Les produits pétroliers formulés actuels tels que les carburants et les lubrifiants doiventrépondre à des cahiers des charges bien précis pour garantir les meilleures performances,fiabilité et longévité des moteurs tout en limitant l’émission de polluants. Ce travail de thèse porte sur le développement de méthodologies d’analyse pour l’identification d’additifs polymériques dans les gazoles et la caractérisation des polyalphaoléfines. L’analyse des additifs a été effectuée par couplage de la chromatographie liquide, de la spectrométrie de mobilité ionique et de la spectrométrie de masse (LC-IMSMS), l’ionisation étant obtenue par electrospray (ESI). Après ajustement des paramètres expérimentaux, les différents additifs ont été identifiés dans les gazoles sans préparation d'échantillon. Le couplage de la chromatographie liquide aux conditions critiques (LCCC) avec la spectrométrie de masse a également été évalué dans l’objectif d’améliorer la séparation des additifs de la matrice gazole. La caractérisation des polyalphaoléfines (PAO) a été réalisée par couplage IMS-MS associé à la source ASAP (sonde d’analyse de solide à pression atmosphérique) ou la source APPI (photoionisation à pression atmosphérique). En ASAP, outre les ions de pyrolyse, des espèces intactes peuvent être détectées pour les PAO de faible grade. Dans le cas des PAO de haut grade, seuls des ions fragments pyrolytiques ont été détectés, permettant toutefois d’identifier les alpha-oléfines utilisées pour produire les PAOs. En APPI, l’utilisation de solvants halogénés et de toluène, a permis d’observer des espèces intactes pour les PAOs de haut grade via la formation d’adduits halogénés. Le couplage IMS-MS a permis de différencier les polyalphaoléfines par l’étude des temps de dérive et des largeurs de signaux IMS. / Nowadays, formulated petroleum products such as fuels and lubricants must respond toprecise technical requirements to ensure the best performance, reliability and longevity ofengines while limiting the emission of pollutants. This thesis work focused on the development of analytical methodologies for the identification of polymeric additives in diesel fuels and the characterization of polyalphaolefins. The additive analysis was performed by coupling of liquid chromatography, ion mobility spectrometry and mass spectrometry (LC-IMS-MS), the ionization was performed by electrospray (ESI). After adjusting the experimental parameters, all additives were identified in the diesel fuel without sample preparation. The coupling of liquid chromatography at the critical condition chromatography (LCCC) with mass spectrometry was also evaluated in order to improve the separation of additives from the diesel fuel matrix. The characterization of polyalphaolefins (PAO) was carried out by IMS-MS with ASAP (atmospheric solids analysis probe) or APPI (atmospheric pressure photoionization) sources. With ASAP, in addition to pyrolysis ions, intact species were detected for low PAO grades. In the case of high PAO grades, only pyrolytic fragments were detected, yet it was possible to identify the alphaolefins used to produce the PAOs. In APPI, the use of halogenated solvents and toluene, allowed to observe intact species for high PAO grades through the formation of halogenated adducts. With IMS-MS coupling polyalphaolefins were differentiated the by the study of drift times and full width at half maximum.

<p>Mass spectrometry, the science and technology of ions, owes much of its current popularity to the development of electrospray ionization. The development of electrospray ionization, along with its low flow-rate analog nanoelectrospray ionization, has increased the chemical space that can be investigated using mass spectrometers by orders of magnitude. While the interfacial chemistry of charged microdroplets that are generated by nanoelectrospray has been studied in detail, the physics of their motion, particularly in the presence of an applied field at ambient pressures, remains relatively unexplored. In this dissertation, an increase in ion currents detected by a commercial triple quadrupole mass spectrometer is used to demonstrate that: (i) the orthogonal injection of counterions into an electrode assembly can compensate for space charge effects and enhance the sampling of charged microdroplets from a nanoelectrospray focused electrostatically under ambient conditions into the mass spectrometer; and (ii) the ease of ion evaporation from charged microdroplets may be elucidated for small molecules based on their relative transmission through an electrode assembly for the simultaneous ambient electrostatic focusing of two nanoelectrosprays. In each case, the development is characterized by using ion trajectory calculations in conjunction with experiments, using homebuilt devices designed and fabricated in-house as rapid prototypes via 3D printing. In the open air, charged microdroplets have low kinetic energies with a narrow energy spread. Despite these limitations, this dissertation demonstrates, through the electrostatic manipulation of charged microdroplets produced via nanoelectrospray ionization, that a better understanding of the physics of moving charges in the open air can be used to increase the sensitivity of atmospheric pressure ionization.</p>

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