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Color Changing Hydrogen Sensors

During the Space Shuttle Program, one of the most hazardous operation that occurred was the loading of liquid hydrogen (LH2) during fueling operations of the spacecraft. Due to hydrogen's low explosive limit, any amount leaked could lead to catastrophic event. Hydrogen's chemical properties make it ideal as a rocket fuel; however, the fuel is deemed unsafe for most commercial use because of the inability to easily detect the gas leaking. The increased use of hydrogen over traditional fossil fuels would reduce greenhouse gases and America's dependency on foreign oil. Therefore a technology that would improve safety at NASA and in the commercial sector while creating a new economic sector would have a huge impact to NASA's mission. The Chemochromic Detector for sensing hydrogen gas leakage is a color-changing detector that is useful in any application where it is important to know not only the presence but also the location of the hydrogen gas leak. This technology utilizes a chemochromicpigment and polymer matrix that can be molded or spun into rigid or pliable shapes useable in variable temperature environments including atmospheres of inert gas, hydrogen gas, or mixtures of gases. A change in color of the detector material indicates where gaseous hydrogen leaks are occurring. The irreversible sensor has a dramatic color change from beige to dark grey and remains dark grey after exposure. A reversible pigment changes from white to blue in the presence of hydrogen and reverts back to white in the presence of oxygen. Both versions of the sensor's pigments were comprised of a mixture of a metal oxide substrate and a hydro-chromic compound (i.e., the compound that changed color in the presence of hydrogen) and immediately notified the operator of the presence of low levels of hydrogen. The detector can be used in a variety of formats including paint, tape, caulking, injection molded parts, textiles and fabrics, composites, and films. This technology brings numerous benefits over the traditional hydrogen sensors: The technology has excellent temperature stability (4K to 373 K), it can be used in cryogenic fluid applications, it is easy to apply and remove; it requires no power to operate; it has a quick response time; the leak points can be detected visually or electronically; it is nonhazardous, thus environmentally friendly; it can be reversible or irreversible; it does not require on-site monitoring; has a long shelf life; the detector is very durable; and the technology is inexpensive to manufacture.

Chemochromic sensor↗

Liquid Hydrogen Sensor Considerations for Space Exploration

The on-orbit management of liquid hydrogen planned for the return to the moon will introduce new considerations not encountered in previous missions. This paper identifies critical liquid hydrogen sensing needs from the perspective of reliable on-orbit cryogenic fluid management, and contrasts the fundamental differences in fluid and thermodynamic behavior for ground-based versus on-orbit conditions. Opportunities for advanced sensor development and implementation are explored in the context of critical Exploration Architecture operations such as on-orbit storage, docking, and trans-lunar injection burn. Key sensing needs relative to these operations are also examined, including: liquid/vapor detection, thermodynamic condition monitoring, mass gauging, and leak detection. Finally, operational aspects of an integrated system health management approach are discussed to highlight the potential impact on mission success.

Moran, Matthew E.↗

New Gas Polarographic Hydrogen Sensor

Polarography is the measurement of the current that flows in solution as a function of an applied voltage. The actual form of the observed polarographic current depends upon the manner in which the voltage is applied and on the characteristics of the working electrode. The new gas polarographic H2 sensor shows a current level increment with concentration of the gaseous H2 similar to those relating to metal ions in liquid electrolytes in well-known polarography. This phenomenon is caused by the fact that the diffusion of the gaseous H2 through a gas diffusion hole built in the sensor is a rate-determining step in the gaseous-hydrogen sensing mechanism. The diffusion hole artificially limits the diffusion of the gaseous H2 toward the electrode located at the sensor cavity. This gas polarographic H2 sensor. is actually an electrochemical-pumping cell since the gaseous H2 is in fact pumped via the electrochemical driving force generated between the electrodes. Gaseous H2 enters the diffusion hole and reaches the first electrode (anode) located in the sensor cavity to be transformed into an H+ ions or protons; H+ ions pass through the electrolyte and reach the second electrode (cathode) to be reformed to gaseous H2. Gas polarographic 02 sensors are commercially available; a gas polarographic 02 sensor was used to prove the feasibility of building a new gas polarographic H2 sensor.

Dominguez, Jesus A.↗

Surface acoustic wave hydrogen sensor

The present invention provides a delay line SAW device fabricated on a lithium niobate substrate and coated with a bilayer of nanocrystalline or other nanomaterials such as nanoparticles or nanowires of palladiumn and metal free pthalocyanine which will respond to hydrogen gas in near real time, at low (room) temperature, without being affected by CO, O.sub.2, CH.sub.4 and other gases, in air ambient or controlled ambient, providing sensitivity to low ppm levels.

Bhethanabotla, Venkat R.↗

Micro-machined thin film hydrogen gas sensor, and method of making and using the same

A hydrogen sensor including a thin film sensor element formed, e.g., by metalorganic chemical vapor deposition (MOCVD) or physical vapor deposition (PVD), on a microhotplate structure. The thin film sensor element includes a film of a hydrogen-interactive metal film that reversibly interacts with hydrogen to provide a correspondingly altered response characteristic, such as optical transmissivity, electrical conductance, electrical resistance, electrical capacitance, magnetoresistance, photoconductivity, etc., relative to the response characteristic of the film in the absence of hydrogen. The hydrogen-interactive metal film may be overcoated with a thin film hydrogen-permeable barrier layer to protect the hydrogen-interactive film from deleterious interaction with non-hydrogen species. The hydrogen sensor of the invention may be usefully employed for the detection of hydrogen in an environment susceptible to the incursion or generation of hydrogen and may be conveniently configured as a hand-held apparatus.

DiMeo, Jr., Frank↗

Development of a hydrogen gas sensor using microfabrication technology

Microfabrication and micromachining technologies are used to produce a hydrogen gas sensor based on a palladium-silver film. The sensor uses a heater that is fabricated by diffusing p-type borones into the substrate, forming a resistance heater. A diode for temperature measurement is produced using p-type boron and n-type phosphor diffused into the substrate. A thickness of the palladium-silver film is approximately 300 arcsec. The hydrogen gas sensor employs the proven palladium-silver diode structure and is surrounded by a phosphor doped resistance heater which can be heated up to a temperature of 250 C. Experimental results show that the sensor is capable of operating over a wide range of hydrogen concentration levels between 0-95 percent without any hysteresis effects.

Liu, Chung-Chiun↗

TRACE-P OH and HO2 Measurements with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) on the DC-8

The Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) measures OH and HO2 from the NASA DC-8. This instrument detects OH by laser induced fluorescence (LIF) in detection chambers at low pressure and detects HO2 by chemical conversion with NO followed by LIF detection. The demonstrated detection limit (S/N=2, 5 min.) for OH is about 0.005 pptv (1x10(exp 6)/cu cm at 2 km altitude) and for HO2 is 0.05 pptv (1x10(exp 6)/cu cm at 2 km altitude). We will use ATHOS to measure OH, HO2, and HO2/OH during TRACE- P, analyze these results by comparing them against fundamental relationships and computer models, and publish the analyses. TRACE-P HO(x), measurements will help develop a clearer picture of the atmospheric oxidation and 0 3 production that occur as Asian pollution spreads across the Pacific Ocean.

Brune, William H.↗

Hydrogen Gas Sensors Fabricated on Atomically Flat 4H-SiC Webbed Cantilevers

This paper reports on initial results from the first device tested of a "second generation" Pt-SiC Schottky diode hydrogen gas sensor that: 1) resides on the top of atomically flat 4H-SiC webbed cantilevers, 2) has integrated heater resistor, and 3) is bonded and packaged. With proper selection of heater resistor and sensor diode biases, rapid detection of H2 down to concentrations of 20 ppm was achieved. A stable sensor current gain of 125 +/- 11 standard deviation was demonstrated during 250 hours of cyclic test exposures to 0.5% H2 and N2/air.

Neudeck, Philip G.↗

Laser Raman sensor for measurement of trace-hydrogen gas

A new optical hydrogen sensor based on spontaneous Raman scattering of laser light has been designed and constructed for rugged field use. It provides good sensitivity, rapid response, and the inherent Raman characteristics of linearity and background gas independence of the signal. Efficient light collection and discrimination by using fast optics and a bandpass interference filter compensate for the inefficiency of the Raman-scattering process. A multipass optical cavity with a Herriott-type configuration provides intense illumination from an air-cooled CW gas laser. The observed performance is in good agreement with the theoretical signal and noise level predictions.

Adler-Golden, Steven M.↗

XSP Methane Sensors Test and Evaluation Project “M-Step”

Methane sensor technology is employed in industry sectors from oil and gas to agriculture, landfills, and monitoring of natural emissions. The US oil and gas sector is extensive in scale, critical to fulfilling US energy needs, and deals with commodities presenting enormous challenges for personnel safety and the environment. Thus, it is imperative that they have accurate and responsive sensors to detect hazardous gases such as methane. US space launch systems will increasingly also use liquefied methane and liquefied natural gas (LNG), which is mostly methane, in quantities large and small, as main and auxiliary propulsion and power. Some of these systems will be reusable, which adds the unique challenge of processing a vehicle that has residual commodities and has returned to its launch site to be readied for its next launch. The methane sensors test and evaluation project (M-STEP) began within the context of a reusable launch system, the Defense Advanced Research Projects Agency (DARPA) Experimental Spaceplane (XSP) program, which would have employed a high-pressure gaseous methane and gaseous oxygen reaction control system. Although the XSP partnership between Boeing and DARPA was terminated by Boeing in early 2020, DARPA and KSC have continued to collaborate in the area of gas sensors with the hydrogen sensor test and evaluation project (H-STEP) and with M-STEP. The NASA Launch Services program (LSP) invested in M-STEP in FY 2021 “to evaluate and understand the state-of-the-art in methane gas sensors”. M-STEP and the LSP effort was complementary, pushing in the same direction to understand US launch system stakeholder needs and approaches, requirements internal (NASA) and external, and commercially available or forthcoming methane sensing technologies, practices, and approaches. In addition, M-STEP (as with H-STEP) enhances KSC capabilities and understanding of these technologies, informing agency investments and further research in these areas.

Tracy L. Gibson↗

On Orbit ISS Oxygen Generation System Operation Status

The International Space Station (ISS) United States Orbital Segment (USOS) Oxygen Generation System (OGS) has accumulated almost a year of operation at varied oxygen production rates within the US Laboratory Module (LAB) since it was first activated in July 2007. It was operated intermittently through 2009 and 2010, due to filter clogging and acid accumulation in the recirculation loop. Since the installation of a deionizing bed in the recirculation loop in May of 2011 the OGA has been operated continuously. Filters in the recirculation loop have clogged and have been replaced. Hydrogen sensors have drifted apart, and a power failure may have condensed water on a hydrogen sensor. A pump delta pressure sensor failed, and a replacement new spare pump failed to start. Finally, the voltage across the cell stack increased out of tolerance due to cation contamination, and the cell stack was replaced. This paper will discuss the operating experience and characteristics of the OGS, as well as operational issues and their resolution.

Diderich, Greg S.↗

A Hydrogen Leak Detection System for Aerospace and Commercial Applications

Leaks on the space shuttle while on the launch pad have generated interest in hydrogen leak monitoring technology. Microfabricated hydrogen sensors are being fabricated at Case Western Reserve University (CWRU) and tested at NASA Lewis Research Center (LeRC). These sensors have been integrated into hardware and software designed by Aerojet. This complete system allows for multipoint leak monitoring designed to provide leak source and magnitude information in real time. The monitoring system processes data from the hydrogen sensors and presents the operator with a visual indication of the leak location and magnitude. Although the leak monitoring system was designed for hydrogen propulsion systems, the possible applications of this monitoring system are wide ranged. This system is in operation in an automotive application which requires high sensitivity to hydrogen.

Hunter, Gary W.↗

HO(x) Measurements in SONEX with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS)

SONEX, which was delayed by aircraft inspection problems, began the second week of October and concluded in mid-November with 16 flights. These flights covered the Pacific Ocean off the western United States, transits across the United States, the western coast of Europe, and the North and Central Atlantic Ocean. Particular attention was paid to the North Atlantic Flight Corridor. ATHOS collected high-quality HO(x) data on 15 flights. Observations taken at 5 Hz were typically averaged into 20-second measurements. Each 20-second measurement has precision 1(sigma) of less than 0.01 pptv. OH measurements were generally made from the surface to flight altitudes. HO2 measurements, which require reagent NO flow, were made from flight altitudes to near the top of the planetary boundary layer. Measured OH and HO2 during SONEX was generally lower than the measured OH and HO2 during SUCCESS (April-May, 1996, central United States). Whereas during SUCCESS midday OH was 0.1-0.5 pptv and HO2 was 3-15 pptv, during SONEX midday OH was 0.02-0.2 pptv and HO2 was 0.5-8 pptv. Part of this difference results from the midday solar zenith angles, which were larger during SONEX than during SUCCESS due to both the season and the generally higher latitudes sampled during SONEX. However, some of the difference may be due to differences in HOx sources, since less air influenced by convection was sampled during SONEX. These possibilities await post-flight calibrations of ATHOS and analysis of observations of HO(x) and simultaneously measured meteorology and trace species.

Brune, William M.↗

HO(x) Measurements in PEM Tropics B with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS)

The primary objective of PEM Tropics B was to study the processes responsible for the production and loss of tropospheric ozone over the tropical Pacific. This region of the globe contains very clean air as well as aged, polluted air that was advected from both the Asian and American continents. Understanding ozone requires understanding of HO(x) (HO(x) = OH + HO2) chemistry, since the reaction between H02 and NO leads to ozone production and the production of OH often requires ozone loss. In addition, OH is the atmosphere's primary oxidant. Since most atmospheric oxidation is thought to occur in the tropical lower troposphere, measurements during PEM Tropics B should provide an important test of the OH abundances and distributions. Thus, understanding and thoroughly testing HO(x) processes was an important objective of PEM Tropics B. Several issues need to be tested, One is HO, production rates and sources, since HO,, production directly affects ozone production and loss. Another is HO(x) behavior in and around clouds, since HO(x) is lost to cloud particles, but convection may bring HO(x) precursors from near the surface to the upper troposphere. A third is the rise and fall of HO(x) at sunrise and sunset, since these variations give strong indications of the important sources and sinks of HO(x). Making and interpreting high-quality OH and H02 measurements from the NASA DC-8 during PEM Tropics B is the objective of this research effort.

Brune, William H.↗

High-Temperature Proton-Conducting Ceramics Developed

High-temperature protonic conductors (HTPC) are needed for hydrogen separation, hydrogen sensors, fuel cells, and hydrogen production from fossil fuels. The HTPC materials for hydrogen separation at high temperatures are foreseen to be metal oxides with the perovskite structure A(sup 2+)B(sup 4+)C(sup 2-, sub 3) and with the trivalent cation (M(sup 3+)) substitution at the B(sup 4+)-site to introduce oxygen vacancies. The high affinity for hydrogen ions (H(sup +)) is advantageous for protonic transport, but it increases the reactivity toward water (H2O) and carbon dioxide (CO2), which can lead to premature membrane failure. In addition, there are considerable technological challenges related to the processing of HTPC materials. The high melting point and multi-cation chemistry of HTPC materials creates difficulties in in achieving high-density, single-phase membranes by solid-state sintering. The presence of secondary phases and grain-boundary interfaces are detrimental to the protonic conduction and environmental stability of polycrystalline HTPC materials.

Sayir, Ali↗

Predictive sensor method and apparatus

A microprocessor and electronics package employing predictive methodology was developed to accelerate the response time of slowly responding hydrogen sensors. The system developed improved sensor response time from approximately 90 seconds to 8.5 seconds. The microprocessor works in real-time providing accurate hydrogen concentration corrected for fluctuations in sensor output resulting from changes in atmospheric pressure and temperature. Following the successful development of the hydrogen sensor system, the system and predictive methodology was adapted to a commercial medical thermometer probe. Results of the experiment indicate that, with some customization of hardware and software, response time improvements are possible for medical thermometers as well as other slowly responding sensors.

Cambridge, Vivien J.↗