L’analyse en ligne et in situ constitue aujourd’hui un axe de développement stratégique pour la chimie analytique. C’est particulièrement vrai dans le domaine nucléaire pour lequel les contraintes de sécurité liées à la radioactivité des échantillons, et la nécessité de limiter au maximum les déchets issus des analyses, plaident en faveur de techniques de mesure à distance, sans prélèvement ni préparation d’échantillon. La spectroscopie d’émission de plasma créé par laser (ou LIBS pour laser-induced breakdown spectroscopy), technique d’analyse élémentaire des matériaux basée sur l’ablation laser et la spectroscopie d’émission optique, possède ces qualités. C’est donc une technique de choix pour l’analyse en ligne. Cependant, la maîtrise de la mesure est délicate pour plusieurs raisons. D’abord, la LIBS est multiparamétrique et l’effet des paramètres expérimentaux sur les performances analytiques n’est pas toujours clairement établi. Ensuite, les phénomènes physiques donnant lieu au signal LIBS sont non linéaires, couplés, et transitoires. Enfin, un système d’analyse en ligne doit être le plus robuste possible face aux variations non contrôlées des conditions de mesure. L’objectif de cette thèse est donc d’améliorer la maîtrise et les performances de l’analyse quantitative par LIBS en utilisant des méthodes multivariées capables de gérer la multidimensionalité, la non linéarité et le couplage des paramètres et des données. Pour cela, le travail se décompose en deux parties. Dans un premier temps, nous avons réalisé un plan d’expériences composite centré visant à relier les paramètres expérimentaux de l’ablation laser (énergie de l’impulsion et paramètres de focalisation du faisceau) et de la détection du signal (délai après le tir laser) aux caractéristiques physiques du plasma (masse ablatée, température) et aux performances analytiques (intensité et répétabilité du signal). L’optimisation des paramètres qui en résulte est alors interprétée comme le meilleur compromis, pour l’analyse quantitative, entre efficacité d’ablation laser et chauffage du plasma. Dans un deuxième temps, nous avons développé une méthodologie multivariée basée sur les techniques MCR-ALS, ICA et PLS, pour quantifier certains éléments dans différentes matrices métalliques en exploitant, en plus de la dimension spectrale habituelle, la dimension temporelle du signal LIBS. Cette dernière, pourtant essentielle, est généralement négligée dans la littérature. Dans cette partie, nous discutons donc de l’intérêt de cette approche par rapport aux méthodes usuelles de quantification (univariée et multivariée), et de l’apport de cette méthodologie pour diagnostiquer, comprendre et éventuellement compenser les effets de matrice observés en LIBS. / Online and in situ analysis is now a strategic development for analytical chemistry. This is especially true in the nuclear field for which the security constraints related to the radioactivity of samples, and the need to minimize waste from analyzes argue for remote measurement techniques without sampling or sample preparation. Laser-Induced Breakdown Spectroscopy (LIBS) technique for elemental analysis of materials based on laser ablation and the optical emission spectroscopy, has these qualities. It is a technique of choice for online analysis. However, the processes involved in LIBS, namely laser ablation, atomization, plasma formation and emission, are quite complex and difficult to control because the underlying physical phenomena are coupled and nonlinear. In addition, the analytical performance of the LIBS technique depends strongly on the choice of experimental conditions. Finally, an online analysis system should be as robust as possible face to uncontrolled variations in measurement conditions. The processes involved in LIBS, namely laser ablation, atomization, plasma formation and emission, are quite complex and difficult to control because the underlying physical phenomena are coupled and nonlinear. In addition, the analytical performance of the LIBS technique depends strongly on the choice of experimental conditions. The objective of this thesis is to improve control and performance of quantitative analysis by LIBS using multivariate methods capable of handling multi-dimensionality, nonlinearity and the coupling between parameters and data. For this, the work is divided into two parts. First the optimization is carried out using a central composite design to model the relationship between the experimental parameters of laser ablation (pulse energy and beam focusing parameters) and signal detection (delay time) to the physical characteristics of plasma (ablated mass, temperature) and the analytical performance (intensity and repeatability of the signal). The optimization parameters that results is then interpreted as the best compromise for the quantitative analysis between efficiency of laser ablation and plasma heating. Secondly, we developed a multivariate methodology based on MCR-ALS, ICA and PLS techniques to quantify certain elements in different metallic matrices operator, in addition to the usual spectral dimension, the time dimension of LIBS signal. In this part, we discuss the value of this approach over conventional methods of quantification (univariate and multivariate) and the contribution of this methodology to diagnose, understand and possibly compensate matrix effects observed in LIBS.

Orientador: Celio Pasquini / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T13:37:44Z (GMT). No. of bitstreams: 1 FariasFilho_BeneditoBatista_D.pdf: 5266552 bytes, checksum: 237a6af16ec6a610644e50129eb718d9 (MD5) Previous issue date: 2014 / Resumo: A determinação direta de amostras líquidas utilizando a técnica de Espectroscopia de Emissão Óptica em Plasma Induzido por Laser (LIBS) é muito difícil devido aos limites de detecção insuficientes obtido. Procedimentos de pré-concentração, como o ring oven, permitem que o analito seja determinado a partir de técnicas que utilizam a microanálise como o LIBS, depois da sua transferência para um substrato sólido (papel de filtro). Embora esta abordagem tenha sido praticamente descrita na literatura, o procedimento de medida foi feito manualmente. Assim, neste trabalho foi desenvolvido um sistema de medida mecanizado para analisar por LIBS o conteúdo do anel produzido pela técnica ring oven visando melhorar a precisão e reduzir o tempo de análise. O sistema é composto por um motor contínuo que gira uma plataforma a 10 rpm constituída por um disco de teflon® adaptado ao seu eixo central e que serve como suporte para amostra. A câmara de ICCD do sistema de detecção do LIBS foi programada para integrar o sinal produzido por 120 pulsos do laser que são disparados espaçados uniformemente sobre o contorno do anel durante 6 segundos. Para preparo dos anéis, 60 µL das soluções ou amostras de cachaça eram dispensadas sobre o papel de filtro com vazão de 25 µL min-1 e, em seguida, lavadas com 45 µL de HCl 0,05 mol L-1. Foi utilizado lítio (2 mg L-1; 670,80 nm) como padrão interno para construção das curvas analíticas na faixa de 0 a 8 mg L-1 de cobre (324,75 nm). O padrão interno foi efetivo para corrigir as falhas de amostragem ao longo do contorno do anel durante o processo de medida. As curvas analíticas construídas foram lineares (r > 0,990) na faixa de concentração estudada e o limite de detecção e de quantificação foram de 0,3 mg L-1 e 1,0 mg L-1, respectivamente. Os resultados da determinação de cobre em oito amostras de cachaça mostraram-se estatisticamente indistinguíveis, em nível de 95% de confiança, quando comparados com aqueles obtidos por meio do método oficial de adição de padrão e medidos por espectrometria de absorção atômica em chama (FAAS), com precisão média relativa de 9%. O procedimento de pré-concentração necessitou menos que seis minutos enquanto que as medidas do anel formado, usando o sistema mecanizado, necessitaram no total de dois minutos adicionais. Além disso, foi verificada a potencialidade da técnica ring oven/LIBS para classificação geográfica, por meio de modelos multivariados quimiométricos (LDA, PLS-DA e SIMCA) de cachaças da região de Salinas (MG). A capacidade preditiva das amostras foi melhor para o modelo quimiométrico baseado em Análise Discriminante Linear (LDA), conseguindo classificar corretamente 70% das amostras / Abstract: Direct determination of liquid samples using the technique of Laser-induced breakdown spectroscopy (LIBS) is very difficult due to the insufficient detections limits attained. Procedures of preconcentration, such the ring oven, allow the determination of analyte by microanalysis techniques, after transferring it to a solid substrate (filter paper). Although this approach has been previously described in the literature, the measurement procedure was performed manually. Thus, in this work a mechanized measurement system was developed to analyze by LIBS the contents of the ring produced through the ring oven technique in order to improve the precision and reduce the analysis time. The system consists of a continuous motor that spinning a platform at 10 rpm constituted by a teflon® disc coupled to its axis, serving as a support for the sample. The ICCD camera of the detection system of LIBS was programmed to integrate the signal generated by 120 laser pulses that is fired uniformly spaced on the ring contour during 6 seconds. To prepare the rings, 60 µL of standard solutions or samples of cachaça were dispensed on the filter paper at flow rate of 25 uL min-1 and afterwards washed with 45 µL of HCl 0.05 mol L-1 (42% v/v ethanol). Lithium (2 mg L-1, 670.80 nm) was used as internal standard for the construction of analytical curves in the range from 0 to 8 mg L-1 of copper (324.75 nm). The internal standard was effective to correct the sampling failures around the contour of the ring during the measurement process. Analytical calibration curves were linear (r> 0.99) in the concentration range studied and the limits of detection and quantification were of 0.3 mg L-1 and 1.0 mg L-1, respectively. The results of determination of copper in eight samples of cachaça showed be statistically indistinguishable, at 95% confidence level when compared with the official method of standard addition and measurement by flame atomic absorption spectroscopy (FAAS), with an average relative precision of 9%. The procedure carry out of preconcentration requires less than six minutes, while the measurements of the formed ring, using the mechanized system, requires an total two minutes to be performed. Moreover, it was verified the potentiality of ring oven/LIBS technique for geographic classification of cachaça of Salinas region (Minas Gerais State) using chemometric multivariate modeling (LDA, SIMCA and PLS-DA). The better predictive performace was attained by the chemometric model basead Linear Discriminant Analysis (LDA), achieving correctly classification of 70% of the samples / Doutorado / Quimica Analitica / Doutor em Ciências

Pour répondre aux besoins des nouvelles techniques de caractérisation sur site in-situ et temps réel, l’unité NOVA de l’INERIS en partenariat avec les laboratoires LP3 et GREMI, a entamé des travaux pour étudier deux approches afin d’améliorer les performances de la technique Laser-Induced Breakdown Spectroscopy (LIBS) pour l’analyse des aérosols. LIBS est une technique optique de spectroscopie atomique. Elle consiste à focaliser un faisceau laser impulsionnel sur un échantillon à analyser créant ainsi un plasma. L’émission optique du plasma contient alors la signature des éléments chimiques présents dans l’échantillon. La première approche concerne la détermination de la composition chimique relative (stoechiométrique) d’aérosols sans étalonnage. En effet, l’étalonnage présente des problèmes pratiques. Pour ce faire, les spectres expérimentaux enregistrés lors de l’analyse des particules d’alumine (Al2O3) suspendues dans de l’hélium (He) ont été comparés à des spectres théoriques calculés pour un plasma contenant les mêmes éléments, à l’Équilibre Thermodynamique Local (ETL). L’ajustement des spectres simulés sur les spectres expérimentaux nous a permis de déterminer correctement la composition chimique relative des éléments présents dans le plasma. L’évolution temporelle du plasma a permis de valider l’ETL, et ainsi estimer la meilleure plage temporelle permettant la détermination de la composition relative de l’aérosol. La deuxième approche utilise une cellule radiofréquence (RF) à pression réduite comme piège à particules pour analyser des aérosols contenant des nanoparticules. Un tel piège permet d’améliorer la détection en concentrant spatialement les particules. Les paramètres optimaux d’utilisation de ce système ont été étudiés. Cette étude a permis d’établir que l’émission continue du plasma est fortement réduite dès ses premiers instants de vie. Le volume d’échantillonnage de ce système a été évalué et la limite de détection a été estimée de manière théorique. / New issues related to process control and workplace surveillance accompany the emergence of nanotechnology industry. This involves the development of new real-time and in-situ characterization techniques. In this context, the NOVA unit from the INERIS institute collaborated with LP3 and GREMI laboratories to study two approaches aiming to enhance the LIBS technic performances. The first approach used a flow cell to determine the relative elemental composition of an aerosol with a calibration-free procedure. The recorded spectra were compared to theoretical spectra calculated for a plasma in the Local Thermodynamic Equilibrium LTE. The best agreement between recorded and computed spectra allowed the determination of the relative composition with a good agreement with the reference value, for an alumina aerosol. The study of the temporal evolution of the plasma allowed the estimation of a temporal range within which the LTE hypothesis was verified. The second approach used a low-pressure radiofrequency plasma generated in an inert gas as a particle trap to analyse aerosols and nanoparticles. The use of such a system allowed the enhancement of particles detection by concentrating them spatially. We determined the optimal parameters for the LIBS analysis using this system. Furthermore, we established the plasma continuum was attenuated even at very low time delays. We evaluated the sampling volume of this new system and compared it to case of LIBS analysis on air. Finally, we estimated the detection limits of this system when analysing nanoparticles.

Orientador: Ivo Milton Raimundo Júnior / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T23:35:46Z (GMT). No. of bitstreams: 1 Fontes_LaianedeMoura_D.pdf: 2914385 bytes, checksum: 3a68971b696f9f31967f1132ab348427 (MD5) Previous issue date: 2015 / Resumo: Este trabalho descreve o desenvolvimento de diferentes fases extratoras para a determinação de hidrocarbonetos aromáticos e de íons metálicos em água. Para o desenvolvimento das fases extratoras de polidimetilsiloxano e nanotubos de carbono (PDMS-NTC), os nanotubos foram tratados com ácido nítrico, octadecilamina e hipoclorito de sódio. Este último produziu grupos carboxílicos na superfície do nanomaterial, aumentando sua afinidade por hidrocarbonetos aromáticos. A fase extratora foi preparada pela dispersão dos NTC no PDMS e, depois de pronta, inserida num frasco preenchido com as soluções aquosas dos analitos. Após 60 minutos sob agitação, a fase extratora foi removida da solução, seca e inserida em um sistema de medidas, empregando-se um espectrofotômetro FT-NIR. A fase extratora com NTC oxidados com NaOCl possibilitou um aumento da capacidade de extração de 40% e 20% para tolueno e benzeno, respectivamente. No segundo momento, foram desenvolvidas membranas poliméricas plastificadas utilizando os reagentes complexantes Br-PADAP e TAN para a determinação de cobre e chumbo em água por espectroscopia de emissão óptica com plasma induzido por laser (LIBS). As membranas de PVC não forneceram resultados satisfatórios como fase extratora, pois a homogeneidade e estabilidade da superfície das membranas não puderam ser estabelecidas de maneira satisfatória. Papel de filtro analítico foi utilizado como fase extratora para a pré-concentração de íons cobre e chumbo em meio aquoso de forma eficiente, superando as desvantagens das medidas diretas de líquidos por LIBS. A capacidade de adsorção do papel de filtro foi favorecida pela utilização de soluções básicas, principalmente, entre pH 8,0 e 9,0. O tempo de extração foi de 30 minutos para cobre e 60 minutos para chumbo. Os limites de detecção encontrados foram de 0,22 e 0,53 mg L-1 para cobre e chumbo, respectivamente. Não foi observada interferência dos íons Ni (II), Zn (II), Cd (II) e Fe(III), tampouco influência da força iônica. O método proposto foi utilizado para a determinação de cobre e chumbo em amostra de água de torneira enriquecida em três níveis de concentrações. Recuperações na faixa de 98,8% - 114,3% foram obtidas indicando que a determinação direta de íons cobre e chumbo em amostras aquosas pela técnica LIBS utilizando papel de filtro como fase extratora apresenta potencial para a análise de amostras reais / Abstract: This work describes the development of extraction phases for determination of aromatic hydrocarbons and metal ions in water. For development of the phase based on polydimethilsiloxane and carbon nanotubes (PDMS-NTC), carbon nanotubes were previously functionalized with nitric acid, octadecylamine and sodium hypochlorite. The latter oxidizing agent produced carboxyl groups on the surface of the nanomaterial, increasing its affinity for aromatic hydrocarbons. The extraction phase was prepared by dispersing the functionalized NTC in PDMS, which was polymerized to form cylindrical monoliths. Extractions were performed by immersing the monolith in a flask filled with the aqueous solutions of analytes, containing 2.0 mol L-1 NaCl. After an extraction time of 60 min under constant stirring, the monolith was removed from the flask, dried and inserted in the measuring cell of the FT-NIR spectrophotometer. The extraction phase containing NTC oxidized by sodium hypochlorite allow an increase of the sensitivity of 40% and 20% for toluene and benzene, respectively. In the second part, plasticized polymeric membranes containing Br-PADAP or TAN as complexing reagents were developed for determination of lead and copper in water by laser induced breakdown spectroscopy (LIBS). The PVC membranes did not provide satisfactory results, as the homogeneity and the stability of the membrane could not be attained. Analytical filter paper was then employed as an extraction phase to efficiently pre-concentrate lead and copper ions from aqueous solution, circumventing the disadvantages of direct measurements of liquid phase by LIBS. The sorption capacity of the filter paper was enhanced in basic solutions, mainly within pH 8.0 and 9.0. The ideal extraction time for Cu(II) was 30 minutes and 60 minutes for Pb(II). The detection limits were estimated as 0.22 and 0.53 mg L-1 for Cu(II) and Pb(II), respectively. Interference of Ni (II), Zn (II), Cd (II) and Fe(II) ions were not observed, as well as the influence of the ionic strength. The proposed method was employed for determination of cooper and lead in tap water fortified at three concentrations levels. Recoveries in the range from 98.8% to 114.3% were obtained, indicating that direct determination of these ions in aqueous samples by the LIBS using filter paper as an extraction phase has a potential for analysis of aqueous samples / Doutorado / Quimica Analitica / Doutora em Ciências

Neste trabalho foi desenvolvido uma metodologia para a determinação de metais (Cr, Cu, Fe, Mg, Mo, Pb), em óleos lubrificantes e estes quantificados pela técnica de espectrometria de emissão optica com plasma induzido por laser (LIBS). As amostras de óleo usadas foram coletadas em oficina de troca de óleo, variando-se a quilometragem, ano, marca do carro e a marca do óleo, com o preenchimento de formulários contendo as informações necessárias à pesquisa. A preparação de amostras foi realizada com o depósito ds mesmas em substrato de papel e sequente otimização dos parâmetros instrumentais. Para a calibração, foi utilizado o padrão de óleo S-21 multielementar da Conostan (SCP Science, Champlain, NY). Para a avaliação da exatidão do método desenvolvido foi utilizado o padrão de óleos lubrificantes (SRM 1084a) obtidos junto ao Instituto Nacional de Padrões e Tecnologia (NIST, Gaithersburg, MD). O método proposto apresentou as seguintes vantagens quando comparado com métodos de análise tradicionais (espectrometria de absorção atômica ou espectrometria de emissão optica acoplado ao plasma indutivo com diluição da amostra): mais rápida, sem desgaste do equipamento (em função da não introdução de solvente), geração de resíduo praticamente nula e menor consumo de reagentes. O método desenvolvido foi aplicado em amostras reais e o tratamento de dados realizado por análise estatística (equação de Stuarges, teste não paramétrico de Kruskalwallis). / In this work was developed a methodology for the determination of metals (Cr, Cu, Fe, Mg, Mo, Pb) in lubricating oils and these were quantified by Laser Induced Breakdown Spectroscopy (LIBS). Used oil samples used were collected in shop oil change, varying the mileage year, car make and oil brand with forms containing the information necessary for research filling out. For the calibration, the standard of 500ppm oil of S-21 multielement Conostan (SCP Science, Champlain, NY) was used, which was diluted with blank oil to achieve concentrations from 12.5 to 500 ppm necessary for the construction of analytical curve. For evaluating the accuracy of the method developed, we analyzed the standard of lubricating oils (SRM 1084th) obtained from the National Institute of Standards and Technology (NIST, Gaithersburg, MD). The proposed method has the following advantages compared to traditional methods of analysis (AAS or ICPOES with sample dilution): faster, without wear of the equipment (due to the introduction of non-solvent), generating virtually no residue and lower consumption reagents. The developed method was applied to real samples and the total processing performed by statistical analysis.

This diploma thesis deals with design of positioning unit for laser spectroscopy and its realization to shape of prototype. The design of positioning unit is based on the analysis of the current state of knowledge in the field of remote laser spectroscopy systems. Precise harmonic drive and worm drive with stepper motors are used to drive. The main parts of positioning unit are designed primarily from duraluminium. The positioning unit will be used for experimental measurements at the Institute of Physical Engineering Faculty of Mechanical Engineering Brno University of Technology. 3D digital prototype and technical drawings were created in Autodesk Inventor 2010.

La détermination d’âges absolus est nécessaire pour calibrer la chronologie relative martienne basée sur la densité de cratères d’impact. Dans ce but, nous avons développé au laboratoire GEOPS un prototype pour la datation in-situ des surfaces planétaires par la méthode K-Ar. Cette installation, financée dans le cadre d’un programme de recherche CNES-CNRS, est basée sur l’ablation laser permettant la vaporisation d’un volume reproductible de roche. La composition chimique de la matière ablatée, et en particulier la teneur en potassium (K), est estimée par Laser Induced Breakdown Spectroscopy (LIBS) et la quantité d’argon (Ar) libérée est mesurée par spectrométrie de masse quadripolaire (QMS). La détermination de l’âge K-Ar requiert en outre la quantification précise de la masse d’échantillon ablatée. Après une phase importante de développement instrumental visant à améliorer la précision et la sensibilité de la technique, nos efforts ont porté sur la calibration du dispositif. Pour ce faire, une collection d’échantillons de référence (micas, feldspaths, amphibolite, basaltes) a été réalisée et analysée (chimie totale et mesures d’âges par les techniques K-Ar et ⁴⁰Ar/³⁹Ar classiques). Ces échantillons présentent des teneurs en K de 0,15 à 11% et des teneurs de 1 à 100x10¹⁴ atomes d’⁴⁰Ar* par gramme, équivalent à des basaltes martiens âgés de 700 Ma à 3 Ga pour 0,4%K. Les résultats obtenus ont permis de définir une corrélation entre le temps d'ablation et la masse ablatée selon le type de phase minérale ciblée. Afin de valider cette corrélation, des mesures ont été menées « en aveugle » sur plusieurs échantillons, en particulier un basalte microlitique (Trapps de Viluy) similaire aux basaltes composant la surface de Mars. L’âge K-Ar in-situ de 401 ± 41 Ma obtenu par notre approche est consistant avec l’âge de 381 ± 5 Ma mesuré indépendamment sur populations de minéraux. Plus généralement, cette étude a permis d’obtenir des âges K-Ar mesurés par notre méthode de datation in-situ avec une incertitude inférieure à 15%, y compris sur des roches peu potassiques et relativement jeunes comparées aux roches martiennes. / Absolute age determination is necessary to check and calibrate the relative Martian chronology presently available from meteoritic crater counting. For this purpose, we have developed an in-situ K-Ar dating prototype for planetary surfaces at GEOPS laboratory. This instrument, supported by a CNES-CNRS research program, is a laser ablation-based system built to vaporize a reproducible volume of rock or mineral. It quantifies potassium content (K) by laser-induced breakdown spectroscopy (LIBS) and argon (Ar) by quadrupole mass spectrometry (QMS). The K-Ar age determination also requires accurate quantification of the ablated sample mass. Following an important period of experimental set-up development to improve precision, accuracy and sensitivity of the technique, our efforts focused on the calibration of the different parts of this instrument. To that purpose, a collection of reference samples (micas, feldspars, amphibolite, basalts) was done and analyzed (total chemistry and age measurements by K-Ar and ⁴⁰Ar/³⁹Ar conventional techniques). These samples show a K content between 0,15 and 11% and an Ar content between 1 and 100x10¹⁴ ⁴⁰Ar* atoms per gram, corresponding to Martian basalt from 700 Ma to 3 Ga for 0.4% K. The results obtained evidence a correlation between the ablation time and the ablated mass depending on the mineral phase analyzed. In order to check this correlation, measurements were conducted on several samples, in particular a microlitic basalt (Viluy basalt) similar to Martian basalts. The K-Ar in-situ age of 401 ± 41 Ma obtained by our approach is consistent with the age of 381 ± 5 Ma measured indepedently on mineral populations. More generally, this study allows to obtain K-Ar ages measured by our in-situ dating method with uncertainties lower than 15%, on relatively low-K and young samples compared to Martian rocks.

Laser Induced Breakdown Spectroscopy (LIBS) offers possibility for fast de- tection of sample composition without its preparation. For this reason it is attractive anywhere where the fast detection and no sample preparation are needed. As in many other branches the technical and scientific progress im- proves and spreads the possibilities of LIBS based devices and laboratory appa- ratuses. The time-resolved spectroscopy is allowed by spectrograph equipped with fast camera, broadband spectra can be acquired in single exposition by broadband spectrometers. Smaller and lighter laser sources together with com- pact spectrometers can be implemented to portable device and can be used out of laboratory. Computers offer quick data processing. The device named ChemCam installed on the NASA's next Mars rover, curiosity, is good exam- ple of high technology application in LIBS. However, there are still challenges and we hope that this work will be fruitful for anyone who is interested in the LIBS. The project of presented thesis was performed as a joint supervision project between the Department of Experimental Physics at Comenius University in Bratislava and Laboratiore Interdisciplinaire Carnot de Bourgogne at Univer- sit ́e de Bourgogne in Dijon. The aim of the project was to join experience from both laboratories, experience in laser constructions from Dijon and experience with spectroscopy from Bratislava. The both are essential for LIBS. In Bratislava the work was coordinated by prof.Pavel Veis and it was fo- cused on LIBS under the laboratory conditions. The time-resolved broadband spectrometry was used in the research. In order to achieve required spectra, the spectral response of the optical system was determined which was later used for the corrections. The research of self-absorption phenomena started in the last period with aim to use this effect, usually considered as negative, for the composition determination. In Dijon the work was supervised by Dr. Olivier Musset and directed toward development of LIBS device which could be used out of laboratory. The small 6 7 laser which was previously developed in the laboratory was implemented in the device. The development was successfully finished and testing process began in the last period of the thesis. The geological samples have been used for the testing process which was performed in deep cooperation with geologists. The first chapter comprises a brief introduction to LIBS. It is divided into some parts about laser induced plasma, laser induced breakdown and evolution of the plasma after breakdown. The section dealing with local thermodynamic equilibrium is also included. The section describes importance of LTE and the possibilities to determine this state. The second chapter is dedicated to the developed portable LIBS device. In the introduction, different type of LIBS devices are presented with their possibilities. Then the portable device developed in Dijon is described part by part with brief characteristic of developed software. The device possibilities and limits are sketched in the last section of the chapter with respect to results obtained in the testing process. The third chapter deals with capabilities of LIBS apparatus which was set up in the laboratory. The process of spectral response measurement and its results are presented and consequently used in next sections in process of plasma parameters determination. The composition of used samples are determined by using of calibration free method with aim to choose proper location in the plasma for which results are the most representative. The last chapter includes introduction to the subject of self-absorption phenomena. The simple model and basic theory are presented with suggestion how to use the phenomena in positive way. The simple experiment and its results are presented at the end of the chapter together with discussion about the possibilities and perspectives of the suggested method.

La technique ICP-AES (Inductively-Coupled Plasma Atomic Emission Spectroscopy) est fréquemment appliquée comme méthode de contrôle de la qualité dans l'industrie pharmaceutique pour vérifier le contenu en minéraux de comprimés de multivitamines. C’est une méthode très fiable et éprouvée, mais elle nécessite une longue préparation des échantillons qui réduit l'efficacité du laboratoire. Les techniques XRF (X-Ray Fluorescence) et LIBS (Laser Induced Breakdown Spectroscopy) sont des technologies étudiées afin de déterminer leur potentiel comme une approche alternative à la quantification rapide des minéraux. Leur utilisation permettrait d’économiser sur des consommables dispendieux et nocifs, d’économiser du temps de laboratoire et de quarantaines pour les produits finis. L’objectif de l’étude est de quantifier 10 minéraux dans des comprimés pharmaceutiques avec une précision qui respecte les standards de l’industrie en question. Des méthodes d’analyse appropriées à chacune des technologies évaluées sont proposées pour effectuer une quantification optimale des minéraux. Pour ce faire, une méthodologie adéquate a été développée pour la technologie LIBS permettant de tenir compte de la micro-hétérogénéité des échantillons pharmaceutiques. La méthode permet de déterminer la probabilité d’échantillonnage en fonction des tailles de particules pour chacune des espèces. Ensuite, des modèles quantitatifs multivariés et univariés ont été comparés pour chacune des technologies d’analyse. Il a été démontré que les algorithmes de régression multivariés ne sont pas significativement plus performants que les méthodes traditionnelles pour l’analyse des spectres obtenus. Par contre, en comparant les deux technologies d’analyse, XRF permet d’obtenir des erreurs de prédiction inférieures (MEP = 15 %) à LIBS (MEP = 30 %) ainsi que des courbes de calibration significativement plus linéaires. Toutefois, quoique la technologie LIBS semble obtenir des performances inférieures en général, elle promet certains avantages pour des applications futures telles que les possibilités suivantes : 1- faire du profilage en trois dimensions, 2- échantillonner de très faibles quantités et 3- n’avoir aucune préparation d’échantillon. Au final, LIBS offre davantage de forces pour des applications d’échantillons homogènes ou en profilage alors que XRF serait préférable pour les échantillons hétérogènes. Suite aux efforts de développement de modèles quantitatifs, une analyse des effets de matrice pour la technologie LIBS a permis d’évaluer l’effet de diverses propriétés des matrices en fonction de l’intensité LIBS observée. La concentration volumique élémentaire, la conductivité thermique, la masse volumique des comprimés et la proportion molaire élémentaire dans le plasma sont toutes des propriétés ayant montré des corrélations importantes (R2 ≥ 0.5) avec l’intensité LIBS. En ce qui concerne l’applicabilité au niveau industriel, les erreurs de prédiction obtenues pour les technologies XRF et LIBS ne rencontrent pas les standards pharmaceutiques faisant ainsi que l’application de ces technologies est impossible au moment actuel. Toutefois, d’autres applications simplifiées sont proposées à partir des observations effectuées lors de ces travaux de recherche.

Ce travail de thèse a été consacré à la compréhension du plasma induit par laser sur des matériaux organiqueset à l’application de la technique de laser-induced breakdown spectroscopy (LIBS) à l’analyse quantitative deces matériaux. L’ensemble des travaux contribue donc à approfondir notre connaissance sur les mécanismesphysiques impliqués dans l’interaction laser-matière, dans la génération du plasma et dans l’évolution decelui-ci au cours de son expansion dans le gaz ambiant avec la spécificité de s’adresser à des plasmas induitssur des cibles organiques. Ces travaux visent également à améliorer la performance de la LIBS pour l’analysede matériaux organiques. La spécificité concernant la cible organique répond au besoin actuel de lacommunauté internationale travaillant sur le développement de la LIBS, de mieux maîtriser le plasma induitsur ce genre de matériau qui présente des propriétés optiques bien spécifiques par rapport à des matériauxmieux connus pour l’ablation laser tels que des métaux. Elle répond également au besoin grandissant d’utiliserla technique LIBS aux matériaux organiques pour des applications dans les domaines environnementaux,agroalimentaires, ou encore biomédicaux. Ce mémoire de thèse a été rédigé selon l’organisation suivante. Après l’Introduction Générale qui préciseles contextes scientifiques et technologiques, le Chapitre I rappelle les principes de base nécessaires à lacompréhension du phénomène de génération de plasma par ablation laser, et de l’évolution de celui-ci dans ungaz ambiant. L’accent a été mis sur l’ablation des matériaux organiques. Les procédures et les techniques dediagnostic du plasma induit par laser sont ensuite présentées en insistant sur la nature transitoire etinhomogène d’un plasma en expansion. Le chapitre II s’intéresse à la génération et l’évolution du plasmainduit sur la peau d’une pomme de terre, un échantillon typique de produit agroalimentaire. La caractéristiquedu plasma induit sur une cible organique molle et humide, comme une pomme de terre fraîche était quelquechose d’inconnu au démarrage de la thèse et constituait une base nécessaire à l’analyse quantitative deséléments métalliques en traces et ultra-traces contenus dans un tel échantillon. A l’issue de cettecaractérisation, les données analytiques semi-quantitatives ont été extraites des spectres LIBS correspondant àla peau d’une pomme de terre. Le Chapitre III se situe dans la continuité du Chapitre II pour l’application de laLIBS à des matériaux organiques. Une étude comparative d’analyse de la poudre de lait par la LIBS et parl’ICP-AES permet une évaluation de la performance d’analyse quantitative de la LIBS pour des échantillonsorganiques, et une validation de la procédure CF-LIBS. A la différence des Chapitres II et III où les élémentsde traces métalliques étaient au centre de notre attention, le Chapitre IV étudie le comportement des élémentsmajeurs qui composent la matrice d’un matériau organique, qui sont les 4 éléments organiques, H, C, O, N. Ala décomposition d’un matériau organique par ablation laser, ces éléments peuvent se présenter sous la formede fragments moléculaires, ou encore se recombiner en des espèces moléculaires. Nous étudions alors dans ceChapitre l’évolution de ces espèces en fonction des paramètres du laser utilisé, et notamment la longueurd’onde. Le mémoire se termine par une conclusion générale et des perspectives. / 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.