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Pacific Northwest coastal wetland extent has been significantly reduced due to development. To understand the effects of land use change on carbon cycling in coastal wetlands, we compared soil carbon dynamics in restored, disturbed (by diking or draining), and reference wetlands in both freshwater and saline conditions in Coos Bay, Oregon. We quantified soil carbon pools, measured in situ fluxes of methane (CH4) and carbon dioxide (CO2), and estimated sediment deposition and carbon sequestration rates. We found that land use change influences carbon cycling and storage in coastal wetlands. The disturbed marshes have likely lost all their organic material after draining or diking, except for a shallow A horizon. The restored marsh in situ CH4 and CO2 fluxes were intermediate between the disturbed and reference marshes. Generally, restored marshes showed a partial return of carbon storage functions, or an indication that reference level functions may be achieved over time.

To decrease carbon dioxide emissions into the atmosphere for climate change mitigation it is necessary to modify existing practices in processes where greenhouse gases are emitted. Due to the extremely large volumes of carbon dioxide produced globally, it is generally accepted that although carbon dioxide conversion and utilisation will contribute in the long term, in the short to medium term it will be necessary to capture and store carbon dioxide emissions to progress towards a low carbon future. Current industrial capture processes incur large energy and thus economic penalties. Storage in geological formations requires robust confidence in storage security to be publically accepted. Therefore the objective of this work was to study carbon dioxide capture and storage in processes directly confronting these two major challenges. Carbon dioxide adsorption on oxide materials for advanced carbon capture processes with lower energetic and economic penalties was investigated. Water was shown to play a crucial role in determining the presence of reactive sites, the speciation of carbonates formed and increased sorbent utilisation. A high surface area oxide with specifically exposed facets was prepared and the impact of these facets on carbon dioxide uptake performance was assessed. Volumetric gas adsorption and isotherm modelling supported the presence of two distinct adsorption sites. To enhance confidence in storage security it is necessary to understand storage processes that result in stable products. An apparatus capable of obtaining geological storage conditions was developed and carbonate formation and surface hydration at high pressure was investigated. By locating individual reactive cations on the surface of silica, silicate mineral analogues were prepared. It was shown that carbonate speciation was dependent on the reactive cation and the presence or absence of water.

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In this thesis, synthesis, characterization and electrical transport of Carbon nanotubes (CNTs) have been discussed. The first chapter contains a brief introduction of various forms of carbon including CNT. The CNTs are currently the materials of intense research interest due to their remarkable mechanical and electrical properties. CNTs can be visualized as a graphene sheet that has been rolled into a seamless tube. CNTs are either single-walled carbon nanotubes (SWCNT) or multi-walled carbon nanotubes (MWCNT). SWCNT is a tube with only one wall and MWCNT has many coaxial tubes and weak Van der Waal forces hold them together. The properties depend on chirality, diameter and length of the tubes. Chirality is defined by the symmetry and the chiral angle formed between the carbon bonds. The atomic structure of CNTs is described in terms of the tube chirality, which is defined by the chiral vector Ch and the chiral angle . The chiral vector is Ch = na1 + ma2, where the integers (n, m) are the number of steps along the zig-zag carbon. Depending on the tube chirality the electrical properties of the CNTs differ; they can be metallic or semiconducting. When n-m = 3p, where p is an integer, the CNTs are metallic and when n-m  3p, the CNTs are semiconducting. Due to the high anisotropy and high aspect ratio, CNTs have many potential applications with great technological importance such as functionalized molecules, conductive wires, bearings of rotational motors, field emitters, hydrogen storage, sensors, polymer composites, nanotube yarn and nanotube filters, X-ray generator, electron sources for microscopy and lithography, gas discharge tubes and vacuum microwave amplifiers, etc. The first chapter gives a brief introduction about various forms of carbon and their properties, particularly of CNTs. The nature of the CNTs depends on the method of production, which controls the degree of graphitization, the tube diameter and the chirality. Most synthesis methods originate from the idea of obtaining adequately active carbon atomic species or clusters from carbon sources and assembling them into CNTs without or with catalysts. The commonly used methods for the synthesis of carbon nanotubes are arc-discharge, Laser ablation, high-pressure catalytic decomposition of carbon monoxide (HiPCO), electrophoretic deposition (EPD), flame synthesis, pyrolysis, chemical vapour deposition (CVD), hot-filament CVD, plasma enhanced chemical vapour deposition (PECVD) using DC, RF, and micro wave power sources, hot-filament dc (HF-dc PECVD), inductively coupled plasma (ICPECVD) and electron cyclotron resonance (ECR PECVD). Although many efforts have been made to develop various synthesis methods, most of them require many steps. Moreover, the complicated and rigorous control of parameters and expensive materials are unavoidable that has put limitation in reproducing the same in large scale. In this chapter, a simple method for the synthesis of CNTs on a large scale that eliminates nearly the entire complex and expensive machinery associated with widely used growth techniques has been discussed. In Chapter 2, the synthesis and characterization of entangled CNTs are discussed. It is shown that entangled CNTs can be synthesized in one step by using double stage furnace. Tetrahydrofuran as carbon source material and nickelocene as catalyst source material have been used to synthesize CNTs. With this method CNTs can be synthesized at a temperature as low as at 600 0C. In this technique the self-developed pressure carries the vapours to the hot zone of the furnace. This has led to think in modifying the double stage furnace. A single stage furnace having temperature gradient is made to synthesize CNTs. The vapours are carried from low temperature zone to hot zone where the carbon species and catalysts react to form CNTs. The advantage of this furnace is that it is one-step process. Using another carbon source material such as Diethyl Ether and nickelocene as catalyst source material CNTs are synthesized. The as synthesized and purified CNTs are characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM), high resolution TEM (HRTEM) and Raman spectroscopy. The CNTs are multi-walled in nature as observed by HRTEM. In Chapter 3, the synthesis of aligned CNTs is discussed by using benzene as carbon source and ferrocene as catalyst source materials. Aligned MWCNTs were synthesized in the temperature range between 650 - 1100 0C in a single stage furnace without the need for carrier gas nor predeposited metal catalyst substrate. The essential need of CNTs are (1) to obtain aligned nanotubes with millimeter lengths to enable the formation of novel nanotube-polymer composites that incorporate continuous nanotubes throughout their thickness for highly anisotropic thermal and electrical conductivities; and (2) to provide samples for detailed physical characterization - tensile strength, thermal, electrical conductivity, field emission etc. SEM observation reveals the increase in length of nanotubes from 85 m to 1.4 mm with the increase of preparation temperature. The diameter as investigated by high-resolution transmission electron microscopy (HRTEM) remains almost constant 70-80 nm (75-85 layers). Once nanotube formation is established, the growth continues in the same direction and may well be reinforced by the presence of surrounding CNTs i.e. almost every particle produces a nanotube and bundling of neighboring tubes lead to collective vertical growth. The increase in length is due to the enhanced diffusion of active carbon with increasing preparation temperatures. The alignment of CNTs is also observed to the lateral side of the substrate. In Chapter 4, the synthesis and characterization of carbon nanoribbon and singled crystal iron filled CNTs is discussed. Particularly interesting are those CNTs filled with magnetic nanowires, which can provide an effective barrier against oxidation and consequently ensure a long-term stability in the core. The filling of metals within carbon nanotubes has extended the potential application base of these materials to quantum memory elements, high density magnetic storage media, semiconducting devices, field electron emitters, high resolution magnetic atomic force microscopy tips, magnetic field sensors and scanning probe microscopes etc. Tetrahydrofuran as carbon source material and ferrocene as catalyst materials has been used to synthesize mixture of carbon nanoribbons and iron filled CNTs. The techniques used to characterize the materials are XRD, SEM, HRTEM and superconducting quantum interference device (SQUID). The powder XRD pattern shows that the bcc -Fe phase of iron is present. HRTEM studies reveal the presence of multi-walled carbon nanotubes and well-crystallized -Fe phase filled inside the core region. Closer inspection of the HRTEM images indicated that the bcc structure -Fe nanowires are monocrystalline and Fe (110) plane is indeed perpendicular to the G (002) plane. Large coercivity (i.e. 1037 Oe at 300 K and 2023 Oe at 10 K) in the iron filled CNTs and carbon nanoribbons have been observed. The high coercivity is mainly attributed to the following two factors. Firstly, it is known that due to the uniaxial magnetic anisotropy of the nano size iron in the core region of the carbon nanotubes. Secondly, ferromagnetic behavior exhibited by the localized states at the edges of the carbon nanoribbons. The anisotropic electrical transport property of MWCNTs has been discussed in the chapter 5. The activated diffusive nature of transport along axial direction of CNT is explained. The transport perpendicular to the tube direction is explained in terms of a hopping mechanism. The anisotropic resistivity (N/P) value obtained is 3. The temperature dependent magnetoresistance (MR) is studied in magnetic fields up to 11 Tesla at low temperatures both in the parallel and perpendicular direction of an aligned MWCNT mat. In both cases a negative MR is observed. Chapter 6 discusses the preparation of CNT-polymer composites. The temperature dependence of the conductivity and magnetoresistance (MR) has been studied making four-point contact method on the carbon nanotubes polymer composites as result of increasing CNT content. The conductivity increases with increasing carbon nanotube weight percentage. The increase in conductivity as a function of the CNT weight percent is attributed to the introduction of conducting CNT paths in the polymer matrix. With the increasing CNT content the number of interconnections present in a random system is found to vary. Electrical conduction in nanotube mat or nanotube composites is explained by a variable range hopping (VRH) conduction mechanism. The negative magnetoresistance has been observed for the polymer composites. It is consistent with the report on CNTs bundles and polymer composites. Finally a brief summary of the work presented in this dissertation is discussed along with future directions in this research.

The relationship between surface energy and precipitated graphite form in Fe-C alloys was examined in this thesis.Surface tension and contact angle data were obtained using the sessile drop technique. Carbon saturated, puron iron crucibles were melted on pyrolytic graphite, the effect of time, temperature (1500-1600°C) and additions of Ni, Mn, S or Ce being examined. The graphite form was established by metallographic examination. An average ƔLV of 1152 dynes/cm was determined for the Fe-C alloys (4.6% C) at approximately 1300°C, the average contact angle being 128°. No significant change occurred with additions of Ni ( 0.85%) and Mn ( 1.65%). Additions of S lowered the surface energy and increased the equilibrium contact angle. Ce additions had a similar effect although a direct comparison with the Fe-C alloys could not be made as different temperatures were used. However, the interfacial energy difference apparently increased with increasing Ce content, implying an adsorption of Ce to the graphite-melt interface. The change from the flake to the nodular form was accomplished in several transition stages, the interfacial energy differences being small, indicating a marked dependence on the solidification and growth conditions. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

In this research work, the relationships between structure and properties in micro-composites and nano-composites of polyurethane (PU) and conductive carbon particles have been studied. PU is a class of block copolymers containing the urethane linkage (-NHCO-O-) within its structure. Most PU block copolymers consist of alternating ‘soft’ and ‘hard’ segments. The hard segment used in this study was based on 4,4’-methylenebisphenylisocyanate (MDI) and 2-methyl 1,3 propanediol (MP-Diol) which produced a stiff aromatic polyurethane. Two soft segments; poly(tetrahydofuran) (PTHF) and poly(propylene oxide) based polyol end-capped with ethylene oxide (PPO-EO) were used to study the effects of soft segment structure on PU properties. DMTA, DSC and modulated-DSC indicated that PU-PTHF had higher microphase separation due to greater immiscibility between PTHF and the MDI/MP-Diol hard segments. In order to improve the electrical and mechanical properties of PU, conductive carbon particles were incorporated. The critical factor was the dispersion of these conductive fillers in the PU matrix to obtain optimum properties. The first carbon filler studied was carbon black (CB). PU composites prepared by the adding of MP-Diol plus ultrasonication (MU) gave the best dispersion of CB aggregates resulting in higher thermal decomposition temperature and good conductivity. However, the mechanical toughness was reduced. In subsequent studies, PU composites incorporating three different treated multiwalled carbon nanotubes (MWCNT) were investigated. MWCNT were disentangled and shortened by ultrasonication and acid cutting treatments. The ultrasonicated MWCNT (MWCNT_U) had longer length than the acid-cut MWCNT (MWCNT_AC). Ultrasonication was the best technique for dispersing MWCNT since the storage modulus was increased by ~200% at low MWCNT_U loading and the toughness remained the same as unfilled PU. PU/MWCNT_AC nanocomposites at 1 – 3 wt% of MWCNT_AC exhibited similar electrical conductivities to unfilled PU at an order of 10-8 S/cm, implying that the acid cutting treatment might disturb the inherent conductivity in MWCNT. The conductive percolation thresholds of composites were determined following the percolation theory. It was found that the percolation thresholds for MWCNT-filled composites were significantly lower than that of CB-filled composites. The lowest percolation threshold was observed in MWCNT_U-filled composite at 0.31 wt%.

Single wall carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) were dispersed in mineral oil and epoxy resin. The magnetorheological properties of these dispersions were studied using a parallel plate rheometer. Strain sweeps, frequency sweeps, magneto sweeps and steady shear tests were conducted in various magnetic fields. G', G", h* and ty increased with increasing magnetic field, which was partially attributed to the increasing degree of the alignment of nanotubes in a stronger magnetic field. The SWNT/mo dispersions exhibited more pronounced magnetic field dependence than SWNT/ep and MWNT/mo counterparts due to their much lower viscosity. The alignment of SWNTs in mineral oil increased with rising nanotube concentration up to 2.5vol% but were significantly restricted at 6.41vol% due to nanotube flocculation.

This work investigates the material properties and production parameters of carbon infiltrated carbon nanotube structures (CI-CNT's). The impact of non homogeneous infiltration and the porosity of cross section regions, coupled with changes in designed geometry, in this case beam width, on the density and modulus of elasticity are compared. Three potential geometric models of beam cross section are proposed and evaluated. 3-point bending, SEM images, and numerical optimization are used to assess the validity of each model and the implications they have for future CI-CNT material applications. Carbon capping near exterior beam surfaces is observed and determined to be a contributing factor to variations in material properties correlated with changes in designed geometry and infiltration parameters (temperature, time, and hydrogen flow rate). Unexpected relationships between beam width and elastic modulus are partially explained by modeling the carbon-capped beams as C-shaped structural members consisting of a graphitic carbon shell of varying porosity and thickness and uninfiltrated carbon nanotube internal regions with a near negligible stiffness. Findings of previous works on the effects of infiltration parameters and carbon capping on materials properties are confirmed and expanded. Flange and web thickness and porosity of the graphitic carbon shell are identified as potential design parameters for pursuing tunable material properties in high precision geometry MEMS and compliant mechanism applications.

The objective of this study was to develop a protocol to test the reactivity of glauconite, a Fe/Mg bearing aluminosilicate mineral, in carbon storage. A selected glauconite-rich sample from the Cambrian Riley Formation of Central Texas was used containing glauconite 38 wt%, quartz 58 wt%, and calcite 4 wt%. Ten experiments were conducted using two techniques where total pressure was: 1) controlled by delivering CO2 to a high-pressure apparatus; 2) kept at saturated vapor level in autoclaves. The treated glauconite samples were analyzed with Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (SEM), and X-ray Diffraction techniques (XRD). Although the reaction between glauconite and CO2 was not visible, calcite crystallized in solution when its pH exceeded the value of 6.88. The research provides a foundation to develop further investigations of rock reactions under CO2 saturated conditions.