The work presented in this thesis involves the use of room temperature ionic liquids (RTILs) as solvents in electrochemical experiments for the detection of hydrogen sulfide. The fundamentals of electrochemistry are presented, followed by an overview of RTILs in terms of their properties, applications and their behaviour as electrochemical solvents compared to conventional solvents. This is followed by an outline of electrochemical detection of various gases in aqueous, organic and ionic solvents. The results of 8 original studies are then presented as follows: <ul><li>The study of the electrochemical window of twelve different room temperature ionic liquids using cyclic voltammetry vs. an internal redox couple for two defined current densities, and observation of water uptake of different ionic liquids under different conditions using a Karl Fischer titrator.</li><li>The reduction of hydrogen sulfide in various room temperature ionic liquids at a platinum electrode, measured using cyclic voltammetry. Also, solubilities and diffusion coefficients of hydrogen sulfide determined by potential step chronoamperometry.</li><li>The oxidation of hydrogen sulfide in various room temperature ionic liquids at a platinum electrode measured using cyclic voltammetry and the simulation of the electrochemical signal using experimentally defined parameters.</li><li>The disproportionation of N,N-dimethyl-p-phenylenediamine (DMPD) in room temperature ionic liquids using cyclic voltammetry, and computational simulation of the voltammetry of DMPD using experimentally defined parameters to elucidate kinetic and thermodynamic data. DMPD was examined as a mediating species for hydrogen sulfide detection.</li><li>The oxidation of catechol and dopamine in ionic liquids using cyclic voltammetry and observing adsorption effects when varying solvent anion. Catechol was examined as a mediating species for hydrogen sulfide detection.</li><li>The electrochemical oxidation of NADH in ionic liquids using cyclic voltammetry and observing the ”switching on or off” of the electrochemical signal when varying the solvent anion. NADH was examined as a mediating species for hydrogen sulfide detection.</li><li>The mediated detection of hydrogen sulfide utilizing various mediating species in several ionic liquids using cyclic voltammetry, and the elucidation of the mediating mechanism of hydrogen sulfide in 3,5-tert-butyl-o-benzoquinone.</li><li>The observation of the diffusion of ferrocene in an ionic liquid at ring-recessed disc microelectrode arrays in generator-collector mode using potential step chronoamperometry.</li><ul> The results presented show that room temperature ionic liquids perform well as solvents in gas sensors, and could be viable alternatives to traditional organic solvents. Ionic liquids have also been observed to be tuneable in their reactions with analytes depending on the constituent cations and, in particular, anions. This tuneability is advantageous as specific combinations of cations and anions can be chosen to suit particular experiments.

The ability to detect and quantify presence and concentration of unknown gasses is sought for applications ranging from environmental monitoring to medical analysis. Metal oxide based chemical sensing technology currently exists but the ability to provide a compositional gas breakdown reliably within a short time frame is not readily available. A very small sensor that can differentially identify the type and concentration of a gas is required. Novel methods of creating low cost and easily tuned one and two-dimensional gas sensing elements are explored. Tungsten trioxide has been thoroughly documented as an electrochromic coating, but highly sensitive WO3 elements with beam and nanowire structures have yet to be explored. Research of WO3 as a gas sensor encompasses three major components: A suitable sensing chamber with accurate analyte gas flow control and temperature control, a reliable method for WO3 deposition, and a high yield fabrication process. This thesis explores all three of these technologies. Chapter two starts with a summary of existing tungsten trioxide fabrication methods. An overview of WO3 processing follows. A comprehensive setup was designed and created to test the gas sensing response of a series of metal oxide based resistive elements through conductimetric analysis. Chapter three provides an in depth account of gas sensor test chamber design and testing. Critical test chamber aspects such as temperature control, precise gas flow control, highly efficient analyte gas switching and ease of use are presented. Chapter four outlines WO3 electrodeposition and the fabrication of beam structures for testing, while chapter five explores the templated electrodeposition of WO3 segments intercalated between gold nanowire segments. Finally, chapter six provides a summary of the research presented in this thesis as well as future directions and options available for further exploration of WO3 gas sensing elements. / Micro-Electro-Mechanical Systems (MEMS) and Nanosystems

Advancement in infrared imaging technology has allowed the thermal imaging to detect and visualize several gases, mostly hydrocarbon gases. In addition, infrared cameras could potentially be used as a non-contact temperature measurement for gas and vapor. However, current application of infrared imaging techniques for gas measurements are still limited due to several uncertainties in their performance parameters. The aim of this research work was to determine the key factors in the application of infrared imaging technology for gas visualization and a non-contact temperature measurement. Furthermore, the concentration profile and emission rate of the gas are predicted by combining the application of the infrared imaging method with gas dispersion modeling. In this research, infrared cameras have been used to visualize liquefied natural gas (LNG) plumes from LNG spills on water. The analyses of the thermograms showed that the apparent temperatures were different from the thermocouple measurement which occurred due to the assumption of that the object emissivity was always equal to unity. The emissivity for pure methane gas and a mixture of methane and atmospheric gases were then evaluated in order to obtain the actual temperature distribution of the gas cloud. The results showed that by including the emissivity value of the gas, the temperature profile of the dispersed gas obtained from a thermal imaging measurement was in good agreement with the measurement using the thermocouples. Furthermore, the temperature distribution of the gas was compared to the concentration of a dispersed LNG vapor cloud to obtain a correlation between the temperature and the concentration of the cloud. Other application of infrared imaging technique was also conducted for leak detection of natural gas from a pipeline. The capability of an infrared camera to detect a fugitive gas leak was combined with the simulation of vapor discharge and dispersion in order to obtain a correlation between the emission rates and the sizes of the gas plume to the minimum detectable concentration. The relationship of the methane gas cloud size to the gas emission rate was highly dependent to the prevailing atmospheric condition. The results showed that the correlation were best to predict the emission rate less than 0.2 kg/s. At higher emission rate, the increase in gas release rate did not change the size of the cloud significantly.

No description available.

Optical flow is widely used in image and video processing. This paper describes the definition of optical flow and some basic methods of estimating optical flow. There are three main optical flow methods described in this paper: Horn–Schunck method, Lucas–Kanade method and Anandan method. It will select the most appropriate method to measure the flow in videos containing smoke and gas by comparing those three methods with different criteria. The results are as below 1) Horn–Schunck method is good at measuring flow in infrared video and in horizontal direction, when 2) Anandan method is adept in estimating upward optical flow but not suitable for infrared video. 3) Lucas-Kanade method can be used not only in smoke videos, but also in methane gas videos, and it can detect flow in both horizontal and vertical direction.

Sensing devices developed upon resonant microelectromechanical and nanoelectromechanical (M/NEMS) system technology have become one of the most attractive areas of research over the past decade. These devices make exceptional sensing platforms because of their miniscule dimensions and resonant modes of operation, which are found to be extremely sensitive to added mass. Along their unique sensing attributes, they also offer foundry compatible microfabrication processes, low DC power consumption, and CMOS integration compatibility. In this work, electrostatically and piezoelectrically actuated RF MEMS bulk resonators have been investigated for mass sensing applications. The capacitively-transduced resonators employed electrostatic actuation to achieve desired resonance mode shapes. These devices were fabricated on silicon-on-insulator (SOI) substrates with a device layer resistivity ranging from 0.005 Ω cm to 0.020 Ω cm. The electrode-to-resonator capacitive gap was defined by two different techniques: oxidation enabled gap reduction and sacrificial atomic layer deposition (ALD). For oxidation enabled gap reduction, a hard mask composed of silicon nitride and polysilicon is deposited, patterned, and defined using standard MEMS thin-film layer deposition and fabrication techniques. The initial lithographically-defined capacitive gap of 1 μm is further reduced to ~300 nm by a wet furnace oxidation process. Subsequently, the reduced gap is transferred to the device layer using a customized dry high-aspect-ratio dry etching technique. For sacrificial approach, a ~100 nm-thin ALD aluminum oxide sidewall spacer is chemically etched away as the last microfabrication step to define the ~100 nm capacitive gap. Small capacitive gaps developed in this work results in small motional resistance (Rm) values, which relax the need of the read-out circuitry by enhancing the signal transduction. Piezoelectrically-actuated resonators were developed using thin-film bulk acoustic resonant (FBAR or TFBAR) and thin-film piezoelectric-on-substrate (TPoS) technologies with reported Q factors and resonant frequencies as high as 10,638 and 776.54 MHz, respectively, along with measured motional resistance values as low as 169Ω. To the best of our knowledge, this work is the first one that demonstrated TPoS resonators using LPCVD polysilicon as an alternative low loss structural layer to single-crystal silicon with Q factors as high as ~3,000 (in air) and measured motional resistance values as low as 6 kΩ with an equivalent acoustic velocity of 6,912 m s-1 for a 7 μm thick layer. Polysilicon based TPoS single devices were measured with the coefficient of resonant frequency of -3.77 ppm/°C, which was the lowest ever reported for this type of devices. Also a novel releasing process, thin-piezo on single crystal reactive etched (TPoSCRE), allows us to develop of TPoS resonators without the need to SOI wafers. The fabricated devices using this technique were reported with Q factor exceeding ~1,000 and measured motional resistance values as low as 9 kΩ. The sensitivity of a fourth-order contour mode ZnO-on-SOI disk resonator based mass sensor was determined by performing multiple depositions of platinum micro-pallets using a focus ion beam (FIB) equipped with gas injection system on strategically-chosen locations. It was found out that the sensitivity of the resonator on its maximal and minimal displacement points was of 1.17 Hz fg-1 and 0.334 Hz fg-1, respectively. Also, the estimated limit of detection of the resonator was found to be a record breaking 367 ag (1 ag = 10-18g) compared to devices with similar modes of resonance. Lastly, a lateral-extensional resonator was used to measure the weight of HKUST-1 MOF crystal cluster. The weight of it was found to be 24.75 pg and 31.19 pg by operating two lateral resonant modes, respectively.

Les cellules photoacoustiques sont des capteurs optiques qui utilisent l'absorption des photons par des molécules de gaz pour générer une onde de pression proportionnelle à leur concentration. Le signal photoacoustique est également inversement proportionnel au volume de la cellule. La miniaturisation de la cuve permet donc l’amélioration des performances du capteur. Le travail de cette thèse consiste en la conception, la réalisation et la caractérisation de cellules photoacoustiques résonantes différentielles d’Helmholtz (DHR) miniaturisées. Dans un premier temps, des simulations par la méthode des éléments finis de cellules à l'échelle millimétrique ont permis de montrer que la miniaturisation de ce type de résonateur est une voie prometteuse. Aussi, la réalisation ambitieuse d’une cellule DHR sur silicium a été engagée en utilisant les techniques de la microélectronique. Cependant, cette voie de miniaturisation extrême s'est heurtée à des difficultés de réalisation, qui n'ont pas permis d'obtenir des dispositifs fonctionnels. Une alternative de miniaturisation, à l'échelle centimétrique, utilisant des microphones MEMS du commerce, a donc été engagée. Trois cellules fabriquées par différentes méthodes ont été réalisées et testées pour la détection de méthane. La dernière génération a permis la détection d'environ 100 ppb de méthane avec un laser à cascade interbande commercial à 3,357 µm de longueur d’onde. Pour préparer la prochaine génération de cellules, l'optimisation de la géométrie a été effectuée par simulation. Cette optimisation permet d'envisager une augmentation de 43 % du signal par rapport à la cellule la plus performante. / Photoacoustic cells are optical sensors based on the absorption of photons by gas molecules. The pressure wave created by gas relaxation is proportional to the trace gas concentration. Furthermore the photoacoustic signal is inversely proportional to the cell volume. Thus cell miniaturization enables performances improvements. This work consists in designing, realizing and characterizing miniaturized photoacoustic cells, based on the differential Helmholtz resonator (DHR) principle. In a first phase, modeling by the finite element method of millimeter scale cells has shown that the miniaturization of this type of resonator should effectively improve the detection limit. Thus, the ambitious realization of a DHR cell on silicon by the use of microelectronic techniques has been attempted. However, this extreme miniaturization direction encountered design and fabrication difficulties which made the produced devices unusable. To overcome these difficulties, a miniaturization alternative, at the centimeter scale, using commercial MEMS microphones, has been carried out. Three cells have been built by different methods and have been tested for methane detection. The last cell generation can detect around 100 ppb of methane with a commercial interband cascade laser at 3.357 µm of wavelength. Finally, to anticipate the next cell generation fabrication, a geometry optimization has been performed by simulation. This optimization shows that a 43 % signal improvement, compared to the most performant cell already built.

La détection de gaz suscite depuis une dizaine d'années, un intérêt grandissant voir galopant, cela pour diverses raisons : environnementales, de santé publique, de sécurité (Hommes et infrastructures), etc... Ce dynamisme a pour conséquence un besoin de renouvellement et de perfectionnement des moyens de détection, qui croît à mesure que les normes existantes et les secteurs d'application respectivement, se complexifient et se diversifient. Une telle frénésie entraîne naturellement l'augmentation du nombre de projets de recherche sur cette thématique : le projet ANR PEPS, débuté en 2010, est l'un d'entre-eux. Acronyme de "Pellet Photonique Sensor", il vise à démontrer la faisabilité d'une plateforme de détection photonique multi-gaz exploitant l'effet thermo-optique, grâce à la combinaison de deux éléments centraux : des nanopoudres catalytiques sélectives aux gaz visés (dihydrogène ou monoxyde de carbone) et un composant photonique planaire très sensible aux variations d'indice de réfraction. Ce manuscrit est principalement consacré à la conception (sélection et optimisation) du composant photonique. / For about a decade, gas detection has known a tremendous interest, due to several reasons: environmental issues, public health, people and building safety, etc... This trend, triggered a spectacular and sustainable need of gas detection means improvement and development, which has grown with both standards sophistication and scope extension. As a matter of fact, the number of research projects related to this particular topic increased: PEPS ANR project, begun in 2010, is one of them. This research project, which is the acronym of Pellet Photonique Sensor, aim at developing a photonic multigas detection system based on thermo-optical effect, thanks to the combination of on one hand, catalitic nanopowders which react selectively with the target gas (hydrogen or carbon monoxide) and on the other hand, an high sensitive to refractive index variations planar photonic component. This thesis manuscript mostly treats of the photonic component design (choice and optimization).

Gas sensing is essential for safety and maintenance operations in many industries, including power generation, petrochemical, capture and storage technologies, and the food-processing sector. The properties of fiber-optic sensors make them a superior choice for environmental monitoring applications, especially in extreme conditions, and particularly when compared against conventional electro-optical sensors. Their advantageous properties include immunity to electromagnetic radiation, high temperature durability, high sensitivity and the ability for high resolution detection, as well as multifunctional sensing capabilities such as temperature, humidity, pressure, strain, and corrosion. Among different types of interferometers, Mach-Zehnder Interferometers (MZI) have received significant attention because they are robust, compact, and have high levels of precision. In this dissertation, we present an in-line and compact MZI point sensor designed for sensing refractive index. In comparison with various types of interferometers, fiber MZI based RI sensing was selected based on its enhanced sensitivity and fabrication simplicity. The MZI sensor is developed using photonic crystal fiber and demonstrated for high sensitivity detection and measurement of pure gases. The transmission spectrum of MZI sensors is formed by interference between the cladding and core modes. To construct the device, the sensing element fiber was placed and aligned between two single-mode fibers with air gaps at each side. Two linear-translation micro stages were used to accurately differ and adjust gap lengths from 0 to 5mm. Great measurement repeatability was shown in the cyclic test for the detection of various gases such as methane and helium. A high RI measurement resolution of 2.1 E-7 and a sensitivity of 4629 nm/RIU was achieved, which is among the highest reported. Results show that the sensitivity of the fabricated MZI increases from 3000 nm/RIU to 4600 nm/RIU when the length of the sensing element fiber decreases from 5 mm to 3.3 mm. Furthermore, the device was packaged to demonstrate the laboratory-scale monitoring, as well as leakage detection of different concentrations of CO2 in both subsurface soil and aqueous environments. Two water resistant but gas permeable membranes were used to package the sensor, to achieve a good balance of CO2 permeability and water resistance. The experimental study of this work reveals the great potential of the fiber-optic approach for environmental monitoring of CO2. This study also explores other potential applications. Three types of sensors were fabricated using the proposed configuration employing 4 mm stub of (i) solid core Photonic Crystal Fiber (PCF), (ii) 10 µm Hollow core PCF (HC-PCF), and (iii) 20 µm HC-PCF as the sensing elements. We compared the performance of these sensors for detecting and measuring the quantity of gas present. As the transmission signals correspond to the frequency components in the sensor’s Fast Fourier Transform (FFT) spectrum, the effect of gap distance on the number and amplitude distribution of the modes was examined in an effort to optimize the design elements. The MZI sensors are highly sensitive to low percentages of CH4 and CO2, making them suitable for greenhouse gas measurement. / Graduate

Amperometric gas sensors are widely used for environmental and industrial monitoring. They are sensitive and cheap but suffer from some significant limitations. The aim of the work undertaken in this thesis is the development of ‘intelligent’ gas sensors to overcome some of these limitations. Overall the thesis shows the value of ionic liquids as potential solvents for gas sensors, overcoming issues of solvent volatility and providing a wide potential range for electrochemical measurements. Methods have been developed for sensitive amperometry, the tuning of potentials and especially proof-of-concept (patents Publication numbers: WO2013140140 A3 and WO2014020347 A1) in respect of the intelligent self-monitoring of temperature and humidity by RTIL based sensors. Designs for practical electrodes are also proposed. The specific content is as follows. Chapter 1 outlines the fundamental principles of electrochemistry which are of importance for the reading of this thesis. Chapter 2 reviews the history and modern amperometric gas sensors. Limitations of present electrochemical approaches are critically established. Micro-electrodes and Room Temperature Ionic Liquids (RTILs) are also introduced in this chapter. Chapter 4 is focused on the study of analysing chronoamperometry using the Shoup and Szabo equation to simultaneously determine the values of concentration and diffusion coefficient of dissolved analytes in both non-aqueous and RTIL media. A method to optimise the chronoamperometric conditions is demonstrated. This provides an essential experimental basis for IL based gas sensor. Chapter 5 demonstrates how the oxidation potential of ferrocene can be tuned by changing the anionic component of room temperature ionic liquids. This ability to tune redox potentials has genetic value in gas sensing. Chapters 6 and 7 describe two novel patented approaches to monitor the local environment for amperometric gas detection. In Chapter 6, an in-situ voltammetric ‘thermometer’ is incorporated into an amperometric oxygen sensing system. The local temperature is measured by the formal potential difference of two redox couples. A simultaneous temperature and humidity sensor is reported in Chapter 7. This sensor shows advantageous features where the temperature sensor is humidity independent and vice versa. The Shoup and Szabo analysis (Chapter 4) requires ‘simple’ electron transfer and as such the reduction of oxygen in wet RTILs can be complicated by dissolved water. Chapter 8 proposes a method to stop oxygen reduction at the one electron transfer stage under humid conditions by using phosphonium based RTILs to ‘trap’ the intermediate superoxide ions. Chapters 9 and 10 report the fabrication of low cost disposable electrodes of various geometries and of different materials. The suitability of these electrode for use as working electrodes for electrochemical experiments in aqueous, non-aqueous and RTIL media is demonstrated. Their capability to be used as working probes for amperometric gas sensing systems is discussed.