This dissertation contains the following sections. Chapter 1 contains a detailed description of the theory of thin layer chromatography (TLC). Chapter 2 describes the benefits and practical considerations of elevated temperatures in liquid chromatography (LC). The porous graphitic carbon (PGC) I modified as part of my work is often used in elevated temperature LC. Chapter 3 shows a thermodynamic analysis of chromatographic retention at elevated temperature, and Chapter 4 contains a closer look at the van 't Hoff equation in LC and how it can be used in retention modeling. In Chapter 5, I describe a new procedure for microfabricating TLC plates that avoids the volume/feature distortions that occurred in our first microfabrication. The primary advance of this work was the priming of the carbon nanotube (CNT) forests with chemical vapor deposition (CVD) carbon and atomic layer deposition (ALD) alumina, which permitted effective ALD-like deposition of SiO2. Chapter 6 describes advancements in the microfabrication process of TLC, which excluded the use of the CVD carbon and Al2O3 coating as described in Chapter 5. The use of ozone, to lightly oxidize the CNT surface, primed the material for direct ALD deposition. Chapter 7 gives a detailed surface analysis of the microfabrication process up to and including the CNT forest. It was noticed that a channeling effect was present during Rutherford backscattering analysis of the CNTs. Additionally, characterization of CNTs using time-of-flight secondary ion mass spectrometry in the negative ion mode showed an odd-even effect for a homologous series of carbon, where the even moieties had a stronger signal. Chapter 8 describes the functionalization of PGC with di-tert-amyl peroxide (DTAP) and its effect on increasing the chromatographic performance as seen by a reduction in the tailing factors of test analytes. Chapter 9 -- 13 are detailed X-ray photoelectron analyses of the thin films and CNTs used in producing microfabricated TLC plates.

My work has focused on a variety of different types of diamond-based, core-shell particles. These particles are formed with inert cores and poly(allylamine)/nanodiamond shells. Their intended purpose is to form an LC stationary phase that is stable from pH 1 – 14 and at elevated temperatures. At the beginning of my studies, the particles that had been made in the Linford laboratory were pH stable, but irregular and had poor mechanical stability. Since that time, I have worked to improve the particles by using more spherical zirconia and carbon cores, and I have improved their mechanical stability via chemical crosslinking with epoxides. I have performed van Deemter and van’t Hoff analyses to understand the properties of these columns. Efficiencies greater than 100,000 N/m are routinely achieved with these carbon/nanodiamond-based phases. In addition I contributed to two patents that show innovations in diamond functionalization. My contributions involved reduction of an oxidized diamond surface with LiAlH4 prior to functionalization with isocyanates. I also wrote some application notes for the Flare mixed-mode column, which was recently introduced to the market and contains particles comprised of a carbon core and a polymer/nanodiamond shell. These application notes show the gradient separations of four essential oils (lavender, melaleuca, peppermint and eucalyptus), and the isocratic separations of various triazine herbicides and a mixture of β2-agonists and amphetamines.This dissertation contains the following sections. Chapter 1 is a review of liquid chromatographic history and theory. It also includes a history of the use of diamonds in liquid chromatography. Chapter 2 is a study on a glassy carbon core - polymer/nanodiamond shell particle made in our laboratory. Stability studies at pH 11.3 and 13 were performed and different analytes were retained and/or separated on the column. Chapter 3 is a study performed on the Flare mixed-mode column. Separations of tricyclic antidepressants, β2-andrenergic receptor agonists, and linear chain alkylbenzenes were demonstrated with this phase. Van Deemter and van’t Hoff studies were also performed to probe the efficiency and selectivity of this column with different classes of analytes. Chapter 4 chronicles, via SEM and van Deemter analysis, the improvements that have taken place in our column after many iterations of improved synthetic methods and new materials. These include better particle uniformity, particle stability, and column efficiency. Three different carbon cores were analyzed, each better than the previous one. Appendices 1 – 6 are application notes published by Diamond Analytics of β2-andrenergic receptor agonists and amphetamines, triazine herbicides, and lavender, melaleuca, eucalyptus and peppermint essential oils. Appendices 7 and 8 are patents that contain ideas and research contributed by the author.

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Some climate models predict that, within the next 30-50 years, sea surface temperatures (SSTs) will frequently exceed the current thermal tolerance of corals (Fitt et al. 2001; Hughes et al. 2003; Hoegh-Guldberg et al. 2007). A potential consequence is that mass coral bleaching may take place (i) during warm El Niño-Southern Oscillation (ENSO) events which are predicted to occur in some regions more frequently than the current 3-7 year periodicity (Hoegh-Guldberg 1999; Sheppard 2003) or (ii) perhaps as often as annually or biannually if corals and their symbionts are unable to acclimate to the higher SSTs (Donner et al. 2005, 2007). Global data also indicate an upward trend toward increasing frequencies, intensities, and durations of tropical hurricanes and cyclones (Emanual 2005; Webster et al. 2005). As coral communities have been shown to require at least 10-30 years to recover after a major disturbance (e.g. Connell 1997; Ninio et al. 2000; Bruno & Selig 2007; Burt et al. 2008), it is possible that future coral communities may be in a constant state of recovery, with regeneration times exceeding the periods between disturbances. Life history traits (e.g. reproduction, recruitment, growth and mortality) vary among species of hard corals; thus, gradients in community structures may have a strong influence on susceptibilities to disturbance and rates of recovery (Connell 1997; Ninio & Meekan 2002). Taxa which are more susceptible to bleaching and mechanical disturbance (e.g. tabular and branching acroporids and pocilloporids) may experience continual changes in population structure due to persistent cycles of regeneration or local extirpation, while the more resistant taxa (e.g. massive poritids and faviids) may display relatively stable population structures (Woodley et al. 1981; Hughes & Connell 1999; Baird & Hughes 2000; Marshall & Baird 2000; Loya et al. 2001; McClanahan & Maina 2003). Determining whether resistant coral taxa have predictable responses to disturbances, with consistent patterns over wide spatial scales, may improve predictions for the future affects of climate change and the composition of reefs (Done 1999; Hoegh-Guldberg 1999; McClanahan et al. 2004). The work presented in this dissertation describes the spatial and temporal patterns in community structures for high latitude coral assemblages that have experienced the types of natural disturbances which are predicted to occur in tropical reef systems with increasing frequency as a result of climate change. The primary area of focus is the southeastern Arabian Gulf, where the coral communities are exposed to natural conditions that exceed threshold limits of corals elsewhere in the world, with annual temperature ranges between 14-36°C (Kinzie 1973; Shinn 1976) and salinities above 40 ppt. Two additional regions are included in this study for comparisons of high latitude coral community structures. The northwestern Gulf of Oman is adjacent to the southeastern Arabian Gulf (i.e. the two bodies of water are connected by the Strait of Hormuz); however, the environmental conditions are milder in the Gulf of Oman such that the number of coral taxa therein is threefold that found in the southeastern Arabian Gulf (i.e. 107 coral species in the Gulf of Oman compared to 34 species in this region of the Arabian Gulf (Riegl 1999; Coles 2003; Rezai et al. 2004)). Broward County, Florida is geographically remote from the Gulfs and, therefore, serves as a benchmark for testing whether consistent patterns in community structures exist despite different climatic and anthropogenic influences. The coral communities within the southeastern Arabian Gulf, the northwestern Gulf of Oman, and Broward County, Florida have been exposed to recurrent elevated sea surface temperature (SST) anomalies, sequential cyclone and red tide disturbances, and frequent hurricanes and tropical storms, respectively. These disturbances and other impacts (e.g. bleaching episodes, disease outbreaks, anthropogenic stresses) have affected the more susceptible acroporids and pocilloporids, resulting in significant losses of coral cover by these families and shifts towards massive corals as the dominant taxa. During the post-disturbance scarcity or absence of branching and tabular corals, the resistant massive taxa have become the crux of the essential hard coral habitat for fish, invertebrates and other marine organisms. Because recovery to pre-disturbance community structures may take decades or may not occur at all, it is vital that scientists and resource managers have a better understanding of the spatial and temporal ecology patterns of the corals that survive and fill in the functional gaps that are created by such disturbances. To aid in this understanding, this dissertation presents spatial and temporal patterns for the coral assemblages which have developed after the respective disturbances. Spatial ecology patterns are analyzed using graphical descriptions (e.g. taxa inventories, area cover, densities, size frequency distributions), univariate techniques (e.g. diversity indices), distributional techniques (e.g. k-dominance curves) and multivariate techniques (e.g. hierarchical clustering, multidimensional scaling). Temporal comparisons at monitoring sites within the southeastern Arabian Gulf and northwestern Gulf of Oman describe the coral population dynamics and are used to create size class transition models that project future population structures of massive corals in the recovering habitats.

Metal fatigue is a recurring problem for metallurgists and materials engineers, especially in structural applications. It has been responsible for many disastrous accidents and tragedies in history. Understanding the micro-mechanisms during cyclic deformation and combating fatigue failure has remained a grand challenge. Environmental effects, like temperature or a corrosive medium, further worsen and complicate the problem. Ultimate design against fatigue must come from a materials perspective with a fundamental understanding of the interaction of microstructural features with dislocations, under the influence of stress, temperature, and other factors. This research endeavors to contribute to the current understanding of the fatigue failure mechanisms. Cast aluminum alloys are susceptible to fatigue failure due to the presence of defects in the microstructure like casting porosities, non-metallic inclusions, non-uniform distribution of secondary phases, etc. Friction stir processing (FSP), an emerging solid state processing technique, is an effective tool to refine and homogenize the cast microstructure of an alloy. In this work, the effect of FSP on the microstructure of an A356 cast aluminum alloy, and the resulting effect on its tensile and fatigue behavior have been studied. The main focus is on crack initiation and propagation mechanisms, and how stage I and stage II cracks interact with the different microstructural features. Three unique microstructural conditions have been tested for fatigue performance at room temperature, 150 °C and 200 °C. Detailed fractography has been performed using optical microscopy, scanning electron microscopy (SEM) and electron back scattered diffraction (EBSD). These tools have also been utilized to characterize microstructural aspects like grain size, eutectic silicon particle size and distribution. Cyclic deformation at low temperatures is very sensitive to the microstructural distribution in this alloy. The findings from the room temperature fatigue tests highlight the important role played by persistent slip bands (PSBs) in fatigue crack initiation. At room temperature, cracks initiate along PSBs in the absence of other defects/stress risers, and grow transgranularly. Their propagation is retarded when they encounter grain boundaries. Another major finding is the complete transition of the mode of fatigue cracking from transgranular to intergranular, at 200 °C. This occurs when PSBs form in adjacent grains and impinge on grain boundaries, raising the stress concentration at these locations. This initiates cracks along the grain boundaries. At these temperatures, cyclic deformation is no longer microstructure- dependent. Grain boundaries don’t impede the progress of cracks, instead aid in their propagation. This work has extended the current understanding of fatigue cracking mechanisms in A356 Al alloys to elevated temperatures.

One of prominent issues related to failures in nuclear power components is attributed to material degradation due the aggressive environment conditions, and mechanical stresses. For instance, reactor core support components, such as fuel claddings, are under prolonged exposure to an intense neutron field from the fission of fuel and operate at elevated temperature under fatigue loadings caused by start up, shut down, and unscheduled emergency shut down. Additionally, exposure to highluence neutron radiation can lead to microscopic defects that result in material hardening and embrittlement, which significantly affects the physical and mechanical properties of the materials, resulting in further reduction in fatigue life of reactor structural components. The effects of fatigue damage on material deterioration can be further exacerbated by the presence of thermal loading, hold-time, and high-temperature water coolant environments. In this study, uniaxial fatigue models were used to predict fatigue behavior based only on simple monotonic properties including ultimate tensile strength and Brinell hardness. Two existing models, the Bäumel Seeger uniform material law and the Roessle Fatemi hardness method, were employed and extended to include the effects of test temperature, neutron irradiation fluence, irradiation induced helium and irradiation induced swellings on fatigue life of austenitic stainless steels. Furthermore, a methodology to estimate fatigue crack length using a strip-yield based model is presented. This methodology is also extended to address the effect of creep deformation in a presence of hold- times, and expanded to include the effects of irradiation and water environment. Reasonable fatigue life predictions and crack growth estimations are obtained for irradiated austenitic stainless steels types 304, 304L, and 316, when compared to the experimental data available in the literature. Lastly, a failure analysis methodology of a mixer unit shaft made of AISI 304 stainless steel is also presented using a conventional 14-step failure analysis approach. The primary mode of failure is identified to be intergranular stress cracking at the heat affected zones. A means of circumventing this type of failure in the future is presented.

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