Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, dois copolímeros à base de 2-vinilpiridina (2Vpy), estireno (Sty) e divinilbenzeno (DVB) foram sintetizados empregando a técnica de polimerização em suspensão aquosa via radical livre. Os copolímeros com diferentes características morfológicas foram preparados variando a composição da mistura diluente, constituída por tolueno e n-heptano, solventes solvatantes e não solvatantes para as cadeias poliméricas. A caracterização estrutural desses materiais foi feita através de medidas de área específica, volume de poros, diâmetro médio de poros e densidade aparente. Além disso, esses materiais foram avaliados por microscopia ótica e eletrônica de varredura, por espectroscopia na região do infravermelho (FTIR), análise termogravimétrica (TGA) e análise elementar. Os copolímeros Sty-DVB-2Vpy foram modificados quimicamente através de reação de quaternização das unidades de 2Vpy usando dois reagentes: iodeto de metila e acrilonitrila. A quaternização dos copolímeros Sty-DVB-2Vpy foi confirmada através de espectroscopia de infravermelho, pelo aparecimento das bandas de absorção características do íon peridíneo e do grupo nitrila e também pela análise do comportamento térmico. Os produtos dessas reações foram submetidos à avaliação da capacidade bactericida através do método de contagem em placas contra suspensão de Escherichia coli. O copolímero do tipo gel quaternizado com iodeto de metila apresentou a maior ação bactericida registrada, com eficiência até a concentração de 104 células/mL. Contudo, a maioria dos materiais quaternizados não apresentou ação biocida significativa. Com o objetivo de maximizar a atividade bactericida dos materiais preparados, os copolímeros quaternizados e não quaternizados foram impregnados com iodo por meio de duas metodologias: em solução e em fase vapor. O teor de iodo incorporado foi quantificado por análise gravimétrica. Foi possível observar que os copolímeros quaternizados e impregnados com iodo se mostraram mais eficientes como agentes bactericidas que os copolímeros não funcionalizados impregnados com iodo. De uma forma geral, foi possível perceber que a ação bactericida dos polímeros é fruto da associação entre as suas características de porosidade, o grau de quaternização alcançado e o teor de iodo incorporado. Para efeito de comparação foram feitos também ensaios bactericidas com uma resina comercial à base de Sty-DVB com grupo amônio quaternário, VP OC 1950. Os testes mostraram que a resina comercial não possui atividade bactericida. A impregnação de iodo a essa resina comercial forneceu um material com ação biocida semelhante à do copolímero do tipo gel, quaternizado com iodeto de metila e impregnado com iodo / In this work two 2-Vinylpyridine-Styrene-Divinylbenzene copolymers with different porosity degrees were synthesized by aqueous suspension polymerization in the presence of diluent mixtures formed by toluene (solvating solvent) and n-heptane (nonsolvating solvent) in different proportions. Their structural characteristics were characterized by determination of surface area, average pore diameter and pore volume by BET/BJH, bulk density, optical and electron microscopies. In addition the chemical morphology those materials were characterized by FT-IR, elemental analysis and thermogravimetry. The pyridine units were quaternized using two reagents: methyl iodide and acrylonitrile. Those reactions were confirmed by FT-IR, the presence of characteristics bands of piridinium ion and nitrile group was used as a qualitative indication of the quaternizations reactions. The extension of those modifications was also evaluated by thermogravimetry. The antibacterial activities of the quaternized materials were determined towards 103 to 107 cells/mL dilutions of the auxotrophic (OHd5 k-12) Escherichia coli strain. The gel type copolymer quaternized with methyl iodide presented the better bactericidal action, with significant efficiency until 104 cells/mL, however most quaternized copolymers did not present significant bactericidal action. In order to maximize the bactericidal performance, the modified and unmodified copolymers were impregnated with iodine using two different methods: solution and vapor. The iodine incorporation was quantified by gravimetry. It was observed that the copolymers quaternized and impregnated with iodine presented higher biocidal action than the unmodified copolymers impregnated with iodine. It was verified that the biocidal action the polymers is a result of three contributions: porous characteristics of the supports, quaternization degree and iodine incorporation degree. The bactericidal performance of a commercial resin with quaternary ammonium groups, VP OC 1950, was also evaluated. The tests showed that the commercial resin did not present bactericidal efficiency. That resin impregnated with iodine presented bactericidal action similar to gel type copolymer quaternized with methyl iodide and impregnated with iodine.

Made available in DSpace on 2016-06-02T19:56:59Z (GMT). No. of bitstreams: 1 6783.pdf: 3853594 bytes, checksum: 5c76462cb2ede47f0f6638372f3f2364 (MD5) Previous issue date: 2015-02-18 / Financiadora de Estudos e Projetos / The fluid catalytic cracking (FCC) is one of the most important process in the petroleum refining industry, being responsible for the increase of the yield of the most valuable light hydrocarbons. On the other hand, the FCC process generates big amounts of CO, NOx and SOx emissions. The CO emissions from the most of pollution sources are abatement using noble metal based catalysts. However, the growing demand and scarcity of those metals have caused an increase in the process cost and consequently promoting studies to find alternative catalysts with comparable efficiency and lower in cost. In this respect, the literature had presented interesting results with transitions metal catalysts. Thus, the objective of this work was to prepare exchanged or impregnated Fe or Mn on H-mordenite or Ce-mordenite, which were evaluated between 150 and 550 oC in the CO oxidation with O2, in the presence or absence of interfering compounds (water steam or SO2). The catalysts were characterized by ICP-OES, DRX, DRS-UV-VIS and Mössbauer spectroscopy. The results showed that the preparation procedures of the interchanged or impregnated Fe or Mn catalysts were adequate, and no mordenite crystallinity loss was observed. Contrary to the exchanged Fe or Mn based catalysts, those based on impregnated Fe or Mn oxides showed a important potential as catalysts in the CO oxidation with O2. Then, in the applied operational conditions the Ce-MOR/Fe10, Ce-MOR/Mn5, Ce-MOR/Mn10 e H-MOR/Mn5 catalysts were able to produce an effluent with CO content lower than 500 ppm, which is the allowed limit by the environmental regulations related with FCC units. In the presence of water steam the evaluated Fe or Mn catalysts presented activity loss that was recovered after the elimination of that interfering from the feed. Nevertheless, in the presence of SO2, the tested catalysts showed an irreversible and significantly activity loss. / O craqueamento catalítico fluido (FCC) é uma das etapas mais importantes no refino de petróleo, sendo responsável pelo aumento do rendimento em frações leves, de maior valor agregado. Por outro lado, o FCC é responsável na refinaria por uma grande parcela das emissões de monóxido de carbono (CO), óxidos de nitrogênio (NOx) e óxidos de enxofre (SOx). O CO, em particular, na maioria das fontes poluidoras é eliminado via oxidação sobre catalisadores à base de metais nobres. Porém, o aumento na demanda desses metais e sua baixa disponibilidade criam um forte impacto no custo do processo, surgindo a necessidade de buscar catalisadores alternativos, com eficiência comparável e de menor custo. Assim, o objetivo deste trabalho foi preparar catalisadores à base de ferro ou manganês impregnados ou trocados em H-mordenita ou Ce-mordenita e avaliá-los entre 150 e 550 oC na oxidação de CO com oxigênio (O2), na ausência ou presença de compostos interferentes à reação como vapor de água e dióxido de enxofre (SO2). Os catalisadores foram caracterizados por espectroscopia de emissão atômica (ICP-OES), difração de raios X (DRX), espectroscopia de reflectância difusa (DRS-UV-VIS), redução com H2 à temperatura programada (RTP-H2) e espectroscopia Mössbauer (MOSS). Os resultados mostraram que os procedimentos de preparação dos catalisadores, trocados ou suportados, foram eficientes, não se observando perda de cristalinidade da mordenita. Os catalisadores com óxidos de Fe ou Mn suportados na mordenita apresentaram um importante potencial para serem utilizados como catalisadores na oxidação de CO com O2, contrário ao que ocorreu com cátions de Fe ou Mn em sítios de troca. Assim, nas condições operacionais utilizadas, os catalisadores Ce-MOR/Fe10, Ce-MOR/Mn5, Ce-MOR/Mn10 e H-MOR/Mn5 foram capazes de converter CO suficiente para produzir um efluente gasoso com teor menor que 500 ppm de CO, sendo essa a concentração limite permitida pela legislação que rege as emissões de unidades FCC. Os catalisadores impregnados com Fe e Mn, quando avaliados na presença de vapor de água e de SO2, ocorreu perda da atividade, a que foi recuperada somente no caso do vapor de água.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, dois copolímeros à base de 2-vinilpiridina (2Vpy), estireno (Sty) e divinilbenzeno (DVB) foram sintetizados empregando a técnica de polimerização em suspensão aquosa via radical livre. Os copolímeros com diferentes características morfológicas foram preparados variando a composição da mistura diluente, constituída por tolueno e n-heptano, solventes solvatantes e não solvatantes para as cadeias poliméricas. A caracterização estrutural desses materiais foi feita através de medidas de área específica, volume de poros, diâmetro médio de poros e densidade aparente. Além disso, esses materiais foram avaliados por microscopia ótica e eletrônica de varredura, por espectroscopia na região do infravermelho (FTIR), análise termogravimétrica (TGA) e análise elementar. Os copolímeros Sty-DVB-2Vpy foram modificados quimicamente através de reação de quaternização das unidades de 2Vpy usando dois reagentes: iodeto de metila e acrilonitrila. A quaternização dos copolímeros Sty-DVB-2Vpy foi confirmada através de espectroscopia de infravermelho, pelo aparecimento das bandas de absorção características do íon peridíneo e do grupo nitrila e também pela análise do comportamento térmico. Os produtos dessas reações foram submetidos à avaliação da capacidade bactericida através do método de contagem em placas contra suspensão de Escherichia coli. O copolímero do tipo gel quaternizado com iodeto de metila apresentou a maior ação bactericida registrada, com eficiência até a concentração de 104 células/mL. Contudo, a maioria dos materiais quaternizados não apresentou ação biocida significativa. Com o objetivo de maximizar a atividade bactericida dos materiais preparados, os copolímeros quaternizados e não quaternizados foram impregnados com iodo por meio de duas metodologias: em solução e em fase vapor. O teor de iodo incorporado foi quantificado por análise gravimétrica. Foi possível observar que os copolímeros quaternizados e impregnados com iodo se mostraram mais eficientes como agentes bactericidas que os copolímeros não funcionalizados impregnados com iodo. De uma forma geral, foi possível perceber que a ação bactericida dos polímeros é fruto da associação entre as suas características de porosidade, o grau de quaternização alcançado e o teor de iodo incorporado. Para efeito de comparação foram feitos também ensaios bactericidas com uma resina comercial à base de Sty-DVB com grupo amônio quaternário, VP OC 1950. Os testes mostraram que a resina comercial não possui atividade bactericida. A impregnação de iodo a essa resina comercial forneceu um material com ação biocida semelhante à do copolímero do tipo gel, quaternizado com iodeto de metila e impregnado com iodo / In this work two 2-Vinylpyridine-Styrene-Divinylbenzene copolymers with different porosity degrees were synthesized by aqueous suspension polymerization in the presence of diluent mixtures formed by toluene (solvating solvent) and n-heptane (nonsolvating solvent) in different proportions. Their structural characteristics were characterized by determination of surface area, average pore diameter and pore volume by BET/BJH, bulk density, optical and electron microscopies. In addition the chemical morphology those materials were characterized by FT-IR, elemental analysis and thermogravimetry. The pyridine units were quaternized using two reagents: methyl iodide and acrylonitrile. Those reactions were confirmed by FT-IR, the presence of characteristics bands of piridinium ion and nitrile group was used as a qualitative indication of the quaternizations reactions. The extension of those modifications was also evaluated by thermogravimetry. The antibacterial activities of the quaternized materials were determined towards 103 to 107 cells/mL dilutions of the auxotrophic (OHd5 k-12) Escherichia coli strain. The gel type copolymer quaternized with methyl iodide presented the better bactericidal action, with significant efficiency until 104 cells/mL, however most quaternized copolymers did not present significant bactericidal action. In order to maximize the bactericidal performance, the modified and unmodified copolymers were impregnated with iodine using two different methods: solution and vapor. The iodine incorporation was quantified by gravimetry. It was observed that the copolymers quaternized and impregnated with iodine presented higher biocidal action than the unmodified copolymers impregnated with iodine. It was verified that the biocidal action the polymers is a result of three contributions: porous characteristics of the supports, quaternization degree and iodine incorporation degree. The bactericidal performance of a commercial resin with quaternary ammonium groups, VP OC 1950, was also evaluated. The tests showed that the commercial resin did not present bactericidal efficiency. That resin impregnated with iodine presented bactericidal action similar to gel type copolymer quaternized with methyl iodide and impregnated with iodine.

Arsenik är en naturligt förekommande halvmetall som orsakar stora hälsoproblem genom exponering t.ex. via dricksvatten. På grund av arseniks negativa effekter på människors hälsa sänktes den tillåtna gränsen i dricksvatten från 50 μg/l till 10 μg/l 2003 av WHO. Arsenik förekommer i huvudsak i två oorganiska former, arsenat (AsO43-) och arsenit (AsO33-), där arsenit är en betydligt mer mobil och toxisk form. Vilken form som dominerar påverkas i första hand av redoxförhållanden men även av pH. Reduktion från arsenat till arsenit är gynnsamma vid lägre pH och vid syrefria (reducerade) förhållanden. I Sverige har tidigare användning av arsenik, t.ex. vid impregneringsanläggningar, orsakat föroreningar som än idag ligger kvar. I Hjältevad i Eksjö kommun drev Televerket under 1940- till 1980-talet en impregneringsanläggning för telefonstolpar. Impregneringsvätska, innehållande bland annat arsenik, kunde spridas inom området till största del på grund av en tank som började läcka under 1960-talet. En omfattande sanering med jordtvätt genomfördes 1997. Senare kontroller har dock påvisat stadigt ökade halter. Med anledning av de ökade halterna har ett arbete inletts för att kartlägga föroreningssituationen. Syftet med examensarbetet är att utvärdera grundvattenkemin i Hjältevad genom att visualisera föroreningsföroreningsplymen, undersöka mobiliteten genom att undersöka samband mellan halten arsenik och kemiska parametrar samt göra en fördjupad analys av spridningsrisken med hjälp av Kd-värden. Data från jord- och grundvattenprovtagningar genomförda under augusti och september 2017 bearbetades med hjälp av ArcMap och Excel. Resultatet visade att låga redoxförhållanden sannolikt har bidragit till ökad spridning av arsenik vilket till stor del förekom i den reducerade formen arsenit. De högsta halterna var koncentrerade till området kring den f.d. läckande tanken, där halter så höga som 2200 μg/l kunde uppmätas i grundvattnet. Vidare visade provtagningsresultaten att mängden förorenad jord missbedömdes vid saneringen 1997 (halter på 238 mg/kg kunde uppmätas i jorden). Slutsatsen drogs att redoxförhållanden inom området är gynnsamma för att arsenik ska förekomma i den reducerade formen arsenit, att arseniks mobilitet med stor sannolikhet är betydligt högre än vad som tidigare bedömdes samt att risker föreligger om inga åtgärder vidtas. / Arsenic is a naturally occurring metalloid that causes major health problems for people affected by exposure, e.g. through their drinking water. Due to the negative effects on human health, the permissible concentration in drinking water was lowered in 2003, from 50 μg/l to 10 μg/l. Arsenic predominantly exists in two inorganic forms, arsenate (AsO43-) and arsenite (AsO33-), where arsenite is a more mobile and toxic. Which forms that dominates is controlled by pH and redox potential. Reduction from arsenate to arsenite is favorable at lower pH and at anoxic (reduced) conditions. In Sweden previous use of arsenic, e.g. at impregnation plants, caused pollution still affecting soils and groundwater. In Hjältevad, Eksjö municipality, an impregnation plant for telephone poles was run by Televerket during the 1940s to 1980s. Impregnating fluid, including arsenic, was spread in the area, mainly due a leaky storage tank during the 1960s. The site was remediated in 1997 using soil washing. However, monitoring program demonstrated steadily increased levels in a well situated downstream the contaminated area. Due to the increased contamination levels of arsenic in the ground water, a detailed investigation was initiated to identify the pollution situation. The main objective was to investigate about the chemical and physical processes affecting the mobilization of arsenic. Groundwater and soil materials were sampled from the area and evaluated using ArcMap and Excel. In support of this evaluation, distribution coefficients (Kd) for soil materials from the aqvifer were obtained by leaching tests performed at oxidized conditions. The result showed that reducing conditions in the aquifer appeared to have caused increased mobilization of arsenic in the area and that large amounts of pollution was not removed at the remediation in 1997 (levels of 238 mg/kg arsenic could be detected in the soil). In the collected samples, arsenic mainly occurred in the reduced form arsenite. The highest levels in the groundwater were found in the area around the former leaky tank, where concentrations up to 2200 μg/l was measured. The conclusion was that large amounts of pollution was not removed at the remediation in 1997, and that arsenic mobility seems to be significantly higher than previously assessed and that action needs to be taken to stop the spread.

L'imprégnation, étape cruciale de la préparation de catalyseurs supportés pour l’hydrotraitement de coupes pétrolières (CoMo / y-Al2O3) , a été étudiée dans ce travail. L'objectif principal a été de déterminer les phénomènes physico-chimiques et les interactions entre la surface du support et les espèces en solution se produisant pendant cette étape puis faire le lien avec l'activité du catalyseur final.La formation directe et la stabilité de la solution (3 Co2+ ; H4Co2Mo10O386-) ont été étudiées de manière poussée en fonction du pH, de la concentration, du rapport Co/Mo. Cela a nécessité le développement de méthodes analytiques quantitatives (spectrométries Raman et UV-visible), réalisées via SIMPLISMA, un algorithme de traitement des données par analyses factorielles. L'étude de l'imprégnation de la solution (3 Co2+ ; H4Co2Mo10O386-) sur y-Al2O3 a mené à une meilleure compréhension de cette étape. Il a été montré que la conservation de cette espèce sur le support dépend principalement de la densité en atomes de Mo / nm², mais également du rapport Co/Mo et du pH initial de la solution d’imprégnation, tous ces paramètres étant liés entre eux. Cette étude a mis en évidence le rôle majeur du support, via ses propriétés surfaciques.L’intérêt d’utiliser (3 Co2+ ; H4Co2Mo10O386-) pour préparer de tels catalyseurs réside dans la proximité du cobalt et du molybdène. La phase active résultante est très bien dispersée et hautement promue, et ce même si le précurseur est décomposé sur le support lors de l’imprégnation. Enfin, la méthodologie développée au cours de ce travail est transposable à la préparation de tout type de catalyseur supporté. / Impregnation, crucial step of the preparation of supported catalysts used for hydrotreatment of petroleum fractions (CoMo / gamma-alumina), has been studied in this work. The main aim has consisted in determining the physico-chemical phenomena and the interactions between the support surface and the aqueous species during this step, and then linking these results to the activity of the final catalyst.The direct formation and stability of the (3 Co2+ ; H4Co2Mo10O386-) solution have been studied as a function of pH, concentration and Co/Mo ratio. This has required the developement of analytical quantitative methods (Raman and UV-visible spectroscopies) carried out thanks to SIMPLISMA, an algorithm of data treatment by factorial analysis. The study of impregnating (3 Co2+ ; H4Co2Mo10O386-) solutions onto gamma alumina has led to a best understanding of this step. It was showed that the conservation of these species on the support mainly depends on the surface density of molybdenum atoms per square nanometer, but also on the Co/Mo ratio and the initial pH of impregnating solutions, all these parameters being linked together. This study has underlined the major role of the surface properties of the support. The interest of using (3 Co2+ ; H4Co2Mo10O386-) solutions to prepare such catalysts lies in the proximity of cobalt and molybdenum. The resulting active phase is very well dispersed and highly promoted, even if the precursor is decomposed on the support during impregnation. Finally, the methodology developed in this work is transferable to the preparation of any supported catalyst.

Carbon fiber is a lightweight, versatile material with many current and potential applications. To be able to expand the market for carbon fiber composites in other areas than special applications the production costs must be reduced. One way of accomplishing this could be to use a less expensive raw material where lignin is a good example as it can be provided at lower cost, is renewable and abundantly available compared to commercially used raw materials today. So far, the mechanical properties of lignin-based carbon fibers are inferior relative to commercial carbon fibers. For lignin-based carbon fibers to enter the commercial market more research is necessary to gain knowledge of the conversion of lignin to carbon fiber. The LightFibre project investigates the possibilities to produce carbon fibers based on a mixture of softwood kraft lignin and cellulose. The kraft lignin is isolated from black liquor in the kraft/sulfate process with the LignoBoost process. This master thesis project was conducted within in the LightFibre project and evaluated whether metal ions generally present in kraft lignin had an influence on the final carbon fiber quality in terms of mechanical properties and morphology. The mechanical properties were determined with tensile testing, the morphology by scanning electron microscopy (SEM) and the relative abundance of studied elements with electron dispersive spectroscopy (EDS). The influence of the chosen metal ions was tested by impregnation of dry-jet wet spun prefibers based on 70 wt.% softwood kraft lignin and 30 wt.% dissolving pulp cellulose. The fibers were impregnated in room temperature with solutions containing Na2SO4, K2SO4, MgSO4, FeSO4 and Al2(SO4)3 salts where the cations were the focus in these trials. The concentrations used for impregnation were 0.2 and 1M of the cations. The obtained mechanical properties of the carbon fibers of the samples impregnated with different metal ions did not deviate significantly from the reference which had a tensile strength of 870 MPa and tensile modulus of 68 GPa. The analysis of morphology with SEM showed no defects or damage of any of the fibers. Therefore, it was concluded that the impregnated metal ions: K+, Na+, Al3+, Mg2+ and Fe2+ at the obtained levels in the fibers cause no effects on the fibers during the stabilization and carbonization that affects the mechanical performance of final carbon fiber.  The amount of potassium in one of the samples was estimated to 0.1 wt.%. From the results of this study it may be suggested that the general recommendation of <0.1 wt.% ash in lignin can be exceeded, for dry-jet wet-spun kraft lignin/cellulose-based carbon fibers.

La question des inégalités environnementales et sociales de santé (IESS) à l’échelle des territoires est rapportée à deux dimensions cumulatives : un niveau d’exposition des populations à un environnement de vie dégradé et un niveau de vulnérabilité face à ces facteurs de risques, capables d’affecter la santé. Ces travaux de recherche concernent les Systèmes d’Information Géographique (SIG) appliqués au domaine de la santé environnementale. Ils ont pour objectifs généraux la caractérisation de la qualité des milieux environnementaux et l’évaluation des IESS. L’atteinte de ces objectifs passe préalablement par la récolte, la genèse et la mise en forme de bases de données environnementales spatialisées. Ces bases issues de la surveillance physico-chimique et de la biosurveillance des milieux sont ensuite cartographiées à l'aide des outils SIG, notamment les méthodes géostatistiques d’interpolation spatiale. En parallèle, les disparités spatiales d'incidence de pathologies sont étudiées grâce à des méthodes de cartographie des maladies (Ratios d'Incidence Standardisés : SIR) et de détection de clusters atypiques d'évènements (statistique de scan) mises en œuvre sur la base de registres de maladies. Finalement des études écologiques spatialisées sont élaborées afin de rapprocher les cartographies environnementales générées aux indicateurs sanitaires et socio-économiques. Ces travaux s’attachent à répondre à la question « les populations présentant un état de santé dégradé vivent-elles dans un environnement dégradé ? » Ce questionnement a été étudié à travers trois axes de recherche. Le premier concerne la caractérisation de l’imprégnation de l’environnement par les éléments traces métalliques (ETM) et l’évaluation des IESS à fine résolution sur trois bassins de vie de la région Nord-Pas de Calais (NPdC). Cette recherche est menée à partir de mesures d’imprégnations biologiques réalisées à la fois chez des lichens épiphytes et chez l’Homme et d’un indicateur de défaveur localisé. Les ETM mesurés ont été considérés de manière individuelle, mais également de manière globale à travers le développement d’un indice intégré multimétallique, afin d’exprimer le niveau d’imprégnation général par plusieurs métaux. Des inégalités environnementales ont été mises en évidence à l’échelle des quartiers du bassin de Dunkerque. Nos résultats supposent également l’implication de l’environnement dans l’imprégnation des populations pour certains ETM.Dans le deuxième axe, nous avons mis en évidence des disparités spatiales d’incidence de l’insuffisance rénale chronique terminale entre les cantons du NPdC et souligné l’implication du statut socio-économique dans l’apparition de ces disparités, contrairement à d’autres facteurs (diabète, maladies cardiovasculaires, pratiques médicales). Seule une partie des disparités de cette pathologie est aujourd’hui expliquée. Il est donc nécessaire de poursuivre sur le rôle des contaminants de l’environnement. Enfin, le troisième axe s’intéresse à l’analyse spatiale et spatio-temporelle de contaminations des eaux souterraines par les ETM, en vue d’identifier de potentiels facteurs de risques environnementaux des maladies inflammatoires chroniques de l’intestin. La réalisation de ces travaux s’appuie sur plusieurs collaborations établies avec le Réseau REIN, le Registre EPIMAD et des équipes de recherche (EA4483 et EA2694 Université Lille 2, TVES EA4477 ULCO).A la suite de ces travaux de thèse, les perspectives de recherche sont de poursuivre le développement d’indicateurs intégrés d’exposition aux contaminations multiples des milieux environnementaux. Les résultats montrent également un manque de renseignement des bases de données environnementales par rapport aux registres de santé. Un travail est donc nécessaire afin de définir le contenu de ces bases, nécessaire pour caractériser la qualité des milieux et faciliter l’étude de l’interaction de l’Homme avec son environnement. / Environmental and social inequalities in health (ESIH) over territories are related to two cumulative dimensions: populations exposed to their living poor quality environment and the vulnerability of these populations to the environmental risk factors, which can affect health. This research deals with the Geographic Information Systems (GIS) applied to the field of environmental health. General purposes are the characterization of environmental media quality and the assessment of ESIH.Achieving these objectives requires a first step of harvest, genesis and formatting spatialized environmental databases. Such data are resulting from physico-chemical monitoring and biomonitoring. They were then mapped using GIS tools, including geostatistical spatial interpolation methods. On the over hand, spatial variability in the incidence of diseases were investigated using disease mapping methods (Standardized Incidence Ratios: SIR) and the detection of atypical clusters of events (scan statistics), which are based on disease registries. Finally, geographical ecological studies are developed to associate the environmental maps generated to health and socio-economic status. Thus, this work aims to answer the question \\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\"do people with poor state of health live in a poor quality environment?\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\" This question has been studied through three main researches.The first relates the characterization of trace elements burdens in the environment and the assessment of ESIH on neighborhood scale, over three territories in the Nord-Pas de Calais (NPdC) region. This research is conducted from measurements of biological burdens performed both in epiphytic lichens and humans and from a localized index of deprivation. The measured metals were considered individually, but also holistically by developing an integrated multimetallic index, in order to describe the general status of environmental pollution by metals. Environmental inequalities were observed on neighborhood scale in Dunkerque. Our results assume that trace elements burdens in populations are affected by environmental burdens.In our second research we revealed spatial disparities in the incidence of end stage renal disease (ESRD) on small area in the NPdC. Unlike other factors (diabetes, cardiovascular disease, medical practices), we highlighted the role of socio-economic status in the occurrence of such disparities. Only a part of the ESRD variability is currently explained. It is therefore necessary to focus on the environmental hypothesis.The third research focuses on the spatial and spatio-temporal analysis of groundwater contamination by trace elements, in order to identify potential environmental risk factors in the incidence of chronic inflammatory bowel disease.This work is based on several collaborations with the REIN network, the EPIMAD registry, and several research teams (EA4483 and EA2694 Université Lille 2, TVES EA4477 ULCO).Following this thesis, the research prospects are to pursue the development of integrated indicators to assess population exposure to the multiple environmental media contamination. The results also indicate a lack of information in environmental databases compared to health registries. A work is thus needed to define the content of such databases. These are necessary to characterize the environmental quality and to help the assessment of interaction between the populations and their living environment.

Doctor Educationis / The research focused on the synthesis, characterisation and activity of zeolite supported metal catalysts for the Friedel-Crafts alkylation of benzene with t-butyl chloride. Alkyl benzenes are traditionally produced via systems that employ the use of Lewis acids or strong mineral acids. There have been widespread concerns over these approaches based on their environmental impacts and separation difficulties. Recent approaches have endeavoured the much to use more environmentally eco-friendly systems and zeolites have proved to be versatile support materials. The use of zeolites has also shown to greatly improve product selectivity as well as easing separation constraints. However the adoption of zeolites on large scale Friedel-Crafts alkylation has been hampered by the high cost of zeolite production from commercial sources. On the other hand fly ash has been found to be a viable starting material for zeolite synthesis. Apart from that South Africa is faced with fly disposal challenges and there is continual accumulation of fly ash at the coal fired power stations, which provide about 77 % of the power produced in the country. In this light the use of fly ash will help to reduce the disposal constraints as well as providing a cheap starting material for zeolite synthesis. In this study the hierarchical Zeolite X has been successfully synthesised from fly ash via a hydrothermal treatment. The zeolite was then loaded with Fe/Mn via two approaches namely liquid phase ion exchange and incipient wetness impregnation. For comparison purposes seasoned commercial support materials namely HBEA and MCM- 41 were also loaded with the same metals and characterised with various techniques namely; HRSEM, EDS, HRTEM, XRD, SAED, ICP-OES and N2 adsorption analysis, It was found from the characterisation undertaken that the integrity of the respective supports was generally retained upon metal loading. Both the ICP-OES and the EDS proved that the desired metals were successfully introduced onto the zeolitic support materials. The calculated percentage metal loading for the catalysts prepared via incipient wetness impregnation was closely related to the actual values obtained from the ICP-OES analysis for both the monometallic and the bimetallic catalysts (Fe/Mn). It was observed that the amount of metal that can be introduced on a zeolite via liquid phase ion exchange is largely dependent on the cation exchange capacity of the zeolite Supported metal catalysts for FC alkylation Page v and of the catalysts prepared using 0.25 M Fe solution it was found that Zeolite X had the highest Fe wt% loading of 11.4 %, with the lowest loading of 2.2 % obtained with the MCM-41 supported catalyst. The XRD patterns for the both HBEA and the MCM-41 supported metal catalysts resembled the patterns of the respective prestine support materials except in the case of catalysts with anFe wt % of more than 10, which exhibited peaks due to the Fe2O3 crystallites. In the case of the hierarchical Zeolite X, the metal loaded support had a significant reduction in the XRD peak intensities. The prepared catalysts were tested for the alkylation of benzene with t-butyl chloride. The benzene was also used as the solvent. The alkylation reaction was carried out in a round bottomed flask under reflux conditions and stirring at a temperature of 45 oC over a period of 5 h. A total of 18 catalysts was tested and the highest percentage conversion of 100 % was obtained with the 10%FeH after a reaction time of 2 h. The general trend obtained with the majority of the catalysts was characterised with a rapid initial increase and then steady state was achieved. Generally after a reaction time of 3 h almost all the catalysts had reached steady state in terms of the percentage conversion obtained. The outcomes reflect that the inclusion of Mn does not enhance the conversion but rather decreases it. It was also found that the Mn was not active in the alkylation of benzene as shown by the inactivity of the 10%MnM, where 10% by weight Mn was loaded on MCM-41. However the other monometallic catalysts containing Mn supported on Zeolite X and HBEA were found to be active. The activity is attributed to the presence of Brønsted acid sites in these zeolites which are not present in MCM-41. The selectivity studies reflect that the inclusion of Mn does slightly improve the selectivity towards the formation of the monoalkylated product (t-butyl benzene). The highest selectivity of 91.1 % was obtained with the 10%FeMnM after a reaction time of 4 h. MCM-41 supported catalysts had a relatively higher selectivity compared to the other supports. Considering the Fe monometallic catalysts tested it generally can be said that the yield were in the order HBEA > MCM-41 > Zeolite X. It however should be noted that the percentage yield is calculated from the conversion and selectivity percentages, this implies that the factors affecting these parameters will consequently affect the percentage yield obtained. Supported metal catalysts for FC alkylation Page vi The alkylation reaction was found to be characterised by the formation of two intermediate products which could not be identified. These products were formed during the transient start up stages of the reaction and would disappear from the reaction mixture with longer reaction times, and after 3 h in almost all the reactions studied the intermediates were not detected in the reaction mixture. The main products found were the monoalkylated product (desired product) and the para isomer (1,4-t-di-butyl benzene). There were no other dialkylated isomers or trialkylated products detected. The formation of the para isomer was usually after a reaction time of 2 h in most reactions. The research managed to show that the hierarchical Zeolites X can be synthesised from fly ash and ion exchange and incipient wetness impregnation are appropriate approaches that can be used to introduce Fe/Mn onto the support materials studied. The catalysts prepared were active to varying degrees in the Friedel-Crafts alkylation of benzene with t-butylchloride, with the exception of the 10%MnM which was found to be inactive.

Les organes de frottement en carbure de silicium répondent à des critères de fonctionnement exigeants grâce aux propriétés offertes par cette céramique. Son faible coefficient de dilatation thermique et sa bonne conductivité thermique la rendent moins sensible aux chocs thermiques que les autres céramiques et particulièrement, en frottement, où la génération locale de chaleur peut s’avérer importante. Ces performances tribologiques sont conditionnées par son environnement mécanique, par la nature de la face de frottement antagoniste et surtout par le comportement des éléments interfaciaux circulant dans le contact. Le frottement du couple homogène SiC/SiC dans une configuration anneau/anneau a tout d’abord été étudié et son mécanisme d’usure a été établi, montrant un glissement sec difficile et une usure prononcée. Des alternatives ont alors été étudiées : revêtement du carbure par du DLC ou remplacement de la contreface par une bague carbone-graphite. Les imprégnations des bagues carbone-graphites par différents composés, polymères avec la résine phénolique et le PTFE ou métallique avec l’antimoine permettent d’en façonner les propriétés et, par conséquent, la réponse tribologique. Les essais sont réalisés à l’aide d’un tribomètre en glissement rotatif et ont permis de caractériser ces comportements tribologiques en fonction de différentes conditions de pression de contact, de vitesse et de température. Une analyse thermique a également été développée grâce à l’utilisation d’une caméra thermique infrarouge et a permis d’identifier les flux thermiques et le champ de températures durant le frottement. Des analyses physico-chimiques par EDS et spectroscopie Raman ont permis de décrire les transferts de matière mis en jeu et ont mis en évidence des phénomènes locaux d’oxydation de l’interface. La forte participation des imprégnants du carbone-graphite à la formation du troisième corps a été montrée. La spectroscopie Raman a également permis d’étudier le caractère cristallin des surfaces et du troisième corps formé et de mettre en évidence des phénomènes de contraintes en surface à l’origine des mécanismes d’endommagement. Il a ainsi pu être reconstitué un scénario complet des différentes étapes du glissement en termes de bilans de matière et d’énergie dans le contact. / Silicon carbide friction bodies fulfill high operation criteria owing to the properties provided by this ceramic. Its low thermal expansion coefficient and good thermal conductivity make it less sensitive to thermal shocks than other ceramics and particularly in friction, where the local heat generation may be significant. These tribological performances are then conditioned by the mechanical environment, by the nature of the counterface and above all by the interfacial elements circulating inside the contact. The friction of the homogeneous SiC/SiC pair in a ring-on-ring configuration was first studied and its wear mechanism was redefined. A hard silicon carbide counterface showed a difficult dry sliding and a high wear, alternative materials were studied: DLC coating on silicon carbide rings or carbon-graphite rings. Impregnation of the carbon-graphite rings with different compounds, polymers with the phenolic resin and PTFE or metal with antimony, shaped its properties and therefore, the tribological behaviour. Friction tests are carried out using a rotary sliding tribometer. They characterized the tribological behaviour for different operating conditions of contact pressure, sliding velocity and temperature of the environment. In addition, a thermal analysis was also implemented by using an infrared thermal camera in order to identify heat flows in the system and the temperature field for the entire duration of the tests. Physico-chemical analysis using EDS and Raman spectroscopy permitted to describe the transfers of material which take place during the tests and highlighted the local oxidation phenomena of the interface. The strong contribution of the carbone-graphite impregnants to the formation of the third body was also shown. Raman spectroscopy was also used to examine the crystalline state of the surfaces and the third body. Raman spectroscopy highlighted also stresses which are the source of the damage mechanisms. The different stages of the phenomena taking place during sliding inside the contact in terms of material and energy balance were then described.

We propose an effective strategy to engineer a unique kind of porous carbon cuboid with tightly anchored cobalt/cobalt oxide nanoparticles (PCC–CoOx) that exhibit outstanding electrochemical performance for many key aspects of lithium-ion battery electrodes. The host carbon cuboid features an ultra-polar surface reflected by its high hydrophilicity and rich surface defects due to high heteroatom doping (N-/O-doping both higher than 10 atom%) as well as hierarchical pore systems. We loaded the porous carbon cuboid with cobalt/cobalt oxide nanoparticles through an impregnation process followed by calcination treatment. The resulting PCC–CoOx anode exhibits superior rate capability (195 mA h g−1 at 20 A g−1) and excellent cycling stability (580 mA h g−1 after 2000 cycles at 1 A g−1 with only 0.0067% capacity loss per cycle). Impressively, even after an ultra-long cycle life exceeding 10 000 cycles at 5 A g−1, the battery can recover to 1050 mA h g−1 at 0.1 A g−1, perhaps the best performance demonstrated so far for lithium storage in cobalt oxide-based electrodes. This study provides a new perspective to engineer long-life, high-power metal oxide-based electrodes for lithium-ion batteries through controlling the surface chemistry of carbon host materials.