Τα τελευταία χρόνια, η φασματοσκοπία πλάσματος επαγόμενο από λέιζερ (LIBS) έχει προσελκύσει μεγάλο ερευνητικό ενδιαφέρον καθώς αποτελεί μία πειραματικά απλή και αποτελεσματική τεχνική, η οποία παρέχει τη δυνατότητα λήψης μετρήσεων για απευθείας ποιοτική και ποσοτική στοιχειακή ανάλυση. Η τεχνική LIBS στηρίζεται στη δημιουργία σπινθήρα/πλάσματος μέσω ισχυρά εστιασμένης δέσμης λέιζερ στην επιφάνεια ή στο εσωτερικό του δείγματος, στην ακόλουθη διέγερση και ατομοποίηση των στοιχείων του στόχου και στην τελική καταγραφή και φασματοσκοπική ανάλυση της εκπεμπόμενης ακτινοβολίας του πλάσματος. Λόγω των πολλών πλεονεκτημάτων που συγκεντρώνει η τεχνική, το LIBS έχει προταθεί για πληθώρα πρακτικών, τεχνικών και τεχνολογικών εφαρμογών σε ένα ευρύ φάσμα ερευνητικών πεδίων. Από την άλλη μεριά, στον τομέα της καύσης, η ποσότητα καυσίμου σε ένα εύφλεκτο μίγμα είναι αντικείμενο μείζονος σημασίας καθώς επηρεάζει σημαντικά την απόδοση των χημικών διεργασιών και την παραγωγή και εκπομπή ρύπων. Επομένως, δημιουργείται η ανάγκη ανάπτυξης μίας γρήγορης και μη παρεμβατικής διαγνωστικής τεχνικής για τη μέτρηση της περιεκτικότητας του καυσίμου τοπικά στη φλόγα με καλή τόσο χωρική όσο και χρονική ανάλυση. Στα πλαίσια της παρούσας διδακτορικής διατριβής, η τεχνική LIBS η οποία συγκεντρώνει όλα αυτά τα πλεονεκτήματα χρησιμοποιήθηκε για αυτό το σκοπό. Κατά τη διάρκεια των πειραμάτων, χρησιμοποιήθηκαν πηγές λέιζερ διάρκειας παλμών ns και fs, ενώ τα συστήματα καύσης που μελετήθηκαν ήταν φλόγες υδρογονανθράκων-αέρα, στρωτής και τυρβώδους ροής, απλής και συνθετότερης γεωμετρίας. Από τα LIBS φάσματα φλογών διαφορετικής σύστασης, προέκυψε λοιπόν ότι υπάρχει μία ισχυρή εξάρτηση μεταξύ των εντάσεων διαφόρων φασματικών γραμμών με το λόγο ισοδυναμίας. Επομένως, μέσω της συσχέτισης αυτής μπορεί να επιτευχθεί με μεγάλη ακρίβεια τόσο η μέτρηση της περιεκτικότητα σε καύσιμο φλογών άγνωστης σύστασης όπως επίσης και η μέτρηση της κατανομής του καυσίμου τοπικά μέσα σε όλη την έκταση της φλόγας παρέχοντας σημαντικές πληροφορίες για την δομή της. Τέλος, εφαρμόστηκε μία παραπλήσια διαγνωστική τεχνική, κατά την οποία η διηλεκτρική κατάρρευση του μέσου ήταν αποτέλεσμα ενός ηλεκτρικού σπινθήρα: electrical Spark Induced Breakdown Spectroscopy (SIBS) όπου και πραγματοποιήθηκε η συγκριτική μελέτη της ακτινοβολίας του πλάσματος επαγόμενο μέσω οπτικής και ηλεκτρικής διέγερσης. / Laser induced breakdown spectroscopy (LIBS) has attracted a lot of scientific interest during the last two decades as it is generally considered to be an experimentally simple and efficient laser-based technique which can perform real-time, qualitative and quantitative elemental analysis. The basic idea of LIBS is the creation of spark/plasma through tight focusing of a laser beam on the surface or into a sample, the subsequent excitation and atomization of the species of the sample at the location where the spark is formed and the final detection and spectroscopic analysis of the emitted radiation from the decaying plasma. Seeing the numerous advantages holding the technique, LIBS has been proposed for many practical, technical and technological applications in various scientific areas. On the other hand, in the field of combustion, the proportion of fuel in a combustible mixture is of great importance as it strongly affects the efficiency of the chemical processes and the production of soot emissions. Therefore, there is a continuously increasing need for the development of a rapid and non-perturbative diagnostic technique for the determination of the fuel content locally in the flame structure with good spatial and temporal resolution. Ιn the present dissertation, LIBS technique which offers such advantages has been applied for combustion diagnostics purposes. During the experiments, laser systems with pulse duration in the scale of ns and fs have been applied as excitation sources, while the combustible mixtures under investigation were hydrocarbon-air flames, of laminar and turbulent flow with simple and more complicated structures. From the LIBS spectra in flames of different compositions, it was exhibited that there is a strong dependence of the intensities of various spectral lines on the equivalence ratio, which demonstrates that the precise determination of the amount of fuel can be performed. Also based on this correlation, the determination of the equivalence ratio locally everywhere within the flame can be achieved giving useful information about its structure. Finally, a similar diagnostic technique has been employed. The dielectric breakdown is held using a spark generator and the technique is called electrical Spark Induced Breakdown Spectroscopy (SIBS). The emitted light of the two plasmas induced by optical and electrical excitation was collected and a comparative study was performed.

Submitted by Bruna Rodrigues (bruna92rodrigues@yahoo.com.br) on 2016-09-15T20:31:27Z No. of bitstreams: 1 DissECA.pdf: 4704364 bytes, checksum: 1909457a146bdb29a74ad65130ca2bd9 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-16T19:58:59Z (GMT) No. of bitstreams: 1 DissECA.pdf: 4704364 bytes, checksum: 1909457a146bdb29a74ad65130ca2bd9 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-16T19:59:07Z (GMT) No. of bitstreams: 1 DissECA.pdf: 4704364 bytes, checksum: 1909457a146bdb29a74ad65130ca2bd9 (MD5) / Made available in DSpace on 2016-09-16T19:59:13Z (GMT). No. of bitstreams: 1 DissECA.pdf: 4704364 bytes, checksum: 1909457a146bdb29a74ad65130ca2bd9 (MD5) Previous issue date: 2015-03-27 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coarse particulate matter with aerodynamic diameter smaller than 10μm (PM10) have long been considered as air pollutants associated with health issues. They penetrate into the upper respiratory tract, causing respiratory problems such as worsening of asthma. The aim of this study was to determine and quantify the distribution of chemical elements in the PM10 particulate matter present in the atmosphere of the city of Sao Carlos (Sao Paulo). Samples were collected daily for a period of 23h and 30 minutes, from April 16, 2014 to April 16, 2015. A high-volume sampler (AGV-PM10) with micro quartz and fiber glass filters were used. The filters were subjected to gravimetric analysis to obtain the mass of PM10 and were then analyzed by energy dispersive X-ray fluorescence and Laser Induced Breakdown Spectroscopy to identify and quantify the chemical composition of the samples. The highest average concentration during twelve-month period was 70.41μg/m³ (August, 2014) and the smallest was 22.59μg/m³ (January, 2015). The annual arithmetic average found for the twelve months period was 42.71μg/m³. If compared with annual arithmetic average limit of 40μg/m³, established by CETESB, the value is slightly above and below 50 μg/m³ (CONAMA). If we consider the limit established by the World Health Organization (WHO), which is 20μg/m³, this value is much higher than recommended. The chemicals elements found were characteristic of urban areas / O material particulado, cujo diâmetro aerodinâmico é menor do que 10μm vem sendo considerado como poluente atmosférico muito associado a questões de saúde, uma vez que são os que penetram em vias respiratórias, agravando problemas como o da asma, por exemplo. O objetivo deste trabalho foi avaliar os níveis de concentração de material particulado (MP10) e determinar a distribuição dos elementos químicos deste material particulado presente no ar atmosférico do centro da cidade de São Carlos (São Paulo). As amostras foram coletadas diariamente, por um período de 23h e 30 minutos, entre 16 de abril de 2014 a 16 de abril de 2015. Foi utilizado um amostrador de grandes volumes (AGV-MP10), submetendo os filtros, de fibra de vidro e de micro quartzo, à análise gravimétrica para obtenção de massa de MP10, Fluorescência de Raios-X de Energia Dispersiva de (EDX) e a Espectroscopia de ruptura induzida por laser (LIBS) para identificação e quantificação da composição química elementar das amostras. A maior concentração média do período de doze meses amostrado foi de 70,41μg/m³ em agosto/2014 e a menor de 22,59μg/m³ em janeiro/2015. A média aritmética anual encontrada para o período de doze meses foi de 42,71μg/m³. Se comparada com a média aritmética anual do limite estabelecido pela CETESB, de 40μg/m³, o valor está um pouco acima e um pouco abaixo de 50 μg/m³(CONAMA). Se for considerado o limite estabelecido pela Organização Mundial da Saúde (OMS), que é de 20 μg/m³, este valor encontra-se muito acima do recomendado. Os elementos químicos encontrados são característicos de áreas urbanas e apresentam resultados semelhantes a estudos anteriores na cidade.

LIBS é um método baseado na espectrometria de emissão óptica que emprega a microamostragem por ablação por laser e formação de um microplasma para a determinação dos elementos químicos presentes na amostra. Neste trabalho, o método foi avaliado para a análise de embalagens plásticas produzidas com polietileno de alta densidade e polipropileno. A construção de curvas de calibração com amostras dos polímeros contendo diferentes concentrações de Cd, Cr e Pb e a determinação desses analitos, assim como os efeitos da taxa de repetição do laser, número de pulsos, fluência e diâmetro de focalização foram estudados. O sistema LIBS utilizado foi composto por um laser pulsado de Nd:YAG operando a 064 nm, com pulsos de 5 ns e máxima energia de 360 mJ/pulso. Os sinais de emissão foram coletados por um conjunto de lentes acoplado por fibra óptica ao espectrômetro com montagem Echelle e detector ICCD. Os parâmetros instrumentais foram ajustados em 10 pulsos acumulados, 2 \'mü\'s de atraso e 6 \'mü\'s de integração. O software ESAWIN, o banco de dados de espectros atômicos e iônicos do NIST e algoritmo desenvolvido em ambiente MATLAB® foram utilizados para aquisição e tratamento dos dados. A avaliação da topografia das crateras nas placas dos polímeros foi feita por perfilometria e microscopia eletrônica de varredura, que proporcionaram informações úteis para a caracterização das crateras. As massas removidas das placas de polietileno de alta densidade e de polipropileno foram calculadas a partir dos volumes das crateras obtidos pelas análises perfilométricas. A taxa de repetição e número de pulsos do laser tiveram efeitos marcantes na ablação dos polímeros, e as principais causas foram atribuídas ao grau de cristalinidade, à temperatura de fusão cristalina (Tm) e à temperatura de transição vítrea (Tg). Os resultados desta tese indicaram que diâmetros de focalização da ordem de 600 \'mü\'m e fluências entre 50 e 85 J cm-2 podem ser recomendados para análises de PEAD e PP por LIBS com laser de Nd:YAG@1064 nm (pulsos de 5 ns) e taxa de repetição de 10Hz. Nessas condições, as curvas de calibração obtidas apresentaram boa correlação. Identificaram-se três amostras contaminadas por Cd, Cr e Pb dentre 60 embalagens plásticas analisadas. A comparação dos resultados obtidos por LIBS e ICP OES apresentou concordâncias e algumas diferenças significativas (teste t ao nível de 95% de probabilidade) que foram associadas a efeitos de matriz observados na análise dos polímeros por LIBS / LIBS is an optical emission spectroscopy technique that employs a laser for micro sampling and induction of a plasma for determination of chemical elements in a sample. In this work, LIBS was evaluated for the analysis of plastic packaging produced with high density polyethylene (HDPE) and polypropylene (PP). Plates of these polymers with different concentrations of Cd, Cr and Pb were prepared for evaluating the effects of laser repetition rate, number of pulses, fluence and laser focusing as well as for building the analytical calibration curves. The LIBS system was designed by using a Q-Switch Nd:YAG laser operating at 1064 nm (5 ns, 360 mJ/pulse) and the emission signals were collected by lenses into an optical fiber coupled to a high-resolution echelle spectrometer equipped with ICCD. Instrumental parameters consisted of 10 accumulated laser pulses, 2 \'mü\'s delay time and 6 \'mü\'s integration time gate. Software ESAWIN, NIST atomic database and an algorithm develop in MATLAB® were used for acquisition and data processing. The evaluation of topographical features of craters on the plates of the polymers was carried out by perfilometry and scanning electron microscopy, and provides useful information for the characterization of the craters. The mass removal of HDPE and PP were calculated using craters volume obtained in perfilometric analysis. The repetition rate and number of laser pulses affect the ablation process in polymers. Moreover, the main properties of polymers that affect the ablation are degree of crystallinity, crystalline melting temperature (Tm) and glass transition temperature (Tg). The results indicated that laser focusing of 610 \'mü\'m and fluences between 50 and 85 J cm-2 can be indicated for LIBS analysis of HDPE and PP with Nd:YAG@1064 nm, 5 ns and 10 Hz. Under these conditions the calibration curves obtained presented good correlations and 3 samples containing Cd, Cr and Pb were identified from 60 samples from the local market. LIBS results compared well with ICP OES but some data presented significant differences by applying a t-test at 95 % confidence level, which were mainly associated to matrix effects observed in the analysis of polymers by LIBS

A influência das variáveis associadas ao laser como a fluência, o comprimento de onda, e a duração do pulso, assim como as relacionadas às propriedades das amostras, como a distribuição do tamanho das partículas e as características químicas da matriz, foram avaliadas visando à determinação quantitativa de macro- (P, K, Ca, Mg) e micronutrientes (Cu, Fe, Mn, Zn, B) em pastilhas de materiais vegetais por espectrometria de emissão óptica com plasma induzido por laser (LIBS). Os efeitos da distribuição do tamanho das partículas e da fluência do laser foram investigados a partir da análise de amostras peneiradas (150-20 µm) empregando-se um sistema LIBS, em regime temporal de nanossegundos (ns-LIBS), montado com um laser de Nd:YAG a 1064 nm (pulsos de 5 ns e 360 mJ)e um espectrômetro com óptica Echelle e detector ICCD. Observou-se um aumento na sensibilidade e na precisão das medições com a diminuição do tamanho das partículas usadas no preparo das pastilhas, e uma diminuição dos efeitos de matriz causados por diferenças no tamanho das partículas, quando pastilhas preparadas com partículas < 75 µm foram analisadas com pulsos de 50 J cm-2. Verificou-se uma melhora significativa na exatidão das medições de Mg, Fe, Mn e Zn feitas em um conjunto de pastilhas de folhas de cana-de-açúcar (partículas < 75 µm) empregando-se esta fluência. Em uma segunda etapa, observou-se que variações no comprimento de onda do laser de Nd:YAG (1064, 532, 355 e 266 nm) não influenciaram de maneira significativa a precisão e exatidão das medições em pastilhas de folhas de cana-de-açúcar, obtendo-se correlações lineares entre as intensidades dos sinais de emissão e as correspondentes frações de massa dos analitos. Variações no comprimento de onda do laser de Nd:YAG não afetaram a análise de um conjunto heterogêneo de amostras, composto por pastilhas de folhas de plantas de diferentes espécies, como soja, cana-de-açúcar, milho, citros, café, por exemplo, por ns-LIBS. No entanto, diferentemente do observado para o conjunto de pastilhas de folhas de cana-de-açúcar, observou-se, uma baixa correlação (r cal < 0,90) entre as frações de massa de Ca, Mg, P, Cu, Fe, Mn e Zn determinadas por ns-LIBS e os valores de referência, o que demonstra a baixa robustez de ns-LIBS frente às variações na composição química das matrizes. Posteriormente, analisou-se este conjunto heterogêneo de amostras com sistema LIBS, em regime temporal de femtossegundos (fs-LIBS), montado com laser de Ti:Safira (pulsos de 60 fs e 1,65 mJ) e espectrômetro com óptica Czerny-Turner e ICCD. Demonstrou-se que o uso de pulsos em regime de fs proporcionou calibrações e validação menos dependentes da composição química das matrizes. As frações de massa de Ca, Mg, P, Fe e Mn previstas por fs-LIBS foram estatisticamente concordantes com os valores de referência, independentemente do modelo de calibração usado. Além disso, o uso de calibração multivariada melhorou a capacidade preditiva de ns-LIBS, assemelhando-se à de fs-LIBS. Concluiu-se que o emprego de fs-LIBS foi a estratégia mais robusta e que ofereceu maior flexibilidade à variabilidade matricial / The influence of laser properties, such as fluence, wavelength and pulse duration, as well as sample characteristics, such as particle size distribution and chemical matrix composition, was evaluated aiming at the quantitative determination of macro- (P, K, Ca, Mg) and micronutrients (Cu, Fe, Mn, Zn, B) in pellets of plant materials by laser-induced breakdown spectroscopy (LIBS). Firstly, the effects of particle size distribution and laser fluence on the analysis of pellets (test samples) prepared with sieved samples (from 150 to 20 µm apertures) were investigated. Experiments were carried out with a nanosecond LIBS (ns-LIBS) system by using a Q-switched Nd:YAG laser at 1064 nm (5 ns; 360 mJ) and a spectrometer with Echelle optics and intensified charge-coupled device (ICCD) detector. Results indicated that smaller particles yielded to sensitivities\' enhancement and attained better measurements\' precision. Moreover, matrix effects were reduced by analyzing pellets prepared from < 75 ?m sieved fractions and pulses of 50 J cm-2. In addition, there was a significant improvement on accuracy of Mg, Fe, Mn and Zn measurements in a set of test samples of sugarcane leaves by using this fluence. In a second experiment, variations in the Nd:YAG laser wavelength (1064, 532, 355 and 266 nm) did not affect the analysis of test samples of sugarcane leaves, and provided linear correlations between emission signal intensities and corresponding analytes mass fractions. In addition, variations within Nd:YAG laser wavelength did not affect the analysis of a heterogeneous sample set composed by pellets of leaves from different crops, such as soy, sugarcane, maize, citrus and coffee by ns-LIBS. However, in contrast to previous findings, the univariate calibration models for ns-LIBS presented lower linearity (r cal < 0.90) for Ca, Mg, P, Cu, Fe, Mn and Zn, no matter the laser wavelength used for the analysis. These circumstances reflect the low robustness of ns-LIBS to variations within matrix chemical composition among test samples. Afterwards, test samples from different crops were analyzed by a femtosecond LIBS (fs-LIBS) by using a Ti:Sapphire laser, including a mode-locked oscillator and an ultrafast amplifier (60 fs; 1.65 mJ per pulse), and a spectrometer with Czerny-Turner optics and ICCD. Findings indicated that the pulse duration was a decisive variable for providing accurate quantification of nutrients in different plant species, which present substantial differences in terms of matrix chemical composition. Close agreement between Ca, Mg, P, Fe and Mn mass fractions predicted by fs-LIBS and those determined by ICP OES was evidenced, whatever the modeling approach used. Contrarily, for ns-LIBS analysis of test samples from different crops, only the use of multivariate partial least squares (PLS) regression appears capable for resolving the non-linear transformations of the emission intensities according to the physical mechanisms governing this temporal regime of ablation. Thus, when using multivariate modeling, the figures-of merit reflecting the predictive capabilities of ns-LIBS resemble to those achieved by fs-LIBS. Either way, fs-LIBS is a more robust approach that better offers larger flexibility to the matrix variability

L'utilisation de lasers est largement répandue dans le domaine de la microanalyse directe des solides. La matière vaporisée, en focalisant un faisceau laser de forte puissance sur la cible, peut être analysée soit par spectrométrie d'émission optique sur plasma induit (LIBS, acronyme anglais pour Laser Induced Breakdown Spectroscopy), soit par une source à plasma induit par haute fréquence couplée à la spectrométrie d'émission optique (ICP-AES) ou à la spectrométrie de masse (ICP-MS). Avec une résolution spatiale à l'échelle microscopique, les techniques d'ablation laser permettent ainsi d'accéder à la composition élémentaire locale de la surface d'un matériau. Néanmoins, les performances analytiques de ces techniques pourraient être améliorées par l'utilisation combinée des informations LIBS et ICP afin également de comprendre et maîtriser davantage l'interaction laser/matière. Dans ce but, ce travail a consisté à développer une technique de microanalyse par ablation laser couplée avec une détection en simultané par ICP et par LIBS afin d'étudier les potentialités analytiques de cet instrument pour cartographier la surface des matériaux. Les performances et les limitations de ce système ont été évaluées d'une part, en caractérisant les aérosols produits par ablation laser et d'autre part, en étudiant les signaux LIBS et ICP obtenus à partir d'un même prélèvement de matière. Le phénomène de fractionnement élémentaire rencontré sur des matrices critiques telles que le laiton a été mis en évidence en microablation malgré des caractéristiques de l'interaction laser/matière différente de la macroablation. Une méthode de correction, a posteriori, par l'efficacité d'extraction de la cellule d'ablation a été proposée afin de pallier ces effets limitatifs pour l'analyse quantitative. Une cellule d'ablation, optimisée à partir d'une étude de simulation numérique, a été développée afin de s'adapter aux applications de cartographies de surface. Les performances analytiques du système ont été évaluées en termes de stabilité (8-10%), de résolution spatiale (5 µm) et de limites de détection (de l'ordre de la ppm dans le solide avec un détecteur de masse). La complémentarité des mesures LIBS et ICP représente à la fois un outil de diagnostic de l'interaction laser/matière et un instrument d’analyse très complet grâce à la double détection qui permet de suivre simultanément des traces et des majeurs sur une large gamme d'éléments de la classification périodique / Laser ablation is widely spread for solid sample microanalysis. A tightly focused laser beam allows direct sampling of matter, the ablated mass can then be analysed either with LIBS (Laser Induced Breakdown Spectroscopy) or with an inductively coupled plasma source combined with an optical emission spectrometer (ICP-AES) or a mass spectrometer (ICP-MS). With spatial resolution down to the micron scale, laser ablation techniques permit local elemental analysis of sample surface. Nevertheless, analytical performances of such techniques could be improved by combining LIBS and ICP information to understand and control laser/matter interaction. For this purpose, this work aimed to develop a microanalytical technique based on laser ablation coupled to simultaneous detection with LIBS and ICP to study analytical potentialities of such technique for elemental mapping of material surface. Performances and limitations of the system were studied on one hand, by characterizing laser-induced aerosols and on the other hand, by studying simultaneous LIBS and ICP signals. Elemental fractionation on critical matrices such as brass was evidenced in microablation despite a different laser/matter interaction compared with macroablation. A correction procedure a posteriori using the total extraction efficiency of the ablation cell was proposed to overcome this problem for quantitative analysis. An ablation cell, optimized from a numerical simulation study, was developed for mapping applications. Analytical performances were evaluated in terms of stability (8-10 %), spatial resolution (5 µm) and detection limits (in the ppm range with ICP-MS). The LIBS and ICP complementarity makes the double detection system a diagnostic tool for laser/matter interaction and an analytical instrument allowing simultaneous monitoring of traces and majors from a large element range of the periodic classification

Ce mémoire présente des travaux portant sur le développement de trois sources lasers pompées longitudinalement par diodes laser et déclenchées activement par modulateur électro-optique pour deux applications spécifiques : la LIBS et le marquage par laser. Ces travaux ont été réalisés en collaboration avec deux sociétés : Bertin Technologies et SDAE.Le premier chapitre de ce manuscrit présente le développement d’une nouvelle source laser compacte, réalisée pour la société Bertin Technologies dans le cadre d’un projet de tri de matériaux plastiques par analyse spectroscopique de plasma induit par laser (LIBS). Cette technique d’analyse ponctuelle ainsi que le contexte spécifique du projet sont détaillés dans la première partie de ce chapitre. Ensuite, les différentes étapes de recherche et de développement qui ont permis d’aboutir à cette nouvelle source laser innovante, compacte et de hautes performances seront décrites en détail. Le second chapitre présente le développement de deux sources lasers pour le marquage industriel réalisées en partenariat avec la société SDAE. Après avoir présenté les principes et techniques généraux de l’application marquage ainsi que les contraintes spécifiques au projet, les deux sources lasers développées seront décrites. Des tests de LIBS et de marquage ont été réalisés grâce aux lasers développés / This thesis deals with the development of three lasers end-pumped by laser diode and actively Q-Switched by electro-optic Pockels cells for two specific applications: Laser Induced Breakdown Spectroscopy (LIBS) and marking. This work was done in collaboration with two companies: Bertin Technologies and SDAE.In the first part, we present the development of a new compact laser source, made for Bertin Technologies as part of sorting of plastics waste by LIBS. This analysis technique and the specific context of the project will be detailed in the first part of this chapter. Then, the different steps of research and development which have resulted in this innovative, compact and high performance new laser are described in detail. The second part is devoted to the development of lasers for industrial marking accomplished in partnership with SDAE. More precisely, the general principles and techniques of laser marking are described as well as the specific constraints of this project. LIBS and laser marking tests will be done with these lasers

Les plasmas induits par laser (PIL) ont depuis leurs apparitions dans les années soixante suscité un très grand intérêt notamment comme source de données spectroscopiques. Ils ont également acquis des nombreuses applications, comme sources des rayons X pour la lithographie, l’allumage plasma, la déposition par laser pulsé, ou sont devenues la base d’une technique d’analyse très populaire – la LIBS (laser induced breakdown spectroscopy). Cette dernière peut s’appliquer in situe à tout type d’échantillon et sans préparation. Toutefois, les mesures faites par cette méthode sont latéralement intégrées nécessitant des techniques d’inversion, mais dépendent également des conditions d’équilibre thermodynamiques local (ETL) dans le plasma. Afin de valider les mesures effectuées par LIBS, la diffusion Thomson qui est une méthode spatialement résolue et indépendante des hypothèses d’équilibre thermodynamique a été appliquée pour caractériser les PIL. Des plasmas d’ablation et de claquage ont donc été caractérisés à la fois par spectroscopie d’émission et par diffusion Thomson. La comparaison des paramètres température et densité électronique obtenues par les deux méthodes d’une part, et le critère de McWhirter ainsi que les temps de relaxation et les longueurs de diffusions des espèces contenues dans le plasma d’autre part, ont permis de statuer sur l’ETL. / Laser induced plasma (LIP) which was first reported in the beginning of sixties, has achieved a great interest as a source of spectroscopic data. It has also many applications like X-ray sources for lithography, plasma igniters, pulsed laser deposition or it has become a basis of a very popular analytical technique – LIBS (laser induced breakdown spectroscopy). The latter is mainly due to its applicability to different kinds of samples, no sample preparation or in-situ and remote sensing capability. However, LIBS measurements are laterally integrated and Abel inversion must be performed. Also the method assumes the plasma to be in local thermodynamic equilibrium (LTE). In order to validate LIBS measurements, Thomson scattering (TS) method which is spatially resolved and free from equilibrium assumption was applied. Thus, ablation and breakdown plasmas were characterized by both two methods. Comparison between plasma parameters (temperature and electron density) obtained by the two methods and McWhirter criterion as well as relaxation times and diffusion lengths of species in the plasma allowed to estimate LTE.

A feasibility of rapid setting cement (RSC) as an agent of immobilization for certain elements such as fission products or radioactive materials was explored. Cerium (Ce) and cesium (Cs) have been selected as a surrogate for U and/or Pu and fission products, respectively, in this study in three phases. In Phase I, RSC was evaluated for physical properties (e.g., porosity, density, pH values, etc.) using two groups methods—the cement powder at different concentrations of Ce (2 – 10 wt%) with deionized water (DIW) and artificial seawater (ASW). The results showed that the final setting time and compressive strength of RSC in DIW and ASW solutions decreased as Ce content increased. The X-ray diffraction patterns revealed two newly identified phases, namely CeAl11O18 and Ce4.667 (SiO4)3O. The morphology of matrix samples showed that the existence of Ce distributed on the pore wall or clustered with Si, Al, Mg, K, P, Fe, and O. In Phase II, laser-induced breakdown spectroscopy (LIBS) technique together with univariate and multivariate analyses of the principal component analysis (PCA) and partial least squares (PLS) were applied to detect the surrogate elements (Ce (0.5 – 8 wt%) and Cs (0.5 – 4 wt%)) for nuclear materials captured in ceramic materials. The best calibration curves for Ce and Cs in samples were created using the peak areas of the Ce 571.8 nm line and Cs 697.1 nm line, respectively. PCA method was applied to explain 85.5 % for Ce-cement samples in DIW and 91.4 % for those in ASW. Samples with Cs indicated similar PCA trends. The PLS calibration curves for Ce and Cs samples in DIW and those in ASW were made using seven and eight latent variables (LV). In Phase III, the leaching behaviors of Ce and Cs mixture with DIW and ASW under both dynamic and static leach conditions were investigated according to the ANSI/ANS 16.1-2003 standard method. Elemental compositions were analyzed using an inductively coupled plasma-mass spectrometry (ICP-MS) for the leaching periods of 2, 7, and 24 hours and 2, 3, 4, 5, 14, 28, 43, and 90 days. Three mathematical models—first-order reaction model (FRM), diffusion model (DM), and first-order reaction/diffusion model (FRDM)—were fitted to assess the leaching parameters of immobilized radionuclides in the RSC matrix. Results showed that leaching of 140Ce and 133Cs from RSC matrices with (DIW and ASW) under both dynamic and static leach conditions was less than 20%. It was found that the leaching phenomena of 140Ce and 133Cs was dominantly controlled by FRM with a weak effect of DM, which was best fitted by FRDM. Here, the average leachability index (L) for 140Ce and 133Cs, are greater than the recommended minimum of 6 that allowed their acceptance for disposal. These studies indicated a good feasibility of using RSC with DIW and ASW for immobilizing non-radioactive Ce and Cs and RSC had a potential for applying to actual radioactive materials.

Ce travail a été réalisé dans le but de sonder des surfaces solides en utilisant la technique « LIPS » (Spectroscopie de plasmas induits par laser). Le comportement de ce type de plasmas est difficile à simuler étant donné la petitesse des échelles de temps et d'espace considérées. En plus du diagnostic classique de spectroscopie d'émission, nous avons mis en oeuvre une expérience originale d'absorption qui produit des valeurs fiables et de nombreuses informations sur la température et les densités constitutives du plasma. Cette étude, qui couple expérience et théorie dans le cadre de la résolution de l'équation de transfert radiatif, est basée sur la comparaison entre des spectres calculés et expérimentaux des raies à 308.21 et 396.15 nm de l'aluminium. Une attention spéciale a été portée à l'écriture de l'élargissement électronique et ionique par effet Stark et aux effets d'auto-absorption. Un écart important à l'équilibre a été mis en évidence tout au long de la relaxation du plasma. La mesure de la densité de l'état fondamental de l'aluminium, qui est de première importance pour valider un code collisionnel - radiatif consacré à cette situation complexe, a été menée à bien dans une large gamme de pression (5 à 1E5 Pa). La mesure des constantes de temps de relaxation met en évidence le rôle majeur joué par la diffusion dans la relaxation des espèces du plasma.

La spectroscopie de plasma (10e4 K et 10e16 électron.cm-3) induit par laser pulsé ns (LIBS) est développée pour caractériser tout échantillon chimique ou biologique (gaz, surface homogène ou hétérogène, aérosol), de façon in situ, rapide (~10e-6 s), sensible et reproductible, à des fins de classification, voire d'identification. Le volume échantillonné optiquement est reproductible pour les plasmas dans les gaz (~1 mm3) et sur surfaces (diamètre d'impact~10e2 µm2). Cela permet d'étalonner la technique pour le dosage multiélémentaire à des seuils de l'ordre du ppm, voire du ppb, y compris pour des particules microniques. Les marqueurs spectraux des matériaux biologiques (Ca, Mg, Na, K, P et C) sont identifiés par traitement statistique selon une analyse en composantes principales permettant de classer les échantillons par nature. On vérifie comment les observables discriminantes sont détectés pour diverses formes bactériennes : pastilles compressées de bactéries lyophilisées, cultures végétatives sur boîtes de Pétri à un seuil minimal déterminé d'environ 10e3 bactéries, et aérosols suspendus. L'exploitation statistique des identifiants permet de distinguer les bactéries par rapport à des milieux nutritifs et des leurres. Dans le cas de l'analyse au vol de bactéries aérosolisées, la détection est plus complexe et aléatoire du fait des faibles teneurs élémentaires disponibles, ce qui nécessite leur concentration préalable. La LIBS, calibrée pour les gaz, surfaces et aérosols, est alors transposée en outil transportable, polyvalent et sensible ouvrant de vastes champs applicatifs : diagnostics biomédicaux, suivi en ligne de procédés industriels, contrôle qualité environnementale...