Microfabrication methods to improve the kinetics of the yttria stabilized zirconia -- platinum -- oxygen electrode

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2006.This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.Includes bibliographical references (p. 183-194).Solid oxide fuel cells are a potential electrical power source that is silent, efficient, modular, and capable of operating on a wide variety of fuels. Unfortunately, current technologies are severely limited in that they provide sufficient power output only at very high temperatures (>800°C). One reason for this is because the electrodes have very poor (and poorly understood) kinetics. The work described in this dissertation involves the microfabrication of model systems with triple phase boundary lengths that varied over an order of magnitude to systematically quantify and ultimately improve the kinetics of platinum electrodes on the surface of yttria stabilized zirconia electrolytes. Platinum electrodes with well controlled geometry were sputtered onto the surface of bulk YSZ and onto sputtered YSZ thin films. An unexpected result was found whereby YSZ films of composition Y0.09Zr0.91O2-x had an ionic conductivity remarkably enhanced by a factor of 20-30. This is attributed to the films exhibiting nanometric grain sizes and thereby stabilizing the cubic morphology at considerably lower yttrium levels than is normally needed. This metastable cubic phase is suspected of having reduced defect ordering.(cont.) Grain boundary resistance, which in YSZ is normally due to impurities that segregate and block ionic transfer, was found to also be significantly reduced in YSZ films. The films had a specific grain boundary conductivity enhanced by a factor of 30-100 compared to the bulk polycrystalline sample. This was believed to be due to the very low impurity content of the film grain boundaries. Concerning the electrode polarization resistance, it was found that the electrodes placed on bulk standards and films deposited at high temperatures were on par with the best electrode conductance values from the literature. However, when the electrolyte surface was a film deposited at reduced temperature, the resistance decreased further by a factor of 300-500. The cause of this was revealed to be silicon contamination on the surfaces of the poorer-performing electrolytes. Triple phase boundary length-specific resistances as low as 3.7·104 O·cm at 378°C and 4.0·107 O·cm at 215°C were measured; these appear to be the lowest ever recorded. The measurements are possibly the first electrochemical characterization of nearly silicon-free YSZ surfaces. This study emphasizes the key role of chemical purity at the electrode-electrolyte interface.(cont.) Photolithography alone is unlikely to give technologically useful triple phase boundary lengths. In an attempt to achieve the triple phase boundary lengths needed for a practical device, reactive co-sputtering was used to produce composite Pt-YSZ thin films with a bi-continuous network morphology and grain sizes on the order of 30 nm. Such intimate mixing of the electronic and ionic conducting phases created an effective mixed ionic-electronic conductor with the entire surface of the film electrochemically active to the electrode reaction. The best processing conditions resulted in electrodes with an area specific polarization resistance less than 500 O·cm2 at 400°C and, by extrapolation, 10 O·cm2 at 511°C and 1 O·cm2 at 608°C. These films may enable operation of a micro-solid oxide fuel cell at intermediate temperatures (400-500°C), and perhaps even lower temperatures with further microstructural optimization.by Joshua L. Hertz.Ph.D

Backward Masked Snakes and Guns Modulate Spatial Attention

Fearful faces are important social cues that alert others of potential threat. Even backward masked fearful faces facilitate spatial attention. However, visual stimuli other than fearful faces can signal potential threat. Indeed, unmasked snakes and spiders modulate spatial attention. Yet, it is unclear if the rapid threat-related facilitation of spatial attention to backward masked stimuli is elicited by non-face threat cues. Evolutionary theories claim that phylogenetic threats (i.e. snakes and spiders) should preferentially elicit an automatic fear response, but it is untested as to whether this response extends to enhancements in spatial attention under restricted processing conditions. Thirty individuals completed a backward masking dot-probe task with both evolutionary relevant and irrelevant threat cues. The results suggest that backward masked visual fear stimuli modulate spatial attention. Both evolutionary relevant (snake) and irrelevant (gun) threat cues facilitated spatial attention

Mass production of volume phase holographic gratings for the VIRUS spectrograph array

The Visible Integral-field Replicable Unit Spectrograph (VIRUS) is a baseline array of 150 copies of a simple, fiber-fed integral field spectrograph that will be deployed on the Hobby-Eberly Telescope (HET). VIRUS is the first optical astronomical instrument to be replicated on an industrial scale, and represents a relatively inexpensive solution for carrying out large-area spectroscopic surveys, such as the HET Dark Energy Experiment (HETDEX). Each spectrograph contains a volume phase holographic (VPH) grating with a 138 mm diameter clear aperture as its dispersing element. The instrument utilizes the grating in first-order for 350-550 nm. Including witness samples, a suite of 170 VPH gratings has been mass produced for VIRUS. Here, we present the design of the VIRUS VPH gratings and a discussion of their mass production. We additionally present the design and functionality of a custom apparatus that has been used to rapidly test the first-order diffraction efficiency of the gratings for various discrete wavelengths within the VIRUS spectral range. This device has been used to perform both in-situ tests to monitor the effects of adjustments to the production prescription as well as to carry out the final acceptance tests of the gratings' diffraction efficiency. Finally, we present the as-built performance results for the entire suite of VPH gratings.Comment: 16 pages, 11 figures, 2 tables. To be published in Proc. SPIE, 2014, "Advances in Optical and Mechanical Technologies for Telescopes and Instrumentation", 9151-53. The work presented in this article follows from arXiv:1207:448

Monitoring Aromatic ps-ns Dynamics in Proteins via 13C Relaxation: Expanding Perturbation Mapping of the Rigidifying Core Mutation, V54A, in eglin c

Long-range effects, such as allostery, have evolved in proteins as a means of regulating function via communication between distal sites. An NMR-based perturbation mapping approach was used to more completely probe the dynamic response of the core mutation V54A in the protein eglin c by monitoring changes in ps-ns aromatic side-chain dynamics and H/D exchange stabilities. Previous side-chain dynamics studies on this mutant were limited to methyl-bearing residues, most of which were found to rigidify on the ps-ns timescale in the form of a contiguous ‘network’. Here, high precision 13C relaxation data from 13 aromatic side chains were acquired by applying canonical relaxation experiments to a newly-developed carbon labeling scheme [Teilum K. et al. (2006) J. Am. Chem. Soc. 128, 2506–2507]. The fitting of model-free parameters yielded S2 variability which is intermediate with respect to backbone and methyl-bearing side chain variability and τe values that are approximately one nanosecond. Inclusion of the aromatic dynamic response results in an expanded network of dynamically coupled residues, with some aromatics showing increases in flexibility, which partially offsets the rigidification in methyl side chains. Using amide hydrogen exchange, dynamic propagation on a slower timescale was probed in response to the V54A perturbation. Surprisingly, regional stabilization (slowed exchange) 10–12 angstroms from the site of mutation was observed despite a global destabilization of 1.5 kcal·mol−1. Furthermore, this unlikely pocket of stabilized residues co-localizes with increases in aromatic flexibility on the faster timescale. Because the converse is also true (destabilized residues co-localize with rigidification on the fast timescale), a plausible entropy-driven mechanism is discussed for relating co-localization of opposing dynamic trends on vastly different timescales

Light-Element Abundance Variations at Low Metallicity: the Globular Cluster NGC 5466

We present low-resolution (R~850) spectra for 67 asymptotic giant branch (AGB), horizontal branch and red giant branch (RGB) stars in the low-metallicity globular cluster NGC 5466, taken with the VIRUS-P integral-field spectrograph at the 2.7-m Harlan J. Smith telescope at McDonald Observatory. Sixty-six stars are confirmed, and one rejected, as cluster members based on radial velocity, which we measure to an accuracy of 16 km s-1 via template-matching techniques. CN and CH band strengths have been measured for 29 RGB and AGB stars in NGC 5466, and the band strength indices measured from VIRUS-P data show close agreement with those measured from Keck/LRIS spectra previously taken of five of our target stars. We also determine carbon abundances from comparisons with synthetic spectra. The RGB stars in our data set cover a range in absolute V magnitude from +2 to -3, which permits us to study the rate of carbon depletion on the giant branch as well as the point of its onset. The data show a clear decline in carbon abundance with rising luminosity above the luminosity function "bump" on the giant branch, and also a subdued range in CN band strength, suggesting ongoing internal mixing in individual stars but minor or no primordial star-to-star variation in light-element abundances.Comment: 10 pages, emulateapj format, AJ accepte

Inter-individual Differences in Tolerance to a Simulated Hemorrhage Challenge During Heat Stress: Cerebrovascular Control

A high degree of inter-individual variability exists in heat stress (HS) -induced reductions in orthostatic tolerance relative to normothermia (NT), which may be associated with HS-mediated reductions in cerebral perfusion, and thus mechanisms of cerebrovascular control during hypotensive challenges. This study tested two hypotheses; 1) the magnitude of increase in cerebral autoregulation (CA) would be negatively correlated with the difference in tolerance to graded lower body negative pressure (LBNP) 30 [assessed with a cumulative stress index (CSI)] during HS relative to NT (CSIdiff), and 2) cerebrovascular sensitivity to HS-induced hypocapnia would be positively correlated with CSIdiff. Subjects (N=13) were exposed to LBNP on two occasions (NT and HS) separated by \u3e72h to assess CSI. On a third day, indices of CA were assessed during NT and HS by spectral and transfer function analyses, and cerebrovascular sensitivity to changes in PaCO2 was determined during NT, HS, and HS+LBNP (-20 mm Hg; HSLBNP). Estimates of CA were improved during HS compared to NT (P0.05). Hyperventilation-induced hypocapnia reduced cerebral vascular conductance (CVCi) during HS and HSLBNP relative to NT (P0.05 for all). In summary, HS augments mechanisms of cerebrovascular control to protect against orthostatic challenges; however, individual differences in these responses do not predict tolerance to a simulated hemorrhage when internal temperature is elevated