Thesis advisor: Lawrence T. Scott / The distinctive molecular structure of carbon nanotubes makes them desirable for electronic and chemical materials; however, current production methods are limited with respect to purity and chirality. Geodesic polyarenes serve as superb templates for the bottom up synthesis of carbon nanotube end-caps, setting the chirality and dimensions of the carbon nanotubes. The work herein describes the synthetic efforts towards the rational synthesis of a [6,6] carbon nanotube end-cap. Chapter 1 describes the efforts towards the synthesis of a C60H12 end-cap, in which the synthesis of an advanced intermediate, peri-bis(dibenzo[a,g]corannulene) is complete; however, the insolubility of this material proved to be problematic in a subsequent cycloaddition reaction. This reaction is examined computationally in order to understand the failure of the addition of dienophile, maleic anhydride, to peri-bis(dibenzo[a,g]corannulene). In Chapters 2 and 3, the development of solubility-enhancing methods is described. The development of a solubility-enhancing dienophile is successfully employed to induce the solubility of a formerly insoluble diene, peri-bis(dibenzo[a,g]corannulene), through Diels-Alder addition. Another method, employs the incorporation of tert-butyl groups onto peri-bis(dibenzo[a,g]corannulene) to successfully induce solubility. The enhanced-solubility enables the successful Diels-Alder addition of simple maleimide dienophiles, installing all necessary carbon atoms for the desired end-cap. Pyrolysis of the bis-anhydride derived from the aromatized bis-maleimide adduct afforded the C60H12 end-cap, which is the second carbon nanotube end-cap ever synthesized and the first of these dimensions. Chapter 3 also explores a palladium catalyzed intramolecular arylation reaction to form a pivotal intermediate in the synthesis of the end-cap, dibenzo[a,g]corannulene. The mechanism for the formation of a problematic byproduct resulting from reductive dehalogenation is discussed. Utilizing a deuterium labeled solvent, it is found that deuterium is incorporated onto the hydrocarbon, indicating that the solvent (N,N-dimethylformamide-d7) is the source of hydrogen for the reductive dehalogenation. These conditions are further exploited in Chapter 4 for the convenient perdeuteration of a variety of polycyclic aromatic hydrocarbons. Chapter 5 describes the first synthesis of a nitrogen containing geodesic polyarene, dibenzo[g,m]azacorannulene. This synthesis is completed in seven steps from a commercially available source in a 28% overall yield. / Thesis (PhD) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

This thesis deals with the analytical study of vibration of carbon nanotubes and graphene plates. First, a brief overview of the traditional Bresse-Timoshenko models for thick beams and Uflyand-Mindlin models for thick plates will be conducted. It has been shown in the literature that the conventionally utilized mechanical models overcorrect the shear effect and that of rotary inertia. To improve the situation, two alternative versions of theories of beams and plates are proposed. The first one is derived through the use of equilibrium equations and leads to a truncated governing differential equation in displacement. It is shown, by considering a power series expansion of the displacement, that this is asymptotically consistent at the second order. The second theory is based on slope inertia and results in the truncated equation with an additional sixth order derivative term. Then, these theories will be extended in order to take into account some scale effects such as interatomic interactions that cannot be neglected for nanomaterials. Thus, different approaches will be considered: phenomenological, asymptotic and continualized. The basic principle of continualized models is to build continuous equations starting from discrete equations and by using Taylor series expansions or Padé approximants. For each of the different models derived in this study, the natural frequencies will be determined, analytically when the closed-form solution is available, numerically when the solution is given through a characteristic equation. The objective of this work is to compare the models and to establish the eventual superiority of a model on others. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2018. / FAU Electronic Theses and Dissertations Collection

Multiwall carbon nanotubes filled with continuous single-crystals of the ferromagnetic phase -Fe were produced with two new synthesis methods: the boundary layer chemical vapour synthesis and the perturbed vapour chemical vapour deposition. In the first method, the nanotubes nucleate and grow radially from a central agglomeration of homogeneously nucleated spherical particles in a randomly fluctuating vapour created in the viscous boundary layer between a rough surface and a laminar pyrolyzed-ferrocene/Ar vapour flow. In the second method, the nanotubes nucleate and form in a flower-like arrangement departing from homogeneously nucleated particles. These particles are produced by the creation of a local perturbation in a vapour with a high density of Fe and C species obtained from the pyrolysis of ferrocene in a laminar Ar flow. Electron microscopy investigations revealed that the continuous single crystals obtained with both methods exhibit diameters much lower than the critical diameter for a single magnetic domain of -Fe (~ 66 nm). In the radial structures, the single-crystal diameter is in the range of ~ 17-37 nm, while in the flower-like structures the single crystals show mainly a diameter of ~ 30 nm and ~ 55 nm. The average single crystals length is 7-8 m in the case of the radial structures and 19-21 m in the case of the flower-like structures. DC magnetization measurements at 5 K show different magnetic behaviours. The flower-like structures present a very high saturation magnetization of 189.5 emu/g and a high coercivity of 580 Oe. The radial structures exhibit an exchange-coupled ferromagnetic/antiferromagnetic system despite only 2% of -Fe is present inside the nanotubes. The radial structures obtained at flow-rates of 3.5 ccm and 20 ccm, show saturation-magnetizations of 31emu/g and 13 emu/g, and coercivities of 790 Oe and 843 Oe respectively.

No description available.

No description available.

Carbon based materials such as CNTs and graphene have been widely studied over the last few years. The outstanding electrical and mechanical properties of these materials attracted researchers to find ways to grow and use them in nano-devices. Among the different techniques, PECVD is a relatively simple and low temperature process. It facilitates the growth of CNTs and graphene on particular sites of the substrate. The objective of this research project was to study the growth of CNTs and graphene using PECVD system and to employ them in renewable energy devices. Excimer laser processed materials were also the focus for flexible material for fuel cells and other applications to show the way to a one step manufacturing process that lends itself to large area and low cost processing using standard tools.In the growth of CNTs, the roll of a buffer layer and catalyst materials were studied in depth. Different metals were tested for best results in optimising nanotube growth for the selected applications. The role of the buffer layer in the formation of nanoparticles and their surface adhesion was studied. Different materials were used as a catalyst and analysed for best performance in the PECVD system. Growth parameters such as temperature, pressure, gas flow rate and plasma power were studied during the growth of CNTs in the PECVD system. The growth of graphene has been conducted in two ways: firstly, by the traditional mechanical exfoliation technique (with the help of Manchester University) and second by PECVD techniques.Polymer materials are promising flexible substrates for electronic and energy devices. An excimer laser was used to transform thin metallic films into nanoparticles which could play the role of the catalyst in proton exchange membrane fuel cells. In this study experiments have been conducted into a single step process to convert the poly ethylene naphthalate (PEN) surface to a robust mesoporous carbon material that conducts electrons, whilst depositing the catalyst. Such a technique has been developed for the first time in this work. Laser modification here produced a conical carbon structure and dense arrays of well defined catalysts.A prototype fuel cell was designed and crafted to employ the laser processed PEN as a proton exchange membrane. Some experiments were conducted regarding the transport of protons through laser processed PEN and the conventionally used fuel cell electrolyte, Nafion. It has been observed that the hydrophilic property of Nafion allowed proton transport across this material. It was also observed that PEN is not a good membrane for protonic transport. This material does not have free sites for vehicle transport. The catalytic activity of laser ablated Ni nanoparticles on PEN substrate was studied in temperature programme reaction (TPR) and it was observed that the metallic nanoparticles had some activity at higher temperature. Both Ni and Pt nanoparticles were tested as catalysts on the standard Nafion electrolyte. It was observed that Pt is active for the hydrogen combustion reaction and Ni has less activity for this purpose.It was not expected in this work that efficient hydrogen transport through the polymer would occur, but that future modification of the internal chemistry of PEN can be developed.

Thesis (Ph. D.)--University of Texas at Austin, 2006. / Vita. Includes bibliographical references.

none

"none"

Two polyelectrolytes were synthesized with reversible addition-fragmentation chain transfer (RAFT) polymerization and Grignard metathesis (GRIM) polymerization for the functionalization of carbon nanotubes. The responses of functionalized carbon nanotubes towards different substrates were well studied. A diblock polyelectrolyte with methacrylic acid containing block and pyrene pendant block was synthesized by RAFT polymerization. The pyrene pendant block anchored on the surface of carbon nanotubes while the methacrylic acid containing block dissolved in methanol to disperse individual carbon nanotubes. The dispersed carbon nanotubes have shown morphological responsive towards substrates with pyridine groups and amino groups on surface. The thickness of functionalized carbon nanotubes on these substrates increased from tens of nanometers to hundreds of nanometers due to the swelling of the methacrylic acid containing block. The methacrylic acid units were deprotonated by pyridine groups and amino groups on the surface so the polymer chains in the methacrylic acid containing block stretched into rigid rod structure leading to the swelling effect. A polythiophene-based conjugated polyelectrolyte with positive quaternary ammonium species on its side chains was synthesized by GRIM polymerization. The self-assembly behaviors of this conjugated polyelectrolyte in solvents with different polarities led to solvatochromism and different efficiencies for dispersion of carbon nanotubes. The efficiency of this conjugated polyelectrolyte for the dispersion of carbon nanotubes was highest when no aggregation was formed. The functionalized carbon nanotubes could be deposited on conductive substrates applied with negative potential due to the positive quaternary ammonium species. The density of carbon nanotubes deposited on the substrate increased with the potential applied. The electro-deposition of this functionalized carbon nanotubes could be applied for large scale fabrication of carbon nanotubes thin film. / published_or_final_version / Chemistry / Master / Master of Philosophy