance increased with defect density.</p><p>A BDD electrode was characterized for use in a module designed to disinfect human liquid waste as a part of a new advanced energy neutral, water and additive-free toilet designed for treating waste at the point of source. The electrode was utilized in a batch process system that generated mixed oxidants from ions present in simulated urine and inactivated E. Coli bacteria. Among the mixed oxidants, the concentration of chlorine species was measured and was found to correlate to the reduction in E. Coli concentration. Finally, a new operating mode was developed that involved pulsing the voltage applied to the BDD anode led to 66% saving in energy required for disinfection and yet successfully reduced E. Coli concentration to less than the disinfection threshold.</p> / Dissertation

Carbon nanostructures have been extensively used in different applications; ranging from electronic and optoelectronic devices to energy conversion. The interest stems from the fact that covalently bonded carbon atoms can form a wide variety of structures with zero-, one- and two-dimensional configuration with different physical properties. For instance, while fullerene molecules (zero-dimensional carbon structures) realize semiconductor behavior, two-dimensional graphene shows metallic behavior with exceptional electron mobility. Moreover the possibility to even further tune these fascinating properties by means of doping, chemical modification and combining carbon based sub-classes into new hybrid structures make the carbon nanostructure even more interesting for practical application.  This thesis focuses on synthesizing SWCNT and different C60 one-dimensional structures as well as tuning their properties by means of different chemical and structural modification. The purpose of the study is to have better understanding of the synthesis and modification techniques, which opens for better control over the properties of the product for desired applications. In this thesis carbon nanotubes (CNTs) are grown by chemical vapor deposition (CVD) on iron/cobalt catalyst particles. The effect of catalyst particle size on the diameter of the grown CNTs is systematically studied and in the case of SWCNTs it is shown that the chirality distribution of the grown SWCNTs can be tuned by altering the catalyst particle composition. In further experiments, incorporation of the nitrogen atoms in SWCNTs structures is examined. A correlation between experimental characterization techniques and theoretical calculation enable for precise analysis of different types of nitrogen configuration in SWCNTs structure and in particular their effect on growth termination and electronic properties of SWCNTs are studied. C60 one-dimensional structures are grown through a solution based method known as Liquid-liquid interfacial precipitation (LLIP). By controlling the crystal seed formation at the early stage of the growth the morphology and size of the grown C60 one-dimensional structures where tuned from nanorods to large diameter rods and tubes. We further introduce a facile solution-based method to photo-polymerize the as-grown C60 nanorods, and show that such a method crates a polymeric C60 shell around the nanorods. The polymeric C60 shell exhibits high stability against common hydrophobic C60 solvents, which makes the photo-polymerized nanorods ideal for further solution-based processing. This is practically shown by decoration of both as grown and photo-polymerized nanorods by palladium nanoparticles and comparison between their electrochemical activities. The electrical properties of the C60 nanorods are also examined by utilizing a field effect transistor geometry comprising different C60 nanorods. In the last part of the study a variant of CNT is synthesized in which large diameter, few-walled CNTs spontaneously transform to a collapsed ribbon shape structure, the so called collapsed carbon nanotube (CCNT). By inserting C60 molecules into the duct edges of CCNT a new hybrid structure comprising C60 molecules and CCNT is synthesized and characterized. A further C60 insertion lead to reinflation of CCNTs, which eventually form few-walled CNT completely filled with C60 molecules.

In this thesis, I have developed a tunable two-color two-stage ultrafast Yb:fiber chirped pulse amplifier for the generation of short-pulse mid-infrared (MIR) radiation in the long-wavelength side of the "molecular fingerprint" (2.5-25 μm) using difference frequency generation (DFG) technique. The two colors called blue and red are in the wavelengths 1.03-1.11 μm and are amplified simultaneously in the same Yb-doped fiber amplifier (YDFA) stages in order to reduce the induced environmental noise on the phase difference of the pulses and to minimize the complexity and system cost. I will present numerical simulations on the two-stage YDFA system to amplify a two-color spectrum in the wavelengths 1.03-1.11 μm. The first and second YDFA called preamplifier and main amplifier are single-clad, single-mode and double-clad, single-mode YDFA respectively. From numerical simulations, the optimal length of the preamplifier to have equal power at two colors centered at 1043 nm and 1105 nm are in agreement with experimental results. It is well known that the power of MIR radiation generated by difference frequency mixing of two wavelengths scales up with the product of mixing powers in a fixed-field approximation. Furthermore, for the gain narrowing effect on the short-wavelength side of the YDFA gain profile, the spectral bandwidth of the blue color decreases resulting in pulse broadening. In addition, for the two colors separated largely, the amplified spontaneous emission is intensified. Considering the cited factors, I will present the modeling results on the two-color, two-stage YDFA system that the product of the power of the two colors is maximized for a maximized wavelength separation between the two mixing colors and a minimized gain narrowing on the blue color in order to build an as broadly tunable and powerful as possible ultrafast mid-infrared source by difference frequency mixing of the two colors. In this research, I achieved a wavelength separation as broad as 71 nm between pulses centered at 1038 nm and 1109 nm from the two-color ultrafast YDFA system. I achieved combined average powers of 2.7 W just after the main amplifier and 1.5 W after compressing the two-color pulses centered at 1041 nm and 1103 nm to nearly Fourier transform limited pulses. From autocorrelation measurements, the full width at half maximum (FWHM) of the compressed two-color pulses with the peak wavelengths of 1041 nm and 1103 nm was ~500 fs. By mixing the tunable two-color pulses in a 1-mm-thick GaSe crystal using DFG technique, I achieved tunable short-pulse MIR radiation. In this research, I achieved short-pulse MIR radiation tunable in the wavelengths 16-20 μm. The MIR tuning range from the lower side was limited to the 16 μm because of the 71-nm limitation on the two-color separation and from the upper side was limited to the 20 μm because of the 20-μm cutoff absorption wavelength of GaSe. Based on measured MIR spectra, the MIR pulses have a picosecond pulse duration in the wavelengths 16-20 μm. The FWHM of measured spectra of the MIR pulses increases from 0.3 μm to 0.8 μm as the MIR wavelength increases from 16 μm to 20 μm. According to Fourier transform theory, the FWHM of the MIR spectra corresponds to the bandwidth of picosecond MIR pulses assuming that the MIR pulses are perfectly Fourier-transform-limited Gaussian pulses. In this research, I achieved a maximum average power of 1.5 mW on short-pulse MIR radiation at the wavelength 18.5 μm corresponding to the difference frequency of the 500-fs two-color pulses with the peak wavelengths of 1041 nm and 1103 nm and average powers of 1350 mW and 80 mW respectively. Considering the gain bandwidth, Ti:sapphire is a main competitor to the YDFA to be used in the two-color ultrafast laser systems. In the past, the broad gain bandwidth of Ti:sapphire crystal has resulted in synchronized two-color pulses with a wavelength separation up to 120 nm. Apart from its bulkiness and high cost, Ti:sapphire laser system is limited to a watt-level output average power at room temperature mainly due to Kerr lensing problem that occurs at high pumping powers. In comparison, YDFA as a laser amplifier has a narrower gain bandwidth but it is superior in terms of average power. Optical parametric generation (OPG) and optical parametric amplification (OPA) techniques are two competitors to DFG technique for the generation of short-pulse long-wavelength MIR radiation. Although OPG offers a tunability range as broad as DFG, the MIR output power is lower because of the absence of input signal pulses. From the OPA technique, the tunability range is not as broad as the DFG technique due to limitations with the spectral bandwidth of the optical elements. Currently, quantum cascade lasers (QCLs) are the state-of-art MIR laser sources. At the present time, the tunability range of a single MIR QCL is not as abroad as that achieved from the DFG technique. More, mode-locked MIR QCLs are not abundant mainly because of the fast gain recovery time. Thus, the generation of widely tunable short-pulse MIR radiation from DFG technique such as that developed in this thesis remains as a persistent technological solution. The application of the system developed in this thesis is twofold: on one hand, the tunable two-color ultrashort pulses will find applications for example in pump-probe ultrafast spectroscopy, short-pulse MIR generation, and optical frequency combs generation. On the other hand, the short-pulse MIR radiation will find applications for example in time-resolved MIR spectroscopy to study dynamical behavior of large molecules such as organic and biological molecules.

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2008. / Includes bibliographical references (leaves 86-101). Also available in electronic version.

Thesis (M.S.)--Ohio University, August, 1997. / Title from PDF t.p.

Thesis (Ph. D.)--University of Canterbury, 2009. / Typescript (photocopy). Includes bibliographical references. Also available via the World Wide Web.