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Highly Selective and Stable Multivariable Gas Sensors for Enhanced Robustness and Reliability of SOFC Operation

GE Global Research, in partnership with SUNY Polytechnic Institute (SUNY Poly) and GE–Fuel Cells LLC, designed, built, and tested multi-gas sensor prototypes for in situ monitoring of gases produced during steam reforming in solid oxide fuel cell (SOFC) systems. To be widely adopted and to deliver a lower operating cost for customers, SOFC systems should enhance their operation reliability and improve stack robustness. These needs can be achieved by early diagnostics of potential upsets by using in-situ gas sensors for the real-time monitoring of gas mixture compositions. Thus, this project objective was to achieve selectivity and stability of sensing of gases for SOFC applications by implementing a new generation of gas sensors, known as multivariable sensors. Such sensors are intended to complement the mature traditional analytical instruments based on sensor performance and design characteristics. The key sensor-performance characteristics include accurate detection and quantitation of several gases in their mixtures and stability of operation in unattended applications. The key design characteristics of sensors include their unobtrusive form factor and cost-effectiveness. The duration of the project was 18 months with the project structure that included three technical tasks such as (1) design and laboratory validation of multivariable sensors for selective detection of H 2 and CO gases, (2) laboratory validation of sensor stability over a two-week testing, and (3) field-validation of the developed multivariable sensor system prototype at GE–Fuel Cells factory. Multi-gas detection was achieved with multivariable photonic sensors designed to operate at elevated temperature. The sensor design was based on three-dimensional (3D) bio-inspired photonic nanostructure that was fabricated using materials responsive to gases of interest such as H 2 and CO. The gas discrimination and the rejection of interferences such as CH 4 , H 2 O, and others was performed by optimizing the design parameters of the 3D photonic nanostructures such as their composition and morphology. Planar sol-gel and sputtered sensing films were fabricated as controls. As a result of the fabrication, functionalization, excitation, and performance testing of 3D photonic sensors, we developed initial design rules for high temperature multivariable sensors. These design rules pave the way for the new generation of cost-effective industrial sensors. Stability of sensor operation was tested in the laboratory conditions under variations of the ambient environments. Stability tests were designed in the order of enhanced complexity and realism of sensor operation and included quantitation of a single gas, quantitation of a single gas in the presence of interferences, and quantitation of two and three gases. We have found that conventional machine learning data analysis stools were unable to correct for the sensor drift. Thus, we have developed new methods of machine learning data analysis that provided us with needed performance stability. Such performance improvement in gas sensing was a significant milestone in bringing our multivariable sensors to practical applications. The project culminated with initial field validation of developed multivariable sensor prototypes at GE–Fuel Cells LLC. The in situ data generated by the sensor system in the lab and field conditions provided inputs that advanced our fundamental understanding of gas sensing at high temperatures to enable sensors for SOFC applications and allowed development of the recommendations for further deliverables.

47 OTHER INSTRUMENTATION↗

High Temperature Capacitive Pressure Sensor Employing a SiC Based Ring Oscillator

In an effort to develop harsh environment electronic and sensor technologies for aircraft engine safety and monitoring, we have used capacitive-based pressure sensors to shift the frequency of a SiC-electronics-based oscillator to produce a pressure-indicating signal that can be readily transmitted, e.g. wirelessly, to a receiver located in a more benign environment. Our efforts target 500 C, a temperature well above normal operating conditions of commercial circuits but within areas of interest in aerospace engines, deep mining applications and for future missions to the Venus atmosphere. This paper reports for the first time a ring oscillator circuit integrated with a capacitive pressure sensor, both operating at 500 C. This demonstration represents a significant step towards a wireless pressure sensor that can operate at 500 C and confirms the viability of 500 C electronic sensor systems.

Meredith, Roger D.↗

PEDOT:PSS/QCM-based multimodal humidity and pressure sensor

A room-temperature multimodal sensor composed of PEDOT:PSS deposited on an AT-cut quartz crystalmicrobalance (QCM) crystal has been fabricated. The nonlinear resistive and frequency sensor responses aredeconvolved using an articial neural network (ANN), which allows the single sensor to function simultane-ously as a relative humidity (RH) sensor and a pressure sensor using only two electrodes. We demonstratethat the predictive ability of the sensor is highly inuenced by the data used to train the ANN. When trainingsets are tailored to resemble the operating conditions of the sensor, the sensor achieves an average resolutionof < 3% RH from 0-100% RH, even after H 2 O saturation occurs on the surface. Our results indicate thatANNs show strong promise for improving the resolution of low cost gas sensors and for expanding the rangeof environmental conditions in which a given sensor can operate.

47 OTHER INSTRUMENTATION↗

Tunable Diode Laser Sensors to Monitor Temperature and Gas Composition in High-Temperature Coal Gasifiers

The integrated gasification combined cycle (IGCC) when combined with carbon capture and storage can be one of the cleanest methods of extracting energy from coal. Control of coal and biomass gasification processes to accommodate the changing character of input-fuel streams is required for practical implementation of integrated gasification combined-cycle (IGCC) technologies. Therefore a fast time-response sensor is needed for real-time monitoring of the composition and ideally the heating value of the synthesis gas (here called syngas) as it exits the gasifier. The goal of this project was the design, construction, and demonstration an in situ laserabsorption sensor to monitor multiple species in the syngas output from practical-scale coal gasifiers. This project investigated the hypothesis of using laser absorption sensing in particulateladen syngas. Absorption transitions were selected with design rules to optimize signal strength while minimizing interference from other species. Successful in situ measurements in the dusty, high-pressure syngas flow were enabled by Stanford’s normalized and scanned wavelength modulation strategy. A prototype sensor for CO, CH4, CO2, and H2O was refined with experiments conducted in the laboratory at Stanford University, a pilot-scale at the University of Utah, and an engineering-scale gasifier at DoE’s National Center for Carbon Capture with the demonstration of a prototype sensor with technical readiness level 6 in the 2014 measurement campaign.

01 COAL, LIGNITE, AND PEAT↗

Development of a high temperature static strain sensor

The goal of this program is to develop an electrical resistance strain gage system which will accurately measure the static strains of superalloy blades and vanes in gas turbine engines running on a test stand. Accurate knowledge of these strains is essential to reaching the goals of the HOST program in the selection and experimental verification of the various theoretical models developed to understand and improve the performance of these engines. The specific objective is to develop a complete system capable of making strain measurements of up to + or - 10 percent of full scale during a 50 hour period at temperatures as high as 1250 K. In addition to survival and stability, attaining a low temperature coefficient of resistance, of the order of 20 ppm/K or less, was a major goal. This requirement arises from the presently unavoidable uncertainties in measurement of the exact temperatures inside gas turbines for use in making corrections for apparent strain due to temperature.

Hulse, Charles O.↗

Zeolitic imidazolate framework-coated acoustic sensors for room temperature detection of carbon dioxide and methane

The integration of nanoporous materials such as metal organic frameworks (MOFs) with sensitive transducers can result in robust sensing platforms for monitoring gases and chemical vapors for a range of applications. Here, we report on an integration of the zeolitic imidazolate framework – 8 (ZIF-8) MOF with surface acoustic wave (SAW) and thickness shear mode quartz crystal microbalance (QCM) devices to monitor carbon dioxide (CO 2 ) and methane (CH 4 ) under ambient conditions. The MOF was directly coated on the Y-Z LiNbO 3 SAW delay lines (operating frequency, f 0 = 436 MHz) and AT-cut quartz TSM resonators (resonant frequency, f 0 = 9 MHz) and the devices were tested for various gases in N 2 under ambient conditions. The devices were able to detect the changes in CO 2 or CH 4 concentrations with relatively higher sensitivity to CO 2 , which was due to its higher adsorption potential and heavier molecular weight. The sensors showed full reversibility and repeatability which were attributed to the physisorption of the gases into the MOF and high stability of the devices. Both types of sensors showed linear responses relative to changes in the binary gas compositions thereby allowing to construct calibration curves which correlated well with the expected mass changes in the sorbent layer based on mixed-gas gravimetric adsorption isotherms measured on bulk samples. For 200 nm thick films, the SAW sensitivities to CO 2 and CH 4 were 1.44 × 10 -6 /vol% and 8 × 10 -8 /vol%, respectively, against the QCM sensitivities 0.24 × 10-6/vol% and 1 × 10 -8 /vol%, respectively, which were evaluated as the fractional change in the signal. The SAW sensors were also evaluated for 100 nm–300 nm thick films, the sensitivities of which were found to increase with the thickness due to the increased number of pores for the adsorption of a larger amount of gases. Finally, in addition, the MOF-coated SAW delay lines had a good response in wireless mode, demonstrating their potential to operate remotely for the detection of the gases at emission sites across the energy infrastructure.

36 MATERIALS SCIENCE↗

Absorption spectroscopy based high-speed oxygen concentration measurements at elevated gas temperatures

A sensor built upon tunable diode laser absorption spectroscopy (TDLAS) has been developed for concentration measurements in high-temperature (up to 800 K) gas streams; while the sensor measures gas oxygen and water concentration, temperature and pressure, this work focuses on the challenges and solutions to transient oxygen measurement. A 760-nm diode laser was used to probe a pair of oxygen absorption transitions, and a Herriott cell based multi-pass arrangement was utilized to compensate for the extremely weak oxygen absorption as well as the high gas temperature. This multi-pass arrangement provides a 4297.4-mm absorption path length across a 76.2-mm diameter duct, and an O 2 detection limit ([O 2 ] where SNR=1) of ca. 0.1%. Laboratory validation of the HITRAN spectral parameters of the chosen absorption transitions was performed over a range of high temperatures and oxygen concentrations relevant to engine-exhaust applications. The insensitivity of the Herriott cell arrangement to vibrations and spatial temperature gradients was demonstrated. Conclusions from applications to single- and multi-cylinder engine exhaust are presented and demonstrate the new sensor’s ability to measure fast intra-cycle gas-property transients, and provide insights relevant to advancing internal-combustion-engine technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-temperature performance of MoS{sub 2} thin-film transistors: Direct current and pulse current-voltage characteristics

We report on fabrication of MoS{sub 2} thin-film transistors (TFTs) and experimental investigations of their high-temperature current-voltage characteristics. The measurements show that MoS{sub 2} devices remain functional to temperatures of at least as high as 500 K. The temperature increase results in decreased threshold voltage and mobility. The comparison of the direct current (DC) and pulse measurements shows that the direct current sub-linear and super-linear output characteristics of MoS{sub 2} thin-films devices result from the Joule heating and the interplay of the threshold voltage and mobility temperature dependences. At temperatures above 450 K, a kink in the drain current occurs at zero gate voltage irrespective of the threshold voltage value. This intriguing phenomenon, referred to as a “memory step,” was attributed to the slow relaxation processes in thin films similar to those in graphene and electron glasses. The fabricated MoS{sub 2} thin-film transistors demonstrated stable operation after two months of aging. The obtained results suggest new applications for MoS{sub 2} thin-film transistors in extreme-temperature electronics and sensors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Multi-Wavelength Based Optical Density Sensor for Autonomous Monitoring of Microalgae

A multi-wavelength based optical density sensor unit was designed, developed, and evaluated to monitor microalgae growth in real time. The system consisted of five main components including (1) laser diode modules as light sources (2) photodiodes as detectors, (3) driver circuit, (4) flow cell and (5) sensor housing temperature controller. The sensor unit was designed to be integrated into any microalgae culture system for both real time and non-real time optical density measurements and algae growth monitoring applications. It was shown that the sensor unit was capable of monitoring the dynamics and physiological changes of the microalgae culture in real-time. Algae biomass concentration was accurately estimated with optical density measurements at 650, 685 and 780 nm wavelengths used by the sensor unit. The sensor unit was able to monitor cell concentration as high as 1.05 g L -1 (1.51x10 8 cells mL -1 ) during the culture growth without any sample preparation for the measurements. Since high cell concentrations do not need to be diluted using the sensor unit, the system has the potential to be used in industrial microalgae cultivation systems for real time monitoring and control applications that can lead to improved resource use efficiency.

09 BIOMASS FUELS↗

Testing and characterizations of infrared sensor over the temperature range of 2 Kelvin to 300 Kelvin

Various cryogenic techniques were used to evaluate state of the art electro-optic devices. As research, development, and production demands require more sensitive testing techniques, faster test results, and higher production throughput, the emphasis on supporting cryogenic systems increases. The three traditional methods currently utilized in electro-optic device testing are discussed: (1) liquid contaiment dewars; (2) liquid transfer systems; and (3) closed cycle refrigeration systems. Advantages, disadvantages, and the current state of the art of each of these cryogenic techniques is discussed.

Hansen, R. G.↗

High temperature static strain sensor development program

The development of resistance strain gages which are useful for static strain measurements on nickel or cobalt superalloy parts inside a gas turbine engine on a test stand were examined. These measurements of a strain gage alloy development program which to be followed by an optional investigation of complete strain gage systems which will use the best of the alloys developed together with other system improvements is reviewed. The specific goal for the complete system is to make measurements to 2,000 micro epsilon with error of only + or - 10% over a 50 hour period. In addition to simple survival and stability, attaining a low thermal coefficient to resistivity, of order 100 ppm/K or less, is also a major goal. The first task was to select candidate alloys or alloy systems using a search of the literature and the available metallurgical theory. Alloy candidates were evaluated and compared by a grading system. Equipment and techniques were developed which are suitable for iterative studies of a variety of compositions. Many compositions were examined and significantly improved alloys were identified.

Hulse, C.↗

Development of advanced high-temperature heat flux sensors. Phase 2: Verification testing

A two-phase program is conducted to develop heat flux sensors capable of making heat flux measurements throughout the hot section of gas turbine engines. In Phase 1, three types of heat flux sensors are selected; embedded thermocouple, laminated, and Gardon gauge sensors. A demonstration of the ability of these sensors to operate in an actual engine environment is reported. A segmented liner of each of two combustors being used in the Broad Specification Fuels Combustor program is instrumented with the three types of heat flux sensors then tested in a high pressure combustor rig. Radiometer probes are also used to measure the radiant heat loads to more fully characterize the combustor environment. Test results show the heat flux sensors to be in good agreement with radiometer probes and the predicted data trends. In general, heat flux sensors have strong potential for use in combustor development programs.

Atkinson, W. H.↗

High temperature static strain sensor development program

Electrical resistance strain gages useful for static strain measurements on nickel or cobalt superalloy parts inside a gas turbine engine on a test stand are being developed. Measurements of this type are of great importance in meeting the goals of the HOST program because, without reliable knowledge of the stresses and strains which exist in specific components, it will be difficult to fully appreciate where improvements in design and materials can be implemented. The first part of the effort consisted of a strain gage alloy development program which will be followed by an investigation of complete strain gage systems which will use the best of the alloys developed together with other system improvements.

Hulse, C.↗