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Modified hydrogen sensor replaces oxygen cathode with a cathode consisting of a sealed paste of gold hydroxide and a pure gold current collector. The net reaction which occurs during cell operation is the reduction of the gold hydroxide to gold and water, with a half-cell potential of 1.4 volts.
The NREL Hydrogen sensor laboratory aims to ensure that hydrogen sensor technology is available to meet end-user needs and to foster the proper use of sensors by advancing next generation sensing and analysis techniques, supporting codes and standards development, and improving component reliability systems.
The performance requirements for hydrogen detection in aerospace applications often exceed those of more traditional applications. In order to ascertain the applicability of existing hydrogen sensors to aerospace applications, a survey was conducted of commercially available point-contact hydrogen sensors, and their operation was analyzed. The operation of the majority of commercial hydrogen sensors falls into four main categories: catalytic combustion, electrochemical, semiconducting oxide sensors, and thermal conductivity detectors. The physical mechanism involved in hydrogen detection for each main category is discussed in detail. From an understanding of the detection mechanism, each category of sensor is evaluated for use in a variety of space and propulsion environments. In order to meet the needs of aerospace applications, the development of point-contact hydrogen sensors that are based on concepts beyond those used in commercial sensors is necessary.
The detection of hydrogen leaks in aerospace applications, especially those involving hydrogen fuel propulsion systems, is of extreme importance for reasons of reliability, safety, and economy. Motivated by leaks occurring in liquid hydrogen lines supplying the main engine of the Space Shuttle, NASA Lewis has initiated a program to develop point-contact hydrogen sensors which address the needs of aerospace applications. Several different approaches are being explored. They include the fabrication of PdAg Schottky diode structures, the characterization of PdCr as a hydrogen sensitive alloy, and the use of SiC as a semiconductor for hydrogen sensors. This paper discusses the motivation behind and present status of each of the major components of the NASA LeRC hydrogen sensor program.
Application specifications for the methane sensor were assembled and design guidelines, development goals and evaluation criteria were formulated. This was done to provide a framework to evaluate sensor performance and any design adjustments to the preprototype sensor that could be required to provide methane sensitivity. Good response to hydrogen was experimentally established for four hydrogen sensor elements to be later evaluated for methane response. Prior results were assembled and analyzed for other prototype hydrogen sensor performance parameters to form a comparison base. The four sensor elements previously shown to have good hydrogen response were experimentally evaluated for methane response in 2.5% methane-in-air. No response was obtained for any of the elements, despite the high methane concentration used (50% of the Lower Flammability Limit). It was concluded that the preprototype sensing elements were insensitive to methane and were hydrogen specific. Alternative sensor operating conditions and hardware design changes were considered to provide methane sensitivity to the preprototype sensor, including a variety of different methane sensing techniques. Minor changes to the existing sensor elements, sensor geometry and operating conditions will not make the preprototype hydrogen sensor respond to methane. New sensor elements that will provide methane and hydrogen sensitivity require replacement of the existing thermistor type elements. Some hydrogen sensing characteristics of the modified sensor will be compromised (larger in situ calibration gas volume and H2 nonspecificity). The preprototype hydrogen sensor should be retained for hydrogen monitoring and a separate methane sensor should be developed.
This paper provides a description of the hydrogen sensor Orbital Replacement Unit (ORU) used on the Oxygen Generation Assembly (OGA), to be operated on the International Space Station (ISS). The hydrogen sensor ORU is being provided by Makel Engineering, Inc. (MEI) to monitor the oxygen outlet for the presence of hydrogen. The hydrogen sensor ORU is a triple redundant design where each sensor converts raw measurements to actual hydrogen partial pressure that is reported to the OGA system controller. The signal outputs are utilized for system shutdown in the event that the hydrogen concentration in the oxygen outlet line exceeds the specified shutdown limit. Improvements have been made to the Micro-Electro-Mechanical Systems (MEMS) based sensing element, screening, and calibration process to meet OGA operating requirements. Two flight hydrogen sensor ORUs have successfully completed the acceptance test phase. This paper also describes the sensor s performance during acceptance testing, additional tests planned to extend the operational performance calibration cycle, and integration with the OGA system.
In order to ascertain the applicability of hydrogen sensors to aerospace applications, a survey was conducted of promising experimental point-contact hydrogen sensors and their operation was analyzed. The techniques discussed are metal-oxide-semiconductor or MOS based sensors, catalytic resistor sensors, acoustic wave detectors, and pyroelectric detectors. All of these sensors depend on the interaction of hydrogen with Pd or a Pd-alloy. It is concluded that no single technique will meet the needs of aerospace applications but a combination of approaches is necessary. The most promising combination is an MOS based sensor with a catalytic resistor.
Microelectromechanical-systems- (MEMS-) based hydrogen sensor technology developed by the NASA Glenn Research Center at Lewis Field and Case Western Reserve University was demonstrated on shuttle missions STS-95 (Senator Glenn s mission) and STS-96. These smart sensors, commercialized by Makel Engineering Inc., were part of an "Integrated Vehicle Health Monitoring HEDS Technology Demonstration" series conducted at the NASA Kennedy Space Center. The experiments were designed to demonstrate the effect of technological upgrades on shuttle performance. The hydrogen sensors were micro-fabricated for minimal size, weight, and power consumption. A temperature detector and heater were included on the sensor for temperature control. Two palladium chrome (PdCr) hydrogen detection devices were included in each sensor package: a Schottky diode for low concentrations and a resistor for high concentrations. These sensor designs allow operation in inert environments. "Smart" electronics developed by Makel Engineering were integrated with the sensors to control the sensor temperature and process the output of the various sensors. This complete hydrogen detection system (two sensors on a chip with smart electronics) flew on STS-95 (launched October 1998) and STS-96 (launched May 1999). It was installed in the aft compartment of the shuttle and used to monitor the hydrogen concentration in that region. Up to this time, a mass spectrometer had monitored the hydrogen concentration in the aft compartment before launch, and "grab" bottles had been used after launch. The inside of these bottles is at vacuum. During flight, the grab bottles are pyrotechnically opened for a brief period, and the gas in the aft compartment is captured in the bottle. Several of these bottles are opened at different times during takeoff, and their contents are used to determine the time profile of the gases in the aft chamber. However, this information is not available until after the flight. On the launch pad, results from the new sensor technology paralleled the responses of the mass spectrometer with, in some cases, a quicker response time. In flight, data from the new sensors agreed with those derived from analyzing the contents of the grab bottles. Moreover, this microsensor can monitor the aft compartment continuously and, in principle, could monitor the health of the vehicle in real time during flight.
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.
Leaks on the Space Shuttle while on the Launch Pad have generated interest in hydrogen leak monitoring technology. An effective leak monitoring system requires reliable hydrogen sensors, hardware, and software to monitor the sensors. The system should process the sensor outputs and provide real-time leak monitoring information to the operator. This paper discusses the progress in developing such a complete leak monitoring system. Advanced microfabricated hydrogen sensors are being fabricated at Case Western Reserve University (CWRU) and tested at NASA Lewis Research Center (LeRC) and Gencorp Aerojet (Aerojet). Changes in the hydrogen concentrations are detected using a PdAg on silicon Schottky diode structure. Sensor temperature control is achieved with a temperature sensor and heater fabricated onto the sensor chip. Results of the characterization of these sensors are presented. These sensors can detect low concentrations of hydrogen in inert environments with high sensitivity and quick response time. Aerojet is developing the hardware and software for a multipoint leak monitoring system 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. Work has commenced on integrating the NASA LeRC-CWRU hydrogen sensors with the Aerojet designed monitoring system. Although the leak monitoring system was designed for hydrogen propulsion systems, the possible applications of this monitoring system are wide ranged. Possible commercialization of the system will also be discussed.
The motivation and present status of each of the major components of the NASA Lewis Research Center hydrogen sensor program. The testing facility used to test the sensors and the proposed expansion of this facility are discussed. The Schottky diode prototype sensors, the use of SiC as a semiconductor for a hydrogen sensor, and the present characterization of PdCr are addressed. Future directions for the program are examined. It is concluded that results thus far are encouraging and that further development work is necessary.
Chemiresistive gas sensors based on semiconductor metal oxides, such as tin dioxide (SnO₂), are indispensable for detecting and monitoring toxic gases and pollutants, making them critical components in industrial and environmental applications. To enhance their performance, the metal oxides are loaded with noble metals such as palladium (Pd). However, ambient humidity poses a significant challenge to their performance. The presence of adsorbed water molecules on the oxide surface can considerably impair sensor sensitivity and overall performance. To address this issue, in this paper, we report on the application of an ultrathin, hydrophobic layer of hexamethyldisilazane to the surface of a Pd/SnO 2 sensor. This study investigates the influence of hydrophobic surface modifications on the metal oxide interface, focusing on their impact on sensor sensitivity and selectivity. The resulting sensor exhibits superior hydrogen sensing capabilities, operating effectively at low temperatures even in high humidity environments. Furthermore, the hydrophobic modification reduces the sensor’s susceptibility to interfering gases, thus enhancing its selectivity. The combined enhancements in moisture resistance and selectivity achieved through HMDS surface modification, along with the superior sensitivity of Pd/SnO₂ sensors, facilitate the development of gas sensors with enhanced humidity tolerance and broader applications.
To meet sensing and calibration needs, an in situ calibration technique was developed. It is based on electrolytic generation of a hydrogen/air atmosphere within a hydrogen sensor. The hydrogen is generated from water vapor in the air, and being electrical in nature, the in situ calibration can be performed completely automatically in remote locations. Triply redundant sensor elements are integrated within a single, compact housing, and digital logic provides inter-sensor comparisons to warn of and identify malfunctioning sensor elements. An evaluation of this concept is presented.
Advanced chemical sensors are used in aeronautic and space applications to provide safety monitoring, emission monitoring, and fire detection. In order to fully do their jobs, these sensors must be able to operate in a range of environments. NASA has developed sensor technologies addressing these needs with the intent of improving safety, optimizing combustion efficiencies, and controlling emissions. On the ground, the chemical sensors were developed by NASA engineers to detect potential hydrogen leaks during Space Shuttle launch operations. The Space Shuttle uses a combination of hydrogen and oxygen as fuel for its main engines. Liquid hydrogen is pumped to the external tank from a storage tank located several hundred feet away. Any hydrogen leak could potentially result in a hydrogen fire, which is invisible to the naked eye. It is important to detect the presence of a hydrogen fire in order to prevent a major accident. In the air, the same hydrogen-leak dangers are present. Stress and temperature changes can cause tiny cracks or holes to form in the tubes that line the Space Shuttle s main engine nozzle. Such defects could allow the hydrogen that is pumped through the nozzle during firing to escape. Responding to the challenges associated with pinpointing hydrogen leaks, NASA endeavored to improve propellant leak-detection capabilities during assembly, pre-launch operations, and flight. The objective was to reduce the operational cost of assembling and maintaining hydrogen delivery systems with automated detection systems. In particular, efforts have been focused on developing an automated hydrogen leak-detection system using multiple, networked hydrogen sensors that are operable in harsh conditions.
Photovoltaic device senses hydrogen developed to test degradation of diodes with platinum flash gates on backs. Sensing element is p/n junction rather than conventional Schottky barrier or metal oxide/silicon field-effect transistor. Hydrogen-indicating electrical signal modulated optically rather than electrically. Layered structure of hydrogen detector and principle of operation resemble silicon solar photovoltaic cell. Hydrogen detector responds to hydrogen in atmosphere within minutes and recovers quickly when hydrogen removed.
Currently, NASA Kennedy Space Center’s Exploration Ground Systems (EGS) uses liquid hydrogen (LH 2 ) as fuel for launches and ensures hydrogen is no longer in the fill lines by sampling gas into a controlled environment. Then they use a catalytic sensor that detects when hydrogen interacts with oxygen. However, this procedure requires repeatedly backfilling and flushing with helium, which can be wasteful during a global helium shortage and expensive for each sampling port. Therefore, the team at KSC set out to establish proof-of-concept of a plasma-based hydrogen sensor that is anaerobic – and can in fact detect in most environments and below atmospheric pressures – and with a small footprint and more sensitive than other hydrogen sensors currently on the market. The technology development was done by testing known concentrations of hydrogen in argon gas fed through a vacuum cube containing an electrode feedthrough at varying pressures. The resultant emission spectra were recorded with a fiber optic spectrometer and analyzed to determine the instrument's accuracy. Throughout testing, efforts were made to prove the off-the-shelf capabilities of the setup. The traditional high voltage AC-power source was switched to an affordable, handheld plasma lighter. Additionally, the spectrometer was supplemented with a double photodiode circuit to take targeted measurements of the Balmer-α and - β lines in the hydrogen spectrum. From this, we established a proof of concept sensor. SLS required it to detect as low as 100 ppm whereas we detected hydrogen in concentrations as low as 50 ppm and in an anaerobic environment. * Work supported by NASA Kennedy Space Center’s Science Mission Directorate Innovative Research and Development Fund.
Currently, NASA Kennedy Space Center’s Exploration Ground Systems (EGS) uses liquid hydrogen (LH2) as fuel for launches and ensures hydrogen is no longer in the fill lines by sampling gas into a controlled environment. Then they use a catalytic sensor that detects when hydrogen interacts with oxygen. However, this procedure requires repeatedly backfilling and flushing with helium, which can be wasteful during a global helium shortage and expensive for each sampling port. Therefore, the team at KSC set out to establish proof-of-concept of a plasma-based hydrogen sensor that is anaerobic – and can in fact detect in most environments and below atmospheric pressures – and with a small footprint and more sensitive than other hydrogen sensors currently on the market. The technology development was done by testing known concentrations of hydrogen in argon gas fed through a vacuum cube containing an electrode feedthrough at varying pressures. The resultant emission spectra were recorded with a fiber optic spectrometer and analyzed to determine the instrument's accuracy. Throughout testing, efforts were made to prove the off-the-shelf capabilities of the setup. The traditional high voltage AC-power source was switched to an affordable, handheld plasma lighter. Additionally, the spectrometer was supplemented with a double photodiode circuit to take targeted measurements of the Balmer-α and - β lines in the hydrogen spectrum. From this, we established a proof of concept sensor. SLS required it to detect as low as 100 ppm whereas we detected hydrogen in concentrations as low as 50 ppm and in an anaerobic environment.
As fossil fuel supplies decline, hydrogen is quickly becoming an increasingly important fuel source. Currently hydrogen is the prime fuel of today's space vehicles (e.g., Space Shuttle) and featured as a fuel for some prototype vehicles such as the BMW seven series model. Hydrogen is a colorless, odorless gas with a 4% lower explosive limit which makes leak detection a priority. In an effort to support the use of hydrogen, a chemochromic (color changing) sensor was developed that is robust, simple to use, and does not require active operation. It can be made into a thin tape which can be conveniently used for leak detection at flanges, valves, or outlets. Chemochromic sensors can be either reversible or irreversible; however, irreversible chemochromic sensors will be analyzed in this report. The irreversible sensor is useful during hazardous operations when personnel cannot be present. To actively monitor leaks, testing of the irreversible sensor against environmental effects was completed and results indicated this material is suitable for outdoor use in the harsh beachside environment of Kennedy Space Center. The experiments in this report will give additional results to the environmental testing by adding solid rocket booster residue as a variable. The primary motivation for these experiments is to prepare the sensors for the launch pad environment at the Kennedy Space Center. In an effort to simulate the atmosphere at the pads before and after launch, the chemochromic sensors are exposed to solid rocket residue under various conditions.