Planetary Penetrators for Sample Return Missions

Thesis (Master's)--University of Washington, 2016-06

Direct quantification of rare earth element concentrations in natural waters by ICP-MS

A direct quadrupole ICP-MS technique has been developed for the analysis of the rare earth elements and yttrium in natural waters. The method has been validated by comparison of the results obtained for the river water reference material SLRS-4 with literature values. The detection limit of the technique was investigated by analysis of serial dilutions of SLRS-4 and revealed that single elements can be quantified at single-digit fg/g concentrations. A coherent normalised rare earth pattern was retained at concentrations two orders of magnitude below natural concentrations for SLRS-4, demonstrating the excellent inter-element accuracy and precision of the method. The technique was applied to the analysis of a diluted mid-salinity estuarine sample, which also displayed a coherent normalised rare earth element pattern, yielding the expected distinctive marine characteristics. (c) 2006 Published by Elsevier Ltd.

Aquatic geochemistry of the rare earth elements and yttrium in the Pioneer River catchment, Australia

The rare earth elements are strong provenance indicators in geological materials, yet the potential for tracing provinciality in surface freshwater samples has not been adequately tested. Rare earth element and yttrium concentrations were measured at 33 locations in the Pioneer River catchment, Mackay, central Queensland, Australia. The rare earth element patterns were compared on the basis of geological, topographical and land-use features in order to investigate the provenancing potential of these elements in a small freshwater system. The rare earth element patterns of streams draining single lithological units with minor land modification show strongly coherent normalised behaviour, with a loss of coherence in agricultural locations. Evidence is reported for an anthropogenic Gd anomaly that may provide a useful hydrological tracer in this region since the introduction of magnetic resonance imaging in 2003. Several samples display a superchondritic Y/Ho mass ratio (up to 44), which is not explainable within the constraints imposed by local geology. Instead, it is suggested that the additional Y is derived from a marine source, specifically marine phosphorites, which are a typical source of fertiliser phosphorus. The data indicate that, under some circumstances, scaled and normalised freshwater rare earth patterns behave conservatively.

Transport phenomena in hydrogel membranes

In this thesis the factors surrounding the permeation of alkali and alkaline earth metal salts through hydrogel membranes are investigated. Although of relevance to aqueous separations in general, it was with their potential application in sensors that this work was particularly concerned. In order to study the effect that the nature of the solute has on the transport process, a single polymer matrix, poly (2-hydroxyethyl methacrylate), was initially studied. The influence of cation variation in the presence of a fixed anion was looked at, followed by the effect of the anion in the presence of a fixed cation. The anion was found to possess the dominant influence and tended to subsume any influence by the cation. This is explained in terms of the structure-making and structure-breaking characteristics of the ions in their solute-water interactions. Analogies in the transport behaviour of the salts are made with the Hofmeister series. The effect of the chemical composition of the polymer backbone on the water structuring in the hydrogel and, consequently, transport through the membrane, was investigated by preparing a series of poly (2-hydroxyethyl methacrylate) copolymer membranes and determining the permeability coefficient of salts with a fixed anion. The results were discussed in terms of the `free-volume' model of permeation and the water structuring of the polymer backbone. The ability of ionophores to selectively modulate the permeation of salts through hydrogel membranes was also examined. The results indicated that a dualsorption model was in operation. Finally, hydrogels were used as membrane overlays on coated wire ion-selective electrodes that employed conventional plasticised-PVC-valinomycin based sensing membranes. The hydrogel overlays were found to affect the access of the analyte but not the underlying electrochemistry.

All-optical 42.6 Gbit/s NRZ to RZ format conversion by cross-phase modulation in single SOA

A 42.6 Gbit/s all-optical non-retum-to-zero (NRZ) to return-to-zero (RZ) format converter using a single SOA followed by an asymmetrical Mach-Zehnder interferometer is presented. The format converter generates a correctly-coded RZ signal with a controllable duty-cycle. It has the advantages of flexible input N RZ wavelength, preserved input polarity, negative bit error rate power penalty and low switching pulse energy (15fJ).

Performance enhancement of asymmetric filtered 40 Gb/s carrier suppressed return to zero-differential phase shift keying receiver in a 50 GHz grid

The authors present the impact of asymmetric filtering of strong (e.g. 35 GHz) optical filters on the performance of 42.7 Gb/s 67% (carrier suppressed return to zero)-differential phase shift keying systems. The performance is examined (in an amplified spontaneous emission (ASE) noise-limited regime and in the presence of chromatic dispersion) when offsetting the filter at the receiver by substantial amounts via balanced, constructive and destructive single-ended detections. It is found that with a slight offset (vestigial side band) or an offset of almost half of the modulation frequency (single-side band), there is a significant improvement in the calculated 'Q'. © The Institution of Engineering and Technology 2013.

Optimally-designed single fiber Bragg grating filter scheme for RZ-OOK/DPSK/DQPSK to NRZ-OOK/DPSK/DQPSK format conversion

We investigate return-to-zero (RZ) to non-return-to-zero (NRZ) format conversion by means of the linear time-invariant system theory. It is shown that the problem of converting random RZ stream to NRZ stream can be reduced to constructing an appropriate transfer function for the linear filter. This approach is then used to propose novel optimally-designed single fiber Bragg grating (FBG) filter scheme for RZ-OOK/DPSK/DQPSK to NRZ-OOK/DPSK/DQPSK format conversion. The spectral response of the FBG is designed according to the optical spectra of the algebraic difference between isolated NRZ and RZ pulses, and the filter order is optimized for the maximum Q-factor of the output NRZ signals. Experimental results as well as simulations show that such an optimallydesigned FBG can successfully perform RZ-OOK/DPSK/DQPSK to NRZOOK/ DPSK/DQPSK format conversion.

Simultaneous multichannel carrier-suppressed return-to-zero to non-return-to-zero format conversion using a fiber Bragg grating

A novel multichannel carrier-suppressed return-to-zero (CSRZ) to non-return-to-zero (NRZ) format conversion scheme based on a single custom-designed fiber Bragg grating (FBG) with comb spectra is proposed. The spectral response of each channel is designed according to the algebraic difference between the CSRZ and NRZ spectra outlines. The tailored group delays are introduced to minimize the maximum refractive index modulation. Numerical results show that four-channel 200-GHz-spaced CSRZ signals at 40 Gbits/s can be converted into NRZ signals with high Q-factor and wide-range robustness. It is shown that our proposed FBG is robust to deviations of bandwidth and central wavelength detuning. Another important merit of this scheme is that the pattern effects are efficiently reduced owing to the well-designed spectra response.

Three essays on the interrelationships among financial restatements, corporate governance, market microstructure and the firm's rate of return

The increase in the number of financial restatements in recent years has resulted in a significant decrease in the amount of market capitalization for restated companies. Prior literature did not differentiate between single and multiple restatements announcements. This research investigated the inter-relationships among multiple financial restatements, corporate governance, market microstructure and the firm’s rate of return in the form of three essays by differentiating between single and multiple restatement announcement companies. First essay examined the stock performance of companies announcing the financial restatement multiple times. The postulation is that prior research overestimates the abnormal return by not separating single restatement companies from multiple restatement companies. This study investigated how market penalizes the companies that announce restatement more than once. Differentiating the restatement announcement data based on number of restatement announcements, the results supported the non persistence hypothesis that the market has no memory and negative abnormal returns obtained after each of the restatement announcements are completely random. Second essay examined the multiple restatement announcements and its perceived resultant information asymmetry around the announcement day. This study examined the pattern of information asymmetry for these announcements in terms of whether the bid-ask spread widens around the announcement day. The empirical analysis supported the hypotheses that the spread does widen not only around the first restatement announcement day but around every subsequent announcement days as well. The third essay empirically examined the financial and corporate governance characteristics of single and multiple restatement announcements companies. The analysis showed that corporate governance variables influence the occurrence of multiple restatement announcements and can distinguish multiple restatements announcement companies from single restatement announcement companies.

Effect of water on olivine single crystals plasticity, deformed under high pressure and high temperature

The Earth's upper mantle, mainly composed of olivine, is seismically anisotropic. Seismic anisotropy attenuation has been observed at 220km depth. Karato et al. (1992) attributed this attenuation to a transition between two deformation mechanisms, from dislocation creep above 220km to diffusion creep below 220km, induced by a change in water content. Couvy (2005) and Mainprice et al. (2005) predicted a change in Lattice Preferred Orientation induced by pressure, which comes from a change of slip system, from [100] slip to [001] slip, and is responsible for the seismic anisotropy attenuation. Raterron et al. (2007) ran single crystal deformation experiments under anhydrous conditions and observed that the slip system transition occurs around 8GPa, which corresponds to a depth of 260Km. Experiments were done to quantify the effects of water on olivine single crystals deformed using D-DIA press and synchrotron beam. Deformations were carried out in uniaxial compression along [110]c, [011]c, and [101]c, crystallographic directions, at pressure ranging from 4 to 8GPa and temperature between 1373 and 1473K. Talc sleeves about the annulus of the single crystals were used as source of water in the assembly. Stress and specimen strain rates were calculated by in-situ X-ray diffraction and time resolved imaging, respectively. By direct comparison of single crystals strain rates, we observed that [110]c deforms faster than [011]c below 5GPa. However above 6GPa [011]c deforms faster than [110]c. This revealed that [100](010) is the dominant slip system below 5GPa, and above 6GPa [001](010) becomes dominant. According to our results, the slip system transition, which is induced by pressure, occurs at 6GPa. Water influences the pressure where the switch over occurs, by lowering the transition pressure. The pressure effect on the slip systems activity has been quantified and the hydrolytic weakening has also been estimated for both orientations. Data also shows that temperature affects the slip system activity. The regional variation of the depth for the seismic anisotropy attenuation, which would depend on local hydroxyl content and temperature variations and explains the seismic anisotropy attenuation occurring at about 220Km depth in the mantle, where the pressure is about 6GPa. Deformation of MgO single crystal oriented [100], [110] and [111] were also performed. The results predict a change in the slip system activity at 23GPa, again induced by pressure. This explains the seismic anisotropy observed in the lower mantle.

Three Essays on the Interrelationships Among Financial Restatements, Corporate Governance, Market Microstructure and the Firm's Rate of Return

The increase in the number of financial restatements in recent years has resulted in a significant decrease in the amount of market capitalization for restated companies. Prior literature does not differentiate between single and multiple restatements announcements. This research investigates the inter-relationships among multiple financial restatements, corporate governance, market microstructure and the firm's rate of return in the form of three essays by differentiating between single and multiple restatement announcement companies. First essay examines the stock performance of companies announcing the financial restatement multiple times. The postulation is that prior research overestimates the abnormal return by not separating single restatement companies from multiple restatement companies. This study investigates how market penalizes the companies that announce restatement more than once. Differentiating the restatement announcement data based on number of restatement announcements, the results support for non persistence hypothesis that the market has no memory and negative abnormal returns obtained after each of the restatement announcements are completely random. Second essay examines the multiple restatement announcements and its perceived resultant information asymmetry around the announcement day. This study examines the pattern of information asymmetry for these announcements in terms of whether the bid-ask spread widens around the announcement day. The empirical analysis supports the hypotheses that the spread does widen not only around the first restatement announcement day but around every subsequent announcement days as well. The third essay empirically examines the financial and corporate governance characteristics of single and multiple restatement announcements companies. The analysis shows that corporate governance variables influence the occurrence of multiple restatement announcements and can distinguish multiple restatements announcement companies from single restatement announcement companies.

Rare earth element concentrations and geochemistry of carbonate minerals from the Logatchev Hydrothermal Field and the Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like 87Sr/86Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~100 °C), and yet its 87Sr/86Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine-talc fault schists form north of the LHF. These calcites show unradiogenic 87Sr/86Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.

Mesoscale Optoelectronic Design of Wire-Based Photovoltaic and Photoelectrochemical Devices

The overarching theme of this thesis is mesoscale optical and optoelectronic design of photovoltaic and photoelectrochemical devices. In a photovoltaic device, light absorption and charge carrier transport are coupled together on the mesoscale, and in a photoelectrochemical device, light absorption, charge carrier transport, catalysis, and solution species transport are all coupled together on the mesoscale. The work discussed herein demonstrates that simulation-based mesoscale optical and optoelectronic modeling can lead to detailed understanding of the operation and performance of these complex mesostructured devices, serve as a powerful tool for device optimization, and efficiently guide device design and experimental fabrication efforts. In-depth studies of two mesoscale wire-based device designs illustrate these principles—(i) an optoelectronic study of a tandem Si|WO3 microwire photoelectrochemical device, and (ii) an optical study of III-V nanowire arrays.

The study of the monolithic, tandem, Si|WO3 microwire photoelectrochemical device begins with development and validation of an optoelectronic model with experiment. This study capitalizes on synergy between experiment and simulation to demonstrate the model’s predictive power for extractable device voltage and light-limited current density. The developed model is then used to understand the limiting factors of the device and optimize its optoelectronic performance. The results of this work reveal that high fidelity modeling can facilitate unequivocal identification of limiting phenomena, such as parasitic absorption via excitation of a surface plasmon-polariton mode, and quick design optimization, achieving over a 300% enhancement in optoelectronic performance over a nominal design for this device architecture, which would be time-consuming and challenging to do via experiment.

The work on III-V nanowire arrays also starts as a collaboration of experiment and simulation aimed at gaining understanding of unprecedented, experimentally observed absorption enhancements in sparse arrays of vertically-oriented GaAs nanowires. To explain this resonant absorption in periodic arrays of high index semiconductor nanowires, a unified framework that combines a leaky waveguide theory perspective and that of photonic crystals supporting Bloch modes is developed in the context of silicon, using both analytic theory and electromagnetic simulations. This detailed theoretical understanding is then applied to a simulation-based optimization of light absorption in sparse arrays of GaAs nanowires. Near-unity absorption in sparse, 5% fill fraction arrays is demonstrated via tapering of nanowires and multiple wire radii in a single array. Finally, experimental efforts are presented towards fabrication of the optimized array geometries. A hybrid self-catalyzed and selective area MOCVD growth method is used to establish morphology control of GaP nanowire arrays. Similarly, morphology and pattern control of nanowires is demonstrated with ICP-RIE of InP. Optical characterization of the InP nanowire arrays gives proof of principle that tapering and multiple wire radii can lead to near-unity absorption in sparse arrays of InP nanowires.

Earth-Abundant Zinc-IV-Nitride Semiconductors

This investigation is motivated by the need for new visible frequency direct bandgap semiconductor materials that are abundant and low-cost to meet the increasing demand for optoelectronic devices in applications such as solid state lighting and solar energy conversion. Proposed here is the utilization of zinc-IV-nitride materials, where group IV elements include silicon, germanium, and tin, as earth-abundant alternatives to the more common III-nitrides in optoelectronic devices. These compound semiconductors were synthesized under optimized conditions using reactive radio frequency magnetron sputter deposition. Single phase ZnSnN₂, having limited experimental accounts in literature, is validated by identification of the wurtzite-derived crystalline structure predicted by theory through X-ray and electron diffraction studies. With the addition of germanium, bandgap tunability of ZnSn_xGe_1-xN₂ alloys is demonstrated without observation of phase separation, giving these materials a distinct advantage over In_xGa_1-xN alloys. The accessible bandgaps range from 1.8 to 3.1 eV, which spans the majority of the visible spectrum. Electron densities, measured using the Hall effect, were found to be as high as 10²² cm⁻³ and indicate that the compounds are unintentionally degenerately doped. Given these high carrier concentrations, a Burstein-Moss shift is likely affecting the optical bandgap measurements. The discoveries made in this thesis suggest that with some improvements in material quality, zinc-IV-nitrides have the potential to enable cost-effective and scalable optoelectronic devices.

Methods of earth building in the Huila Province, Angola

In Angola, the construction made of raw earth is a cultural heritage widely used by low income households, representing over 80% of the population [1, 3]. In Huila province is evident construction in raw earth in a large scale, either in urban or in periurban and rural areas. The construction methods follow the ancestral standards, distributed throughout the region of Huila, being built by the several ethnic groups. Among the construction techniques in earth, stand out: the adobe, wattle-and-daub and more recently on CEB (Compressed Earth Block). The type of soil used to make the adobes is mainly silty-clayed sand [1]. The most applied materials are: rods, reeds, wood, grass, straw, soil and stone, almost with the same characteristics [2]. The manufacture of adobe, consists essentially in mixing clay and grass (plant fibers), then put the mixture inside a wooden mold, having a size of 42 cm long and 18 cm high and taking three to four days to dry and be applied in housing construction. The application of these materials makes the construction less expensive because they are collected, transformed and applied by the owner himself of housing without any project, based only on the result of the practice and experience acquired from their ancestors. They are simple constructions, presenting a typology of grouped and isolated single-family housing, ranging between 2 and 3 bedrooms [2]. The construction techniques used in such small housings have positive environmental aspects, both as regards the materials employed, such as the manner in which the constructions are raised, showing special concerns for the quality improvement of them, as regards the resistance, durability and comfort [4].