Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 195-204).

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Carbonized organic precursors such as wood, shells and some plant seeds are very porous. They are nanostructured and tend to be hard, but have pure mechanical properties as a result of their porosities. An attempt was made to carbonize an organic precursor to produce a bulk material with much less porosity for possible use in structural applications such as reinforcement in metal and polymer matrices. A bulk nanocarbon (BNC) material was synthesized using high energy ball milling and the carbonization of corn cob. Corn cob was mechanically milled for up to 20 hours by applying high energy ball milling to produce the milled powder. The milled powder was cold-compacted and carbonized at up to 1500°C to fabricate the BNC material. The material revealed both micro and nano-porosities; the porosities decreased with carbonizing temperature and hold time. Micropores were mostly closed for samples carbonized above 1300oC, whereas they formed interconnected network at lower carbonization temperatures. BNC has a young's modulus of 120 GPa, about ten times that of extruded graphite. / Master of Science / Wood, shells, and plant seeds are examples of organic precursors. When organic precursors are carbonized, they can become very porous, nanostructured, and hard, but deliver pure mechanical properties because of their porosities. A selected organic precursor was carbonized, in an attempt, to produce a bulk material with much less porosity for possible use in structural applications such as reinforcement in metal and polymer matrices. A bulk nanocarbon (BNC) material was made using high energy ball milling and the carbonization of corn cob (the selected organic precursor). This bulk material revealed both micro and nano-porosities, and a young's modulus of 120 GPa, about ten times that of extruded graphite.

The United Kingdom Government has mandated ambitious carbon objectives, requiring an 80% reduction in emissions by 2050, and a 20% interim reduction by 2020. Their achievement will require government and large companies to work together, and for each to be assured of the other’s strategic intent. An emergent carbon accounting can provide reassurance if it produces credible information that supports the claims made by each party. This thesis investigates the extent to which carbon reduction narratives are supported or contradicted by actual carbon emissions disclosed in corporate accounting reports. It also investigates whether large corporations have delivered absolute carbon reductions in support of the government’s legally binding objectives. As a result of these and other investigations, the thesis contributes to the carbon accounting literature by critiquing the method of framing emissions employed by the Greenhouse Gas Protocol, the extent to which carbon reduction is supported by meaningful managerial incentives and the means by which analysts might rebalance financial return with carbon risk in portfolio construction. Following a middle ground approach, the research employs a numbers and narratives analysis in which critical alternative narratives are created at national, sectoral and firm levels. The analysis disaggregates macro carbon emissions data, and considers carbon emissions at a corporate meso and micro level. Narratives constituted out of these numbers, together with counter-narratives generated from corporate disclosures, are then evaluated to assess their credibility. The thesis adopts a practical approach, utilising multiple framing devices. In addition to reporting scopes 1, 2 and 3 carbon emissions, it describes a business model framework in which firms are expected to disclose their carbon-material stakeholder relations. Further recommendations are aimed at aligning the interests of corporate managers, investors and financial analysts with government carbon policy in order to modify behaviour and reduce emissions trajectories towards a lower carbon future.

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abstract / Chemistry / Doctoral / Doctor of Philosophy

Small amounts of carbon from glucose and leucine added at natural concentrations to seawater were biologically transformed to higher molecular weight (MW) dissolved materials which persisted through six months of incubation. These materials were resistant to biological utilization: only 1 to 17% of the higher MW carbon was respired when re-incubated with seawater microbial populations. Over the same time span, 40 to 75% of the monomers were respired. In situ transformations of biologically-available carbon may be important mechanisms for the production of refractory dissolved organic carbon in the oceans. / Graduation date: 1987

Temperate forests are an important carbon sink, yet there is debate regarding the net effect of forest management practices on carbon storage. Few studies have investigated the effects of different silvicultural systems, and the relative strength of in-situ forest carbon versus wood products pools remains in question. Our research (1) describes the impact of harvesting frequency and degree of post- harvest structural retention on carbon storage in northern hardwood-conifer forests, and (2) tests the significance of including harvested wood products in carbon accounting at the stand scale. We stratified Forest Inventory and Analysis (FIA) plots to control for environmental, forest structural and compositional variables, resulting in 32 FIA plots distributed throughout the northeastern U.S. We used the USDA Forest Vegetation Simulator to project stand development over a 160 year period under nine different forest management scenarios. Simulated treatments represented a gradient of increasing structural retention and decreasing harvesting frequencies and included a “no harvest” scenario. The simulations incorporated carbon flux between aboveground forest biomass (dead and live pools) and harvested wood products (including carbon storage in landfills). Mean carbon storage over the simulation period, including carbon stored in harvested wood products, was calculated for each silvicultural scenario. We investigated tradeoffs among scenarios using a factorial treatment design and two-way ANOVA. The predictive strength of management scenarios relative to site-specific variables was evaluated using Classification and Regression Trees. Mean carbon sequestration was significantly (a = 0.05) greater for “no management” compared to any of the active management scenarios. Of the harvest treatments, those favoring high levels of structural retention and decreased harvesting frequency stored the greatest amounts of carbon. In order to isolate the effect of in-situ forest carbon storage and harvested wood products, we did not include the emissions benefits associated with substituting wood fiber for other construction materials or energy sources. Modeling results from this study show that harvesting frequency and structural retention significantly affect mean carbon storage. Our results illustrate the importance of both post-harvest forest structure and harvesting frequency in carbon storage, and are valuable to land owners interested in managing forests for carbon sequestration.

A suite of four samples of nitrogen doped carbon microspheres, each with a di erent level of nitrogen dopant, was synthesised in a horizontal chemical vapour deposition reaction. The samples were characterized using scanning electron microscopy, Raman spectroscopy and electron paramagnetic resonance spectroscopy. Scanning electron microscopy showed that microspheres were produced by the reaction. Raman spectroscopy con rmed the graphitic nature of the samples. Electron paramagnetic resonance spectroscopy determined that nitrogen was present in the graphitic lattice and was used as a non-destructive technique to measure the amount of substitutional nitrogen present in the samples. In order to perform electrical transport measurements an automated magneto-transport measurement station was developed in the laboratory. This transport station was computer controlled and contained all of the necessary hardware and software required to perform magneto-electrical transport measurements. Variable temperature electrical transport measurements were performed on all samples to determine their conductive properties. Resistance measurements showed that two of the samples were semiconductors while the other two samples displayed a transition to metallic behaviour at higher temperatures. This transition can be ascribed to the thermal desorption of nitrogen dopant. Models were tted to the data and the semiconducting behaviour is best explained by a model of uctuation induced tunnelling while the metallic behaviour is best explained by a quasi-1 dimensional metallic term based on electron-phonon interactions. The IV characteristics of two of the samples display increasing non-linearity of the current's voltage dependence with decreasing temperature. The other two samples exhibit this behaviour at lower temperatures while higher temperature IV data displays a current saturation with increasing voltage. The same models used to explain the resistance measurements can be used to explain the IV characteristics data extremely well. The magnetoresistance data taken with the direction of current ow orientated both parallel and perpendicular to the eld, show a transition from negative to positive magnetoresistance with decreasing temperature. The results of these experiments are inconclusive, as a theoretical model of magnetoresistance in systems that conduct via uctuation induced tunnelling is not well de ned. A comparison between the resistance measurements of all four samples was made to determine the e ect of nitrogen doping on the samples' electronic transport properties. The result of this comparison was indeterminate. This was due to samples with identical nitrogen dopant levels displaying vastly di erent conductive properties and indicates that very strict synthesis conditions need to be adhered to in order to ensure sample quality. Resistance measurements were rerun on the two samples that displayed purely semiconducting behaviour to investigate the possibility of atmospheric doping. It was found that the samples now displayed a transition to metallic behaviour and a reduced resistance. These results are suggestive of atmospheric doping by oxygen and water vapour.

Carbon nanotubes (CNTs) have attracted significant attention as novel one-dimensional nanomaterials due to their unique structures and properties. Aggregate properties of CNTs such as high surface area, length, or chemical composition are further tailored to enhance their potential application in nanomedicine, through post synthesis chemical modification procedures. These modifications simultaneously alter their aggregate physiochemical properties and this has a direct impact on cytotoxicity of CNTs in cells. A lot of research has been done towards the toxicity of CNTs, however, there is need for results that are consistent and standardized if the application of CNTs in nanomedicine is to be a reality. Indeed the toxicology study of CNTs has been compromised by conflicting toxicity results due to lack of physiochemical characterization, regulation of the synthesis and standardized cytotoxicity assays. Herein, the effects of the physiochemical characteristics of riluzole loaded CNTs on their toxicity in neuronal cells is evaluated to elucidate a better understanding of CNTs toxicity. Furthermore the cellular uptake and overall efficacy of riluzole loaded CNTs is evaluated. As prepared multiwalled carbon nanotubes (MWCNTs) synthesized by the Catalytic Chemical Vapor Deposition (CCVD) method were initially acid oxidized using strong acids at different temperature and reaction time so as to remove impurities whilst introducing carboxylic groups on to the surface. The drug riluzole was then conjugated to the oxidized MWCNTs via carbodiimide activated amidation. The purification and functionalization led to the isolation of physicochemical properties as characterized by the Transmission Electron Microscopy (TEM), Raman spectroscopy, BET surface area analysis and Thermogravimetric Analysis (TGA). These physiochemical properties i.e. length, surface area, degree of fictionalization and amount of chemical impurities were key determinants of the drug loaded MWCNTs’ cytotoxicity. The data from this study supports the hypothesis that physiochemical modifications of MWCNTs that occur due to the functionalization of the drug to its surfaces alter their toxicity in neuronal systems. The riluzole loaded MWCNTs with <15% metallic residue, 500-2000nm length, and high surface area (30-76 m2/g) were found to cross the cell membrane without causing toxic effects as all the cells were viable compared to the untreated cells control. Covalently linking riluzole to MWCNTs and the consequent changes in the physiochemical properties did not lead to the generation of toxic effects in cells. Furthermore chemically binding riluzole to the MWCNTs did not deactivate the drug and reduce its ability to be antiglutamate. The identification of specific physiochemical properties governing CNTs toxicity presents the opportunity for carbon nanotube based drug delivery system designs or applications that reduce human and environmental impacts.