Electronic and Simple Oscillatory Conduction in Ferrite Gas Sensors: Gas-Sensing Mechanisms, Long-Term Gas Monitoring, Heat Transfer, and Other Anomalies.

Abstract

The early detection and warning of the presence of hazardous gases have been well studied. We present a study that focuses on some fundamental properties of gas sensors for liquefied petroleum gas (LPG) using spinel nanoferrites, namely, CoSm0.1Fe1.9O4, CoCe0.1Fe1.9O4, MgCe0.1Fe1.9O4, and MgFe2O4. A highly sensitive and selective response of 846.34 at 225 °C toward 10,000 ppm concentration of LPG was recorded. Other flammable gases tested were hydrogen, methane, propane, and butane. Electronic conduction of LPG sensors near saturation showed simple electrical oscillations that can be attributed to the self-dissociation of water molecules physically adsorbed on the surface of the chemisorbed oxygen species due to proton transfer. The oscillatory behaviors follow fluctuations in the operating temperature attributed to heat transfer between the physisorbed water molecules and the hot sensor surface. This depends on the LPG concentration because higher LPG concentration gives rise to greater heat transfer from the sensors. The adsorption and desorption of these water molecule multilayers take a few hundreds of seconds at low concentrations, while the adsorption formation process takes longer at higher concentrations. Other parameters such as LPG exposure time, bias voltage, relative humidity, ambient conditions, operating temperatures, and temperature of the gas not only affect electrical oscillations and thermal fluctuations but also switch the dominant charge carriers from p- to n-type or vice versa. The type of sensor surface, either p- or n-type, did not appear to affect the oscillatory behavior, while the exposure time, short or long, determined the appearance and further behavior of the oscillations. The long-time exposure to 10,000 ppm concentration resulted in the resistance gradually decreasing due to the lack of oxygen supply, while at 5000 ppm, this was constant, stable, and oscillated indefinitely. Changing the dry air to argon gas as a carrier and for dilution of the hazardous gas prevented the electrical oscillations and thermal fluctuations and significantly lowered the response values. Both the inert ambient (argon gas) and changing operating temperature flipped the dominant charge carriers of these sensors. The concentration of these chemisorbed oxygen species governs the charge space and depletion layers. In addition, the spinel nanoferrites used contained higher oxygen vacancies than the lattice oxygen and chemisorbed oxygen. When using dry air, the oscillations were observed at 3000 ppm concentration, while using argon gas, they were observed at 7000 ppm concentration. The room-temperature LPG responses were about 35 and 80 under 45% relative humidity using dry air and argon gas, respectively. These room-temperature measurements showed electrical oscillations but did not show any thermal fluctuations or heat transfer phenomena. This study presents a deeper insight into the fundamentals of gas-sensing mechanisms and energy costs involved.