Le projet Cigéo, mené par l’ANDRA, vise à permettre à l’horizon 2030 le stockage géologique des déchets les plus radioactifs du parc nucléaire français. Ces déchets, qui seraient placés dans des alvéoles souterraines de plusieurs centaines de mètres, sont susceptibles de relâcher de l’hydrogène gazeux (H2), un gaz inflammable dans l’air lorsque sa concentration dépasse 4%. Pour la sécurité des installations, il est indispensable de s’assurer que la concentration de H2 dans les alvéoles de stockage reste inférieure à sa limite de dangerosité. L’objectif de cette thèse, menée à l’ONERA, est de concevoir et réaliser un Lidar permettant de profiler à distance la concentration de H2 (0-4%), sur plusieurs centaines de mètres, avec une forte résolution spatiale (< 3 m), et de proposer ainsi un moyen non intrusif de détection et de prévention du risque lié à l’hydrogène. Le principe retenu est celui d’un Lidar Raman vibrationnel dans le domaine ultra-violet (355 – 420 nm). Pour sa conception, nous avons pris en compte les conditions particulières prévues dans les alvéoles de stockage. Une chaine de détection très sensible à comptage de photons a été choisie et mise en oeuvre, basée sur des détecteurs SiPM (Silicium Photomultiplier). La nécessité d’employer une voie de mesure de la vapeur d’eau, simultanément à l’hydrogène, a été mise en évidence et est liée au recouvrement partiel des spectres de diffusion Raman de H2 et H2O. Un analyseur spectral à trois voies de mesure (H2, H2O, et N2 utilisé comme référence) a été conçu et mis en place. Une méthode de traitement de signal en temps réel a enfin été réalisée pour visualiser les profils de concentrations de H2 et H2O. L’ensemble du système lidar a pu être testé dans une scène de portée réduite (100 m) permettant des relâchements d’hydrogène. Des mesures simultanées de profils de vapeur d’eau naturelle et de dihydrogène (0-2%) ont pu être démontrées avec succès à 85 m, avec une résolution spatiale et temporelle de 1 mètre et 1 minute respectivement, pour une détectivité de 600 ppm. / The CIGEO project, led by the ANDRA agency, aims at enabling future deep geological disposal of french nuclear waste packages. Those packages could be stored in hundred-meters long underground galleries, and may release hydrogen gas (H2), which is explosive at concentrations above 4% in the air. For safety concerns, it is important to ensure that H2 concentration remains well below the lower explosive limit. The objective of this thesis work, conducted at the ONERA agency, is to design and build a lidar which enable high-resolution (3 m) remote profiling of H2 concentration (0-4%) over hundreds of meters. Such a lidar could perform nonintrusive H2 detection and then prevent H2-related explosion risks. This lidar measures vibrational Raman scattering in the UV domain (355 – 420 nm). Its design takes into account the specific conditions expected in storage galleries. A highspeed and sensitive detection stage has been chosen, based on SiPM (Silicium Photomultiplier) technology in photon counting mode. Due to a spectral overlap between molecular hydrogen and water vapor Raman spectra, the need of a H2O measurement channel has been demonstrated. A three-channel spectral analyzer (H2, H2O and N2 used as reference) has been designed and implemented. Signal processing in real time has been developed to display H2 and H2O concentration profiles. This lidar has been tested in a reduced range scene (100 m) enabling hydrogen gas releases. Simultaneous measurements of concentration profiles of natural water vapor and hydrogen gas (0-2%) have been performed at 85 m with 1-meter and 1-minute resolution and a 600 ppm detectivity.

Os transformadores de potência são alguns dos elementos mais importantes dos sistemas elétricos. A confiabilidade e o bom funcionamento destes equipamentos são vitais para que as companhias de energia forneçam eletricidade com qualidade e segurança. Um dos principais parâmetros que envolvem a normalidade da operação dos transformadores é o estado da isolação interna formada pelo óleo mineral e o papel que cobre as bobinas. Danos nessa isolação resultam na degradação destes dielétricos e, por conseqüência, na diminuição da vida útil dos transformadores. Essa degradação, que advém de processos elétricos, térmicos, ou mesmo mecânicos, geram gases combustíveis cujas quantidades individuais podem indicar o tipo de falha e a gravidade do problema. Desta forma, é importante detectar os principais gases envolvidos. O objetivo deste trabalho é realizar análises e estudos quantitativos da presença de gases inflamáveis dissolvidos no óleo, surgidos através da degradação deste líquido isolante. O cerne deste trabalho está em elaborar ensaios de formação de arco no óleo e, posteriormente, aquecer o fluido para medir a quantidade dos gases combustíveis antes dissolvidos nele. Este estudo visa à melhoria na confiabilidade dos equipamentos projetados para detectar e monitorar o surgimento de gases inflamáveis no interior de transformadores de potência existentes em subestações de companhias de eletricidade. / Power transformers are some of the most important elements of electrical systems. The trustworthiness and the good functioning of this equipment permit power utilities to supply electricity with quality and security. One of the main parameters for transformer\'s operation normality is the state of the internal insulation formed by the mineral oil and the paper that covers the bobbins. Damages in this insulation cause its dielectric degradation and, consequently, the reduction of the equipment useful life. This degradation which originates from electrical, thermal, or even mechanical processes generates chemical products such as gases whose individual amounts may indicate the type of imperfection and gravity of the problem. That\'s why the detection of the main involved gases is important. This work intends to elaborate analyses and studies of the presence of inflammable gases dissolved in oil through the degradation of the insulating liquid. The principal topic of this work is the arc formation elaboration in the oil and later the heating of the oil to measure the amount of gases previously dissolved in it. This study also aims to improve the trustworthiness of the projected equipments in order to detect and monitor the sprouting of existing inflammable gases in the interior of power transformers in substations of power utilities.

Os transformadores de potência são alguns dos elementos mais importantes dos sistemas elétricos. A confiabilidade e o bom funcionamento destes equipamentos são vitais para que as companhias de energia forneçam eletricidade com qualidade e segurança. Um dos principais parâmetros que envolvem a normalidade da operação dos transformadores é o estado da isolação interna formada pelo óleo mineral e o papel que cobre as bobinas. Danos nessa isolação resultam na degradação destes dielétricos e, por conseqüência, na diminuição da vida útil dos transformadores. Essa degradação, que advém de processos elétricos, térmicos, ou mesmo mecânicos, geram gases combustíveis cujas quantidades individuais podem indicar o tipo de falha e a gravidade do problema. Desta forma, é importante detectar os principais gases envolvidos. O objetivo deste trabalho é realizar análises e estudos quantitativos da presença de gases inflamáveis dissolvidos no óleo, surgidos através da degradação deste líquido isolante. O cerne deste trabalho está em elaborar ensaios de formação de arco no óleo e, posteriormente, aquecer o fluido para medir a quantidade dos gases combustíveis antes dissolvidos nele. Este estudo visa à melhoria na confiabilidade dos equipamentos projetados para detectar e monitorar o surgimento de gases inflamáveis no interior de transformadores de potência existentes em subestações de companhias de eletricidade. / Power transformers are some of the most important elements of electrical systems. The trustworthiness and the good functioning of this equipment permit power utilities to supply electricity with quality and security. One of the main parameters for transformer\'s operation normality is the state of the internal insulation formed by the mineral oil and the paper that covers the bobbins. Damages in this insulation cause its dielectric degradation and, consequently, the reduction of the equipment useful life. This degradation which originates from electrical, thermal, or even mechanical processes generates chemical products such as gases whose individual amounts may indicate the type of imperfection and gravity of the problem. That\'s why the detection of the main involved gases is important. This work intends to elaborate analyses and studies of the presence of inflammable gases dissolved in oil through the degradation of the insulating liquid. The principal topic of this work is the arc formation elaboration in the oil and later the heating of the oil to measure the amount of gases previously dissolved in it. This study also aims to improve the trustworthiness of the projected equipments in order to detect and monitor the sprouting of existing inflammable gases in the interior of power transformers in substations of power utilities.

Noise-immune cavity-enhanced optical heterodyne molecular spectro-metry (NICE-OHMS) is one of the most sensitive laser-based absorption techniques. The high sensitivity of NICE-OHMS is obtained by a unique combination of cavity enhancement (for increased interaction length with a sample) with frequency modulation spectrometry (for reduction of noise). Moreover, sub-Doppler detection is possible due to the presence of high intensity counter-propagating waves inside an external resonator, which provides an excellent spectral selectivity. The high sensitivity and selectivity make NICE-OHMS particularly suitable for trace gas detection. Despite this, the technique has so far not been often used for practical applications due to its technical complexity, originating primarily from the requirement of an active stabilization of the laser frequency to a cavity mode. The main aim of the work presented in this thesis has been to develop a simpler and more robust NICE-OHMS instrumentation without compro-mising the high sensitivity and selectivity of the technique. A compact NICE-OHMS setup based on a fiber laser and a fiber-coupled electro-optic modulator has been constructed. The main advantage of the fiber laser is its narrow free-running linewidth, which significantly simplifies the frequency stabilization procedure. It has been demonstrated, using acetylene and carbon dioxide as pilot species, that the system is capable of detecting relative absorption down to 3 × 10-9 on a Doppler-broadened transition, and sub-Doppler optical phase shift down to 1.6 × 10-10, the latter corresponding to a detection limit of 1 × 10-12 atm of C2H2. Moreover, the potential of dual frequency modulation dispersion spectrometry (DFM-DS), an integral part of NICE-OHMS, for concentration measurements has been assessed. This thesis contributes also to the theoretical description of Doppler-broadened and sub-Doppler NICE-OHMS signals, as well as DFM-DS signals. It has been shown that the concentration of an analyte can be deduced from a Doppler-broadened NICE-OHMS signal detected at an arbitrary and unknown detection phase, provided that a fit of the theoretical lineshape to the experimental data is performed. The influence of optical saturation on Doppler-broadened NICE-OHMS signals has been described theoretically and demonstrated experimentally. In particular, it has been shown that the Doppler-broadened dispersion signal is unaffected by optical saturation in the Doppler limit. An expression for the sub-Doppler optical phase shift, valid for high degrees of saturation, has been derived and verified experimentally up to degrees of saturation of 100.

Le besoin d'analyse de gaz à l'état de traces s'est accentué ces dernières années en raison des préoccupations du public et de l'industrie sur des questions telles que le contrôle des émissions de polluants atmosphériques, la surveillance de l'environnement au sens large, la santé et la sécurité au travail. Il est donc nécessaire de posséder des instruments de détection sélectifs, sensibles et capables d'effectuer une mesure directe en temps réel. La fiabilité des systèmes de mesure est également un critère important et, selon l'application envisagée, s'ajoute aussi le besoin de miniaturisation pour aller vers des microsystèmes permettant le développement de dispositifs portables pour des opérations sur site.Le travail de thèse présenté dans ce manuscrit est situé dans ce contexte et porte sur l'étude et la mise au point d'un système sensible, efficace et assez simple à mettre en œuvre permettant de réaliser des mesures de traces de gaz sélectives, en temps réel et in-situ. Ce système est basé sur la spectroscopie d'absorption par quartz (QEPAS, Quartz Enhanced PhotoAcoustic Spectrocopy) qui consiste en la mesure d'une onde acoustique générée après la relaxation non-radiative des molécules excitées par l'absorption de la lumière modulée émise par des diodes lasers accordables, à l'aide d'un diapason à quartz (QTF). Le fonctionnement des sources lasers accordables et du QTF ainsi que différentes configurations du spectrophone (association du micro-résonateur et du QTF) utilisés dans cette technique QEPAS sont détaillés. Une modélisation de l'onde acoustique et de la réponse du capteur est également proposée. Deux dispositifs ont été réalisés. Le premier, nommé banc QEPAS prototype, est dédié à la mesure de l'éthylène avec une diode laser DFB émettant à 3,32 µm. Le second dispositif est une nouvelle version de capteur QEPAS, plus compacte que des dispositifs existant actuellement, dans laquelle il est possible de placer tout type de diode laser commerciale montée dans des supports de type T0xx. Ce banc compact est utilisé pour la mesure de méthane avec notamment une diode laser DFB émettant à 3,26 µm. / The need for trace gas analysis has increased in recent years due to an important concern of the public and industry on issues such as the control of emissions of air pollutants, environmental monitoring, health and security. It is therefore necessary to have the trace gas sensors able of high selectivity, sensitivity and a direct measurement in real time. The reliability of the measurement systems is also an important criterion, depending on the intended application, the need to move towards miniaturization of microsystems for the development of portable devices for on-site operations is also interesting.This thesis is in this context and focuses on the study and development of a sensitive, efficient and simple setup to make selective, in-situ and in real time measurements of trace gases. This system is based on quartz enhanced photoacoustic spectrocopy (QEPAS) which consists on the measurement of an acoustic wave generated by the non-radiative relaxation of the excited molecules after light absorption, with a quartz tuning fork (QTF). The operation of tunable laser sources, of QTF and different spectrophone configurations (combination of the micro-resonator and QTF) used in QEPAS technique are detailed. A model of the acoustic wave and the response of the sensor are also proposed. Two devices have been designed. The first one is a QEPAS prototype bench, dedicated to the measurement of ethylene with a DFB laser diode emitting at 3.32 µm. The second device is a new version of QEPAS sensor that is more compact than the currently existing devices and where it is possible to place any type of commercial laser diode. This compact bench is used for methane measurement with a DFB laser diode emitting at 3.26 µm.

Le besoin d’appareils compacts et autonomes dédiés à la détection d’espèces chimiques pour des analyses de terrain est d’actualité dans un contexte international en rapide mutation (agroalimentaire, développement durable, sécurité, etc.). La thèse présentée au sein de ce manuscrit, financée par la Délégation Générale de l’Armement, développe de nouvelles solutions de capteurs résonants à ondes élastiques de volume à modes harmoniques élevés (HBARs) pour la détection de gaz et plus particulièrement de composés explosifs. Ces résonateurs de très haute compacité se composent d’un transducteur reporté ou déposé sur une cavité résonante multimode, produisant un spectre de raies modulant sa propre réponse fréquentielle. De nature dipolaire, ces résonateurs permettent toutefois la mise au point de quadripôles par couplage latéral de modes mis à profit dans nos travaux. L’étude théorique du comportement de résonateurs à base de niobate de lithium aminci et reporté sur quartz ou fondés sur un empilement de nitrure d’aluminium et de silicium a permis de déterminer les propriétés gravimétriques spécifiques de chaque combinaison de matériaux et des modes associés. Des méthodes de calibrage en phase liquide et gazeuse sont proposées pour valider l’analyse théorique et permettre le choix de la structure la mieux adaptée à une configuration expérimentale donnée. Les résultats obtenus, comparés à ceux d’une microbalance à ondes guidées sur quartz, mettent en évidence les forces (compacité, cinétique chimique réduite, nature multi-physique des mesures) et faiblesses (sensibilité gravimétrique imposant des structures d’épaisseur inférieure à 100 μm) de notre solution face à cette référence. Nous avons également développé une électronique de traitement en boucle ouverte des informations issues de nos dispositifs, permettant des modes de détection rapide ou de haute précision (quelques milli-degrés de variation de phase). L’électronique dédiée a pour vocation de fournir la flexibilité nécessaire au suivi de nombreux modes à diverses fréquences fixes et de s’affranchir des temps longs de balayage en fréquence des analyseurs de réseaux généralistes. Une version à8 voies permet enfin la manipulation de plusieurs capteurs ou l’étude en parallèle des modes de 2 HBARs, donnant ainsi lieu à un système multi-physique efficace associé à des capteurs capables de sonder plusieurs grandeurs dans un volume de très petite dimension (quelques mm3). La limite de détection est déterminée par le bruit de phase de l’oscillateur local. Le système ainsi réalisé est exploité pour la détection de gaz mais aussi pour le pilotage de grandeurs physiques telles que la température ou la viscosité (milieux aqueux) dans différents contextes expérimentaux. / The demand for compact and autonomous systems devoted to field detection of gaseous compounds is still persisting in arapidly changing international context (food-processing, sustainable development, security, and so on). The thesis reportedin this manuscript, supported by the Délégation Générale de l’Armement, develops new resonant sensor solutions basedon high overtone bulk acoustic waves (so-called HBARs) for chemical compound detection and more specifically explosivesubstances. These high compactness resonators are built using a transducer bound or deposited onto a resonant cavity,yielding a comb spectrum modulating its own frequency response. They are used generally as dipoles, but a quadrupolestructure allowing for transverse mode coupling has been particularly used for our developments. A theoretical study ofthe behaviour of these devices based on lithium niobate-on-quartz or qluminum nitride-on-silicon material stack has beenachieved to determine the gravimetric properties of these configurations accounting for their mode specificities. Variouscalibration techniques have been implemented to confirm the theoretical analysis and to define the most appropriate structurefor a given application. The produced results have been compared to those of a quartz guided-wave micro-balance toemphasize the strength (compactness, reduced chemical kinetics, multiphysics measurements) and weakness (gravimetricsensitivity requiring device thickness less than 100 μm) of our devices. An embedded signal processing electronics alsohas been developed to treat the information provided by our sensors, offering fast or accurate (millidegree range) detectionprotocols. The dedicated electronics aims at providing the flexibility needed to track multiple modes at variaous fixed frquencieswhile getting rid of the long sweep time of general purpose network analyzers. A eight-channel version of thissystem has been set to process several sensor in parallel or to monitor several modes of two HBAR sensors for effectivemuti-physics measurements in a reduced analysis domain (a few cubic mm). Phase noise is the limiting factor determiningthe detection limit. The system has been deployed for gas detection as well as for monitoring other physical parameters suchas temperature or viscosity under various experimental condition including fluid media.

The diploma thesis introduces the reader to the problems of chemical sensors and the basics of degradation processes in materials of animal origin. It describes some types of sensors and their principles. Atmel ATmega328 microprocessor, its parameters and programming are described. In the next part of the thesis there is a proposal and production of equipment for monitoring of degradation processes in materials of animal origin. Sample sof chicken and milk were mesuared. From these measurements, the gas concentration values were determined, where samples can be considered suitable for consumation.

Tato práce se zabývá vývojem platforem na bázi křemíkového substrátu pro selektivní integraci polovodivých nanostruktur oxidu kovu (MOX) a jejich použití v perspektivních mobilních zařízeních jako vysoce citlivé a selektivní prvky pro detekci analytů plynů. Polovodičové nanostruktury MOX, například nanodráty, prokázaly lepší schopnosti pro snímání plynů včetně citlivosti, stability a do jisté míry také selektivity, ve srovnání s jejich protějšky na bázi vrstev. Rovněž použití jednoho (nebo několika) nanodrátů zapojených paralelně se ukázalo jako ideální architektura pro dosažení dobře definovaného vodivého kanálu snadno modulovatelného interakcemi na přechodu plynná-pevná látka. Dosavadní způsoby integrace struktur na bázi jednoho nanodrátu do funkčních zařízení však stále představují technologickou výzvu, protože většina metod vyžaduje asistenci technik, jako je soustředěný iontový paprsek (FIB), který omezuje škálovatelnost a zvyšuje náklady a čas výroby. V této souvislosti je práce zaměřena na optimalizaci technologických procesů pro výrobu systémů založených na elektrodových polích s jedním polovodivým nanodrátem. V této práci byly vyvinuty tři verze elektrodových platforem pro selektivní integraci jednoho nanodrátu z MOX materiálu citlivého na plyn. Jako klíčové technologie výroby byly použity nejmodernější vícestupňové výrobní postupy a litografie s využitím elektronového paprsku (nanofabrikace), které umožňují vývoj elektrodových polí s přímými nanoelektrodami, ale i dalších funkčních nanostruktur. Výsledky demonstrují výrobu elektrodové platformy s přímými nanoelektrodami (šířky 100–300 nm), na kterých se nachází úzká dielektrická okna s šířkou blízké průměru nanodrátu (přibližně 100–200 nm). Tyto nanoelektrody byly použity jako mechanická podpora pro zarovnání jednoho nanodrátu a rovněž jako elektrické kontakty pro měření elektrické změny nanodrátu během detekování plynu. Výsledky také zahrnují optimalizaci technik pro odstraňování a opětovné nanášení nanodrátů pro dosažení jedno nanodrátových propojení v poli paralelních elektrod pomocí střídavého elektrického pole jako jednoduché a účinné metody pro zarovnávání nanodrátů (dielektroforéza). Ověření těchto systémů vůči různým plynným látkám (oxidačním a redukčním plynům) bylo provedeno za použití nefunkcionalizovaných a Pt-funkcionalizovaných WO3 nanodrátů syntetizovaných pomocí aerosolové chemické depozice par (AACVD) a topného prvku na bázi tlusté vrstvy na korundové keramice (s provozní teplotou 250 °C), sestaveného spolu s elektrodovou platformou na pouzdru TO-8. Snímací vlastnosti takových systémů vykazovaly lepší citlivost v odporovém režimu na oxid dusičitý (NO2) a ethanol (EtOH) než jejich protějšky využívající nanodrátových filmů. Poslední verze systému pro snímání plynu vyvinutého v této práci (popsaná jako třetí generace čipů) obsahuje třetí izolovanou elektrodu zabudovanou (utopenou) pod citlivým nanodrátem pro zvýšení detekční schopnosti snímání plynu. Testy odezvy na vodík (H2) a oxid dusičitý (NO2) potvrdily zvýšenou funkčnost tohoto systému modulující odezvu senzoru pomocí externího elektrického napětí na utopené elektrodě.

This work deals with branch of gas sensors, their construction and methodology of testing. The general aim is a design and implementation of a station for simple testing of conduction gas sensors. The whole station is conceived as virtual measuring apparatus, operated by PC in LabView environment. The station enables mixing of any two gases at concentration demanded and measuring of the basic conduction characteristics of the thick-film and thin-film gas sensors. The central communication interface and modular conception enable easy expansion of possibilities of the whole apparatus in the future. It is possible to measure up to eight gas sensors split into two TO-12 packages simultaneously.

Both ammonia and phosphine are widely used in industrial processes, and yet they are noxious and exhibit detrimental effects on human health. Despite the remarkable progress on sensors development, there are still some limitations, for instance, the requirement of high operating temperatures, and that most sensors are solely dedicated to individual gas monitoring. Herein, an ultrasensitive, highly discriminative platform is demonstrated for the detection and identification of ammonia and phosphine at room temperature using a graphene nanosensor. Graphene is exfoliated and successfully functionalized by copper phthalocyanine derivate. In combination with highly efficient machine learning techniques, the developed graphene nanosensor demonstrates an excellent gas identification performance even at ultralow concentrations: 100 ppb NH3 (accuracy—100.0%, sensitivity—100.0%, specificity—100.0%) and 100 ppb PH3 (accuracy—77.8%, sensitivity—75.0%, and specificity—78.6%). Molecular dynamics simulation results reveal that the copper phthalocyanine derivate molecules attached to the graphene surface facilitate the adsorption of ammonia molecules owing to hydrogen bonding interactions. The developed smart gas sensing platform paves a path to design a highly selective, highly sensitive, miniaturized, low-power consumption, nondedicated, smart gas sensing system toward a wide spectrum of gases.