Comme l’a montré l’utilisation de sarin en Syrie en 2013, les agents chimiques de guerre restent une menace. L’exposition de populations est une situation d’urgence qui nécessite des moyens rapides et efficaces. La décontamination et le soin des personnes exposées restent une priorité. Les cheveux représentent une matrice couramment utilisée dans le domaine médico-légal. Dans ce travail, notre intérêt se porte sur la capacité du cheveu à capter et libérer des composés dans l’air, notamment l’ypérite, ainsi que sur l’efficacité de décontamination de cette matrice. Pour ce travail, nous avons utilisé deux composés aux propriétés physiques/chimiques proches de celles de l’ypérite : le salicylate de méthyle et le 2-chloroéthyl éthyl sulfure. Les deux similis ont été retenus par le cheveu avec une plus grande affinité pour le salicylate de méthyle. Nous avons observé une corrélation entre l’intensité d’exposition (influence de la dose et du temps) et la teneur en contaminants retrouvés sur les cheveux. Ces résultats montrent qu’il est possible d’utiliser le cheveu pour détecter une exposition individuelle. Après exposition, la teneur dans des cheveux laissés à désorber a été mesurée avec le salicylate de méthyle. Les résultats obtenus ont montré que les cheveux contaminés sont susceptibles de libérer les toxiques. Cela peut poser un problème sanitaire, qui implique donc que la décontamination des cheveux soit étudiée. Les protocoles de décontamination testés montrent une efficacité partielle (élimination de 40 à 80%). Ces résultats impliquent la nécessité d’optimiser les procédures actuelles ou de définir de nouveaux outils pour la décontamination du cheveu après exposition. / As shown by sarin use in Syria (2013), chemical warfare agents remain a threat. Chemical exposure of populations is an emergency situation, where quick and efficient means are mandatory. Decontamination and care of the victims are a priority. Scalp hair is routinely used as a biological matrix in forensic sciences. In this thesis work, interest focuses on hair capacity to trap and release compounds from atmosphere, especially sulphur mustard, as well as decontamination of this matrix. For this work, two molecules with similar physical/chemical properties to sulphur mustard were used: methyl salicylate and 2-chloroethyl ethyl sulphide. Both simulants were trapped by scalp hair, with higher affinity towards methyl salicylate. We observed a correlation between exposure intensity (influence from dose and time) and simulant content recovered from hair analysis. Results suggest that hair can be used to assess individual contamination. After exposure, evolution of methyl salicylate hair content has been measured. Results pointed out that contaminated hair can thereafter release the simulants. This can lead to health issue, highlighting the fact that hair decontamination must be investigated. Tested decontamination protocols showed a partial efficacy (40-80% removal). Those results evidenced the need to optimise current procedures or define new tools for hair decontamination after chemical exposure.

Le travail effectué durant cette thèse est basé sur l’étude de la photoréactivité de l’acrylonitrile et du propionitrile (composés présents dans l’atmosphère de Titan) lorsque nous simulons en laboratoire les conditions spécifiques de ce satellite.Leur photochimie à haute énergie (λ>120 nm) a été étudiée en matrices cryogéniques afin de simuler la phase gazeuse présente à haute altitude dans l’atmosphère de Titan. Nous avons pu identifier des photoproduits qui sont connus pour être présents dans cette même atmosphère comme le cyanoacétylène, l’acétylène, l’éthylène et l’acide cyanhydrique. La formation d’isonitriles a également été caractérisée permettant ainsi d’envisager leur présence dans cette atmosphère.Les processus photochimiques en phase solide ont également été étudiés à différentes températures afin de simuler les aérosols présents à différentes altitudes de l’atmosphère de Titan. Les mêmes photoproduits qu’en matrices cryogéniques ont été identifiés et des rapports de branchement ont été mesurés pour les différentes températures. L’irradiation VUV de la phase solide (acrylonitrile ou propionitrile) conduit à la formation de résidus non volatils qui seront comparés avec les données de la littérature.Enfin, nous avons étudié l’impact que peut avoir une incorporation de ces molécules dans un mélange gazeux N2/CH4 (les deux composants les plus abondants de l’atmosphère de Titan) lors de la formation de résidus par application d’un plasma simulant le bombardement de la haute atmosphère par des particules lourdes. / This work focused on studying the photoreactivity of acrylonitrile and propionitrile (molecules present in Titan) when the specific conditions of its atmosphere are simulated in laboratory.High energetic photochemistry (λ>120 nm) has been investigated in cryogenic matrices in order to reproduce the gazeous phase present in high altitude. We identified the photoproducts which are known to be detected in Titan such as cyanoacetylene, acetylene, ethylene and cyanhydric acid. We also noticed the formation of isonitriles for which their future detection became predictable.Solid phase photochemical processes have also been studied at different temperatures in order to reproduce the aerosols present at different altitudes. The same photoproducts than in matrices were obtained and branching ratios were determined for the different temperatures. Solid phase (acrylonitrile or propionitrile) VUV radiation leads to the formation of non volatile residues that will be compared to literature data.Finally, we studied the effect of the inclusion of these molecules in an initial gaseous mixture composed of nitrogen and methane (the two most abundant species in the atmosphere of Titan) during the formation of residues by application of plasma simulating the heavy particles shelling in high altitude.

Hydrogen embrittlement is a problem that offers challenges both to technology and to the theory of metallurgy. In the presence of a hydrogen rich environment, applications such as rolling bearings display a significant decrease in alloy strength and accelerated failure due to rolling contact fatigue. In spite of these problems being well recognised, there is little understanding as to which mechanisms are present in hydrogen induced bearing failure. The objective of this thesis are twofold. First, a novel alloy combining the excellent hardness of bearing steels, and resistance to hydrogen embrittlement, is proposed. Second, a new technique to identify the nature of hydrogen embrittlement in bearing steels is suggested. The new alloy was a successful result of computer aided alloy design; thermodynamic and kinetic modelling were employed to design a composition and heat treatment combining (1) fine cementite providing a strong and ductile microstructure, and (2) nano-sized vanadium carbide precipitates acting as hydrogen traps. A novel technique is proposed to visualise the migration of hydrogen to indentation-induced cracks. The observations employing this technique strongly suggest that hydrogen enhanced localised plasticity prevails in bearing steels. While proposing a hydrogen tolerant bearing steel grade, and a new technique to visualize hydrogen damage, this thesis is expected to aid in increasing the reliability of bearings operating in hydrogen rich environments.

Afin de pallier aux problèmes dus aux limites de détection des capteurs et des détecteurs usuels, un système de préconcentration est indispensable. Ce microcomposant permet d’accumuler le ou les vapeur(s) à détecter à l’aide d’un adsorbant et permet de les libérer sous l’effet d’une montée brutale de la température vers un détecteur. Une amplification de la concentration et donc du signal est ainsi obtenue.Cette thèse poursuit le développement d’un préconcentrateur pour la détection de vapeurs toxiques et d’explosifs. Ce préconcentrateur sera constitué d’un microcomposant en silicium rempli d’un adsorbant et muni d’une résistance de chauffage sur sa face inférieure. Des capillaires métalliques permettent d’assurer la circulation du gaz dans le dispositif. Différents types de préconcentrateurs ont été développés avec différents adsorbants afin satisfaire les conditions pour des applications concernant les composés organiques volatils (COV) et les explosifs. L’optimisation des phases d’adsorption et de désorption est cruciale pour le procédé.Le couplage entre un micro-chromatographe et un préconcentrateur a été réalisé et a montré l’apport de ce microcomposant pour la chromatographie. L’analyse d’un mélange de COV a pu être réalisée avec des concentrations initiales de l’ordre de 40 ppb alors que la limite de détection de l’appareillage était de quelques ppm. Un facteur d’enrichissement de 800 a été atteint.L’avantage de l’utilisation du silicium poreux a également été mis en évidence pour l’adsorption de gaz avec des faibles pressions de vapeur saturante. Cette propriété est intéressante pour la préconcentration de vapeur d’explosifs. / In order to overcome problems due to the conventional sensors detection limits, a preconcentration system is required. Accumulation of vapor(s) for detection is possible with an adsorbent and allows releasing them toward a detector, under the effect of a sudden rise of the temperature. Amplification of the concentration and the signal are obtained.This thesis continues the development of a preconcentrator for the detection of toxic gas and explosives. This preconcentrator is made of a silicon microcomponent filled with an adsorbent and a heater at its back. Two metal capillary allow ensuring the gas flow into the device. Various designs of preconcentrators were developed with different adsorbents to satisfy the requirements for volatile organic compounds (VOCs) and explosives applications.The optimization of adsorption and desorption phases is very important for the process.The coupling between a micro-chromatograph and a preconcentrator was conducted and showed the contribution of the microcomponent to the chromatography. Analysis of a VOCs mixture was achieved with initial concentrations in the order of 40 ppb, whereas the detection limit was of a few ppm. An enrichment factor of 800 was achieved.The advantage of using porous silicon was also demonstrated for the gas adsorption with low saturation vapor pressure. This result is interesting for explosive vapor préconcentration.

Coatings for exterior wood have two basic functions. One isto give an aesthetically acceptable surface appearance andcolour. The other is to provide protection against wooddegradation by microbiological or physical attack. Theseprotective properties, often called the barrier properties,play an important role in the selection of proper material forsupreme durability. The assessment of these barrier propertiesis of great importance. Within the CEN Technical Committee 139,Working Group 2, Coatings for exterior wood test methods andperformance specifications have been established. Forassessment of water protection efficiency a standard testprocedure, EN 927-5, has been launched. The present work hasfocused on its applicability in assessing water protectionefficiency in relation to the degradation of coatings duringexposure. Assessments according to EN 927-5 is shown to givesignificant differences in water absorption values fordifferent types of coatings on wood. The proposed performancespecifications in ENV 927 - 2 for the water absorption valuesfor coatings to be used in different constructions seem to beset at acceptable levels. It has been shown that there is agood correlation between the level of water absorption andpractical experience of the performance of paints inScandinavia. However, it has also been shown that thecombination of a standard procedure for water absorptionmeasurement and an artificial weathering procedure gives moreinformation regarding expected durability and longtermperformance than a single measurement of water absorption onfresh, unweathered coated wood. A combination of waterabsorption measurement and artificial weathering could become auseful tool in product development as well as in benchmarking.Together with statistical tools, such as reliability-basedservice life prediction methodologies for predicting theservice life of coating systems a reduction in testing timesmay be achieved. Surface-active substances in coatings have a negative effecton the coatings ability to prevent water ingress, which mostprobably is due to the hydrophilic character of thesesubstances. The presence of these substances, which are commonin waterborne coatings, alters the moisture sorptioncharacteristics of wood. Considering that these substancesoccur in waterborne coatings, may be mobilised during and afterfilm formation and accumulate at the coating/substrateinterface, there is a great probability that these substanceschange the moisture sorption characteristics of the woodsubstrate in an unfavourable way and create unexpected dynamicmoisture conditions at the coating/wood interface. Computerized tomography has been found to be a valuable,non-destructive tool for visualising the spatial moisturedistribution of water and moisture in coated wood panels. Themethod is suitable for recurrent testing of a specimen exposedto a series of processes of wetting, drying. This thesis showsthat high moisture contents occur locally at and around cracks.In these areas there is an increased risk of internal tensionand stress resulting in crack initiation and propagation andthat high moisture contents may occur in the first fewmillimetres under waterborne coatings despite intact coatingfilms. Even with good barrier properties of the coating,moisture may accumulate by water-vapour absorption in air gapsbehind the cladding thus causing favourable conditions formicrobiological colonization. The work that has been carried out regarding assessment ofthe water protection efficiency shows promising resultsregarding the possibility to use reliability-based service lifeprediction methodology for the assessment. The aim of futurework will be to establish more reliable techniques andprotocols for assessing service life expectancy and durability,especially for waterborne coatings with special focus ontendencies to early failure and robustness of the coatingsystems. Keywords:Coatings, surfactants, water absorption value,EN 927, paint, additives, moisture dynamics, absorption,desorption, artificial weathering, artificial exposure,computerized tomography, MRI. / <p>NR 20140805</p>

Nowadays, huge amounts of drugs get into watercourses and soil due to wrong disposal in sewage treatment plants. In this work, the sorption and desorption behavior of Ibuprofen in the soil system was studied, especially in relation to humic acids. The degree of sorption and desorption was defined from the change in ibuprofen concentration analyzed by UV-VIS spectrometry, changes in conductivity and pH were also observed. Ibuprofen shows good sorption properties, desorption was really minimal. It can be assumed that there is a strong bond between ibuprofen and both soil and lignite humic acids and therefore there is no risk of leaching back into solutions. Therefore, if ibuprofen entered the environment, it would be sorbed into the humic acids contained in lignite or soil, which means that it should not be harmful in any way.

Les recherches s’inscrivent dans une prospection qui étudie la viabilité de la valorisation du CO2 d’un incinérateur de déchets industriels. Plusieurs licences commerciales existent pour le captage du CO2 dans des gaz de combustion mais il n’existe pas de référence pour le traitement de fumées d’incinérateur de déchets. Les travaux évaluent, à l’aide d’une installation pilote, la viabilité du captage du CO2 en postcombustion par absorption/désorption avec un solvant à 30 % massique en monoéthanolamine (MEA). Tout d’abord, une synthèse bibliographique identifie les verrous technologiques. Puis, le fonctionnement de l’installation est détaillé. Ensuite, une étude paramétrique a évalué les performances de captage du CO2 et la consommation énergétique du pilote. Enfin, des expériences sur une période de 5 jours ont étudié la résistance chimique du solvant face des gaz de combustion. Les travaux de recherche ont permis une première validation du procédé pour un incinérateur de déchets. / This research is part of a survey designed to establish the viability of the CO2 recovery as a raw material from an industrial waste incinerator.. Several commercial licenses are available to capture CO2 in flue gas, but there are no references for incinerators. This work studies with a pilot the post-combustion CO2 capture from incinerator flue gas using absorption/desorption process with 30 %wt monoethanolamine (MEA). A literature review identifies the technology gaps. Then, the pilot setup was described. A parametric study has evaluated the pilot performance for CO2 capture and energy consumption. Finally, Long runs (5 days) have studied the solvent chemical stability in front of incinerator flue gas. The laboratory experiments show that CO2 capture form incinerator flue gas is possible.

<p>Prirodna organska materija zemlji&scaron;ta/sedimenata predstavlja glavnu oblast<br />za sorpciju hidrofobnih organskih jedinjenja, a njene osobine utiču na stepen<br />retencije i konsekventnu (bio)dostupnost organskih jedinjenja. Da bi se procenio<br />ekotoksikolo&scaron;ki rizik zagađenih zemlji&scaron;ta/sedimenata po okolinu, dizajnirala<br />odgovarajuća strategija remedijacije ili predvidela sudbina i transport organskih<br />polutanata u zagađenim zonama, neophodno je razumevanje mehanizma sorpcije i<br />desorpcije na nivou mehanizma uspostavljenih veza. U radu je izvr&scaron;eno ispitivanje<br />sorpcije i desorpcije odabranih hidrofobnih organskih polutanata, pentahlorbenzena<br />i lindana, na sekvencijalno ekstrahovanim huminskim kiselinama i huminima iz<br />jednog uzorka sedimenta u cilju pronalaženja veze između strukturnih<br />karakteristika izolovanih huminskih kiselina i humina i sorpcionih i desorpcionih<br />parametara. Afinitet za sorpciju, nelinearnost izotermi i prividna sorpciono-desorpciona histereza korelirani su&nbsp; sa osobinama sorbenata dobijenim iz<br />elementarne i FTIR spektroskopske analize. Predloženo je da je mehanizam<br />sorpcije na huminskim kiselinama rezultat odigravanja raspodele i specifične<br />adsorpcije, pri čemu se pri nižim koncentracijama pentahlorbenzena i lindana prvo<br />popune sorpciona mesta u kondenzovanoj aromatičnoj oblasti, a tek potom pri<br />vi&scaron;im koncentracijama sorpciona mesta u amorfnim alifatičnim oblastima.<br />Sveukupno vi&scaron;i koeficijenti nelinearnosti dobijeni za sorpciju pentahlorbenzena na huminskim kiselinama u odnosu na nelinearnost sorpcionih izotermi lindana, ukazuju na to da u ukupnoj sorpciji pentahlorbenzena veći značaj ima mehanizam raspodele i sme&scaron;tanje molekula pentahlorbenzena u hidrofobne &scaron;upljine huminskih kiselina, u odnosu na specifičnu adsorpciju. Ovi zaključci su potvrđeni rezultatima spektroskopskih istraživanja interakcija&nbsp; odabranih organskih jedinjenja i N-metilformamida. Predloženi mehanizam sorpcije ne može objasniti sorpciju pentahlorbenzena i lindana na uzorcima humina, većje pretpostavljeno da nelinearna sorpcija za uzorke humina može biti rezultat ostvarivanja povr&scaron;inskih interakcija, a visoki afinitet za sorpciju rezultat je raspodele organskih jedinjenja u amorfnim alifatičnim oblastima koje pružaju odlično okruženje za sorpciju.</p><p>U cilju daljeg proučavanja mehanizma sorpcije, izvr&scaron;eno je ispitivanje kinetike<br />desorpcije tri odabrana hidrofobna organskajedinjenja, pentahlorbenzena, lindana i<br />pentahloranilina, posredstvom&nbsp; čvrstog adsorbenta, XAD-4 makroporozne<br />jonoizmenjivačke smole. Na osnovu rezultata dobijenih za uzorak sedimenta i<br />frakciju &lt; 125 &micro;m za dva ravnotežna vremena (15 i 90 dana) i za sva odabrana<br />organska jedinjenja može se zaključiti da se za procenu potencijalne (bio)dostupne<br />frakcije organskih jedinjenja može koristiti jednostavna desorpcija u prisustvu<br />XAD-4 makroporozne jonoizmenjivačke smole i to na dva načina: (1) ekstrakcijom<br />sedimenta tokom 24 časa, kada frakcija koja se desorbuje odgovara frakciji<br />jedinjenja koja se nalazi u brzo-desorbujućem domenu organske materije, ili (2)<br />ekstrakcijom tokom 6 časova, kada frakcija koja se desorbuje odgovara polovini<br />one frakcije jedinjenja koja se nalazi u brzo-desorbujućem domenu organske<br />materije.</p> / <p>Natural organic matter of soil/sediment make the main region for&nbsp;sorption of hydrophobic organic compounds, ant its properties influence the degree&nbsp;of retention and, consequently, (bio)availability of organic compounds. In order to&nbsp;assess the ecotoxicological risks of contaminated soils/sediments to the&nbsp;environment and design the appropriate remediation strategy or predict the fate and&nbsp;transport of organic pollutants in contaminated zones, it is necessary to understand&nbsp;the mechanisms of sorption/desorption at the level of the mechanism of established&nbsp;bonds. Study of the sorption and desorption of selected hydrophobic organic&nbsp;pollutants, pentachlorobenzene and lindane, on sequentially extracted humic acids&nbsp;and humins from a single sediment sample with the aim of finding the relationship&nbsp;between the structural characteristics of the isolated humic acids and humin and&nbsp;sorption and desorption parameters. Sorption affinity, nonlinearity of isotherms,&nbsp;and apparent sorption-desorption hysteresis were correlated to the sorbent&nbsp;characteristics obtained from elemental analysis and FTIR spectroscopic data. The&nbsp;proposed sorption mechanism on humic acids assumes that at low concentrations&nbsp;of pentachlorobenzene and lindane the sorption sites in the condensed aromatic&nbsp;region are occupied first, and then, at their higher concentrations, the sorption sites&nbsp;in the amorphous and aliphatic regions. Generally higher nonlinearity coefficient obtained for the sorption of pentachlorobenzene on &nbsp;umic acids compared with the nonlinearity of sorption isotherms for lindane, indicate that in the overall sorption of pentachlorobenzene of higher significance is the &nbsp;echanism of distribution and insertion of pentachlorobenzene molecule into hydrophobic dips of humic acids, compared to specific adsorption. These conclusions were confirmed with the results of spectroscopic investigation of &nbsp;intermolecular interaction of chosen organic compounds and N-methylformamide.Since suggested sorption mechanism could not explain sorption of &nbsp;pentachlorobenzene and lindane onto humin samples, it is supposed that the nonlinearity can be a result of surface interactions, while the high sorption affinity is result of distribution of organic compounds in the amorphous aliphatic regions that offer an excellent environment for sorption.</p><p>With the aim of further insight into the sorption mechanism, investigation of&nbsp;desorption kinetics of three chosen hydrophobic organic compounds,&nbsp;pentachlorobenzene, lindane and pentachloroaniline, in the presence of &nbsp;soild&nbsp;adsorbent XAD-4 macroporous ion-exchange resin was performed. On the basis of&nbsp;the results obtained for sediment sample and fraction &lt; 125 &micro;m at two equilibrium&nbsp;times (15 and 90 days) and for all selected organic compounds, it can be concluded&nbsp;that the assessment of the potential (bio)avialable fraction of organic compounds&nbsp;may be obtained by using simple method of desorption in the presence of XAD-4&nbsp;macroporous ion-exchange resin, performed in two ways: (1) by sediment&nbsp;<br />extraction during 24 hours, when the desorbing fraction corresponds to the fraction&nbsp;of &nbsp;he compound that is found in the fast-desorbing domain of organic matter, or&nbsp;(2) by 6-hour extraction, when the desorbing fraction corresponds to one half of the&nbsp;fraction appearing in the fast-desorbing domain of the organic matter.</p>

In dieser Arbeit wurden einzelne Siliziumdioxid-Partikel (Durchmesser 500nm) in einer elektrodynamischen Vierpolfalle gespeichert und mit Hilfe eines Kohlendioxidlasers aufgeheizt. Die Masse eines gespeicherten Partikels wurde dabei mit hoher Präzision und in situ aus der Auswertung von Streulichtmodulationen gewonnen. Es wurden anhand der zeitlichen Masseänderung laserinduzierte Desorptionen und Adsorptionen von Molekülen beobachtet. Dazu wurde eine weitgehend automatisierte Versuchsanlage aufgebaut. Eine rechnergesteuerte Durchführung der Experimente erfolgte jeweils bis zu einer Dauer mehrerer Tage (Langzeitmessungen). Die Temperatur und die thermische Abstrahlleistung isolierter Partikel wurde mit Hilfe einer modifizierten Planck'schen Strahlungsformel abgeschätzt.

ermal desorption spectroscopy (TDS) is a common method for surface analysis of adsorbed molecules. In chapter 1 the work deals with the theoretical background of this method and shows the principles of a desorption process influenced by subsurface diffusion. Chapter 2 first shows application of TDS for detection of surface molecules and determination of binding energy.Experiments were mainly focused on ditermination of surface adsorbents and impurities on Si wafers. The second part of chapter 2 describes desorption of atoms of a Ga layer on Si surface and their subsurface diffusion. A Ga diffusion process was also observed by with secondary ion mass spectrometry (SIMS) and numerically simulated.