Applicability of a Metal Oxide Sensor for Hydrogen Detection and Quantification at Vacuum
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Hydrogen content of mixture of hydrogen and helium gases computed from measurements of pressure, density, and temperature of mixture. Here purpose is to estimate size of leak of combustible gas into cavity purged by pressurized inert gas.
The development of a functional hydrogen detection system is a multifaceted process that integrates hardware, deployments strategies, and analytics which can be supported by the NREL Sensor Laboratory: 1. Support of the design, validation and optimization of sensing prototypes; 2. Guide optimized sensing element development, including control electronics; 3. Laboratory testing to validate/optimize metrological performance (measurement range, detection limit, etc.); 4. Provide test sites for field deployments representative of real-world scenarios with controlled hydrogen releases; 5. Develop sensor placement and operation guidance; 6. Provide guidance on electronics to accommodate facility integration; 7. Electrical safety designs to allow for operation within restricted zones; 8. Integration into facility monitoring and control systems; 9. Guide incorporation of cyber security elements to protect facilities from malicious attacks; 10. Modeling and application of advanced analytics to detect and quantify emissions; 11. Higher Order dispersion models to guide sensor placement for reliable detection; 12. Advanced analytics for improved metrological performances, and to inform inverse modeling; 13. Market support and commercialization (national and international markets); 14. Commercial deployments in H2@SCALE markets (e.g., HUBs and other large-scale hydrogen markets); and 15. Leverage off international collaborations/partnerships (e.g., NREL is on the advisory board for the European initiative "pre-Normative Research on Hydrogen Releases Assessment"-NHyRA).
Development of device for detecting hydrogen in ambient environments
A hydrogen sensitive metal alloy contains palladium and titanium to provide a larger change in electrical resistance when exposed to the presence of hydrogen. The alloy is deposited on a substrate and a thin film and connected across electrical circuitry to provide a sensor device that can be used for improved sensitivity and accuracy of hydrogen detection.
Hydrogen and hydrocarbon detection in aeronautical applications is important for reasons of safety and emissions control. The use of silicon carbide as a semiconductor in a metal-semiconductor or metal-insulator-semiconductor structure opens opportunities to measure hydrogen and hydrocarbons in high temperature environments beyond the capabilities of silicon-based devices. The purpose of this paper is to explore the response and stability of Pd-SiC Schottky diodes as gas sensors in the temperature range from 100 to 400 C. The effect of heat treating on the diode properties as measured at 100 C is explored. Subsequent operation at 400 C demonstrates the diodes' sensitivity to hydrogen and hydrocarbons. It is concluded that the Pd-SiC Schottky diode has potential as a hydrogen and hydrocarbon sensor over a wide range of temperatures but further studies are necessary to determine the diodes' long term stability.
Hydrogen propellant leakage poses significant operational problems in the rocket propulsion industry as well as for space exploratory applications. Vigorous efforts have been devoted to minimizing hydrogen leakage in assembly, test, and launch operations related to hydrogen propellant. The objective has been to reduce the operational cost of assembling and maintaining hydrogen delivery systems. Specifically, efforts have been made to develop a hydrogen leak detection system for point-contact measurement. Under the auspices of Lewis Research Center, the Electronics Design Center at Case Western Reserve University, Cleveland, Ohio, has undertaken the development of a point-contact hydrogen gas sensor with potential applications to the hydrogen propellant industry. We envision a sensor array consisting of numbers of discrete hydrogen sensors that can be located in potential leak sites. Silicon-based microfabrication and micromachining techniques are used in the fabrication of these sensor prototypes. Evaluations of the sensor are carried out in-house at Case Western Reserve University as well as at Lewis Research Center and GenCorp Aerojet, Sacramento, California. The hydrogen gas sensor is not only applicable in a hydrogen propulsion system, but also usable in many other civilian and industrial settings. This includes vehicles or facility use, or in the production of hydrogen gas. Dual space and commercial uses of these point-contacted hydrogen sensors are feasible and will directly meet the needs and objectives of NASA as well as various industrial segments.
Infrared sensitive vidicon camera system, utilizing a single camera operating in the near infrared, detects a hydrogen flame burning in a bright sunlit environment.
Hydrogen fire detection system discovers fires by detecting the flickering ultraviolet radiation emitted by the OH molecule, a short-lived intermediate combustion product found in hydrogen-air flames. In a space application, the system discriminates against false signals from sunlight and rocket engine exhaust plume radiation.
The NREL Hydrogen Sensor Laboratory was commissioned in 2010 as a resource for sensor developers, end-users, and regulatory agencies within the national and international hydrogen community. The Laboratory continues to provide as its core capability the unbiased verification of hydrogen sensor performance to assure sensor availability and their proper use. However, the mission and strategy of the NREL Sensor Laboratory has evolved to meet the needs of the growing hydrogen market. The Sensor Laboratory program has expanded to support research in conventional and alternative detection methods as hydrogen use expands to large-scale markets as envisioned by the DOE National Clean Hydrogen Strategy and Roadmap. Current research encompasses advanced methods of hydrogen leak detection including stand-off and wide area monitoring approaches for large scale and distributed applications. In addition to safety applications, low-level detection strategies to support the potential environmental impacts of hydrogen and hydrogen product losses along the value chain are being explored. Many of these applications utilize detection strategies that supplement and may supplant the use of traditional point sensors. The latest results of the hydrogen detection strategy research at NREL will be presented.
A fiber optic probe has been built and demonstrated that utilizes back scattered spontaneous Raman spectroscopy to detect and identify gaseous species. The small probe, coupled to the laser and data acquisition equipment with optical fibers, has applications in gaseous leak detection and process monitoring. The probe design and data acquisition system are described. Raman scattering theory has been reviewed and the results of intensity calculations of hydrogen and nitrogen Raman scattering are given. Because the device is in its developmental stage, only preliminary experimental results are presented here. Intensity scans across the rotational-vibrational Raman lines of nitrogen and hydrogen are presented. Nitrogen at a partial pressure of 0.077 MPa was detected. Hydrogen at a partial pressure of 2 kPa approached the lower limit of detectability with the present apparatus. Potential instrument improvements that would allow more sensitive and rapid hydrogen detection are identified.
Safety is always a concern in all applications that utilize hydrogen (H(sub2)) in one form or the other. Hydrogen leaks are invisible and odorless. In addition, blending odorants or additives into hydrogen in a manner similar to natural gas is generally undesirable for certain applications including proton exchange membrane fuel cells. To facilitate detection of the location of hydrogen leaks, a special chemochromic H(sub2) sensing material that employs titania (Ti0(sub2)) supported palladium oxide (PdO) pigments encapsulated within a special silicone matrix has been developed at the Florida Solar Energy Center (FSEC). Several batches of PdO H(sub2) sensing pigments were synthesized using various Ti0(sub2) supports and their hydrogen detection activity determined. TEM and Particle size distribution analysis showed that smaller particles with hemispherical crystalline structure produced faster coloration kinetics when exposed to H(sub2) gas. However, uniformly distributed PdO particles on the Ti0(sub2) surface displayed greater color contrast, quantified by delta epsilon measurements. XRD analysis indicated that the crystalline phase of Ti0(sub2) had no effect on the chemochromic performance of the pigments in laboratory environment.
Semiquantitative spot test detection of peroxide in low concentrations of hydrogen peroxide
Kennedy Space Center scientists developed a hydrogen leak sensor utilizing a combination of chemochromic pigment and polymer that can be molded or fiber spun into rigid or flexible shapes such as tape. The sensor turns a dark color when exposed to hydrogen gas. This sensor has proven to be very effective for pinpointing the exact location of leaks in hydrogen gas lines and fittings at launch pads. Kennedy Space Center exclusively licensed this technology to the University of Central Florida (UCF), who also holds patents that are complimentary to KSC's. UCF has bundled the patents and exclusively licensed the portfolio to HySense Technology LLC, a startup company founded by a UCF professor who supports the UCF Florida Solar Energy Center (FSEC). HySense has fully developed its product (known as Intellipigment"TM"), and currently has five commercial customers. The company recently won the $100,000 first-place award at the CAT5 innovation competition at the Innovation Concourse of the Southeast: Safety & Manufacturing event in Orlando, FL. Commercial production and sales of this technology by HySense Technology will make this leak sensor widely available for use by NASA, DoD, and industries that utilize hydrogen gas.
The Gencorp Aerojet Automated Hydrogen Gas Leak Detection System was developed through the cooperation of industry, academia, and the Government. Although the original purpose of the system was to detect leaks in the main engine of the space shuttle while on the launch pad, it also has significant commercial potential in applications for which there are no existing commercial systems. With high sensitivity, the system can detect hydrogen leaks at low concentrations in inert environments. The sensors are integrated with hardware and software to form a complete system. Several of these systems have already been purchased for use on the Ford Motor Company assembly line for natural gas vehicles. This system to detect trace hydrogen gas leaks from pressurized systems consists of a microprocessor-based control unit that operates a network of sensors. The sensors can be deployed around pipes, connectors, flanges, and tanks of pressurized systems where leaks may occur. The control unit monitors the sensors and provides the operator with a visual representation of the magnitude and locations of the leak as a function of time. The system can be customized to fit the user's needs; for example, it can monitor and display the condition of the flanges and fittings associated with the tank of a natural gas vehicle.
Hydrogen is a critical strategy to decarbonize energy and manufacturing industries. Hydrogen is nontoxic and can be handled safely, but potential for secondary greenhouse impacts. Hydrogen releases arise from a variety of mechanisms (process, design features, "leaks") that contribute to total hydrogen releases. Detection methodologies will be critical to detect and quantify hydrogen emissions. Detection is to be integrated with advanced analytics (AI) and behavior modelling to effectively identify, quantify, and source locate hydrogen releases. Modelling of emissions will contribute to facility safety and reliability. DOE is committed to develop the tools to model and mitigate the impact of hydrogen releases which include: Support modeling to elucidate released hydrogen degradation; Support the development of tools for emissions quantitation; and Support engineering advancements to minimize hydrogen losses along the value chain (including process, design features, and leaks).
Nine basic techniques are discussed, ranging from concentration (parts per million) to dosage only (parts per million-seconds) measurement techniques. Data for each technique include lower detection limit, response time, instrument status, and in some cases, specificity. Several techniques discussed can detect ambient hydrogen chloride concentrations below 1 part per million with a response time of seconds.
This slide presentation reviews the characteristics of the Hydrogen Sensor database. The database is the result of NASA's continuing interest in and improvement of its ability to detect and assess gas leaks in space applications. The database specifics and a snapshot of an entry in the database are reviewed. Attempts were made to determine the applicability of each of the 65 sensors for ground and/or vehicle use.