Dr. J. T. Wolan “Quick Glance” Project Info Faculty/Industry Collaborators: Dr. Stephen E. Saddow (USF Electrical Engineering) Current funding: Office of Naval Research (ONR) and National Science Foundation (NSF) General Area/Focus: High power SiC fuel cells Application(s): A solid-state, thin-film, SiC-based fuel cell, and gas sensor, for use in harsh environments Project Title and Detailed Description Project#1: “Novel All Solid-State SiC Fuel Cell for High Power Applications: A Materials-By-Design Approach” This research effort is focused on the integration of three critical components toward the realization of a *solid-state thin-film SiC-based **fuel cell and gas sensor for use in harsh environments. Our objective is to use novel porous Silicon Carbide (PSC) materials to develop an all-solid state fuel cell that will more than double the output power of Si-based fuel cells while completely eliminating the problem of CO poisoning of expensive electrodes. In order to advance the current fundamental knowledge base and realize this device, three areas of research must be interwoven: ***heterogeneous catalysis, gas-sensitive electronic structures, and novel fuel cell technologies. Although we have achieved promising result, a deeper understanding of the fundamental interactions between energetic gases/solid surfaces plays a key role in this application. There is little doubt that microsystems will enable high-density power generation with an efficiency and durability much exceeding current batteries. Helpful Definitions: *solid-state = crystalline materials with electronic properties **fuel cell = device which utilizes a chemical reaction to produce an electric current ***heterogeneous catalysis = a mixture of substances that speeds up a chemical process Faculty/Industry Collaborators: Dr. Stephen E. Saddow (USF Electrical Engineering), Prof. W. J. Choyke Research Professor of Physics, Department of Physics and Astronomy, University of Pittsburgh, Pittsburgh, PA Current funding: Office of Naval Research (ONR) General Area/Focus: Solid-state Hydrogen gas sensing Application(s): Hydrogen gas leak detection and sensing in harsh environments Faculty/Industry Collaborators: Dr. Take Constantinesu R&D director, Vandeputte Oleochemicals Current funding: ONR General Area/Focus: Heterogeneous catalysts for Project#2: “SiC-Based Smart Hydrogen Sensor for Extreme Applications” Effective hydrogen sensors and *ancillaries, to accurately and quickly respond to hydrogen gas leaks, will be critical in the safe deployment of mobile, hydrogenbased vehicles and stationary hydrogen-derived power sources. Successful hydrogen-leak detection will depend on the following factors: no false alarms; integrated autonomous shutoff/venting procedures; **multiplexed sensor arrays; and reliable sensing, calibration and self-testing. In other words, a smart, robust device is needed. Our objective is to use novel porous Silicon Carbide (PSC) materials to develop an all-solid-state gas sensor that can be used over a wide range of extreme conditions and hydrogen concentrations, with minimal interferences from other gases. The net result is a rather simple and inexpensive gas sensing device that completely eliminates the need for transition metals and is totally compatible with current IC processing techniques. Helpful Definitions: *ancillaries = ** multiplexed senor arrays = a grid of specialized sensors with different functionalities. Project #3 “ Partial Oxidation of Butane into Maleic Acid” We are investigating the use of nanoporous SiC supported vanadium phosphorus oxide (VPO) catalysts with proprietary promoters to be used in a fixed-bed micro reactor. The reaction is very *exothermic and traditional ceramic-based supports do not allow sufficient heat dissipation. This results in hot-spots in the catalytic bed and destruction of the catalyst. The use of nanoporous SiC supports will: 1) increase the surface area of the bed thus reducing the amount of catalyst needed and speeding up the reaction, and 2) act as a very efficient heat sink. SiC selective alkane oxidation Application(s): Maleic acid is a precursor to a large variety of industrial products such as resins for boats, autos, pipelines etc. Faculty/Industry Collaborators: Dr. Julie Harmon, Chemistry Department, USF Current funding: NSF General Area/Focus: nanocrystalline SiC/polycarbonate composites Application(s): For the production of polymer composite materials that: have low index of refractions, are radiation hard, exhibit increased strength and resistance to fracture. approaches heat transfer abilities as that of copper metal. In this way, heat generated by the reaction can be removed quickly. Helpful Definitions: * exothermic = gives off heat Project #4 “ *Nanocrystalline SiC Polymer Composites” A main area of this research is concerned with optical fiber materials. This includes developing fiber core and cladding materials with controlled refractive indexes. Another project involves the design in transparent, low refractive index **cladding materials. In addition to stringent optical and mechanical criterion, the effect of ionizing radiation on optical and mechanical properties of these materials is also characterized. This work is applicable to space environments and to particle accelerators where scintillating optical fibers are used. Research involves collaborations with Optical Polymer Research Inc. and Honeywell Space Systems Group. The object is to use nanocrystallites of SiC as radiation sinks, dissipating energy and decreasing the frequency of radiolysis events. Most recently, progress has been made in solubilizing the nanocrystallite SiC in polymer matrices. Transparent polymer/nanocrystallite SiC samples have been prepared. The group is in the process of analyzing these new materials. Helpful Definitions: * nanocrystalline = crystalline particles < 30 nm in diameter ** cladding = optical confinement of light in certain frequencies Faculty/Industry Collaborators: Dr. Stephen Saddow (USF Electrical Engineering) Dr. Serguei Ostapenko (USF, Nanomaterials and Nanomanufacturing Research Center) Current funding: NSF General Area/Focus: Characterization of nanoporous SiC layers Application(s): Development of the non-contact and nondestructive methodology applicable to diagnostics of epitaxial SiC films on wafers with a nano-porous buffer layer. Faculty/Industry Collaborators: Dr. Robert Benson (Marine Sciences, USF) Dr. L. Stefanakos (Electrical Project #5 “Spatially Resolved Characterization of Nano-Porous SiC Layers” This program addresses fundamental aspects of the nature and distribution of point and extended defects in full-size bulk silicon carbide (SiC) wafers and *epitaxial films for electronic applications. A specific goal of the program is development of the non-contact and non-destructive methodology applicable to diagnostics of epitaxial SiC films on wafers with a nano-porous buffer layer. The superior properties of SiC make it an excellent candidate for high temperature, high voltage, high frequency and high power applications. In addition, the large Si-C bond energy makes this material resistant to chemical attack and ionizing radiation, which is critical in terms of radiation stability and operation in a hostile environment. However, the yield and performance of SiC based devices is limited by poor substrate quality and subsequent epitaxial films. One approach to improve homo-and heteroepitaxial films is to use a substrate containing a porous buffer layer with controlled porosity and morphology. Nano-porous SiC can be fabricated using UV light-assisted anodization, a procedure similar to the creation of porous-Si layers. This approach in the area of **nano-technology has demonstrated great benefits in reducing the defect concentration in epi-layers deposited on porous structures compared to layers grown on standard SiC substrates. Helpful Definitions: * epitaxial = to grow upon ** nano-technology = dealing in the size-scale of 10-9 meters Project #6: “Hydrogen Production from the Electro-catalysis of Methane” The production of hydrogen to meet the pending “Hydrogen Economy” mandate is a formidable technical challenge. NASA utilizes and great deal of hydrogen as Engineering, USF) Current funding: NASA General Area/Focus: Novel production of hydrogen Application(s): Development of a novel process for the production of hydrogen from common feed stocks. Faculty/Industry Collaborators: Dr. Stephen Saddow (Electrical Engineering, USF), Dr. George Nolas (Physics Department, USF) Current funding: USF Interdisciplinary Award General Area/Focus: Novel/safe storage of hydrogen Application(s): Development of a novel process for the safe and efficient storage of hydrogen to meet the DOE onboard storage mandate for 2010. a fuel source for the current shuttle program. Unlike most fuels, hydrogen is not found in nature in a free state but must be produced. We are investigating a novel *electrocatalytic process that utilizes a natural gas feed-stock and converts it to hydrogen along with other useful by-products. This novel process is portable, requires very little energy and may be powered by photovoltaic cells. Helpful Definitions: * electrocatalytic = using a combination of a catalysts and an electronic bias Project #7: “Si and SiC type-I clathrates: Scientifically interesting materials with technological importance” Scientifically interesting materials with technological importance for the United States power generation and alternative fuel needs.” As the Chemical Engineering component of the integrated team, my primary function will be the integration of *clathrate technology to for hydrogen storage in applications of solid-state fuel cells. The research is extremely timely with funding opportunities related to the Hydrogen Economy Initiative. Hydrogen may actually be the only meaningful link between renewable energy and chemical energy carriers such as gasoline, propane, butane, etc. However, significant technical issues of safe transport, storage and retrieval must be addressed. One of the outcomes of this work is to demonstrate a safe, energy efficient method to store transport and retrieve hydrogen for portable use. Herein we propose to begin an experimental investigation on a unique material system that has potential technological importance in power generation from waste heat and alternative fuels such as hydrogen storage. The clathrate crystal structure is formed from two types of face-sharing **polyhedra, or fullerene-like ensembles. This unique property lends itself to novel properties, thus not only will this work be important from the standpoint of potential applications but it also presents an opportunity to investigate fundamental properties of novel crystal structures. Indeed, the properties of SiC clathrates have, as of yet, not been investigated. The goal will be to understand the properties as they relate to structure and stoichiometry and thus develop optimization routes for thermoelectric and hydrogen storage and fuel-cell applications. In the case of ***thermoelectrics, altering the thermal conductivity of materials in general is difficult to control however this system offers the opportunity to control the thermal as well as the electronic transport as a function of structure and stoichiometry. In potential fuel-cell studies, the polyhdra that form the crystal lattice lend themselves to unique structural locations whereby hydrogen can interstitially be placed. We expect the work under this proposed research to yield preliminary technological results that will lead to further funding opportunities from DoD, DoE, NASA and the automotive industry. In addition the new fuel cell initiative presented by our President in his State of the Union Address will open the potential for substantial federal funding in this area. This research is therefore very timely while providing the environment for a distinctive educational opportunity for our students. Helpful Definitions: *clathrates = cage-like chemical structures ** polyhedra = many sided 3D geometric structure ***thermoelectronics = deals with the thermal and electrical transport through materials Faculty/Industry Collaborators: Dr. Stephen Saddow (Electrical Engineering, USF), M.G. Mynbaeva, Ioffe PhysicoTechnical Institute, Polytechnicheskaya 26, St Petersburg 194021, Russia Current funding: ONR General Area/Focus: Production of Semi-insulating SiC substrates Application(s): Development of a novel process for the production of of Semi-insulating SiC substrates for isolation purposes in high temperature and high power electric devices . Project #8: “Semi-insulating porous SiC substrates” Semi-insulating SiC substrates were fabricated on a base of porous silicon carbide made from *4H and 6H commercial SiC wafers. Porous SiC (PSC) layers, 3 µm in thickness, were made by surface **anodization of SiC wafers and then impregnated with excessive Si from a sputtered SiO2 film during thermal processing at 1200 C. The processed structures were studied by ***Auger electron spectroscopy (AES), secondary ion mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS). The Si/C ratio in the processed porous layers showed a measurable change from 1:1 to 2.3:1 due to the diffusion of Si from the SiO2 film into the PSC layer during thermal processing. The value of specific resistivity achieved was found to be 5 × 1011 cm at 470 K and 2 × 106 cm at 700 K, respectively, with an activation energy of resistivity of 1.53 eV. Applications will include highpower, high-temperature, and high-density microwave integrated circuits and vertical ****MESFETs Helpful Definitions: *4H, 6H = refers to the hexagonal crystal type of SiC ** anodization = to subject a material to electrolytic action as the anode of a cell ***AES, SIMS, and XPS = a series of material characterization techniques ****MESFETs = metal-semiconductor field effect transistor