On the Influence of Humidity on a Thermal Conductivity Sensor for the Detection of Hydrogen.

Thermal conductivity sensors face an omnipresent cross-influence through varying humidity levels in real-life applications. We present the results of investigations on the influence of humidity on a hydrogen thermal conductivity sensor and approaches for predicting the behavior of thermal conductivity towards humidity. A literature search and comparison of different mixing equations for binary gas mixtures were carried out. The theoretical results were compared with experimental results from three different thermal conductivity sensors with mixtures of water vapor in nitrogen. The mixing equations show a large discrepancy between each other. Some of the models predict a continuously decreasing thermal conductivity and some predict an increasing thermal conductivity for increasing levels of humidity. Our measurements indicate an increase in thermal conductivity followed by a decrease after reaching a peak value. It is shown that the measured behavior is reproducible with different sensors. Depending on the sensor, this corresponds to an error up to 2 vol.% in the measured hydrogen value. The measured behavior is consistent with only one of the three models. Compared to this model, our own sensor shows a maximum deviation of 1.4%. Mixing equations for gas mixtures must be chosen carefully, taking into consideration whether mixing partners include polar or non-polar molecules. Some simplified mixing equations cannot be used to calculate the thermal conductivity of water vapor in air or nitrogen.

Co3O4-Based Materials as Potential Catalysts for Methane Detection in Catalytic Gas Sensors.

The present work deals with the development of Co3O4-based catalysts for potential application in catalytic gas sensors for methane (CH4) detection. Among the transition-metal oxide catalysts, Co3O4 exhibits the highest activity in catalytic combustion. Doping Co3O4 with another metal can further improve its catalytic performance. Despite their promising properties, Co3O4 materials have rarely been tested for use in catalytic gas sensors. In our study, the influence of catalyst morphology and Ni doping on the catalytic activity and thermal stability of Co3O4-based catalysts was analyzed by differential calorimetry by measuring the thermal response to 1% CH4. The morphology of two Co3O4 catalysts and two NixCo3-xO4 with a Ni:Co molar ratio of 1:2 and 1:5 was studied using scanning transmission electron microscopy and energy dispersive X-ray analysis. The catalysts were synthesized by (co)precipitation with KOH solution. The investigations showed that Ni doping can improve the catalytic activity of Co3O4 catalysts. The thermal response of Ni-doped catalysts was increased by more than 20% at 400 °C and 450 °C compared to one of the studied Co3O4 oxides. However, the thermal response of the other Co3O4 was even higher than that of NixCo3-xO4 catalysts (8% at 400 °C). Furthermore, the modification of Co3O4 with Ni simultaneously brings stability problems at higher operating temperatures (≥400 °C) due to the observed inhomogeneous Ni distribution in the structure of NixCo3-xO4. In particular, the NixCo3-xO4 with high Ni content (Ni:Co ratio 1:2) showed apparent NiO separation and thus a strong decrease in thermal response of 8% after 24 h of heat treatment at 400 °C. The reaction of the Co3O4 catalysts remained quite stable. Therefore, controlling the structure and morphology of Co3O4 achieved more promising results, demonstrating its applicability as a catalyst for gas sensing.

Towards a Miniaturized Photoacoustic Sensor for Transcutaneous CO2 Monitoring.

A photoacoustic sensor system (PAS) intended for carbon dioxide (CO2) blood gas detection is presented. The development focuses on a photoacoustic (PA) sensor based on the so-called two-chamber principle, i.e., comprising a measuring cell and a detection chamber. The aim is the reliable continuous monitoring of transcutaneous CO2 values, which is very important, for example, in intensive care unit patient monitoring. An infrared light-emitting diode (LED) with an emission peak wavelength at 4.3 µm was used as a light source. A micro-electro-mechanical system (MEMS) microphone and the target gas CO2 are inside a hermetically sealed detection chamber for selective target gas detection. Based on conducted simulations and measurement results in a laboratory setup, a miniaturized PA CO2 sensor with an absorption path length of 2.0 mm and a diameter of 3.0 mm was developed for the investigation of cross-sensitivities, detection limit, and signal stability and was compared to a commercial infrared CO2 sensor with a similar measurement range. The achieved detection limit of the presented PA CO2 sensor during laboratory tests is 1 vol. % CO2. Compared to the commercial sensor, our PA sensor showed less influences of humidity and oxygen on the detected signal and a faster response and recovery time. Finally, the developed sensor system was fixed to the skin of a test person, and an arterialization time of 181 min could be determined.

A Portable Laser Spectroscopic System for Measuring Nitrous Oxide Emissions on Fertilized Cropland.

Nitrous oxide (laughing gas, N2O) is a relevant greenhouse gas. Agriculture contributes significantly to its emissions. As nitrogen fertilization has been identified as one of the main sources of N2O, controlled application and reduction of the amount of fertilizer adapted to crop demand is essential to reduce N2O emissions. This requires detailed studies of the local distribution of the N2O emission fluxes on different croplands. Consequently, frequent spatially resolved field measurements of N2O concentrations are needed. A precision in the ppb range close to the ambient N2O level of 333 ppb is necessary. Tunable laser absorption spectroscopy using quantum-cascade lasers (QCL) as a light source is an established technique for the measurement of N2O traces. We present the development and validation of a compact portable setup for on-site measurement of N2O emissions from the soil. The setup differs from previous solutions by using an interband cascade laser (ICL), which has significantly lower power consumption compared to a QCL. The portable measurement setup allows N2O emission fluxes to be determined with a precision of 3.5% with a measuring duration of 10 min. The developed system enables the detection of increased N2O emissions because of the fertilization of fields. High N2O emission fluxes are indicators of the overfertilization of the field. Directly after fertilization, N2O fluxes between 2.9 and 5.3 µL m-2 min-1 depending on the gas acquisition site are measured during the field tests. Over time, the fluxes decrease. The obtained results compare well with data from more precise but also more complex and maintenance-intensive instruments for atmospheric research. With this system, the soil moisture as well as the air humidity and air temperature are recorded. Strong influences on N2O fluxes by soil moisture were observed. The presented measurement system is a contribution to the establishment of mobile N2O screening systems that are robust in the field and suitable for comprehensive and routine detection of N2O emissions from soil.

Detection of SO2F2 Using a Photoacoustic Two-Chamber Approach.

The wide use of sulfuryl difluoride (SO2F2) for termite control in buildings, warehouses and shipping containers requires the implementation of suitable sensors for reliable detection. SO2F2 is highly toxic to humans and the environment, and moreover, it is a potent greenhouse gas. We developed two photoacoustic two-chamber sensors with the aim to detect two different concentration ranges, 0-1 vol.-% SO2F2 and 0-100 ppm SO2F2, so that different applications can be targeted: the sensor for high concentrations for the effective treatment of buildings, containers, etc., and the sensor for low concentrations as personal safety device. Photoacoustic detectors were designed, fabricated, and then filled with either pure SO2F2 or pure substituent gas, the refrigerant R227ea, to detect SO2F2. Absorption cells with optical path lengths of 50 mm and 1.6 m were built for both concentration ranges. The sensitivity to SO2F2 as well as cross-sensitivities to CO2 and H2O were measured. The results show that concentrations below 1 ppm SO2F2 can be reliably detected, and possible cross-sensitivities can be effectively compensated.

Rapid Quantitative Analysis of IR Absorption Spectra for Trace Gas Detection by Artificial Neural Networks Trained with Synthetic Data.

Infrared absorption spectroscopy is a widely used tool to quantify and monitor compositions of gases. The concentration information is often retrieved by fitting absorption profiles to the acquired spectra, utilizing spectroscopic databases. In complex gas matrices an expanded parameter space leads to long computation times of the fitting routines due to the increased number of spectral features that need to be computed for each iteration during the fit. This hinders the capability of real-time analysis of the gas matrix. Here, an artificial neural network (ANN) is employed for rapid prediction of gas concentrations in complex infrared absorption spectra composed of mixtures of CO and N2O. Experimental data is acquired with a mid-infrared dual frequency comb spectrometer. To circumvent the experimental collection of huge amounts of training data, the network is trained on synthetically generated spectra. The spectra are based on simulated absorption profiles making use of the HITRAN database. In addition, the spectrometer's influence on the measured spectra is characterized and included in the synthetic training data generation. The ANN was tested on measured spectra and compared to a non-linear least squares fitting algorithm. An average evaluation time of 303 µs for a single measured spectrum was achieved. Coefficients of determination were 0.99997 for the predictions of N2O concentrations and 0.99987 for the predictions of CO concentrations, with uncertainties on the predicted concentrations between 0.04 and 0.18 ppm for 0 to 100 ppm N2O and between 0.05 and 0.18 ppm for 0 to 60 ppm CO.

Homogeneity Measurements of Li-Ion Battery Cathodes Using Laser-Induced Breakdown Spectroscopy.

We study the capability of nanosecond laser-induced breakdown spectroscopy (ns-LIBS) for depth-resolved concentration measurements of Li-Ion battery cathodes. With our system, which is optimized for quality control applications in the production line, we pursue the goal to unveil manufacturing faults and irregularities during the production process of cathodes as early as possible. Femtosecond laser-induced breakdown spectroscopy (fs-LIBS) is widely considered to be better suited for depth-resolved element analysis. Nevertheless, the small size and intensity of the plasma plume, non-thermal energy distribution in the plasma and high investment costs of fs-LIBS make ns-LIBS more attractive for inline application in the industrial surrounding. The system, presented here for the first time, is able to record quasi-depth-resolved relative concentration profiles for carbon, nickel, manganese, cobalt, lithium and aluminum which are the typical elements used in the binder/conductive additive, the active cathode material and the current collector. LIBS often causes high variations in signal intensity from pulse to pulse, so concentration determination is, in general, conducted on the average of many pulses. We show that the spot-to-spot variations we measure are governed by the microstructure of the cathode foil and are not an expression of the limited precision of the LIBS setup.

Towards a Miniaturized Photoacoustic Detector for the Infrared Spectroscopic Analysis of SO2F2 and Refrigerants.

Sulfuryl fluoride (SO2F2) is a toxic and potent greenhouse gas that is currently widely used as a fumigant insecticide in houses, food, and shipping containers. Though it poses a major hazard to humans, its detection is still carried out manually and only on a random basis. In this paper, we present a two-chamber photoacoustic approach for continuous SO2F2 sensing. Because of the high toxicity of SO2F2, the concept is to use a non-toxic substituent gas with similar absorption characteristics in the photoacoustic detector chamber, i.e., to measure SO2F2 indirectly. The refrigerants R227ea, R125, R134a, and propene were identified as possible substituents using a Fourier-transform infrared (FTIR) spectroscopic analysis. The resulting infrared spectra were used to simulate the sensitivity of the substituents of a photoacoustic sensor to SO2F2 in different concentration ranges and at different optical path lengths. The simulations showed that R227ea has the highest sensitivity to SO2F2 among the substituents and is therefore a promising substituent detector gas. Simulations concerning the possible cross-sensitivity of the photoacoustic detectors to H2O and CO2 were also performed. These results are the first step towards the development of a miniaturized, sensitive, and cost-effective photoacoustic sensor system for SO2F2.

Anodically Bonded Photoacoustic Transducer: An Approach towards Wafer-Level Optical Gas Sensors.

We present a concept for a wafer-level manufactured photoacoustic transducer, suitable to be used in consumer-grade gas sensors. The transducer consists of an anodically bonded two-layer stack of a blank silicon wafer and an 11 µm membrane, which was wet-etched from a borosilicate wafer. The membrane separates two cavities; one of which was hermetically sealed and filled with CO2 during the anodic bonding and acts as an infrared absorber. The second cavity was designed to be connected to a standard MEMS microphone on PCB-level forming an infrared-sensitive photoacoustic detector. CO2 sensors consisting of the detector and a MEMS infrared emitter were built up and characterized towards their sensitivity and noise levels at six different component distance ranging from 3.0 mm to 15.5 mm. The signal response for the sample with the longest absorption path ranged from a decrease of 8.3% at a CO2 concentration of 9400 ppm to a decrease of 0.8% at a concentration of 560 ppm. A standard deviation of the measured values of 18 ppm was determined when the sensor was exposed to 1000 ppm CO2.

Tunable dual-comb spectrometer for mid-infrared trace gas analysis from 3 to 4.7†µm.

Dual-frequency comb spectroscopy has emerged as a disruptive technique for measuring wide-spanning spectra with high resolution, yielding a particularly powerful technique for sensitive multi-component gas analysis. We present a spectrometer based on two electro-optical combs with subsequent conversion to the mid-infrared via tunable difference frequency generation, operating in the range from 3 to 4.7 µm. The repetition rate of the combs can be tuned from 250 to 500 MHz. For 500 MHz, the number of detected comb modes is 440 with a signal-to-noise ratio exceeding 105 in 1 s. The conversion preserves the coherence of the combs within 3 s measurement time. Concentration measurements of 5 ppm methane at 3.3 µm, 100 ppm nitrous oxide at 3.9 µm and a mixture of 15 ppm carbon monoxide and 5% carbon dioxide at 4.5 µm are demonstrated with a noise-equivalent absorption coefficient of 6.4(3) x 10-6 cm-1 Hz-1/2.

Methane leak detection by tunable laser spectroscopy and mid-infrared imaging.

Tunable laser spectroscopy (TLS) combined with mid-infrared imaging is a powerful tool for a sensitive and quantitative visualization of gas leaks. This work deals with standoff methane leak detection within 2 m by an interband cascade laser (3270 nm wavelength) and an infrared camera. The concept demonstrates visualization of methane leakage rates down to 2 ml/min by images and sequences at frame rates up to 125 Hz. The gas plume and leak can be localized and quantified within a single image by direct absorption spectroscopy (DAS). The HITRAN database allows a calibration-free, pixelwise determination of the concentration in ppm*m. The active optical imaging concept showed pixelwise sensitivities around 1 ppm*m.

On-Board Monitoring of SO2 Ship Emissions Using Resonant Photoacoustic Gas Detection in the UV Range.

A photoacoustic gas detector for SO2 was developed for ship exhaust gas emission monitoring. The basic measurement setup is based on the absorption of electromagnetic radiation of SO2 at 285 nm wavelength. A commercially available ultraviolet (UV) light-emitting diode (LED) is used as the light source and a micro-electro-mechanical system (MEMS) microphone as the detector. In order to achieve the required detection limits in marine applications, a measuring cell which allows an acoustically resonant amplification of the photoacoustic signal was developed and characterized. A limit of detection of 1 ppm was achieved in lab conditions during continuous gas flow. Long-term measurements on a container ship demonstrated the application relevance of the developed system.

Screen-Printed Sensors for Colorimetric Detection of Hydrogen Sulfide in Ambient Air.

A fast and sensitive method to monitor hydrogen sulfide (H2S) in ambient air based on a visible color change of a printed disposable sensor has been developed. As gas-sensitive material, an immobilized copper(II) complex of the azo dye 1-(2-pyridylazo)-2-naphtol (H-PAN) was synthesized and prepared in an ethyl cellulose matrix for screen printing. If H2S is present in ambient air, the gas sensitive layer changes its color from purple to yellow. A pre-primed polyethylene (PE) foil and a coated offset paper served as the printing substrate. The colorimetric response to the target gas was measured by UV/Vis spectroscopy in reflection at H2S concentrations between 1 to 20 ppm. Possible cross-sensitivities of the printed sensors towards methane (CH4), formaldehyde (CH2O), carbon monoxide (CO), ammonia (NH3), and nitrogen dioxide (NO2), as well as the long-term stability was investigated. Furthermore, reflection measurements of the Cu-PAN complex on an amorphous silica powder under gas admission served as preliminary test for the subsequent paste development.

Resonant Photoacoustic Spectroscopy of NO2 with a UV-LED Based Sensor.

Nitrogen dioxide (NO 2 ) is a poisonous trace gas that requires monitoring in urban areas. Accurate measurement in sub-ppm concentrations represents a wide application field for suitable economical sensors. We present a novel approach to measure NO 2 with a photoacoustic sensor using a T-shaped resonance cell. An inexpensive UV-LED with a peak wavelength of 405 nm as radiation source as well as a commercial MEMS microphone for acoustic detection were used. In this work, a cell has been developed that enables a "non-contact" feedthrough of the divergent LED beam. Thus, unwanted background noise due to absorption on the inside walls is minimized. As part of the development, an acoustic simulation has been carried out to find the resonance frequencies and to visualize the resulting standing wave patterns in various geometries. The pressure amplitude was calculated for different shapes and sizes. A model iteratively optimized in this way forms the basis of a construction that was built for gas measurement by rapid prototyping methods. The real resonance frequencies were compared to the ones found in simulation. The limit of detection was determined in a nitrogen dioxide measurement to be 200 ppb (6 σ ) for a cell made of aluminum.

Cavity-Enhanced Raman Spectroscopy for Food Chain Management.

Comprehensive food chain management requires the monitoring of many parameters including temperature, humidity, and multiple gases. The latter is highly challenging because no low-cost technology for the simultaneous chemical analysis of multiple gaseous components currently exists. This contribution proposes the use of cavity enhanced Raman spectroscopy to enable online monitoring of all relevant components using a single laser source. A laboratory scale setup is presented and characterized in detail. Power enhancement of the pump light is achieved in an optical resonator with a Finesse exceeding 2500. A simulation for the light scattering behavior shows the influence of polarization on the spatial distribution of the Raman scattered light. The setup is also used to measure three relevant showcase gases to demonstrate the feasibility of the approach, including carbon dioxide, oxygen and ethene.

A Wireless Gas Sensor Network to Monitor Indoor Environmental Quality in Schools.

Schools are amongst the most densely occupied indoor areas and at the same time children and young adults are the most vulnerable group with respect to adverse health effects as a result of poor environmental conditions. Health, performance and well-being of pupils crucially depend on indoor environmental quality (IEQ) of which air quality and thermal comfort are central pillars. This makes the monitoring and control of environmental parameters in classes important. At the same time most school buildings do neither feature automated, intelligent heating, ventilation, and air conditioning (HVAC) systems nor suitable IEQ monitoring systems. In this contribution, we therefore investigate the capabilities of a novel wireless gas sensor network to determine carbon dioxide concentrations, along with temperature and humidity. The use of a photoacoustic detector enables the construction of long-term stable, miniaturized, LED-based non-dispersive infrared absorption spectrometers without the use of a reference channel. The data of the sensor nodes is transmitted via a Z-Wave protocol to a central gateway, which in turn sends the data to a web-based platform for online analysis. The results show that it is difficult to maintain adequate IEQ levels in class rooms even when ventilating frequently and that individual monitoring and control of rooms is necessary to combine energy savings and good IEQ.

Investigation of Gasochromic Rhodium Complexes Towards Their Reactivity to CO and Integration into an Optical Gas Sensor for Fire Gas Detection.

The detection of the toxic gas carbon monoxide (CO) in the low ppm range is required in different applications. We present a study of the reactivity of different gasochromic rhodium complexes towards the toxic gas carbon monoxide (CO). Therefore, variations of binuclear rhodium complexes with different ligands were prepared. They were characterized by FTIR spectroscopy, ¹H NMR spectroscopy, and differential scanning calorimetry. All complexes are spectroscopically distinguishable and temperature stable up to at least 187 °C. The gasochromic behavior of all different compounds was tested. Therefore, the compounds were dissolved in toluene and exposed to 100 ppm CO for 10 min to investigate their gas sensitivity and reaction velocity. The changes in the transmission spectra were recorded by UV/vis spectroscopy. Furthermore, a significant influence of the solvent to the color dyes’ gasochromic reaction and behavior was observed. After characterization, one complex was transferred as sensing element into an optical gas sensor. Two different measurement principles (reflection- and waveguide-based) were built up and tested towards their capability as gasochromic CO sensors. Finally, different gas-dependent measurements were carried out.

Photo-Induced Room-Temperature Gas Sensing with a-IGZO Based Thin-Film Transistors Fabricated on Flexible Plastic Foil.

We present a gas sensitive thin-film transistor (TFT) based on an amorphous Indium-Gallium-Zinc-Oxide (a-IGZO) semiconductor as the sensing layer, which is fabricated on a free-standing flexible polyimide foil. The photo-induced sensor response to NO2 gas at room temperature and the cross-sensitivity to humidity are investigated. We combine the advantages of a transistor based sensor with flexible electronics technology to demonstrate the first flexible a-IGZO based gas sensitive TFT. Since flexible plastic substrates prohibit the use of high operating temperatures, the charge generation is promoted with the help of UV-light absorption, which ultimately triggers the reversible chemical reaction with the trace gas. Furthermore, the device fabrication process flow can be directly implemented in standard TFT technology, allowing for the parallel integration of the sensor and analog or logical circuits.

Monitoring the Wobbe Index of Natural Gas Using Fiber-Enhanced Raman Spectroscopy.

The fast and reliable analysis of the natural gas composition requires the simultaneous quantification of numerous gaseous components. To this end, fiber-enhanced Raman spectroscopy is a powerful tool to detect most components in a single measurement using a single laser source. However, practical issues such as detection limit, gas exchange time and background Raman signals from the fiber material still pose obstacles to utilizing the scheme in real-world settings. This paper compares the performance of two types of hollow-core photonic crystal fiber (PCF), namely photonic bandgap PCF and kagomé-style PCF, and assesses their potential for online determination of the Wobbe index. In contrast to bandgap PCF, kagomé-PCF allows for reliable detection of Raman-scattered photons even below 1200 cm-1, which in turn enables fast and comprehensive assessment of the natural gas quality of arbitrary mixtures.

Towards Enhanced Gas Sensor Performance with Fluoropolymer Membranes.

In this paper we report on how to increase the selectivity of gas sensors by using fluoropolymer membranes. The mass transport of polar and non-polar gases through a polymer membrane matrix was studied by systematic selection of polymers with different degrees of fluorination, as well as polymers whose monomers have ether groups (-O-) in addition to fluorine groups (-F). For the study, a set of application-relevant gases including H2, CO, CO2, NO2, methane, ethanol, acetone, and acetaldehyde as well as various concentrations of relative humidity were used. These gases have different functional groups and polarities, yet have a similar kinetic diameter and are therefore typically difficult to separate. The concentrations of the gases were chosen according to international indicative limit values (TWA, STEL). To measure the concentration in the feed and permeate, we used tin-dioxide-based metal oxide gas sensors with palladium catalyst (SnO2:Pd), catalytic sensors (also SnO2:Pd-based) and thermal conductivity sensors. This allows a close examination of the interdependence of diffusion and physicochemical operating principle of the sensor. Our goal is to increase the selectivity of gas sensors by using inexpensive fluoropolymer membranes. The measurements showed that through membranes with low polarity, preferably non-polar gases are transported. Furthermore, the degree of crystallization influences the permeability and selectivity of a polymer membrane. Basically the polar polymers showed a higher permeability to water vapor and polar substances than non-polar polymer membranes.