Jacobus H. Visser

CO/HC sensors based on thin films of LaCoO3 and La0.8Sr0.2CoO3−δ metal oxides

Abstract We have demonstrated a new type of mixed potential, zirconia-based sensor that utilizes dense, thin films of either La–Sr–Co–O or La–Co–O perovskite transition metal oxide vs. a Au counter electrode to generate an EMF that is proportional to the oxidizable gas species (carbon monoxide (CO), C3H6, and C3H8) concentration in a gas stream containing oxygen. The devices reported in this work were tested at 600°C and 700°C and in gas mixtures containing 0.1% to 20% O2 concentrations. The metal-oxide-based sensors exhibited an improvement in operating temperature and level stability at elevated temperatures compared to Au–zirconia–Pt mixed potential devices already reported in the literature. However, as with Au–zirconia–Pt devices previously reported, the response behavior reproducibility from device to device was dependent on the Au morphology, which could vary significantly between samples under identical thermal histories. The changing Au morphology on both the Au counter electrode and the Au current collector on the metal oxide electrode were responsible for sensor aging and changes in device response over time. No change in the crystal structure of the perovskite thin film could be seen from XRD. A significant hysteresis in sensor response was found as the background oxygen concentration was cycled through stoichiometry, and this may be attributed to a change in the oxidation state of the cobaltate-based metal oxide electrode. In an effort to mitigate device aging, we replaced the Au counter electrode with a second metal oxide thin film, doped LaMnO3, and demonstrated the operation of a mixed potential sensor based on dual metal oxide electrodes.

Development of ceramic mixed potential sensors for automotive applications

Mixed potential sensors that utilize Gd{sub 0.2}Ce{sub 0.8}O{sub 2} electrolytes and patterned dense 1 {micro}m-thick LaMnO{sub 3} thin films were studied at 600 C and 1%O{sub 2}. The response to C{sub 3}H{sub 6} and CO of two different sensor configurations were studied continuously for 1000 hrs versus an air reference. Although two different current collection schemes and two different metal oxide electrode geometries were employed, the magnitude of the mixed potential generated by both sensors was remarkably similar. From previous work with Au-ceria-Pt mixed potential sensors, this behavior is attributed to precisely controlling the metal oxide electrode/solid electrolyte interface unlike the random interface produced when Au electrodes are used. Although doped ceria is not a suitable electrolyte for automotive exhaust gas applications, this work serves to illustrate design goals for zirconia-based sensors.

Using a MISiC-FET sensor for detecting NH/sub 3/ in SCR systems

One way to decrease the emitted levels of NO/sub x/ from diesel engines is to add NH/sub 3/ in the form of urea to the exhausts after combustion. NH/sub 3/ will react with NO/sub x/ in the catalytic converter to form N/sub 2/ and water, which is called selective catalytic reduction (SCR). The amount of NH/sub 3/ added may be regulated through closed-loop control by using an NH/sub 3/ sensor. The metal-insulator silicon-carbide field-effect transistor (MISiC-FET) sensor has previously been tested for this application and has been shown to be sensitive to NH/sub 3/. Here, the sensors have been further studied in engine SCR systems. Tests on the cross sensitivity to N/sub 2/O and NO/sub 2/, and studies concerning the influence of water vapor have been performed in the laboratory. The difference between Ir and Pt films, with regard to catalytic activity, has also been investigated. The sensors were found to be sensitive to NH/sub 3/ in diesel engine exhausts. The addition of urea was computer controlled, which made it possible to add NH/sub 3/ in a stair-like fashion to the system and detect it with the MISiC-FET sensors. The presence of water vapor was shown to have the largest effect on the sensors at low levels and the NH/sub 3/ response was slightly decreased by a background level of NO/sub 2/.

Dual mode NOx sensor: measuring both the accumulated amount and instantaneous level at low concentrations.

The accumulating-type (or integrating-type) NOx sensor principle offers two operation modes to measure low levels of NOx: The direct signal gives the total amount dosed over a time interval and its derivative the instantaneous concentration. With a linear sensor response, no baseline drift, and both response times and recovery times in the range of the gas exchange time of the test bench (5 to 7 s), the integrating sensor is well suited to reliably detect low levels of NOx. Experimental results are presented demonstrating the sensor’s integrating properties for the total amount detection and its sensitivity to both NO and to NO2. We also show the correlation between the derivative of the sensor signal and the known gas concentration. The long-term detection of NOx in the sub-ppm range (e.g., for air quality measurements) is discussed. Additionally, a self-adaption of the measurement range taking advantage of the temperature dependency of the sensitivity is addressed.

A Potential Soot Mass Determination Method from Resistivity Measurement of Thermophoretically Deposited Soot

Miniaturized detection systems for nanometer-sized airborne particles are in demand, for example in applications for onboard diagnostics downstream particulate filters in modern diesel engines. A soot sensor based on resistivity measurements was developed and characterized. This involved generation of soot particles using a quenched co-flow diffusion flame; depositing the particles onto a sensor substrate using thermophoresis and particle detection using a finger electrode structure, patterned on thermally oxidized silicon substrate. The generated soot particles were characterized using techniques including Scanning Mobility Particle Sizer for mobility size distributions, Differential Mobility Analyzer—Aerosol Particle Mass analyzer for the mass–mobility relationship, and Transmission Electron Microscopy for morphology. The generated particles were similar to particles from diesel engines in concentration, mobility size distribution, and mass fractal dimension. The primary particle size, effective density and organic mass fraction were slightly lower than values reported for diesel engines. The response measured with the sensors was largely dependent on particle mass concentration, but increased with increasing soot aggregate mobility size. Detection down to cumulative mass as small as 20–30 μg has been demonstrated. The detection limit can be improved by using a more sensitive resistance meter, modified deposition cell, larger flow rates of soot aerosol and modifying the sensor surface.

Chemical and physical sensors based on oxygen pumping with solid-state electrochemical cells

Abstract Oxygen sensors based on ZrO 2 electrochemical cells have found extensive use in many applications. The most sensitive of these sensors employ the oxygen-pumping principle with ZrO 2 cells. Oxygen pumping, however, can also be used to generate other chemical and also physical sensors. This paper discusses several of these sensors, e.g., sensors for measuring CO, H 2 , H 2 O, hydrocarbons, gas flow, and gas pressure, and presents results from studies of the properties of some of these devices.

Sensors for measuring combustibles in the absence of oxygen

Calorimetric and semiconductor types of sensors for combustibles generally require the presence of oxygen in the measurement gas. This paper describes sensors incorporating at least one ZrO2 electrochemical cell together with a combustibles-sensing element that are capable of measuring combustibles even in the absence of oxygen. The ZrO2 cell is used as an oxygen pump to introduce into the sensor structure the amount of oxygen necessary for the proper operation of the sensing element. Devices of this type can also be used to determine the composition of simple fuel mixtures. Results of experimental investigation of these devices concepts are presented.

The Effect of the Thickness of the Sensitive Layer on the Performance of the Accumulating NOx Sensor

A novel and promising method to measure low levels of NOx utilizes the accumulating sensor principle. During an integration cycle, incoming NOx molecules are stored in a sensitive layer based on an automotive lean NOx trap (LNT) material that changes its electrical resistivity proportional to the amount of stored NOx, making the sensor suitable for long-term detection of low levels of NOx. In this study, the influence of the thickness of the sensitive layer, prepared by multiple screen-printing, is investigated. All samples show good accumulating sensing properties for both NO and NO2. In accordance to a simplified model, the base resistance of the sensitive layer and the sensitivity to NOx decrease with increasing thickness. Contrarily, the sensor response time increases. The linear measurement range of all samples ends at a sensor response of about 30% resulting in an increase of the linearly detectable amount with the thickness. Hence, the variation of the thickness of the sensitive layer is a powerful tool to adapt the linear measurement range (proportional to the thickness) as well as the sensitivity (proportional to the inverse thickness) to the application requirements. Calculations combining the sensor model with the measurement results indicate that for operation in the linear range, about 3% of the LNT material is converted to nitrate.

MISiCFET chemical sensors for applications in exhaust gases and flue gases

A chemical gas sensor based on a silicon carbide field effect transistor with a catalytic gate metal has been under development for a number of years. The choice of silicon carbide as the semiconductor material allows the sensor to operate at high temperatures, for more than 6 months in flue gases at 300degreesC and for at least three days at 700degreesC. The chemical inertness of silicon carbide and a buried gate design makes it a suitable sensor technology for applications in corrosive environments such as exhaust gases and flue gases from boilers. The selectivity of the sensor devices is established through the choice of type and structure of the gate metal as well as the operation temperature. In this way NH3 sensors with low cross sensitivity to NOx have been demonstrated as potential sensors for control of selective catalytic reduction (SCR) of NOx by urea injection into diesel exhausts. Here we show that sensors with a porous platinum or iridium gate show different temperature ranges for NH3 detection. The hardness of the silicon carbide makes it for example more resistant to water splash at cold start of a petrol engine than existing technologies, and a sensor which can control the air to fuel ratio, before the exhaust gases are heated, has been demonstrated. Silicon carbide sensors are also tested in flue gases from boilers. Efficient regulation of the combustion in a boiler will decrease fuel consumption and reduce emissions.

Dosimeter-Type NOx Sensing Properties of KMnO4 and Its Electrical Conductivity during Temperature Programmed Desorption

An impedimetric NOx dosimeter based on the NOx sorption material KMnO4 is proposed. In addition to its application as a low level NOx dosimeter, KMnO4 shows potential as a precious metal free lean NOx trap material (LNT) for NOx storage catalysts (NSC) enabling electrical in-situ diagnostics. With this dosimeter, low levels of NO and NO2 exposure can be detected electrically as instantaneous values at 380 °C by progressive NOx accumulation in the KMnO4 based sensitive layer. The linear NOx sensing characteristics are recovered periodically by heating to 650 °C or switching to rich atmospheres. Further insight into the NOx sorption-dependent conductivity of the KMnO4-based material is obtained by the novel eTPD method that combines electrical characterization with classical temperature programmed desorption (TPD). The NOx loading amount increases proportionally to the NOx exposure time at sorption temperature. The cumulated NOx exposure, as well as the corresponding NOx loading state, can be detected linearly by electrical means in two modes: (1) time-continuously during the sorption interval including NOx concentration information from the signal derivative or (2) during the short-term thermal NOx release.