This master’s thesis is focused on the LIBS technique for compositional differentiation and relative hardness quantification of selected geological samples. The experimental part of this thesis was conducted at the National Institute of Laser Enhanced Sciences (NILES) in Cairo, Egypt where a simple LIBS system was constructed. In parallel to the experimental work, the literature review was surveyed with the aim to give a thorough view of the history, fundamentals and all the factors related to LIBS. LIBS is a developing analytical technique, which is used to perform qualitative and semi-quantitative elemental analysis of materials (solid, liquid and gas). The fast data collection and the lack of sample preparation made LIBS be an attractive technique to be used for geological samples. This study was done to improve analytical methods for geochemical analysis of samples during different exploration phases (Mining, filed analysis, etc.), as a real-time analysis method to save money and time spent in labs. For a generation of laser induced plasma, a Q-switched Nd: YAG laser operated at 10 Hz and wavelength of 1064 nm was employed on the surface of the samples. A spectrometer fitted with an intensified charge-coupled device (ICCD) was used to disperse and detect the spectrum; then fed to a computer for recording and further processing of the data. The sample set was compiled from samples collected from different areas (South Africa and Namibia). Using principal component analysis (PCA), it was found that LIBS was able to differentiate between the samples even those of the same area. The results from the LIBS technique were correlated with subsequent analysis of the same samples by Particle-induced X-ray emission (PIXE). The feasibility of relative hardness estimation using LIBS was done by measuring the plasma excitation temperature for different samples. LIBS with its advantages as an elemental analysis technique made it possible to estimate the hardness of geological samples. Based on theory and results, an analytical technique for compositional differentiation and quantification of relative hardness of geological samples is proposed. / National Research Foundation (South Africa) / Physics / M Sc. (Physics)

PIXE (Particle Induced X-ray Emission) et PIGE (Particle Induced Gamma-ray Emission) sont des méthodes d’analyse par faisceau d’ions, multiélémentaires et non destructives. Elles sont basées sur la détection des rayons X et gamma caractéristiques émis suite à l’interaction de particules chargées avec la matière. La méthode PIXE permet de quantifier les éléments de numéro atomique Z>11 avec une limite de détection au niveau du μg/g (ppm). Les rayons X émis par les éléments légers (Z<11) sont fortement atténués par la matière, limitant la sensibilité de PIXE pour cette gamme de numéro atomique. Ces éléments peuvent légers être analysés, simultanément, par la méthode PIGE. Un des nombreux avantages de la méthode PIXE/PIGE est sa capacité à pouvoir effectuer différentes analyses (cartographie des concentrations, analyse en profondeur, objets précieux). Il est possible d’analyser des échantillons aussi bien homogènes que non homogènes. La méthode PIXE à haute énergie a été développée au cyclotron ARRONAX avec des faisceaux de particules pouvant atteindre 70 MeV. La technique PIXE à haute énergie permet, notamment, l’analyse d’échantillons épais et limite les risques d’endommagement. Premièrement la plateforme PIXE/PIGE à haute énergie est décrite. Ensuite une étude de la méthode PIGE à haute énergie ainsi que la mise en place d’un protocole de mesure de sections efficaces sont présentées. Pour finir les méthodes mises en place ainsi que les résultats obtenus lors de l’analyse de plusieurs types d’échantillons non homogènes (multicouches et granulaires) sont présentés et discutés. / Particle Induced X-ray Emission (PIXE) and Particle Induced Gamma-ray Emission (PIGE) are multi-elemental and non-destructives techniques. They are based on the detection of characteristic X-ray and gamma emission induced by the interaction of accelerated charged particles with matter. Elements with an atomic number Z> 11 can be quantified reaching a limit of detection in the order of μg/g (ppm). X-rays from light elements are strongly attenuate by matter. Therefore, PIXE shows little sensitivity for lights elements. Those elements are analyzed simultaneously using PIGE. One of the benefits of PIXE/PIGE is its ability to perform analysis with different requirement (elemental concentration mapping, in-depth analysis, valuable objects). Homogeneous and non-homogenous samples can be studied thanks to PIXE/PIGE. High energy PIXE (HEPIXE) has been developed at the ARRONAX cyclotron using particles beams up to 70 MeV. Thus analysis of thick samples is achievable using HEPIXE. Using high energy beams can also reduce the risk of damaging the sample. First of all, the high energy PIXE/PIGE platform develop at ARRONAX is described. Then the results given by high energy PIGE analysis and the experimental procedure for gamma emission cross section measurements are discussed. Finally, the methods developed and the results obtained during the analysis of inhomogeneous samples (multi-layer and granular samples) are presented and discussed.

Die vorliegende Arbeit stellt die Ergebnisse der methodologischen Entwicklung räumlich aufgelöster Analyse mittels Scanning Laserablation-ICP-Massenspektrometrie dar. Eine neue Behandlung zur Quantifizierung transienter analytischer Signale wurde für die Wiederherstellung von Konzentrationsprofilen vorgeschlagen. Die Anwendung der entwickelten Modelle auf die räumlich aufgelöste Analyse mittels LA-ICP-MS ermöglicht verbesserten Informationsgewinn und lässt dadurch eine höhere räumliche Auflösung erreichen. Die Anwendbarkeit der LA-ICP-MS für die räumlich aufgelöste Bestimmung der Stöchiometrie in supraleitenden Borokarbiden wurde untersucht. Der Einfluss apparativer Größen auf das analytische Signal wurde aufgeklärt, um die Messbedingungen zu optimieren. Zusätzlich wurden Fraktionierungseffekte untersucht, um die Ursache und deren Auswirkung auf die Analyse supraleitender Borokarbiden zu erklären. / This work represents the results of the methodological development of spatially resolved analysis by scanning laser ablation ICP mass spectrometry. A new approach to the quantification of transient analytical signals was proposed to reveal the concentration profile. An application of the developed models on spatially resolved analysis by LA-ICP-MS allows to gain more information from experimental data and hence to achieve better spatial resolution. The applicability of LA-ICP-MS to the spatially resolved determination of the stoichiometry of superconducting borocarbides was investigated. The effect of experimental parameters on analytical signals was elucidated in order to optimize the experimental conditions. In addition, fractionation effects were investigated to identify the causes for fractionation and their influence on the analysis of superconducting borocarbides.