Dielectric Properties of Materials Used for Microwave-Based NOx Gas Dosimeters.

Nitrogen oxides (NOx), primarily generated from combustion processes, pose significant health and environmental risks. To improve the coordination of measures against excessive NOx emissions, it is necessary to effectively monitor ambient NOx concentrations, which requires the development of precise and cost-efficient detection methods. This study focuses on developing a microwave- or radio frequency (RF)-based gas dosimeter for NOx detection and addresses the optimization of the dosimeter design by examining the dielectric properties of LTCC-based (Low-Temperature Co-fired Ceramics) sensor substrates and barium-based NOx storage materials. The measurements taken utilizing the Microwave Cavity Perturbation (MCP) method revealed that these materials exhibit more pronounced changes in dielectric losses when storing NOx at elevated temperatures. Consequently, operating such a dosimeter at high temperatures (above 300 °C) is recommended to maximize the sensor signal. To evaluate their high-temperature applicability, LTCC substrates were analyzed by measuring their dielectric losses at temperatures up to 600 °C. In terms of NOx storage materials, coating barium on high-surface-area alumina resolved issues related to limited NOx adsorption in pure barium carbonate powders. Additionally, the adsorption of both NO and NO2 was enabled by the application of a platinum catalyst. The change in dielectric losses, which provides the main signal for an RF-based gas dosimeter, only depends on the stored amount of NOx and not on the specific type of nitrogen oxide. Although the change in dielectric losses increases with the temperature, the maximum storage capacity of the material decreases significantly. In addition, at temperatures above 350 °C, NOx is mostly weakly bound, so it will desorb in the absence of NOx. Therefore, in the future development of a reliable RF-based NOx dosimeter, the trade-off between the sensor signal strength and adsorption behavior must be addressed.

Revealing the Deposition Mechanism of the Powder Aerosol Deposition Method Using Ceramic Oxide Core-Shell Particles.

The powder aerosol deposition (PAD) method is a process to manufacture ceramic films completely at room temperature. Since the first reports by Akedo in the late 1990s, much research has been conducted to reveal the exact mechanism of the deposition process. However, it is still not fully understood. This work tackles this challenge using core-shell particles. Two coated oxides, Al2 O3 core with a SiO2 shell and LiNi0.6 Mn0.2 Co0.2 O2 core with a LiNbO3 shell, are investigated. Initially, the element ratios Al:Si and Ni:Nb of the powder are determined by energy-dispersive X-ray spectroscopy (EDX). In a second step, the change in the element ratios of Al:Si and Ni:Nb after deposition is investigated. The element ratios from powder to film strongly shift toward the shell elements, indicating that the particles fracture and only the outer parts of the particles are deposited. In the last step, this work investigates cross-sections of the deposited films with scanning transmission electron microscopy (STEM combined with EDX and an energy-selective back-scattered electron (EsB) detector to unveil the element distribution within the film itself. Therefore, the following overall picture emerges: particles impact on the substrate or on previously deposited particle, fracture, and only a small part of the impacting particles that originate from the outer part of the impacting particle gets deposited.

Resistive Multi-Gas Sensor for Simultaneously Measuring the Oxygen Stoichiometry (λ) and the NOx Concentration in Exhausts: Engine Tests under Dynamic Conditions.

Due to increasingly stringent limits for NOx emissions, there is now more interest than ever in cost-effective, precise, and durable exhaust gas sensor technology for combustion processes. This study presents a novel multi-gas sensor with resistive sensing principles for the determination of oxygen stoichiometry and NOx concentration in the exhaust gas of a diesel engine (OM 651). A screen-printed porous KMnO4/La-Al2O3 film is used as the NOx sensitive film, while a dense ceramic BFAT (BaFe0.74Ta0.25Al0.01O3-δ) film prepared by the PAD method is used for λ-measurement in real exhaust gas. The latter is also used to correct the O2 cross-sensitivity of the NOx sensitive film. This study presents results under dynamic conditions during an NEDC (new European driving cycle) based on a prior characterization of the sensor films in an isolated sensor chamber with static engine operation. The low-cost sensor is analyzed in a wide operation field and its potential for real exhaust gas applications is evaluated. The results are promising and, all in all, comparable with established, but usually more expensive, exhaust gas sensors.

What Happens during Thermal Post-Treatment of Powder Aerosol Deposited Functional Ceramic Films? Explanations Based on an Experiment-Enhanced Literature Survey.

Powder aerosol deposition (PAD) is a unique ceramic spray coating method that produces dense and well-adhering thick-films directly at room temperature, without requiring any heating or sintering. After the successful film formation, mechanical film properties like hardness or plasma resistance are remarkably good. However, when it comes to electrical properties like permittivity or electrical conductivity, the nanocrystalline structure of PAD films combined with high internal strains deteriorates partly the characteristic properties. The electrical conductivity may already be present within the as-deposited films. However, it is mostly lowered by several orders of magnitude. Therefore, a thermal post-deposition annealing is oftentimes required. In this work, electrically conducting films produced by powder aerosol deposition are surveyed based on published data. Their microstructural and electrical behavior during the post-deposition annealing treatment is summarized and reasons for the lowered electrical conductivity are identified. Additionally, the processes taking place during annealing, which eventually allow to regain bulk-like functional properties, are examined. A universal annealing behavior is found that leads to a quantitative recommendation for the suitable film annealing temperatures to regain the electrical conductivities.

Novel Method for NTC Thermistor Production by Aerosol Co-Deposition and Combined Sintering.

A novel three-stage process to produce NTCR sensors is presented. In this process, an uncalcined powder mixture of NiO and Mn2O3 was deposited onto an alumina substrate via aerosol co-deposition (AcD). Then, an electrode structure was screen-printed onto the surface and the composite film was sintered in a multifunctional temperature treatment. Thereby, the sintering of the electrode, the formation of the NiMn2O4 spinel and the removal of film strains took place simultaneously. This enabled a significant reduction in energy demand and workload. The manufactured sensors, both as first prototypes, as well as miniaturized chip components, were characterized by a single-phase cubic NiMn2O4 spinel structure, mechanical stability and electrical properties that were similar to those of classical NiMn2O4 bulk ceramics or tempered aerosol deposited (AD) NiMn2O4 films. Particularly noteworthy was the high reproducibility and low variation of the NTCR parameters, such as the specific resistivity at 25 °C ρ25, the electrical resistance at 25 °C R25 and the thermistor constant B. The NTCR parameters were as aging-stable as for NiMn2O4 bulk ceramics or tempered NiMn2O4 AD-films and could even be further improved by thermal post-treatment.

Manufacturing Dense Thick Films of Lunar Regolith Simulant EAC-1 at Room Temperature.

The Aerosol Deposition (AD, also known as gas kinetic spraying or vacuum deposition) method is a rather novel coating process to produce dense thick films directly from dry ceramic (or metal) powders on a variety of substrates without any heat treatment. Because of the similarity of the up to now used powders and lunar regolith, it is imaginable to use AD systems for future in situ resource utilization missions on the Moon planned by several space agencies. To test the feasibility of such an endeavor, the processability of lunar mare simulant EAC-1 by the AD method has been examined in this study. Three regolith films with an area of 25 × 10 mm², and thicknesses between 2.50 µm and 5.36 µm have been deposited on steel substrates using a standard AD setup. Deposited films have been investigated by Laser Scanning Microscopy (LSM) and Scanning Electron Microscopy (SEM). Moreover, the roughness and Vickers hardness of the deposited films and the underlying substrates have been measured. It has been shown that dense consolidated films of regolith simulant can be produced within minutes by AD. The deposited films show a higher roughness and, on average, a higher hardness than the steel substrates. Since on the Moon, naturally available regolith powders are abundant and very dry, and since the required process vacuum is available, AD appears to be a very promising method for producing dense coatings in future Moon exploration and utilization missions.

Thermal Treatment of Aerosol Deposited NiMn2O4 NTC Thermistors for Improved Aging Stability.

This paper examines the influence of a short-term thermal treatment of aerosol deposited negative temperature coefficient (NTC) thermistor films on the NTCR characteristics and their long-term stability with different electrode materials. An aerosol deposition of a spinel-based NiMn2O4 powder on alumina substrates with screen-printed AgPd and Au interdigital electrode structures was performed. The manufactured components of the typical size of 1206 were tempered in a moderate temperature range of 200 °C to 800 °C and aged for 1000 h at 125 °C in air. Based on R-T measurements in a high-precision silicone oil thermostat bath and high temperature XRD analyses, the influence of the thermal treatment was analyzed and discussed. A 60-min tempering at 400 °C proved to be optimal, as both the NTCR parameters and their ageing stability could be significantly improved. The findings are explained.

Conductometric Soot Sensors: Internally Caused Thermophoresis as an Important Undesired Side Effect.

Particulate matter sensors are of interest for application in the exhaust of any combustion processes, especially for automotive aftertreatment systems. Conductometric soot sensors have been serialized recently. They comprise planar interdigital electrodes (IDE) on an insulating substrate. Between the IDEs, a voltage is applied. Soot deposition is accelerated by the resulting electric field due to electrophoresis. With increasing soot deposition, the conductance between the IDE increases. The timely derivative of the conductance can serve as a sensor signal, being a function of the deposition rate. An increasing voltage between the IDE would be useful for detecting low particle exhausts. In the present study, the influence of the applied voltage and the sensor temperature on the soot deposition is investigated. It turned out that the maximum voltage is limited, since the soot film is heated by the resulting current. An internally caused thermophoresis that reduces the rate of soot deposition on the substrate follows. It reduces both the linearity of the response and the sensitivity. These findings may be helpful for the further development of conductometric soot sensors for automotive exhausts, probably also to determine real driving emissions of particulate matter.

Annealing of Gadolinium-Doped Ceria (GDC) Films Produced by the Aerosol Deposition Method.

Solid oxide fuel cells need a diffusion barrier layer to protect the zirconia-based electrolyte if a cobalt-containing cathode material like lanthanum strontium cobalt ferrite (LSCF) is used. This protective layer must prevent the direct contact and interdiffusion of both components while still retaining the oxygen ion transport. Gadolinium-doped ceria (GDC) meets these requirements. However, for a favorable cell performance, oxide ion conducting films that are thin yet dense are required. Films with a thickness in the sub-micrometer to micrometer range were produced by the dry room temperature spray-coating technique, aerosol deposition. Since commercially available GDC powders are usually optimized for the sintering of screen printed films or pressed bulk samples, their particle morphology is nanocrystalline with a high surface area that is not suitable for aerosol deposition. Therefore, different thermal and mechanical powder pretreatment procedures were investigated and linked to the morphology and integrity of the sprayed films. Only if a suitable pretreatment was conducted, dense and well-adhering GDC films were deposited. Otherwise, low-strength films were formed. The ionic conductivity of the resulting dense films was characterized by impedance spectroscopy between 300 °C and 1000 °C upon heating and cooling. A mild annealing occurred up to 900 °C during first heating that slightly increased the electric conductivity of GDC films formed by aerosol deposition.

Planar Microstrip Ring Resonators for Microwave-Based Gas Sensing: Design Aspects and Initial Transducers for Humidity and Ammonia Sensing.

A planar microstrip ring resonator structure on alumina was developed using the commercial FEM software COMSOL. Design parameters were evaluated, eventually leading to an optimized design of a miniaturized microwave gas sensor. The sensor was covered with a zeolite film. The device was successfully operated at around 8.5 GHz at room temperature as a humidity sensor. In the next step, an additional planar heater will be included on the reverse side of the resonator structure to allow for testing of gas-sensitive materials under sensor conditions.

Pulsed Polarization-Based NOx Sensors of YSZ Films Produced by the Aerosol Deposition Method and by Screen-Printing.

The pulsed polarization technique on solid electrolytes is based on alternating potential pulses interrupted by self-discharge pauses. Since even small concentrations of nitrogen oxides (NOx) in the ppm range significantly change the polarization and discharge behavior, pulsed polarization sensors are well suited to measure low amounts of NOx. In contrast to all previous investigations, planar pulsed polarization sensors were built using an electrolyte thick film and platinum interdigital electrodes on alumina substrates. Two different sensor layouts were investigated, the first with buried Pt electrodes under the electrolyte and the second one with conventional overlying Pt electrodes. Electrolyte thick films were either formed by aerosol deposition or by screen-printing, therefore exhibiting a dense or porous microstructure, respectively. For screen-printed electrolytes, the influence of the electrolyte resistance on the NOx sensing ability was investigated as well. Sensors with buried electrodes showed little to no response even at higher NOx concentrations, in good agreement with the intended sensor mechanism. Electrolyte films with overlying electrodes, however, allowed the quantitative detection of NOx. In particular, aerosol deposited electrolytes exhibited high sensitivities with a sensor output signal ΔU of 50 mV and 75 mV for 3 ppm of NO and NO2, respectively. For screen-printed electrolytes, a clear trend indicated a decrease in sensitivity with increased electrolyte resistance.

Metal-organic frameworks for sensing applications in the gas phase.

Several metal-organic framework (MOF) materials were under investigated to test their applicability as sensor materials for impedimetric gas sensors. The materials were tested in a temperature range of 120 °C - 240 °C with varying concentrations of O(2), CO(2), C(3)H(8), NO, H(2), ethanol and methanol in the gas atmosphere and under different test gas humidity conditions. Different sensor configurations were studied in a frequency range of 1 Hz -1 MHz and time-continuous measurements were performed at 1 Hz. The materials did not show any impedance response to O(2), CO(2), C(3)H(8), NO, or H(2) in the gas atmospheres, although for some materials a significant impedance decrease was induced by a change of the ethanol or methanol concentration in the gas phase. Moreover, pronounced promising and reversible changes in the electric properties of a special MOF material were monitored under varying humidity, with a linear response curve at 120 °C. Further investigations were carried out with differently doped MOF materials of this class, to evaluate the influence of special dopants on the sensor effect.

CO2 Selective Potentiometric Sensor in Thick-film Technology.

A potentiometric sensor device based on screen-printed Nasicon films was investigated. In order to transfer the promising sensor concept of an open sodium titanate reference to thick film technology, "sodium-rich" and "sodium-poor" formulations were compared. While the "sodium-rich" composition was found to react with the ion conducting Nasicon during thermal treatment, the "sodium-poor" reference mixture was identified as an appropriate reference composition. Screen-printed sensor devices were prepared and tested with respect to CO2 response, reproducibility, and cross-interference of oxygen. Excellent agreement with the theory was observed. With the integration of a screen-printed heater, sensor elements were operated actively heated in a cold gas stream.