Remote sensing of volcanic plumes using the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER).

The Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) has been used to quantify SO2 emissions from passively degassing volcanoes. This dissertation explores ASTER’s capability to detect SO2 with satellite validation, enhancement techniques and extensive processing of images at a variety of volcanoes. ASTER is compared to the Mini UV Spectrometer (MUSe), a ground based instrument, to determine if reasonable SO2 fluxes can be quantified from a plume emitted from Lascar, Chile. The two sensors were in good agreement with ASTER proving to be a reliable detector of SO2. ASTER illustrated the advantages of imaging a plume in 2D, with better temporal resolution than the MUSe. SO2 plumes in ASTER imagery are not always discernible in the raw TIR data. Principal Component Analysis (PCA) and Decorrelation Stretch (DCS) enhancement techniques were compared to determine how well they highlight a variety of volcanic plumes. DCS produced a consistent output and the composition of the plumes was easy to identify from explosive eruptions. As the plumes became smaller and lower in altitude they became harder to distinguish using DCS. PCA proved to be better at identifying smaller low altitude plumes. ASTER was used to investigate SO2 emissions at Lascar, Chile. Activity at Lascar has been characterized by cyclic behavior and persistent degassing (Matthews et al. 1997). Previous studies at Lascar have primarily focused on changes in thermal infrared anomalies, neglecting gas emissions. Using the SO2 data along with changes in thermal anomalies and visual observations it is evident that Lascar is at the end an eruptive cycle that began in 1993. Declining gas emissions and crater temperatures suggest that the conduit is sealing. ASTER and the Ozone Monitoring Instrument (OMI) were used to determine the annual contribution of SO2 to the troposphere from the Central and South American volcanic arcs between 2000 and 2011. Fluxes of 3.4 Tg/a for Central America and 3.7 Tg/a for South America were calculated. The detection limits of ASTER were explored. The results a proved to be interesting, with plumes from many of the high emitting volcanoes, such as Villarrica, Chile, not being detected by ASTER.

In-situ measurement and characterization of cloud particles using digital in-line holography

Satellite measurement validations, climate models, atmospheric radiative transfer models and cloud models, all depend on accurate measurements of cloud particle size distributions, number densities, spatial distributions, and other parameters relevant to cloud microphysical processes. And many airborne instruments designed to measure size distributions and concentrations of cloud particles have large uncertainties in measuring number densities and size distributions of small ice crystals. HOLODEC (Holographic Detector for Clouds) is a new instrument that does not have many of these uncertainties and makes possible measurements that other probes have never made. The advantages of HOLODEC are inherent to the holographic method. In this dissertation, I describe HOLODEC, its in-situ measurements of cloud particles, and the results of its test flights. I present a hologram reconstruction algorithm that has a sample spacing that does not vary with reconstruction distance. This reconstruction algorithm accurately reconstructs the field to all distances inside a typical holographic measurement volume as proven by comparison with analytical solutions to the Huygens-Fresnel diffraction integral. It is fast to compute, and has diffraction limited resolution. Further, described herein is an algorithm that can find the position along the optical axis of small particles as well as large complex-shaped particles. I explain an implementation of these algorithms that is an efficient, robust, automated program that allows us to process holograms on a computer cluster in a reasonable time. I show size distributions and number densities of cloud particles, and show that they are within the uncertainty of independent measurements made with another measurement method. The feasibility of another cloud particle instrument that has advantages over new standard instruments is proven. These advantages include a unique ability to detect shattered particles using three-dimensional positions, and a sample volume size that does not vary with particle size or airspeed. It also is able to yield two-dimensional particle profiles using the same measurements.

Digital processing and data compilation approach for using remotely sensed imagery to identify geological lineaments in hard-rock terrains : an application for groundwater explorations in Nicaragua

Sustainable yields from water wells in hard-rock aquifers are achieved when the well bore intersects fracture networks. Fracture networks are often not readily discernable at the surface. Lineament analysis using remotely sensed satellite imagery has been employed to identify surface expressions of fracturing, and a variety of image-analysis techniques have been successfully applied in “ideal” settings. An ideal setting for lineament detection is where the influences of human development, vegetation, and climatic situations are minimal and hydrogeological conditions and geologic structure are known. There is not yet a well-accepted protocol for mapping lineaments nor have different approaches been compared in non-ideal settings. A new approach for image-processing/synthesis was developed to identify successful satellite imagery types for lineament analysis in non-ideal terrain. Four satellite sensors (ASTER, Landsat7 ETM+, QuickBird, RADARSAT-1) and a digital elevation model were evaluated for lineament analysis in Boaco, Nicaragua, where the landscape is subject to varied vegetative cover, a plethora of anthropogenic features, and frequent cloud cover that limit the availability of optical satellite data. A variety of digital image processing techniques were employed and lineament interpretations were performed to obtain 12 complementary image products that were evaluated subjectively to identify lineaments. The 12 lineament interpretations were synthesized to create a raster image of lineament zone coincidence that shows the level of agreement among the 12 interpretations. A composite lineament interpretation was made using the coincidence raster to restrict lineament observations to areas where multiple interpretations (at least 4) agree. Nine of the 11 previously mapped faults were identified from the coincidence raster. An additional 26 lineaments were identified from the coincidence raster, and the locations of 10 were confirmed by field observation. Four manual pumping tests suggest that well productivity is higher for wells proximal to lineament features. Interpretations from RADARSAT-1 products were superior to interpretations from other sensor products, suggesting that quality lineament interpretation in this region requires anthropogenic features to be minimized and topographic expressions to be maximized. The approach developed in this study has the potential to improve siting wells in non-ideal regions.

Erupted magma volume estimates at Santiaguito and Pacaya Volcanoes, Guatemala using digital elevation models

High resolution digital elevation models (DEMs) of Santiaguito and Pacaya volcanoes, Guatemala, were used to estimate volume changes and eruption rates between 1954 and 2001. The DEMs were generated from contour maps and aerial photography, which were analyzed in ArcGIS 9.0®. Because both volcanoes were growing substantially over the five decade period, they provide a good data set for exploring effective methodology for estimating volume changes. The analysis shows that the Santiaguito dome complex grew by 0.78 ± 0.07 km3 (0.52 ± 0.05 m3 s-1) over the 1954-2001 period with nearly all the growth occurring on the El Brujo (1958-75) and Caliente domes (1971-2001). Adding information from field data prior to 1954, the total volume extruded from Santiaguito since 1922 is estimated at 1.48 ± 0.19 km3. Santiaguito’s growth rate is lower than most other volcanic domes, but it has been sustained over a much longer period and has undergone a change toward more exogenous and progressively slower extrusion with time. At Santiaguito some of the material being added at the dome is subsequently transported downstream by block and ash flows, mudflows and floods, creating channel shifting and areas of aggradation and erosion. At Pacaya volcano a total volume of 0.21 ± 0.05 km3 was erupted between 1961 and 2001 for an average extrusion rate of 0.17 ± 0.04 m3 s-1. Both the Santiaguito and Pacaya eruption rate estimates reported here are minima, because they do not include estimates of materials which are transported downslope after eruption and data on ashfall which may result in significant volumes of material spread over broad areas. Regular analysis of high resolution DEMs using the methods outlined here, would help quantify the effects of fluvial changes to downstream populated areas, as well as assist in tracking hazards related to dome collapse and eruption.

Investigations into the degassing and eruption mechanisms of Nyamuragira volcano, Democratic Republic of the Congo (Africa)

One of two active volcanoes in the western branch of the East African Rift, Nyamuragira (1.408ºS, 29.20ºE; 3058 m) is located in the D.R. Congo. Nyamuragira emits large amounts of SO2 (up to ~1 Mt/day) and erupts low-silica, alkalic lavas, which achieve flow rates of up to ~20 km/hr. The source of the large SO2 emissions and pre-eruptive magma conditions were unknown prior to this study, and 1994-2010 lava volumes were only recently mapped via satellite imagery, mainly due to the region’s political instability. In this study, new olivine-hosted melt inclusion volatile (H2O, CO2, S, Cl, F) and major element data from five historic Nyamuragira eruptions (1912, 1938, 1948, 1986, 2006) are presented. Melt compositions derived from the 1986 and 2006 tephra samples best represent pre-eruptive volatile compositions because these samples contain naturally glassy inclusions that underwent less post-entrapment modification than crystallized inclusions. The total amount of SO2 released from the 1986 (0.04 Mt) and 2006 (0.06 Mt) eruptions are derived using the petrologic method, whereby S contents in melt inclusions are scaled to erupted lava volumes. These amounts are significantly less than satellite-based SO2 emissions for the same eruptions (1986 = ~1 Mt; 2006 = ~2 Mt). Potential explanations for this observation are: 1) accumulation of a vapor phase within the magmatic system that is only released during eruptions, and/or 2) syn-eruptive gas release from unerupted magma. Post-1994 Nyamuragira lava volumes were not available at the beginning of this study. These flows (along with others since 1967) are mapped with Landsat MSS, TM, and ETM+, Hyperion, and ALI satellite data and combined with published flow thicknesses to derive volumes. Satellite remote sensing data was also used to evaluate Nyamuragira SO2 emissions. These results show that the most recent Nyamuragira eruptions injected SO2 into the atmosphere between 15 km (2006 eruption) and 5 km (2010 eruption). This suggests that past effusive basaltic eruptions (e.g., Laki 1783) are capable of similar plume heights that reached the upper troposphere or tropopause, allowing SO2 and resultant aerosols to remain longer in the atmosphere, travel farther around the globe, and affect global climates.

Estimation of vertical groundwater fluxes into a streambed through continuous temperature profile monitoring and the relationship of groundwater fluxes to coaster brook trout spawning habitat

We hypothesized that the spatial distribution of groundwater inflows through river bottom sediments is a critical factor associated with the selection of coaster brook trout (a life history variant of Salvelinus fontinalis,) spawning sites. An 80-m reach of the Salmon Trout River, in the Huron Mountains of the upper peninsula of Michigan, was selected to test the hypothesis based on long-term documentation of coaster brook trout spawning at this site. Throughout this site, the river is relatively similar along its length with regard to stream channel and substrate features. A monitoring well system consisting of an array of 27 wells was installed to measure subsurface temperatures underneath the riverbed over a 13-month period. The monitoring well locations were separated into areas where spawning has and has not been observed. Over 200,000 total temperature measurements were collected from 5 depths within each of the 27 monitoring wells. Temperatures within the substrate at the spawning area were generally cooler and less variable than river temperatures. Substrate temperatures in the non-spawning area were generally warmer, more variable, and closely tracked temporal variations in river temperatures. Temperature data were inverted to obtain subsurface groundwater velocities using a numerical approximation of the heat transfer equation. Approximately 45,000 estimates of groundwater velocities were obtained. Estimated velocities in the spawning and non-spawning areas confirmed that groundwater velocities in the spawning area were primarily in the upward direction, and were generally greater in magnitude than velocities in the non-spawning area. In the non-spawning area there was a greater occurrence of velocities in the downward direction, and velocity estimates were generally lesser in magnitude than in the spawning area. Both the temperature and velocity results confirm the hypothesis that spawning sites correspond to areas of significant groundwater influx to the river bed.

Multimetallic complexes based on phosphine- and phosphine oxide- appended p-hydroquinones

Presented here, is the work done with a series of binucleating ligands based on phosphine and phosphine oxide appended p-hydroquinones and their reactions towards various metals sources. The long term goal of the project was to produce coordination polymers that would have novel electronic, magnetic, and optical properties which would be of use in the field of molecular electronics. Binucleating ligands contained a p-hydroquinone motif in which various phosphine- and phosphine oxide substituents have been placed in the ortho position relative to each of the hydroxy position were synthesized. A previously published synthetic method for such lugands utilized n-BuLi to form a phenyl lithium intermediate which was quenched with chlorodiphenylphosphine. This technique was also used to produce a ligand with diisopropylphosphine groups. Phosphine ligands, containing the same structural motif, were also generated using LDA as the lithiating agent. This technique was found to be higher yielding. Phosphine chalcogenide ligands were accessed by further oxidizing the low valent phosphorous centers with either hydrogen peroxide or with elemental sulfur. These ligands were characterized using multinuclear NMR, low and high resolution mass spectroscopy, FTIR, and single crystal X-ray diffraction. Their electrochemical properties were explored with cyclic voltammetry. The phosphine appended ligands were used in the synthesis of a several bimetallic complexes. It was found that the ligands readily reacted with NiCp2 and NiCp*2, displacing one of the cyclopentadiene (Cp) or pentamethylcyclopentadiene (Cp*) rings. A cyclopentadiene complexes, containing diisopropylphine, was readily oxidized by[FeCp2]PF6 to give a NMR silent mixed valence complex. Cyclic voltammetry of these complexes showed a number of reversible waves with a large potential separation. The mixed valence compounds also showed a large absorbance band in the NIR region which was assigned to be an intervalence charge transfer. The cyclic voltammetry and NIR spectroscopy suggest that these systems are very capable of efficient metal-to-metal charge transfer. These complexes were characterized by multinuclear NMR, single crystal X-ray diffraction, UV/VIS-NIR spectroscopy and elemental analysis. The phosphine oxide ligands were reacted with a variety of different metal sources but limited success was gained in obtaining single crystals, allowing structural characterization of these compounds. Single crystals were obtained from products generated by reacting the diphenylphosphine oxide ligand with (Bipy)Cu(NO3)2 and Cu(NO3)2. In all cases the ligand had been further oxidized to a 2,5-dihydroxy-1,4-benzoquinone motif. In the reaction between the diphenylphosphine oxide ligand and (Bipy)Cu(NO3)2 it was found that the phosphine oxide moiety was involved with intermolecular coordination leading to the formation of a one-dimensional polymer composed of a series of bimetallic complexes tethered together. When NaSbF6 was present in the reaction with (Bipy)Cu(NO3)2 a unique tetrametallic complex was formed. Here the phospine oxide moiety was oriented so that two bimetallic complexes were bound together. If only Cu(NO3)2 was present, a two-dimensional polymeric sheet was formed where the ligand was present in two different coordination modes. The electronic properties of these complexes remained to be assessed.

Genetic association studies under the population stratification, family pedigree and application to genome-wide association studies

This dissertation has three separate parts: the first part deals with the general pedigree association testing incorporating continuous covariates; the second part deals with the association tests under population stratification using the conditional likelihood tests; the third part deals with the genome-wide association studies based on the real rheumatoid arthritis (RA) disease data sets from Genetic Analysis Workshop 16 (GAW16) problem 1. Many statistical tests are developed to test the linkage and association using either case-control status or phenotype covariates for family data structure, separately. Those univariate analyses might not use all the information coming from the family members in practical studies. On the other hand, the human complex disease do not have a clear inheritance pattern, there might exist the gene interactions or act independently. In part I, the new proposed approach MPDT is focused on how to use both the case control information as well as the phenotype covariates. This approach can be applied to detect multiple marker effects. Based on the two existing popular statistics in family studies for case-control and quantitative traits respectively, the new approach could be used in the simple family structure data set as well as general pedigree structure. The combined statistics are calculated using the two statistics; A permutation procedure is applied for assessing the p-value with adjustment from the Bonferroni for the multiple markers. We use simulation studies to evaluate the type I error rates and the powers of the proposed approach. Our results show that the combined test using both case-control information and phenotype covariates not only has the correct type I error rates but also is more powerful than the other existing methods. For multiple marker interactions, our proposed method is also very powerful. Selective genotyping is an economical strategy in detecting and mapping quantitative trait loci in the genetic dissection of complex disease. When the samples arise from different ethnic groups or an admixture population, all the existing selective genotyping methods may result in spurious association due to different ancestry distributions. The problem can be more serious when the sample size is large, a general requirement to obtain sufficient power to detect modest genetic effects for most complex traits. In part II, I describe a useful strategy in selective genotyping while population stratification is present. Our procedure used a principal component based approach to eliminate any effect of population stratification. The paper evaluates the performance of our procedure using both simulated data from an early study data sets and also the HapMap data sets in a variety of population admixture models generated from empirical data. There are one binary trait and two continuous traits in the rheumatoid arthritis dataset of Problem 1 in the Genetic Analysis Workshop 16 (GAW16): RA status, AntiCCP and IgM. To allow multiple traits, we suggest a set of SNP-level F statistics by the concept of multiple-correlation to measure the genetic association between multiple trait values and SNP-specific genotypic scores and obtain their null distributions. Hereby, we perform 6 genome-wide association analyses using the novel one- and two-stage approaches which are based on single, double and triple traits. Incorporating all these 6 analyses, we successfully validate the SNPs which have been identified to be responsible for rheumatoid arthritis in the literature and detect more disease susceptibility SNPs for follow-up studies in the future. Except for chromosome 13 and 18, each of the others is found to harbour susceptible genetic regions for rheumatoid arthritis or related diseases, i.e., lupus erythematosus. This topic is discussed in part III.

Soft Lewis acid catalyzed cycloisomerization of oxo-alkynes and enynes

In the literature, some transition metal salts have been used as soft Lewis acids to activate alkynes toward nucleophilic attack. For example, Pt(II), Au(I) and Pd(II) catalysts can catalyze cycloisomerization reactions of alkynyl compounds to give a variety of cyclic products. In order to expand the scope of these reactions, in chapter 2 of this dissertation, several alkynyl epoxides were isomerized to cyclic allyl vinyl ethers using PtCl2 as the catalyst. Three of these allyl vinyl ethers were hydrolyzed to 2-hydroxymorpholine derivatives and two were converted to piperidine derivatives by thermal Claisen rearrangement. In order to find more benign and inexpensive catalysts for these types of reactions, in chapter 3 of this dissertation, BiCl3 was used to catalyze the isomerization of eight enynes to pyrrolidine derivatives. This reaction was normally catalyzed by expensive noble metal catalysts, such as Pd(II), Pt(II) and Au(I). All the cyclic products are valuable intermediates in the synthesis of bioactive molecules, these soft Lewis acid catalyzed cycloisomerization may find applications in the synthesis of bioactive molecules.

Syntheses and characterization of monomeric Mo(VI) complexes with bidentate phosphine oxide ligands and dimeric and tetrameric Mo(V) clusters with benzoic acid and phosphinic acid derivatives, containing MoO2, Mo2O2(μ-O)2 and Mo4O4(μ3-O)4

Mo(VI) oxo complexes have been persistently sought after as epoxidation catalysts. Further, Mo(V) oxo clusters of the form M4(µ3-X)4 (M = transition metal, X = O, S) have been rigorously studied due to their remarkable structures and also their usefulness as models for electronic studies. The syntheses and characterizations of new Mo(VI) and Mo(V) oxo complexes have been described in this dissertation. Two new complexes MoO2Cl2Ph2P(O)CH2COOH and MoO2Cl2Ph2P(O)C6H4tBuS(O) were synthesized from reactions of “MoO2Cl2” with ligands Ph2P(O)CH2COOH and Ph2P(O)C6H4tBuS(O). Tetrameric packing arrangements comprised of hydrogen bonds were obtained for the complex MoO2Cl2Ph2P(O)CH2COOH and the ligand Ph2P(O)CH2COOH. Further the stability of an Mo-O bond was preferred over the Mo-S bond even though this resulted in the formation of a more strained seven membered ring. Tetranuclear Mo(V) complexes of the form [Mo4(µ3-O)4(µ-O2PR2)4O4], (PR2 = PPh2, PMe2) were synthesized using reactions of MoO2(acac)2 with diphenyl and dimethyl phosphinic acids, in ethanol. In the crystal structure of these complexes four Mo=O units are interconnected by four triply bridging oxygen atoms and bridging phosphinate ligands. The complex exhibited fourfold symmetry as evidenced by a single 31P NMR peak for the P atoms in the coordinated ligands. Reaction of WO2(acac)2 with Ph2POOH in methanol resulted in a dimeric W(VI) complex [(CH3O)2(O)W(µ-O)( µ-O2PPh2)2W(O)(CH3O)2] which contained a packing disorder in its crystal structure. Similar reactions of MoO2(acac)2 with benzoic acid derivatives resulted in dimeric complexes of the form [Mo2O2(acac)2(µ-O)(µ-OC2H5)(µ-O2CR)] (R = C6H5, (o-OH)C6H4, (p-Cl)C6H4, (2,4-(OH)2)C6H3, (o-I)C6H4) and one tetrameric complex [Mo2O2(acac)2(µ-O)(µ-OC2H5)(µ-O2C)C6H4(p-µ-O2C)Mo2O2(acac)2(µ-O)(µ-OC2H5)] with terephthalic acid. 1H NMR proved very useful in the prediction of the formation of dimers with the substituted benzoic acids, which were also confirmed by elemental analyses. The reductive capability of ethanol proved instrumental in the syntheses of Mo(V) tetrameric and dimeric clusters. Synthetic details, IR, 1H and 31P NMR spectroscopy and elemental analyses are reported for all new complexes. Further, single crystal X-ray structures of MoO2Cl2Ph2P(O)CH2COOH, MoO2Cl2Ph2P(O)C6H4tBuS(O), [Mo4(µ3-O)4(µ-O2PR2)4O4], (PR2 = PPh2, PMe2), [(CH3O)2(O)W(µ-O)( µ-O2PPh2)2W(O)(CH3O)2] and [Mo2O2(acac)2(µ-O)(µ-OC2H5)(µ-O2CR)] (R = C6H5, (o-OH)C6H4) are also presented.

Biological materials : Part A. tuning LCST of raft copolymers and gold/copolymer hybrid nanoparticles and Part B. biobased nanomaterials

The research described in this dissertation is comprised of two major parts. The first part studied the effects of asymmetric amphiphilic end groups on the thermo-response of diblock copolymers of (oligo/di(ethylene glycol) methyl ether (meth)acrylates, OEGA/DEGMA) and the hybrid nanoparticles of these copolymers with a gold nanoparticle core. Placing the more hydrophilic end group on the more hydrophilic block significantly increased the cloud point compared to a similar copolymer composition with the end group placement reversed. For a given composition, the cloud point was shifted by as much as 28 °C depending on the placement of end groups. This is a much stronger effect than either changing the hydrophilic/hydrophobic block ratio or replacing the hydrophilic acrylate monomer with the equivalent methacrylate monomer. The temperature range of the coil-globule transition was also altered. Binding these diblock copolymers to a gold core decreased the cloud point by 5-15 °C and narrowed the temperature range of the coil-globule transition. The effects were more pronounced when the gold core was bound to the less hydrophilic block. Given the limited numbers of monomers that are approved safe for in vivo use, employing amphiphilic end group placement is a useful tool to tune a thermo-response without otherwise changing the copolymer composition. The second part of the dissertation investigated the production of value-added nanomaterials from two biorefinery “wastes”: lignin and peptidoglycan. Different solvents and spinning methods (melt-, wet-, and electro-spinning) were tested to make lignin/cellulose blended and carbonized fibers. Only electro-spinning yielded fibers having a small enough diameter for efficient carbonization ( Peptidoglycan (a bacterial cell wall material) was copolymerized with poly-(3-hydroxybutyrate), a common polyhydroxyalkanoate produced by bacteria with the objective of determining if a useful material could be obtained with a less rigorous work-up on harvesting polyhydroxyalkanoates. The copolyesteramide product having 25 wt.% peptidoglycan from a highly purified peptidoglycan increased thermal stability by 100-200 °C compared to the poly-(3-hydroxybutyrate) control, while a less pure peptidoglycan, harvested from B. megaterium (ATCC 11561), gave a 25-50 °C increase in thermal stability. Both copolymers absorbed more moisture than pure poly-(3-hydroxybutyrate). The results suggest that a less rigorously harvested and purified polyhydroxyalkanoate might be useful for some applications.

Functional ZnO nanostructures for electronic and energy applications

ZnO has proven to be a multifunctional material with important nanotechnological applications. ZnO nanostructures can be grown in various forms such as nanowires, nanorods, nanobelts, nanocombs etc. In this work, ZnO nanostructures are grown in a double quartz tube configuration thermal Chemical Vapor Deposition (CVD) system. We focus on functionalized ZnO Nanostructures by controlling their structures and tuning their properties for various applications. The following topics have been investigated: 1. We have fabricated various ZnO nanostructures using a thermal CVD technique. The growth parameters were optimized and studied for different nanostructures. 2. We have studied the application of ZnO nanowires (ZnONWs) for field effect transistors (FETs). Unintentional n-type conductivity was observed in our FETs based on as-grown ZnO NWs. We have then shown for the first time that controlled incorporation of hydrogen into ZnO NWs can introduce p-type characters to the nanowires. We further found that the n-type behaviors remained, leading to the ambipolar behaviors of hydrogen incorporated ZnO NWs. Importantly, the detected p- and n- type behaviors are stable for longer than two years when devices were kept in ambient conditions. All these can be explained by an ab initio model of Zn vacancy-Hydrogen complexes, which can serve as the donor, acceptors, or green photoluminescence quencher, depend on the number of hydrogen atoms involved. 3. Next ZnONWs were tested for electron field emission. We focus on reducing the threshold field (Eth) of field emission from non-aligned ZnO NWs. As encouraged by our results on enhancing the conductivity of ZnO NWs by hydrogen annealing described in Chapter 3, we have studied the effect of hydrogen annealing for improving field emission behavior of our ZnO NWs. We found that optimally annealed ZnO NWs offered much lower threshold electric field and improved emission stability. We also studied field emission from ZnO NWs at moderate vacuum levels. We found that there exists a minimum Eth as we scale the threshold field with pressure. This behavior is explained by referring to Paschen’s law. 4. We have studied the application of ZnO nanostructures for solar energy harvesting. First, as-grown and (CdSe) ZnS QDs decorated ZnO NBs and ZnONWs were tested for photocurrent generation. All these nanostructures offered fast response time to solar radiation. The decoration of QDs decreases the stable current level produced by ZnONWs but increases that generated by NBs. It is possible that NBs offer more stable surfaces for the attachment of QDs. In addition, our results suggests that performance degradation of solar cells made by growing ZnO NWs on ITO is due to the increase in resistance of ITO after the high temperature growth process. Hydrogen annealing also improve the efficiency of the solar cells by decreasing the resistance of ITO. Due to the issues on ITO, we use Ni foil as the growth substrates. Performance of solar cells made by growing ZnO NWs on Ni foils degraded after Hydrogen annealing at both low (300 °C) and high (600 °C) temperatures since annealing passivates native defects in ZnONWs and thus reduce the absorption of visible spectra from our solar simulator. Decoration of QDs improves the efficiency of such solar cells by increasing absorption of light in the visible region. Using a better electrolyte than phosphate buffer solution (PBS) such as KI also improves the solar cell efficiency. 5. Finally, we have attempted p-type doping of ZnO NWs using various growth precursors including phosphorus pentoxide, sodium fluoride, and zinc fluoride. We have also attempted to create p-type carriers via introducing interstitial fluorine by annealing ZnO nanostructures in diluted fluorine gas. In brief, we are unable to reproduce the growth of reported p-type ZnO nanostructures. However; we have identified the window of temperature and duration of post-growth annealing of ZnO NWs in dilute fluorine gas which leads to suppression of native defects. This is the first experimental effort on post-growth annealing of ZnO NWs in dilute fluorine gas although this has been suggested by a recent theory for creating p-type semiconductors. In our experiments the defect band peak due to native defects is found to decrease by annealing at 300 °C for 10 – 30 minutes. One of the major future works will be to determine the type of charge carriers in our annealed ZnONWs.

Eruptive history of Maderas volcano using new 40Ar/39Ar ages and geochemical analyses

Maderas volcano is a small, andesitic stratovolcano located on the island of Ometepe, in Lake Nicaragua, Nicaragua with no record of historic activity. Twenty-one samples were collected from lava flows from Maderas in 2010. Selected samples were analyzed for whole-rock geochemical data using ICP-AES and/or were dated using the 40Ar/39Ar method. The results of these analyses were combined with previously collected data from Maderas as well as field observations to determine the eruptive history of the volcano and create a geologic map. The results of the geochemical analyses indicate that Maderas is a typical Central American andesitic volcano similar to other volcanoes in Nicaragua and Costa Rica and to its nearest neighbor, Concepción volcano. It is different from Concepción in one important way – higher incompatible elements. Determined age dates range from 176.8 ± 6.1 ka to 70.5 ± 6.1 ka. Based on these ages and the geomorphology of the volcano which is characterized by a bisecting graben, it is proposed that Maderas experienced two clear generations of development with three separate phases of volcanism: initial build-up of the older cone, pre-graben lava flows, and post-graben lava flows. The ages also indicate that Maderas is markedly older than Concepción which is historically active. Results were also analyzed regarding geologic hazards. The 40Ar/39Ar ages indicate that Maderas has likely been inactive for tens of thousands of years and the risk of future volcanic eruptions is low. However, earthquake, lahar and landslide hazards exist for the communities around the volcano. The steep slopes of the eroded older cone are the most likely source of landslide and lahar hazards.

Boron nitride nanotubes : synthesis, characterization, functionalization, and potential applications

Boron nitride nanotubes (BNNTs) are structurally similar to carbon nanotubes (CNTs), but exhibit completely different physical and chemical properties. Thus, BNNTs with various interesting properties may be complementary to CNTs and provide an alternative perspective to be useful in different applications. However, synthesis of high quality of BNNTs is still challenging. Hence, the major goals of this research work focus on the fundamental study of synthesis, characterizations, functionalization, and explorations of potential applications. In this work, we have established a new growth vapor trapping (GVT) approach to produce high quality and quantity BNNTs on a Si substrate, by using a conventional tube furnace. This chemical vapor deposition (CVD) approach was conducted at a growth temperature of 1200 °C. As compared to other known approaches, our GVT technique is much simpler in experimental setup and requires relatively lower growth temperatures. The as-grown BNNTs are fully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), Energy Filtered Mapping, Raman spectroscopy, Fourier Transform Infra Red spectroscopy (FTIR), UV-Visible (UV-vis) absorption spectroscopy, etc. Following this success, the growth of BNNTs is now as convenient as growing CNTs and ZnO nanowires. Some important parameters have been identified to produce high-quality BNNTs on Si substrates. Furthermore, we have identified a series of effective catalysts for patterned growth of BNNTs at desirable or pre-defined locations. This catalytic CVD technique is achieved based on our finding that MgO, Ni or Fe are the good catalysts for the growth of BNNTs. The success of patterned growth not only explains the role of catalysts in the formation of BNNTs, this technique will also become technologically important for future device fabrication of BNNTs. Following our success in controlled growth of BNNTs on substrates, we have discovered the superhydrophobic behavior of these partially vertically aligned BNNTs. Since BNNTs are chemically inert, resistive to oxidation up to ~1000°C, and transparent to UV-visible light, our discovery suggests that BNNTs could be useful as self-cleaning, insulating and protective coatings under rigorous chemical and thermal conditions. We have also established various approaches to functionalize BNNTs with polymeric molecules and carbon coatings. First, we showed that BNNTs can be functionalized by mPEG-DSPE (Polyethylene glycol-1,2-distearoyl-sn-glycero-3-phosphoethanolamine), a bio-compatible polymer that helps disperse and dissolve BNNTs in water solution. Furthermore, well-dispersed BNNTs in water can be cut from its original length of >10µm to(>20hrs). This success is an essential step to implement BNNTs in biomedical applications. On the other hand, we have also succeeded to functionalize BNNTs with various conjugated polymers. This success enables the dispersion of BNNTs in organic solvents instead of water. Our approaches are useful for applications of BNNTs in high-strength composites. In addition, we have also functionalized BNNTs with carbon decoration. This was performed by introducing methane (CH4) gas into the growth process of BNNT. Graphitic carbon coatings can be deposited on the side wall of BNNTs with thicknesses ranging from 2 to 5 nm. This success can modulate the conductivity of pure BNNTs from insulating to weakly electrically conductive. Finally, efforts were devoted to explore the application of the wide bandgap BNNTs in solar-blind deep UV (DUV) photo-detectors. We found that photoelectric current generated by the DUV light was dominated in the microelectrodes of our devices. The contribution of photocurrent from BNNTs is not significant if there is any. Implication from these preliminary experiments and potential future work are discussed.

Metal-oxide film and photonic structures for integrated device applications

The application of photonic crystal technology on metal-oxide film is a very promising field for future optical telecommunication systems. Band gap and polarization effects in lithium niobate (LiNbO3) photonic crystals and bismuth-substituted iron garnets (BiYIG) photonic crystals are investigated in this work reported here. The design and fabrication process are similar for these two materials while the applications are different, involving Bragg filtering in lithium niobate and polarization rotation in nonreciprocal iron garnets. The research of photonic structures in LiNbO3 is of high interest for integrated device application due to its remarkable electro-optical characteristics. This work investigated the photonic band gap in high quality LiNbO3 single crystalline thin film by ion implantation to realize high efficiency narrow bandwidth filters. LiNbO3 thin film detachment by bonding is also demonstrated for optical device integration. One-dimensional Bragg BiYIG waveguides in gyrotropic system are found to have multiple stopbands and evince enhancement of polarization rotation efficiency. Previous photon trapping theory cannot explain the phenomena because of the presence of linear birefringence. This work is aimed at investigating the mechanism with the support of experiments. The results we obtained show that selective suppression of Bloch states in gyrotropic bandgaps is the key mechanism for the observed phenomena. Finally, the research of ferroelectric single crystal PMN-PT with ultra high piezoelectric coefficient as a biosensor is also reported. This work presents an investigation and results on higher sensitivity effects than conventional materials such as quartz and lithium niobate.