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

Scaling and Universality of the Complexity of Analog Computation

We apply a probabilistic approach to study the computational complexity of analog computers which solve linear programming problems. We analyze numerically various ensembles of linear programming problems and obtain, for each of these ensembles, the probability distribution functions of certain quantities which measure the computational complexity, known as the convergence rate, the barrier and the computation time. We find that in the limit of very large problems these probability distributions are universal scaling functions. In other words, the probability distribution function for each of these three quantities becomes, in the limit of large problem size, a function of a single scaling variable, which is a certain composition of the quantity in question and the size of the system. Moreover, various ensembles studied seem to lead essentially to the same scaling functions, which depend only on the variance of the ensemble. These results extend analytical and numerical results obtained recently for the Gaussian ensemble, and support the conjecture that these scaling functions are universal.Comment: 22 pages, latex, 12 eps fig

Preparation of Sub-micron Sized Porous Films by General Physical Vapor Deposition Processes Employing Polymethylmethacrylate Microsphere Templates

Nagasaki Symposium on Nano-Dynamics 2008 (NSND2008) 平成20年1月29日(火)於長崎大学 Poster Presentatio

Genome sequence of the tsetse fly (Glossina morsitans):Vector of African trypanosomiasis

Tsetse flies are the sole vectors of human African trypanosomiasis throughout sub-Saharan Africa. Both sexes of adult tsetse feed exclusively on blood and contribute to disease transmission. Notable differences between tsetse and other disease vectors include obligate microbial symbioses, viviparous reproduction, and lactation. Here, we describe the sequence and annotation of the 366-megabase Glossina morsitans morsitans genome. Analysis of the genome and the 12,308 predicted protein-encoding genes led to multiple discoveries, including chromosomal integrations of bacterial (Wolbachia) genome sequences, a family of lactation-specific proteins, reduced complement of host pathogen recognition proteins, and reduced olfaction/chemosensory associated genes. These genome data provide a foundation for research into trypanosomiasis prevention and yield important insights with broad implications for multiple aspects of tsetse biology.IS

Preparation of Sub-micron Sized Porous Films by General Physical Vapor Deposition Processes Employing Polymethylmethacrylate Microsphere Templates

Nagasaki Symposium on Nano-Dynamics 2008 (NSND2008) 平成20年1月29日(火)於長崎大学 Poster Presentatio

Fabrication and structural characterization of self-supporting electrolyte membranes for a micro solid-oxide fuel cell

Micromachined fuel cells are among a class of microscale devices being explored for portable power generation. In this paper, we report processing and geometric design criteria for the fabrication of free-standing electrolyte membranes for microscale solid-oxide fuel cells. Submicron, dense, nanocrystalline yttria-stabilized zirconia (YSZ) and gadolinium-doped ceria (GDC) films were deposited onto silicon nitride membranes using electron-beam evaporation and sputter deposition. Selective silicon nitride removal leads to free-standing, square, electrolyte membranes with side dimensions as large as 1025 µm for YSZ and 525 µm for GDC, with high processing yields for YSZ. Residual stresses are tensile (+85 to +235 MPa) and compressive (–865 to -155 MPa) in as-deposited evaporated and sputtered films, respectively. Tensile evaporated films fail via brittle fracture during annealing at temperatures below 773 K; thermal limitations are dependent on the film thickness to membrane size aspect ratio. Sputtered films with compressive residual stresses show superior mechanical and thermal stability than evaporated films. Sputtered 1025-µm membranes survive annealing at 773 K, which leads to the generation of tensile stresses and brittle fracture at elevated temperatures (923 K)