Laser Induced Breakdown Spectroscopy (LIBS) which is used to determine the elemental content of various samples, inspects the emission spectroscopy of samples of interest for searching certain elements or identifying the unknown content. In this study, spectroscopic analyses of various kinds of metals, namely, Cu, Fe, Mo, Ti, W, some compounds such as CuBe, ZnSe, ZnS, GaSe, some semimetals like Si, Ge and even gases were investigated by means of a compact-commercial portable LIBS system and an independently constructed experimental set-up consisting of a single pulse system and various kinds of double pulse configurations using Nd:YAG lasers. The contributions of this thesis to the LIBS community can be classified into two main groups- which are experimental and code development. One of the experimental contributions was the investigation of the different crystal surfaces of silicon in which dangling bond density were taken into account for a more precise comparison of atomic emissions. The second experimental contribution was the polarization experiments by which polarization dependency, to some extent, was demonstrated. The third and final one was the orthogonal double pulse configuration with a 45 o incidence angle for both lasers in opposite directions by which it was shown that the positioning becomes straightforward yielding the desired reproducible results. The second major contribution was to develop a basic code for analyzing the experimental data more accurately. In conclusion, by means of the different experimental approaches, factors relating to the enhancement in intensity were investigated and as a result of developing the code, flexibility in upgrading the constraints of element searching was obtained and the updating of the database was accomplished.

The need to ignite within a very short time the aircraft engines led to many studies. However, the ignition process is not yet fully understood. Many experimental studies are based on obtaining ignition probability at different points and in different average flow conditions but few have focused on the study of a single ignition event. The reason for the lack of full understanding is transient nature of the the ignition process, which depends on many physical parameters, before, during and after the deposition of spark energy. The purpose of this study is to develop the tools necessary to understand unique events by simultaneously measuring multiple parameters that affect the ignition process. A new technique of measurement, two-dimensional laser-induced plasma spectroscopy (2D-LIPS) was developed for the spatially resolved concentration gradients of species and energy in a laser-induced plasma. This technique is based on the use of two cameras, each provided with an interference filter centered on a transition atomic emission. This technique provides the initial size of plasma containing the minimum fuel concentration, thereby justifying the success/failure of an event. It was first validated in a mixing layer of air/nitrogen mixture to determine and resolve the spatial uncertainty of the technique. It was then applied to an aviation fuel injection system. The flow of air, preheated to 200_C, was set at 10 g/s and drops of dodecane having a Sauter mean diameter between 30 and 40 _m were inserted. This injector has a aerodynamic instability type Precessing Vortex Core around 550 Hz, measured by 2D-PIV on the droplets at 20 kHz. Simultaneous measurements 2D-LIPS and 2D-PIV at 20 kHz have established a scenario of ignition. A minimum concentration of dodecane and a minimum size of plasma are necessary but not sufficient for a successful ignition. The strength of PVC also appears to play a role in the fate of the initial nucleus. The study proposes to establish conditional probabilities of ignition using measurements by 2D LIPS. It is shown that for ignition tests having an unconditioned probability of 33% show a conditional probability of 88% through the 2D-LIPS measurements.

Le besoin d’allumer avec un temps très court les moteurs aéronautiques a conduit à de nombreuses études. Cependant, le processus d’allumage n’est pas encore parfaitement compris. Beaucoup d’études expérimentales sont basées sur l’obtention de probabilité d’allumage en différents points et sous différentes conditions moyennes de l’écoulement mais peu se sont concentrées sur l’étude d’un évènement unique. La raison pour le peu de compréhension totale est la nature transiente de l’allumage, qui dépend de nombreux paramètres physiques, avant, pendant et après le dépôt de l’énergie. Le but de cette étude est de développer les outils nécessaires à la compréhension d’évènements uniques en mesurant simultanément plusieurs paramètres affectant le processus d’allumage. Une nouvelle technique de mesure; la spectroscopie en deux dimensions de plasma induit par laser (2D-LIPS) a été mise au point pour obtenir les gradients de concentration d’espèces et d’énergie dans un plasma induit par laser. Cette technique se base sur l’utilisation de deux caméras, chacune munies d’un filtre interférentiel centré sur une transition atomique. Cette technique permet d’obtenir la taille initiale du plasma contenant une concentration minimale en combustible, ce qui permet de justifier le succès/l’échec d’un évènement. Elle a d’abord été validée dans une couche de mélange air/oxygène afin d’en déterminer les incertitudes et la résolution spatiale. Elle a ensuite été appliquée à un système d’injection aéronautique. Le débit d’air, préchauffé à 200_C, a été fixé à 10 g/s et les gouttes de dodécane avaient un diamètre moyen de Sauter entre 30 et 40 _m. Cet injecteur présente une instabilité aérodynamique de type Precessing Vortex Core aux alentours de 550 Hz, mesurée par 2D-PIV sur les gouttes à 20 kHz . Les mesures simultanées de 2D-LIPS et et 2D-PIV à 20 kHz ont permis d’établir un scénario d’allumage. Une concentration minimum de dodécane ainsi qu’une taille minimum de plasma sont nécessaires mais non suffisants à un allumage réussi. La force du PVC semble aussi jouer un rôle dans le destin du noyau initial. L’étude propose d’établir des probabilités conditionnées d’allumage en utilisant les mesures de 2D-LIPS. Il est ainsi montré que des essais d’allumage menant à une probabilité non conditionnée de 33% peuvent mener, grâce à la 2D-LIPS, à une probabilité conditionnée de 88%. / The need to ignite within a very short time the aircraft engines led to many studies. However, the ignition process is not yet fully understood. Many experimental studies are based on obtaining ignition probability at different points and in different average flow conditions but few have focused on the study of a single ignition event. The reason for the lack of full understanding is transient nature of the the ignition process, which depends on many physical parameters, before, during and after the deposition of spark energy. The purpose of this study is to develop the tools necessary to understand unique events by simultaneously measuring multiple parameters that affect the ignition process. A new technique of measurement, two-dimensional laser-induced plasma spectroscopy (2D-LIPS) was developed for the spatially resolved concentration gradients of species and energy in a laser-induced plasma. This technique is based on the use of two cameras, each provided with an interference filter centered on a transition atomic emission. This technique provides the initial size of plasma containing the minimum fuel concentration, thereby justifying the success/failure of an event. It was first validated in a mixing layer of air/nitrogen mixture to determine and resolve the spatial uncertainty of the technique. It was then applied to an aviation fuel injection system. The flow of air, preheated to 200_C, was set at 10 g/s and drops of dodecane having a Sauter mean diameter between 30 and 40 _m were inserted. This injector has a aerodynamic instability type Precessing Vortex Core around 550 Hz, measured by 2D-PIV on the droplets at 20 kHz. Simultaneous measurements 2D-LIPS and 2D-PIV at 20 kHz have established a scenario of ignition. A minimum concentration of dodecane and a minimum size of plasma are necessary but not sufficient for a successful ignition. The strength of PVC also appears to play a role in the fate of the initial nucleus. The study proposes to establish conditional probabilities of ignition using measurements by 2D LIPS. It is shown that for ignition tests having an unconditioned probability of 33% show a conditional probability of 88% through the 2D-LIPS measurements.

The path explored in this thesis is testing a plasma temperature measurement approach that accounts for interference in a spectrum. The Atomic Emission Spectroscopy (AES) technique used is called Laser Induced Breakdown Spectroscopy (LIBS) and involves focusing a laser pulse to a high irradiance onto a sample to induced a plasma. Spectrally analyzing the plasma light provides a "finger print" or spectrum of the sample. Unfortunately, spectral line broadening is a type of interference encountered in a LIBS spectrum because it blends possible ionic or atomic transitions that occur in plasma. To make use of the information or transitions not resolved in a LIBS spectrum, a plasma temperature method is developed. The basic theory of a LIBS plasma, broadening mechanisms, thermal equilibrium and distribution laws, and plasma temperature methods are discussed as background support for the plasma temperature method tested in this thesis. In summary, the plasma temperature method analyzes the Full Width at Half the Maximum (FWHM) of each spectral line for transitions provided from a database and uses them for temperature measurements. The first implementation of the temperature method was for simulated spectra and the results are compared to other conventional temperature measurement techniques. The temporal evolution of experimental spectra are also taken as a function of time to observe if the newly developed temperature technique can perform temporal measurements. Lastly, the temperature method is tested for a simulated, single element spectrum when considering interferences from all the elements provided in an atomic database. From stimulated and experimental spectra analysis to a global database consideration, the advantages and disadvantages of the temperature method are discussed.

[ES] En los últimos años, la investigación en motores se ha centrado principalmente en la reducción de emisiones contaminantes y en el aumento de la eficiencia. Muchos de los esfuerzos de investigación actuales en este campo están dirigidos a mejorar y desarrollar nuevas estrategias activas para la reducción de emisiones, en particular centradas en los nuevos conceptos de combustión y en la obtención de un mejor control sobre ella. Su desarrollo requiere la aplicación de nuevas herramientas experimentales y teóricas. Estas herramientas deberían permitir tanto la aplicación de nuevas estrategias activas de control de contaminantes como ampliar el conocimiento básico de los fundamentos de los procesos involucrados. En este contexto es donde se encuadra el objetivo de esta Tesis: el desarrollo y optimización de un nuevo sistema de encendido no intrusivo y modulable, que permitirá el control sobre el tiempo y la ubicación del punto de encendido. Dicho sistema se aplicará para el encendido de chorros Diesel de inyección directa. En particular, se pretende evidenciar cómo las condiciones locales al encendido pueden afectar al desarrollo de la combustión posterior. Para lograr este objetivo, el trabajo de investigación se ha dividido en dos bloques principales. El primero se centra en el desarrollo y la optimización del sistema de encendido. Aprovechando las posibilidades que ofrece el proceso de inducción de plasma con láser y, una vez seleccionado el mejor método de inducción para su aplicación en un entorno especifico como el de un motor, se ha llevado a cabo un proceso de optimización y validación del sistema. Tal proceso resulta de importancia básica en el desarrollo de esta investigación, ya que la aplicación de un sistema de encendido totalmente fiable resulta ser fundamental, tanto en términos de su posible aplicación para control de combustión como en términos de las posibilidades de estudios que pueda ofrecer. Al principio, a partir de un extenso estudio de la literatura sobre el proceso de inducción de plasma con láser, se han obtenido los parámetros fundamentales a tener en cuenta para la aplicación del sistema al encendido de chorros de combustible de inyección directa. A partir de estos parámetros, se ha diseñado un primer sistema de encendido. Luego su fiabilidad en la inducción de plasma ha sido estudiada experimentalmente en condiciones ambientales y de motor, aplicando una metodología de optimización desarrollada en este mismo trabajo experimental. Como resultado principal de este primer bloque de trabajo, se ha podido obtener un sistema de encendido por plasma inducido con láser completamente optimizado y fiable, así como un método novedoso para su validación y optimización. El segundo bloque de trabajo corresponde a la aplicación del sistema al encendido de un chorro Diesel de inyección directa en condiciones reales del motor. El objetivo de este bloque era lograr dos hitos principales: la determinación de las capacidades y los límites del sistema en su aplicación, y el desarrollo de un primer estudio experimental sobre la influencia de las condiciones locales de la zona de encendido sobre una combustión Diesel. Para lograrlo, primero se ha validado la capacidad de encendido del sistema bajo un conjunto adecuado de condiciones termodinámicas, previamente seleccionadas para mantener la máxima efectividad. Los resultados de este estudio, en comparación con los típicos parámetros de autoencendido en las mismas condiciones, han permitido demostrar la capacidad de encendido del sistema. Posteriormente, se ha llevado a cabo una variación paramétrica de tiempos y posiciones en las que inducir el plasma, con el fin de determinar el efecto de las condiciones locales sobre el desarrollo de la combustión Diesel. En este caso, al comparar los resultados obtenidos con los parámetros estándar de autoencendido, se han podido obtener tendencias interesantes, que subra / [CA] En els últims anys, la investigació en motors s'ha centrat principalment en la reducció d'emissions contaminants i en l'augment de l'eficiència. Molts dels esforços d'investigació actuals en aquest camp estan dirigits a millorar i desenvolupar noves estratègies actives per a la reducció d'emissions, en particular centrades en els nous conceptes de combustió i en l'obtenció d'un millor control sobre ella. El seu desenvolupament requereix l'aplicació de noves eines experimentals i teòriques. Aquestes eines haurien de permetre tant el desenvolupament i aplicació de noves estratègies actives de control de contaminants com ampliar el coneixement bàsic dels fonaments dels principals processos involucrats. En aquest context és on s'enquadra l'objectiu principal d'aquesta Tesi: el desenvolupament i l'optimització d'un nou sistema d'encés no intrusiu i modulable, que permetrà el control sobre el temps i la ubicació del punt d'encés. Aquest sistema s'aplicarà per a l'encesa de dolls Diesel d'injecció directa. En particular, es pretén evidenciar com les condicions locals a l'encesa poden afectar el desenvolupament de la combustió posterior. Per a aconseguir aquest objectiu, el treball de recerca s'ha dividit en dos blocs principals. El primer se centra en el desenvolupament i l'optimització del sistema d'encesa. Aprofitant les possibilitats que ofereix el procés d'inducció de plasma amb làser i, una vegada seleccionat el millor mètode d'inducció per a la seua aplicació en un entorn especifique com el d'un motor, s'ha dut a terme un procés d'optimització i validació del sistema. Tal procés resulta d'importància bàsica en el desenvolupament d'aquesta investigació, ja que l'aplicació d'un sistema d'encesa totalment fiable resulta ser fonamental, tant en termes de la seua possible aplicació per a control de combustió com en termes de les possibilitats d'estudis que puga oferir. Al principi, a partir d'un extens estudi de la literatura sobre el procés d'inducció de plasma amb làser, s'han obtingut els paràmetres fonamentals a tindre en compte per a l'aplicació del sistema a l'encesa de dolls de combustible d'injecció directa. A partir d'aquests paràmetres, s'ha dissenyat un primer sistema d'encesa. Després la seua fiabilitat en la inducció de plasma ha sigut estudiada experimentalment en condicions ambientals i de motor, aplicant una metodologia d'optimització desenvolupada en aquest mateix treball experimental. Com a resultat principal d'aquest primer bloc de treball, s'ha pogut obtindre un sistema d'encés per plasma induït amb làser completament optimitzat i fiable, així com un mètode nou per a la seua validació i optimització. El segon bloc de treball correspon a l'aplicació del sistema a l'encesa d'un doll Dièsel d'injecció directa en condicions reals del motor. L'objectiu d'aquest bloc era aconseguir dues fites principals: la determinació de les capacitats i els límits del sistema en la seua aplicació a l'encesa de dolls d'injecció directa, i el desenvolupament d'un primer estudi experimental sobre la influència de les condicions locals de la zona d'encesa sobre el desenvolupament posterior d'una combustió Diesel. Per a aconseguir-ho, primer s'ha validat la capacitat d'encesa del sistema sota un conjunt adequat de condicions termodinàmiques, prèviament determinades per a mantindre la màxima efectivitat. Els resultats d'aquest estudi, en comparació amb els típics paràmetres d'autoencesa en les mateixes condicions, han permés demostrar la capacitat d'encesa del sistema. Posteriorment, s'ha dut a terme una variació paramètrica de temps i posicions en les quals induir el plasma per a forçar l'encesa, amb la finalitat de determinar l'efecte de les condicions locals sobre el desenvolupament de la combustió Diesel. En aquest cas, en comparar els resultats obtinguts amb els paràmetres estàndard d'autoencesa, s'han pogut obtindre tendències interessants, que subratl / [EN] In the recent years the engine research has been mainly focused on the pollutant emissions reduction and on increasing the efficiency. Many of the actual research efforts in the field of the Internal Combustion Engines are aimed to improve and develop new active strategies for emission reduction, particularly centered on new combustion concepts and a general improved combustion control. Their development requires the application of new experimental and theoretical tools, allowing both to be directly applied as an active pollutant control strategy and to permit to expand the basic knowledge of the governing processes' fundamentals. This is the concept where the main objective of this Thesis is framed: the development and optimization of a new, non-intrusive and modulable ignition system that will allow the control on the position and timing of the ignition spot. Such system will be applied to the ignition of direct injection diesel sprays in order to expand the knowledge of the ignition process, particularly considering how the local conditions at the ignition are affecting the subsequent combustion development. In order to accomplish the proposed objective, the research work has been divided in two main blocks. The first one is focused on the development and optimization of the ignition system. Taking advantage of the possibilities granted by the laser plasma induction process and, once selected the best induction method for its application in an internal combustion engine environment, a process of optimization of the ignition system has been carried out. Such optimization process results to be of basic importance for this research development. In fact, the application of fully reliable ignition system is fundamental both in terms of its possible direct application for combustion modulation purposes and in terms of the new study possibilities that is able to deliver. At first, from an extensive literature survey upon the plasma laser induction process, the fundamental parameters to focus on for the application of the system to the ignition of direct injection fuel sprays have been obtained. Starting from these parameters, a first ignition system has been designed, and then its reliability in the plasma induction has been experimentally tested under ambient and engine-like conditions, applying an original optimization methodology. As a main result of this first work block, a fully optimized and completely reliable laser induced plasma ignition system has been obtained, and an original system validation and optimization method has been developed. The second work block corresponds to the application of the ignition system to a direct injection diesel spray under real engine conditions. This block aimed to accomplish two main goals: the determination of the system capabilities and limits for the spray ignition application and the development of a first experimental study regarding the influence of the local conditions at the ignition location on the subsequent development of diesel combustion. In order to do so, first the system ignition capability has been tested on a diesel spray, under an adequate set of thermodynamic conditions determined to maintain the maximum possible system feasibility. The results of this study, compared with the standard combustion diagnostics parameters for the autoignition event at the same conditions, proved its ignition capabilities. Then a parametric variation of the local timing and position of the induced plasma generation region has been carried out, in order to determine the effect of the local condition on the combustion development. By comparing the obtained results with standard autoignition parameters at the same conditions, interesting trends have been obtained, that underline the system ability to control and modulate the combustion event / Pinotti, M. (2019). COMBUSTION CONTROL OF DIESEL SPRAYS BY MEANS OF LASER INDUCED PLASMA IGNITION [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/130205

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Η ολοένα αυξανόμενη ανάγκη για γρήγορες, αξιόπιστες και εύκολες στην χρήση αναλυτικές τεχνικές, οι οποίες μπορούν να χρησιμοποιηθούν εντός και εκτός εργαστηρίου, έδωσε ιδιαίτερη ώθηση για ανάπτυξη τεχνικών που να πληρούν τις παραπάνω προϋποθέσεις. Η Φασματοσκοπία Πλάσματος Επαγόμενου από laser (Laser-Induced Breakdown Spectroscopy-LIBS), λόγω των σημαντικών της πλεονεκτημάτων, έχει προταθεί ως μια τεχνική για στοιχειακή ανάλυση υλικών, ανεξαρτήτως της κατάστασής τους (στερεή, υγρή ή αέρια). Κατά την τεχνική LIBS, η ατομοποίηση και η διέγερση των ατόμων του υλικού γίνεται σε ένα στάδιο, ενώ δεν απαιτείται προετοιμασία του δείγματος. Έτσι, τα τελευταία χρόνια η τεχνική LIBS είναι η πιο διαδεδομένη αναλυτική τεχνική βασισμένη στα laser. Στην παρούσα διδακτορική διατριβή η τεχνική LIBS εφαρμόζεται σε δυο διαφορετικά πεδία έρευνας: στις φλόγες υδρογονανθράκων-αέρα και στην μελέτη πολυμερικών/πλαστικών δειγμάτων. Στις φλόγες υδρογονανθράκων-αέρα, η φασματοσκοπία πλάσματος επαγόμενου από laser χρησιμοποιήθηκε για τον καθορισμό του λόγου ισοδυναμίας (φ), ο οποίος εκφράζει την αναλογία καύσιμου προς οξειδωτικό μέσο, σε φλόγες αέριων και υγρών υδρογονανθράκων μέσω των λόγων των εντάσεων των φασματικών γραμμών του υδρογόνου, H, οξυγόνου, O, και άνθρακα, C. Μέσω αυτής της συσχέτισης, πραγματοποιήθηκαν χωρικά αναλυμένες μετρήσεις του φ σε προ-αναμεμιγμένες φλόγες υδρογονανθράκων-αέρα διαφορετικής γεωμετρίας, οι οποίες παρείχαν σημαντικές πληροφορίες για την δομή της φλόγας. Επιπλέον, η τεχνική LIBS χρησιμοποιήθηκε για την ανίχνευση υδρατμών στον αέρα και σε φλόγες υδρογονανθράκων-αέρα και έγινε φανερό πως οι υδρατμοί προκαλούν σημαντικές αλλαγές στην δομή και τα χαρακτηριστικά της φλόγας, ενώ μέσω των φασματικών γραμμών του υδρογόνου, H, οξυγόνου, O, και αζώτου, Ν, οι υδρατμοί μπορούν να καθοριστούν ποιοτικά. Σε ότι αφορά τα πολυμερικά/πλαστικά δείγματα, η τεχνική LIBS μπορεί να αποτελέσει μια σημαντική μέθοδο για την ταυτοποίηση πολυμερικών δειγμάτων, οπότε στην συνέχεια, έγινε μελέτη των χαρακτηριστικών του πλάσματος που δημιουργείται κατά την ακτινοβόληση πολυμερικών/πλαστικών δειγμάτων και πως αυτά επηρεάζονται από τις ιδιότητες της δέσμης laser καθώς και από το περιβάλλον. / The continuously increasing needs for fast, reliable and easy to use analytical techniques operating remotely and in situ, under laboratory and/or field conditions have boosted considerable research efforts towards the development of novel analytical techniques satisfying these requirements. In that view, Laser-Induced Breakdown Spectroscopy (LIBS) has been proposed as an efficient tool for elemental analysis of various types of samples exhibiting several attractive advantages. LIBS is a laser based spectroscopic technique which permits the simultaneous atomization and excitation of the sample in one step, without requiring any sample preparation. In addition, LIBS operates successfully with all kinds of samples while the results are obtained within few seconds. Because of these advantages and its attractive simplicity, LIBS has become rapidly the most popular laser based analytical technique. In this work, LIBS is used in two different fields: the study of combustible hydrocarbon-air mixtures and the study of the created plasma in polymeric samples. In hydrocarbon –air flames, LIBS was applied for the determination of the local equivalence ratio in different hydrocarbon (gaseous and liquid) -air mixtures. In particular, it is shown that the ratio of the intensities of atomic spectral lines of H, C and O, emitted from a laser induced spark in the gaseous mixture, can be used for the rapid and accurate determination of the local equivalence ratio. There are also obtained spatially resolved equivalence ratio profiles in laminar premixed flames of different geometries (Bunsen type and impinging flames), which are used in order to reveal and quantify important flame structure features. Additionally, it is shown that LIBS can be used for the detection of humidity in air and in hydrocarbon-air flames. The results obtained showed that humidity causes significant changes in flame characteristics, and through the atomic spectral lines of H, N and O, humidity can be qualitatively be determined. In polymeric samples, LIBS technique is used for the identification of polymers and plastics for recycling purposes. Due to the importance of this application, the properties of the plasma created are extensively studied. It is shown that plasma generation and expansion is effected by the laser properties (laser energy, laser pulse) and by the environmental conditions (pressure).

This PhD work was devoted to the understanding of the laser-induced plasma on organic materials and theapplication of laser-induced breakdown spectroscopy (LIBS) to quantitative analysis of these materials. Itcontributes to deepen our knowledge on the physical mechanisms involved in laser-matter interaction, plasmageneration, evolution and expansion of the plasma into the ambient gas, with emphasis on plasmas induced onorganic targets. It also intends to improve the performance of LIBS for the analysis of organic materials. Thespecificity for organic targets fits the current focus of the international community working on LIBS, toimprove the control of the plasma induced on this kind of material which has a distinguished optical prosperitywith respect to that of metals, better known for laser ablation. It addresses also the growing need to apply theLIBS technique to organic materials for different applications in the environmental, food, or biomedicaldomains. The works in this thesis were therefore presented in this thesis document according to the followingorganization.After the General Introduction which introduces the scientific and technological contexts, Chapter Irecalls the basic theoretical elements necessary to understand the phenomenon of plasma generation by laserablation, and its evolution in the background gas. Ablation of organic material is emphasized. Procedures andtechniques of diagnostics of laser-induced plasma were then presented with a focus on the transient andinhomogeneous nature of the expanding plasma. Chapter II focuses on the generation and the evolution of theplasma induced on the skin of a potato, a typical sample of agricultural product. The characteristics of plasmainduced on a soft and wet organic target, such as a fresh potato, was something unknown when the thesis workstarted. These characteristics provide the necessary basis for the quantitative analysis of the trace andultra-trace metallic elements in these samples. Following this characterization, semi-quantitative analyticalresults were extracted from LIBS spectra corresponding to potato skin. Chapter III is presented in thecontinuity of Chapter II for the application of LIBS to the quantitative analysis of organic materials. Acomparative study on the analytical results with LIBS and ICP-AES for milk powders allows an assessment ofthe performances of quantitative analysis by LIBS for organic materials, and a validation of the CF-LIBSprocedure that we have developed. Different from Chapters II and III where attention was paid to trace metalelements, Chapter IV studies the behavior of the major elements that make up the matrix of organic material,which are 4 known organic elements: H, C, O, N. During the decomposition of organic material by laserablation, these elements can be found in the form of molecular fragments, or recombined into molecularspecies. We then study in this Chapter the evolution of these species as a function of the laser ablationparameters, the laser wavelength in particular. The thesis document ends with a general conclusion andoutlooks.

In the frame of this thesis, a new experimental setup for the measurement of the energy loss of carbon ions at maximum stopping power in a hot laser-generated plasma has been developed and successfully tested. In this parameter range where the projectile velocity is of the same order of magnitude as the thermal velocity of the plasma free electrons, large uncertainties of up to 50% are present in the stopping-power description. To date, no experimental data are available to perform a theory benchmarking. Testing the different stopping theories is yet essential for inertial confinement fusion and in particular for the understanding of the alpha-particle heating of the thermonuclear fuel. Here, for the first time, precise measurements were carried out in a reproducible and entirely characterized beam-plasma configuration. It involved a nearly fully-stripped ion beam probing a homogeneous fully-ionized plasma. This plasma was generated by irradiating a thin carbon foil with two high-energy laser beams and features a maximum electron temperature of 200 eV. The plasma conditions were simulated with a two-dimensional radiative hydrodynamic code, while the ion-beam charge-state distribution was predicted by means of a Monte-Carlo code describing the charge-exchange processes of projectile ions in plasma. To probe at maximum stopping power, high-frequency pulsed ion bunches were decelerated to an energy of 0.5 MeV per nucleon. The ion energy loss was determined by a time-of-flight measurement using a specifically developed chemical-vapor-deposition diamond detector that was screened against any plasma radiation. A first experimental campaign was carried out using this newly developed platform, in which a precision better than 200 keV on the energy loss was reached. This allowed, via the knowledge of the plasma and of the beam parameters, to reliably test several stopping theories, either based on perturbation theory or on a nonlinear T-Matrix formalism. A preliminary analysis suggests that the energy deposition at maximum stopping power is significantly smaller than predicted, particularly, by perturbation approaches.

La technique laser-induced breakdown spectroscopy (LIBS), qui consiste à exploiter le spectre du plasma induit par laser sur la surface de l'échantillon pour déterminer sa composition élémentaire, a été inventée il y a plus de 50 ans. Récemment, elle connaît un développement rapide, poussée par des besoins d'application dans différents domaines, citons par exemple, exploration océanique, détection de pollution environnementale, ou contrôle de procédés industriels. Cette technique utilise le plasma généré par ablation laser comme la source spectroscopique. La particularité de LIBS est que le plasma induit par laser présente un comportement transitoire et une distribution spatiale qui ne soit pas uniforme en général. Bien que la détection résolue en temps puisse améliorer considérablement la performance de LIBS, surtout pour le procédé de LIBS autocalibration avec une meilleure détermination de température, l'évolution temporelle du plasma est souvent corrélée avec sa morphologie et son inhomogénéité spatiale. L'étude de la morphologie ainsi que la structure interne du plasma avec l'évolution pendant l'expansion de celui-ci dans un gaz ambiant, représente donc un point crucial pour l'optimisation du plasma entant qu'une source spectroscopique. Suite à la thèse de Qianli Ma réalisée dans notre équipe et soutenue en décembre 2012, qui a été notamment consacrée à l'étude de l'effet de la longueur d'onde du laser d'ablation sur les propriétés et l'évolution du plasma dans un gaz ambiant d'argon, la présente thèse s'intéresse aux effets des autres paramètres, la fluence du laser d'ablation, la durée de l'impulsion, et les différents gaz ambiants (argon ou air), sur la morphologie et la structure du plasma. Par ailleurs, les mécanismes microscopiques conduisant à l'onde de détonation soutenue par laser dans argon ou dans l'air sont aussi étudiés. Lors du refroidissant du plasma dans l'air, des oxydes métalliques peuvent se former. L'étude de la formation de molécules, au-delà de l'intérêt pratique pour la LIBS, fournit également un aperçu de la cinétique chimique dans le plasma, ce qui est intéressant pour l'étude de la transformation du plasma en phase gazeuse à une phase recondensée de nanoparticules / Laser-induced breakdown spectroscopy (LIBS) has been invented for more than 50 years, which analyzes the spectrum of the laser-induced plasma to determine the elemental composition of the ablated sample. Recently, LIBS technique has been well developed and applied in different domains, for example oceanic exploration, pollution monitoring in the environment. LIBS uses the ablation plasma as a light source that contains the elemental composition information of the sample. However, the laser-induced plasma exhibits a transient behavior. Although time-resolved and gated detection can greatly improve the performance of the LIBS technique especially that of calibration-free LIBS (CF-LIBS) with a better determination of plasma temperature, the temporal evolution of the plasma is correlated to its morphology and its spatial inhomogeneity. The determination of the morphology as well as the internal structure of the plasma together with their evolution during plasma expansion into the ambient gas is therefore crucial for the optimization of the use of ablation plasma as a spectroscopic emission source. Evolutions of the morphology and the internal structure of the ablation plasma are considered as the consequence of its hydrodynamic expansion into the ambient gas. Following the thesis of Qianli Ma which has studied the effect of laser wavelength on the behavior of the plasma induced in an ambient gas of argon, the present thesis has used the same diagnostic techniques (time- and space-resolved emission spectroscopy and fast spectroscopic images) together with 1064 nm ns laser pulse ablation of a target of aluminum to investigate the effects of other parameters, such as the fluence and the duration of laser pulse, the effect of different ambient gases (argon and air), on the morphology and internal structure of the plasma. Furthermore, in order to understand the effects of these parameters on the properties of the plasma, the microscopic mechanisms during post ablation and the propagation of the plasma are also studied. While the plasma cools down in air, molecules are formed, AlO for instance. So the thesis also studied the condition for the formation of the molecules in the plasma. Beyond the practical interest of this study for LIBS, it provides also insights to the kinetics of the AlO molecule formation in laserinduced plasma