Low-Cost Metal Bipolar Plate Carbon Coating Technology for Heavy Duty Fuel Cells (HDFC)
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This Final Report documents the entire four years of the Cooperative Agreement DE-FE0011822, from October 1, 2013 through September 30, 2017, that was competitively awarded under Funding Opportunity Announcement DE-FOA-0000795 in support of the U.S. Department of Energy’s (DOE) National Energy Technology Laboratory (NETL) University Turbine Systems Research (UTSR) Program. Under the UTSR Program, DOE typically issues Funding Opportunity Announcement (FOA) solicitations every 1-2 years so that U.S. colleges/universities may propose research & development (R&D) projects in specific technical topic areas (e.g., combustion, aerodynamics/heat transfer, advanced materials) that have been identified as both scientifically and industrially relevant to the gas turbine industry. The primary objectives of this Purdue University project (in collaboration with Princeton University through a sub-award) was to develop experimental methods, kinetic models, and numerical tools to help quantify and predict the impact of exhaust gas recirculation (EGR) on NOx and CO emissions, combustion kinetics, radiation heat transfer, turbulent combustion, and combustion instabilities for natural gas and high hydrogen content (HHC) fuels by using laminar and turbulent flow reactors and gas turbine combustors operating at high temperatures and pressures. This project has obtained detailed data for improving chemical kinetic models to study EGR effects and provide insight into the effects of EGR on flame speeds and turbulent flame structure, as well as assessing the impact of EGR on emissions in a high-pressure combustion test rig. The project was divided into six primary tasks: 1) Project Management and Program Planning; 2) Flow Reactor Investigation of EGR Chemical Kinetics; 3) Combustion Bomb Investigation of EGR Effects on Flame Speed; 4) Investigation of EGR Effects on Turbulent Flame Structure in Reactor-Assisted Turbulent Slot (RATS) Burner; 5) Investigation of EGR Effects in Purdue Staged Combustion Test Rig; and 6) Development and Validation of a Large Eddy Simulation (LES) Tool for Gas Turbine Combustion and Emission Modeling using HHC Fuels. Details on the execution and results of each of these tasks are provided in the main report. To assist the reader, each task is described in a chapter-like format with its own separate listing of tables, figures, and references so that the results of each task/subtask (i.e., technical sections covering various experiments and modeling work focused on a specific area) can be quickly obtained while also getting an overall feel of the project execution. This chapter-like format also allows for acknowledgement of support from other programs relative to specific tasks. In this manner, the reader can more conveniently digest the R&D results in the various task/subtask sections that may be of most interest to the reader. In addition to this Final Report, the Purdue/Princeton team was able to publish 7 journal articles and provide 7 presentations at national scientific meetings/conferences to disseminate results. A listing of these journal articles and presentations is provided at the end of this report
CERMET fuel materials for Nuclear Thermal Propulsion (NTP) are currently being developed at NASA's Marshall Space Flight Center. The work is part of NASA's Advanced Space Exploration Systems Nuclear Cryogenic Propulsion Stage (NCPS) Project. The goal of the FY12-14 project is to address critical NTP technology challenges and programmatic issues to establish confidence in the affordability and viability of an NTP system. A key enabling technology for an NCPS system is the fabrication of a stable high temperature nuclear fuel form. Although much of the technology was demonstrated during previous programs, there are currently no qualified fuel materials or processes. The work at MSFC is focused on developing critical materials and process technologies for manufacturing robust, full-scale CERMET fuels. Prototypical samples are being fabricated and tested in flowing hot hydrogen to understand processing and performance relationships. As part of this initial demonstration task, a final full scale element test will be performed to validate robust designs. The next phase of the project will focus on continued development and optimization of the fuel materials to enable future ground testing. The purpose of this paper is to provide a detailed overview of the CERMET fuel materials development plan. The overall CERMET fuel development path is shown in Figure 2. The activities begin prior to ATP for a ground reactor or engine system test and include materials and process optimization, hot hydrogen screening, material property testing, and irradiation testing. The goal of the development is to increase the maturity of the fuel form and reduce risk. One of the main accomplishmens of the current AES FY12-14 project was to develop dedicated laboratories at MSFC for the fabrication and testing of full length fuel elements. This capability will enable affordable, near term development and optimization of the CERMET fuels for future ground testing. Figure 2 provides a timeline of the development and optimization tasks for the AES FY15-17 follow on program.
The zero boil-off storage of liquid hydrogen using active cooling (cryocoolers) with a two-stage cooling approach is being investigated by NASA. In interest of advancing the technology to enable extended duration storage for the agency’s future long duration missions, NASA’s Technology Demonstration Mission Program has funded this five-year effort which includes the design, build and testing of a test article to demonstrate this concept. This paper includes discussions of the multiple Cryogenic Fluid Management technologies that were studied under NASA’s Cryogenic Propellant Storage and Transfer project, design of the test article to be demonstrated, then the planned test objectives which include characterization testing of the active cooling system, demonstration of the control system, preliminary testing with liquid nitrogen, and a complete demonstration of zero boil-off storage of liquid hydrogen. The full demonstration will be conducted in the East Test Area at NASA Marshall Space Flight Center and is currently scheduled to begin on October 1st, 2024.
Natural organisms make a wide variety of exquisitely complex, nano-, micro-, and macroscale structured materials in an energy-efficient and highly reproducible manner. During these processes, the information-carrying biomolecules (e.g., proteins, peptides, and carbohydrates) enable (1) hierarchical organization to assemble scaffold materials and execute high-level functions and (2) exquisite control over inorganic materials synthesis, generating biominerals whose properties are optimized for their functions. Inspired by nature, significant efforts have been devoted to developing functional materials that can rival those natural molecules by mimicking in vivo functions using engineered proteins, peptides, DNAs, sequence-defined synthetic molecules (e.g., peptoids), and other biomimetic polymers. Among them, peptoids, a new type of synthetic mimetics of peptides and proteins, have received particular attention because they combine the merits of both synthetic polymers (e.g., high chemical stability and efficient synthesis) and biomolecules (e.g., sequence programmability and biocompatibility). The lack of both chirality and hydrogen bonds in their backbone results in a highly designable peptoid-based system with reduced structural complexity and side chain-chemistry-dominated properties. Here in this Account, we present our recent efforts in this field by programming amphiphilic peptoid sequences for (1) the controlled self-assembly into different hierarchically structured nanomaterials with favorable properties and (2) manipulating inorganic (nano)crystal nucleation, growth, and assembly into superstructures. First, we designed a series of amphiphilic peptoids with controlled side chain chemistries that self-assembled into 1D highly stiff and dynamic nanotubes, 2D membrane-mimetic nanosheets, hexagonally patterned nanoribbons, and 3D nanoflowers. These crystalline nanostructures exhibited sequence-dependent properties and showed promise for different applications. The corresponding peptoid self-assembly pathways and mechanisms were also investigated by leveraging in situ atomic force microscopy studies and molecular dynamics simulations, which showed precise sequence dependency. Second, inspired by peptide- and protein-controlled formation of hierarchical inorganic nanostructures in nature, we developed peptoid-based biomimetic approaches for controlled synthesis of inorganic materials (e.g., noble metals and calcite), in which we took advantage of the substantial side chain chemistry of peptoids and investigated the relationship between the peptoid sequences and the morphology and growth kinetics of inorganic materials. For example, to overcome the challenges (e.g., complexity of protein- and peptide-folding, poor thermal and chemical stabilities) facing the area of protein- and peptide-controlled synthesis of inorganic materials, we recently reported the design of sequence-defined peptoids for controlled synthesis of highly branched plasmonic gold particles. Moreover, we developed a rule of thumb for designing peptoids that predictively enabled the morphological evolution from spherical to coral-shaped gold nanoparticles (NPs). With this Account, we hope to stimulate the research interest of chemists and materials scientists and promote the predictive synthesis of functional and robust materials through the design of sequence-defined synthetic molecules.
The objective of this project was to develop high temperature membranes to facilitate the wide-spread deployment of hydrogen fuel cells. High temperature membranes offer significant advantages in PEM system operation, overall capital and operating costs. State-of-the-art Nafion-based membranes are inadequate for the high temperature operation. These conventional membranes become unstable at higher temperatures (90-120°C) and lose their conductivity, particularly at low relative humidity. In this program, alternate materials were developed to enable fabrication of novel high performance composite membranes. FCE’s concept for the multi-component composite membrane, named mC2, has been used in the design of more conductive membranes.
In gas cooled Very High Temperature Reactor concepts, tritium is produced as a tertiary fission product and by activation of graphite core contaminants, such as lithium; of the helium isotope, He-3, that is naturally present in the He gas coolant; and the boron in the B4C burnable poison. Because of its high mobility at the reactor outlet temperatures, tritium poses a risk of permeating through the walls of the intermediate heat exchanger (IHX) or steam generator (SG) systems, potentially contaminating the environment and in particular the hydrogen product when the reactor heat is utilized in connection with a hydrogen generation plant. An experiment to measure tritium permeation in structural materials at temperatures up to 1000 C has been constructed at the Idaho National Laboratory Safety and Tritium Applied Research (STAR) facility within the Next Generation Nuclear Plant program. The design is based on two counter flowing helium loops to represent heat exchanger conditions and was optimized to allow control of the materials surface condition and the investigation of the effects of thermal fatigue. In the ongoing campaign three nickel alloys are being considered because of their high-temperature creep properties, alloy 617, 800H and 230. This paper introduces the general issues related to tritium in the on-going assessment of gas cooled VHTR systems fission product transport and outlines the planned research activities in this area; outlines the features and capabilities of the experimental facility being operated at INL; presents and discusses the initial results of hydrogen permeability measurements in two of the selected alloys and compares them with the available database from previous studies.
The accidents at the Three Mile Island Unit 2 (TMI-2) Pressurized Water Reactor (PWR) and the Daiichi Units 1, 2, and 3 Boiling Water Reactors (BWRs) provide unique opportunities to evaluate instrumentation exposed to severe accident conditions. Conditions associated with the release of coolant and the hydrogen burn that occurred during the TMI-2 accident exposed instrumentation to harsh conditions, including direct radiation, radioactive contamination, and high humidity with elevated temperatures and pressures. As part of a program initiated in 2012 by the Department of Energy Office of Nuclear Energy (DOE-NE), a review was completed to gain insights from prior TMI-2 sensor survivability and data qualification efforts. This initial review focused on the set of sensors deemed most important by post-TMI-2 instrumentation evaluation programs. Instrumentation evaluation programs focused on data required by TMI-2 operators to assess the condition of the reactor and containment and the effect of mitigating actions taken by these operators. In addition, prior efforts focused on sensors providing data required for subsequent forensic evaluations and accident simulations. To encourage the potential for similar activities to be completed for qualifying data from Daiichi Units 1, 2, and 3, this report provides additional details related to the formal process used to develop a qualified TMI-2 data base and presents data qualification details for three parameters: primary system pressure; containment building temperature; and containment pressure. As described within this report, sensor evaluations and data qualification required implementation of various processes, including comparisons with data from other sensors, analytical calculations, laboratory testing, and comparisons with sensors subjected to similar conditions in large-scale integral tests and with sensors that were similar in design to instruments easily removed from the TMI-2 plant for evaluations. As documented in this report, results from qualifying data for these parameters led to key insights related to TMI-2 accident progression. Hence, these selected examples illustrate the types of activities completed in the TMI-2 data qualification process and the importance of such a qualification effort. These details are documented in this report to facilitate implementation of similar process using data and examinations at the Daiichi Units 1, 2, and 3 reactors so that BWR-specific benefits can be obtained.
Accurate modeling of cryogenic boiling heat transfer is vital for the development of extended-duration space missions. Such missions may require the transfer of cryogenic propellants from in-space storage depots or the cooling of nuclear reactors. Purdue University in collaboration with NASA has assembled a database of cryogenic flow boiling data points from heated-tube experiments dating back to 1959, which has been used to develop new flow boiling correlations specifically for cryogens. Computational models of several of these experiments have been constructed in the Generalized Fluid System Simulation Program (GFSSP), a network flow code developed at NASA’s Marshall Space Flight Center. The new Purdue-developed correlations cover the full boiling curve: onset of nucleate boiling, nucleate boiling, critical heat flux, and film boiling. These correlations have been coded into GFSSP user subroutines. The fluids modeled are hydrogen and helium. Predictions of wall temperature, heat transfer coefficient, and pressure drop are presented and compared to the test data.
The National Renewable Energy Laboratory (NREL), in association with the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE), held a Biogas and Fuel Cells Workshop on June 11–13, 2012, in Golden, Colorado, to discuss biogas and waste-to energy technologies for fuel cell applications. The meeting was spearheaded by the Fuel Cell Technologies Program in coordination with the Biomass Program. The overall objective was to identify opportunities for coupling renewable biomethane with highly efficient fuel cells to produce electricity; heat; combined heat and power (CHP); or combined heat, hydrogen and power (referred to as CHHP or “trigeneration”) for stationary or motive applications. The workshop focused on biogas sourced from wastewater treatment plants (WWTPs), landfills, and industrial facilities that generate or process large amounts of organic waste, including large biofuel production facilities (biorefineries).
The accident at the Three Mile Island Unit 2 (TMI-2) reactor provided a unique opportunity to evaluate sensors exposed to severe accident conditions. Conditions associated with the release of coolant and the hydrogen burn that occurred during this accident exposed instrumentation to harsh conditions, including direct radiation, radioactive contamination, and high humidity with elevated temperatures and pressures. As part of a program initiated in 2012 by the Department of Energy Office of Nuclear Energy (DOE-NE), a review was completed to gain insights from prior TMI-2 sensor survivability and data qualification efforts. This new effort focussed upon a set of sensors that provided critical data to TMI-2 operators for assessing the condition of the plant and the effects of mitigating actions taken by these operators. In addition, the effort considered sensors providing data required for subsequent accident simulations. Over 100 references related to instrumentation performance and post-accident evaluations of TMI-2 sensors and measurements were reviewed. Insights gained from this review are summarized within this report. For each sensor, a description is provided with the measured data and conclusions related to the sensor’s survivability, and the basis for conclusions about its survivability. As noted within this document, several techniques were invoked in the TMI-2 post-accident evaluation program to assess sensor status, including comparisons with data from other sensors, analytical calculations, laboratory testing, and comparisons with sensors subjected to similar conditions in large-scale integral tests and with sensors that were similar in design but more easily removed from the TMI-2 plant for evaluations. Conclusions from this review provide important insights related to sensor survivability and enhancement options for improving sensor performance. In addition, this document provides recommendations related to the sensor survivability and data evaluation process that could be implemented in upcoming Fukushima Daiichi recovery efforts.
The accident at the Three Mile Island Unit 2 (TMI-2) reactor provided a unique opportunity to evaluate sensors exposed to severe accident conditions. Conditions associated with the release of coolant and the hydrogen burn that occurred during this accident exposed instrumentation to harsh conditions, including direct radiation, radioactive contamination, and high humidity with elevated temperatures and pressures. As part of a program initiated in 2012 by the Department of Energy Office of Nuclear Energy (DOE-NE), a review was completed to gain insights from prior TMI-2 sensor survivability and data qualification efforts. This new effort focused upon a set of sensors that provided critical data to TMI-2 operators for assessing the condition of the plant and the effects of mitigating actions taken by these operators. In addition, the effort considered sensors providing data required for subsequent accident simulations. Over 100 references related to instrumentation performance and post-accident evaluations of TMI-2 sensors and measurements were reviewed. Insights gained from this review are summarized within this report. For each sensor, a description is provided with the measured data and conclusions related to the sensor’s survivability, and the basis for conclusions about its survivability. As noted within this document, several techniques were invoked in the TMI-2 post-accident evaluation program to assess sensor status, including comparisons with data from other sensors, analytical calculations, laboratory testing, and comparisons with sensors subjected to similar conditions in large-scale integral tests and with sensors that were similar in design but more easily removed from the TMI-2 plant for evaluations. Conclusions from this review provide important insights related to sensor survivability and enhancement options for improving sensor performance. In addition, this document provides recommendations related to the sensor survivability and data evaluation process that could be implemented in upcoming Fukushima Daiichi recovery efforts.
States and the federal government are increasingly engaged in the challenges around decarbonizing the electric grid. In particular, regulators, consumers, stakeholders, and utilities recognize the need to carefully consider the role natural gas will play in a decarbonized future. A variety of technology and policy options to reduce greenhouse gas emissions associated with natural gas use are available, including energy efficiency programs, demand reduction tools, strategic electrification, and strategies to reduce emissions from natural gas production, transportation, and consumption. Low-carbon fuels – mainly renewable natural gas (RNG) and clean hydrogen – are being considered an important component of decarbonization goals. RNG and hydrogen may be able to meaningfully reduce emissions from processes independent of geologic natural gas, displacing emissions of methane, a powerful greenhouse gas. Although RNG and hydrogen are not cost-competitive today with geologic natural gas and are smaller in scale and potential than other decarbonization options, they can be explored as potential critical tools to decarbonize sectors that are difficult to electrify or shift off of natural gas entirely, such as air travel, industrial processes, maritime transport, long-distance trucking, space heating on cold days, and railroads (Nadel, 2022). The role of this report is to provide informational context for state utility regulators to understand the impacts of and challenges associated with broader integration of low-carbon fuels, followed by examples of state regulatory actions taken to date to facilitate the development of low-carbon fuels. Setting clear guidance to calculate the environmental benefits of low-carbon fuels and continuing federal and state investments in research and development to reduce costs relative to fossil fuels will be important steps to take to signal the desire to grow the market for these fuels. State public utility commissions may play a key role in setting regulatory frameworks for low-carbon fuels and ensuring that ratepayer funds, if utilized, are done so to further the public interest. This report is intended to summarize decisions that states have made to date on low-carbon fuels. In the spirit of understanding the current market and sharing information, this report provides success stories, and lessons learned across states as regulators implement varying strategies to achieve decarbonization objectives while maintaining their focus on affordability, safety, and reliability of the energy system. The report begins with an introduction of the role of natural gas in the U.S. economy (Section I) and background information on natural gas use, decarbonization, and low-carbon fuels (Section II). Next, the report describes the current market by discussing the scale of current production, emissions intensity, resource potential, and costs of low-carbon fuels compared to geologic natural gas (Section III). Following these sections, the report describes four strategies states have employed to facilitate low-carbon fuels: opening exploratory dockets, approving voluntary tariffs for customers, approving interconnection tariffs for producers, and considering portfolio-wide procurement targets (Section IV). This section lists states that have taken actions in each category, citing utility filings, commission decisions, stakeholder comments, and other relevant sources. Finally, the report concludes with suggested questions regulators may wish to consider regarding low-carbon fuels, in the interest of preparing to make decisions in the future (Section V). These questions include: Are there existing regulatory or technical barriers to voluntary purchases of low-carbon fuels? Can customers work with utilities to procure low-carbon fuels; are producers able to interconnect projects without significant barriers to entry? Should the infrastructure and/or commodity costs of low-carbon fuels be socialized among all ratepayers, or borne solely by the large commercial and industrial (C&I) customers currently driving the market? Should regulated natural gas and/or electric utilities own and operate low-carbon fuel production? How should regulators consider the unique decarbonization potential of low-carbon fuels, particularly for hard-to-abate sectors, in decision-making? Is additional direction or clarity from state policymakers needed? What no-regrets approaches can help facilitate both near-term RNG development and long-term development of hydrogen and other zero-carbon fuels? We collectively wish to express our gratitude to the U.S. Department of Energy, Office of Fossil Energy and Carbon Management, for supporting this report and other technical assistance resources for state regulators on natural gas topics. State regulators operate under a variety of policy environments, and states have vastly different types of energy resources, infrastructure, and customers. While there is no optimal regulatory, policy, or technological solution that will be successful in every state, state regulators can benefit by exchanging lessons learned with their peers across the country. We look forward to continued engagement with our fellow commissioners, commission staff, NARUC, the U.S. Department of Energy, and other stakeholders to develop sound regulation in the public interest.
Auxiliary power units operating on hydrogen and oxygen have the potential for significantly improved performance and payload for the Space Shuttle vehicles. In order to identify the technologies required for these units and to identify promising system configurations, contracted studies provided component and system-configuration screening analysis and detailed analysis of two preliminary system layouts. From these studies, Lewis Research Center has selected for further investigation a recuperated open-cycle hydrogen-oxygen turbine-driven APU concept with pressure-modulated reactant control. This paper discusses the reference system, the control mode, component arrangement, performance potential, and the technology program for this system.
The H2-O2 space shuttle auxiliary power unit (APU) program is a NASA-Lewis effort aimed at hardware demonstration of the technology required for potential use on the space shuttle. It has been shown that a hydrogen-oxygen power unit (APU) system is an attractive alternate to the space shuttle baseline hydrazine APU system for minimum weight. It has the capability for meeting many of the heat sink requirements for the space shuttle vehicle, thereby reducing the amount of expendable evaporants required for cooling in the baseline APU. Volume 1 of this report covers preliminary design and analysis of the current reference system and detail design of the test version of this reference system. Combustor test results are also included. Volume 2 contains the results of the analysis of an initial version of the reference system and the computer printouts of system performance. The APU consists of subsystems for propellant feed and conditioning, turbopower, and control. Propellant feed and conditioning contains all heat exchangers, valves, and the combustor. The turbopower subsystem contains a two-stage partial-admission pressure-modulated, 400-hp, 63,000-rpm turbine, a 0-to 4-g lubrication system, and a gearbox with output pads for two hydraulic pumps and an alternator (alternator not included on test unit). The electronic control functions include regulation of speed and system temperatures; and start-and-stop sequences, overspeed (rpm) and temperature limits, failsafe provisions, and automatic shutdown provisions.
The hydrochlorination of silicon tetrachloride with hydrogen and metallurgical grade (m.g.) silicon metal, 3 SiCl4 + 2 H2 + Si yields 4 SiHCl3 was shown to be an efficient process to produce trichlorosilane. A research and development program was carried out to study the hydrochlorination reaction over a wide range of reaction conditions. Equilibrium constant and reaction kinetics measurements were made to provide the basis for a theoretical study on the hydrochlorination process. Thermodynamic properties of the hydrochlorination reaction were also measured. The effects of temperature, pressure, and concentration on the equilibrium constant, K sub p, were studied.
To account for the turbulent temperature and species-concentration fluctuations, a model is presented on the effects of chemical reaction rates in computer analyses of turbulent reacting flows. The model results in two parameters which multiply the terms in the reaction-rate equations. For these two parameters, graphs are presented as functions of the mean values and intensity of the turbulent fluctuations of the temperature and species concentrations. These graphs will facilitate incorporation of the model into existing computer programs which describe turbulent reacting flows. When the model was used in a two-dimensional parabolic-flow computer code to predict the behavior of an experimental, supersonic hydrogen jet burning in air, some improvement in agreement with the experimental data was obtained in the far field in the region near the jet centerline. Recommendations are included for further improvement of the model and for additional comparisons with experimental data.
The progress on the Space Station Propulsion Technology Program is described. The objectives are to provide a demonstration of hydrogen/oxygen propulsion technology readiness for the Initial Operating Capability (IOC) space station application, specifically gaseous hydrogen/oxygen and warm hydrogen thruster concepts, and to establish a means for evolving from the IOC space station propulsion to that required to support and interface with advanced station functions. The evaluation of concepts was completed. The accumulator module of the test bed was completed and, with the microprocessor controller, delivered to NASA-MSFC. An oxygen/hydrogen thruster was modified for use with the test bed and successfully tested at mixture ratios from 4:1 to 8:1.