Le travail reporté dans ce manuscrit concerne l’élaboration de matériaux conducteurs protoniques destinés à une application en tant que membrane de PEMFC. L’approche considérée, relativement récente dans ce domaine, consiste à élaborer des réseaux seminterpénétrés(semi-IPN). Pour ce faire, un polymère linéaire conducteur protonique (unPEEK sulfoné) a été associé à un réseau réticulé fluoré de type poly(aryl étherperfluorocyclobutane) (PFCB). Ces macromolécules sont obtenues par cyclodimérisationthermique de monomères bis et tris-trifluorovinyléther (TFVE). Différentes séries de semi-IPN ont été élaborées en faisant varier la nature du PFCB, le taux de réticulation, le procédéde mise en oeuvre et le taux de réseau incorporé au sPEEK. L’ensemble des résultats montrequ’il existe une composition pour laquelle les propriétés de conductivité, de gonflement et detenue mécanique sont optimales. Une membrane ayant une conductivité de 155 mS.cm-1 et ungonflement à l’eau deux fois inférieur à celui du sPEEK (dont la conductivité s’élève à127 mS.cm-1) a été obtenue grâce à un ajout de 10 % en masse en réseau fluoré. Par ailleurs,l’incorporation dans le réseau PFCB de monomères contenant des fonctions sulfoniques a étéenvisagée. Un travail important de chimie organique a permis d’obtenir des molécules bis-TFVE comportant des fonctions sulfonées protégées sous forme d’ester sulfonique. Lapolycondensation directe de ces molécules a permis la synthèse de polymères PFCB linéairesconducteurs protoniques d’une CEI préalablement déterminée. / This thesis deals with the conception of proton conducting materials used as PEMFCmembrane. The proposed approach is quite new in this application field and is based on thedevelopment of semi-interpenetrating networks (semi-IPN). A linear conducting polymer(sulfonated PEEK) was combined with a crosslinked fluorinated network, a poly(aryl etherperfluorocyclobutane) (PFCB). These macromolecules are obtained by thermalcyclodimerization of bis and tris trifluorovinylether monomers (TFVE). Different series ofsemi-IPN were prepared by changing the PFCB nature, the crosslinking degree, the synthesisprocess and the proportion of the network added to the sPEEK. The overall results show aspecific semi-IPN composition for which the conductivity, the swelling and mechanicalstrength properties are optimal. A membrane with a proton conductivity of 155 mS.cm-1 and alimited water swelling (50 % lower than for a sPEEK membrane which exhibits a protonconductivity of 127 mS.cm-1) is obtained by adding 10 wt-% of fluorinated network. Inaddition, the incorporation of sulfonated TFVE monomers into the network PFCB has beenconsidered. A significant effort in organic chemistry enabled the synthesis of bis-TFVEmolecules containing protected sulfonated functions in a sulfonate ester form. Linearconducting PFCB polymers with a predeterminated IEC were obtained by directcopolycondensation of these monomers.

Perfluorinated compounds are organic compounds in which all hydrogen atoms in a carbon chain are substituted with fluorine atoms. These compounds are highly stable, persistent and bioaccumulative. They are purely anthropogenic compounds contained in biota and abiota. Partition coefficient between n-octanol and water is the essential toxicological parameter of a compound. This parameter helps us to assess behaviour of compound in the environment as well as in the living organisms. The shake flask method and the RP-HPLC method were employed to measure the Kow of nine perfluorinated acids. Using the shake flask method, the surface activity of compounds and the acid dissociation caused false results of the measurement. But behaviour of these compounds in the environment can be assess. Accurate and precise results were measured by the RP-HPLC method using an acetate buffer. Log Kow of perfluoro- carboxylic acids, with the carbon chain length of 5-14, were found out, their final value ranging between 1.66 and 5.10. Log Kow of acid with 12 carbons was estimated based on the linear regression of dependence of log Kow on the number of carbons. There were significant differences in the results obtained by various software. Thus, the results cannot be considered relevant. These software are not suitable for...

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Ce travail décrit le développement de membranes réticulées et de membranes composites inorganique-organique basées sur des polymères perfluorosulfoniques (PFSA) à chaîne longue (LSC) et courte (SSC) et à faible masse équivalente, pour application dans une pile à combustible fonctionnant à moyenne température et à faible humidité relative. Des membranes (LSC-PFSA) réticulées par des groupements sulfonimide ont été préparées à partir de membranes fonctionnalisées par des groupements fluorure de sulfonyle. Les membranes réticulées de type SSC-PFSA ont été préparées à partir d'un polymère à chaînes 2-bromo-1,1,2,2-tetrafluoroéthoxy pendantes et réticulables, par traitement thermique pour former des ponts perfluoro. Les membranes préparées ont été caractérisées par spectroscopies IR, Raman, RMN et XPS, par MEB-EDX et ATG. Les membranes de LSC-PFSA et SSC-PFSA réticulées présentent une stabilité dimensionnelle accrue et une meilleure performance en pile à combustible hydrogène-oxygène jusqu'à 110°C que celles des membranes de PFSA non modifiées. Une procédure d'échange ionique/précipitation a été utilisée pour la préparation de systèmes composites à partir de membranes de LSC-PFSA et SSC-PFSA. Plusieurs techniques ont été utilisées pour caractériser les matériaux préparés. Les membranes de type SSC-PFSA-ZrP présentent une morphologie distincte, et différente de celle des membranes LSC-PFSA-ZrP. En pile à combustible, ces membranes composites autorisent une température de fonctionnement plus élevée et une humidité relative plus faible, que les membranes non modifiées. / The objective of this research was to develop cross-linked and composite inorganic-organic membranes based on long and short side chain (LSC, SSC) perfluorosulfonic acid (PFSA) polymers with low equivalent weight/high ion exchange capacity for operation at medium temperature and low relative humidity in proton exchange membrane fuel cells. Covalently cross-linked LSC-PFSA membranes were prepared from sulfonyl fluoride form membranes by reaction with an ammonium base followed by thermal processing to give cross-linking through sulfonimide groups. Covalently cross-linked SSC-PFSA membranes were prepared by formation of perfluoro-cross-links under thermal treatment of solution cast polymers containing cross-linkable 2-bromo-1,1,2,2-tetrafluoroethoxy side chains. Evidence for cross-linking was provided by IR, Raman, NMR and XPS spectroscopies, SEM-EDX, tensile testing and TGA. Cross-linked LSC and SSC-PFSA membranes have increased dimensional stability and improved performance in a single hydrogen-oxygen cell fuel up to 110°C compared with the corresponding non-cross-linked membranes. Composite PFSA-zirconium phosphate membranes, based on LSC and SSC PFSA (or cross-linked PFSA) membranes were prepared using an ion exchange/precipitation procedure. The physical properties of LSC-PFSA-ZrP and SSC-PFSA-ZrP have been compared and the morphology of the composite membranes shown to differ in SSC and LSC membranes. Composite membranes enabled fuel cell operation at higher temperature/lower RH than non-composite PFSA. Preliminary results indicated that association of cross-linking and composite membrane formation is a clear future perspective of this work.

Cette thèse porte sur l’évaluation de l’impact de certains composés environnementaux sur la fécondité féminine, tel que mesuré par le délai de conception (« time to pregnancy » en anglais, ou TTP). Cette recherche a été réalisée dans le cadre de l’Étude mère-enfant sur les composés chimiques de l’environnement (MIREC), une cohorte de grossesse de 2001 femmes recrutées durant le premier trimestre dans dix villes canadiennes de 2008 à 2011. Les données des questionnaires et les échantillons biologiques ont servi à évaluer l’effet de deux groupes de composés : les persistants [composés perfluorés – perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA) et perfluorohexane sulfonate (PFHxS)] et les non persistants (bisphénol A, triclosan et phtalates). Cette thèse comprend également une analyse du potentiel du ratio index-annulaire (2D:4D) comme mesure de sensibilité endocrinienne. À ce jour, des mesures anthropométriques ont été collectées sur environ 800 mères-enfants dans le cadre de l’Étude mère-enfant sur les composés chimiques de l’environnement : biomonitoring et neurodéveloppement à la petite enfance (MIREC CD Plus), un suivi de la cohorte MIREC portant sur la croissance et le développement des enfants jusqu’à 5 ans. Sur l’ensemble, les résultats de cette thèse permettent d’étoffer les preuves concernant les effets adverses potentiels de plusieurs contaminants environnementaux sur la fécondité féminine, telle que mesurée par le TTP. Dans le premier article, nous avons montré une association entre les PFOA et les PFHxS et une baisse de fécondité, ce que d’autres recherches avaient déjà révélé. Dans le deuxième article, nous avons évalué l’effet du triclosan sur le TTP, ce qui n’avait jamais été examiné, pour montrer un délai plus élevé chez les femmes du quartile supérieur d’exposition. De plus, nos résultats sont en accord avec ceux de la seule étude ayant évalué l’effet du Bisphénol A sur la fécondité féminine, qui n’avait pas détecté d’effet. Finalement, nos données semblent indiquer une association entre l’exposition des femmes aux phtalates et un TTP plus court, mais ces résultats ne sont pas statistiquement significatifs. En ce qui a trait au potentiel du ratio index-annuaire (2D:4D) pour mesurer la sensibilité endocrinienne chez les femmes, nos données ne permettent pas d’établir une association entre ce ratio et le TTP. Pour ce qui est des enfants, nous n’avons pas trouvé d’effet adverse entre le tabagisme de la mère durant la grossesse et leur ratio 2D:4D. Par conséquent, nos données ne semblent pas justifier l’utilisation du ratio 2D:4D pour mesurer la sensibilité endocrinienne en lien avec le potentiel reproducteur (basé sur le TTP) ou l’exposition des enfants au tabac durant le premier trimestre de grossesse. / In this thesis, we aimed to evaluate the impact of selected environmental compounds on female fecundity as measured by time to pregnancy (TTP). This research was conducted in the framework of the Maternal-Infant Research on Environmental Chemicals (MIREC) study, a pregnancy cohort of 2001 women recruited during the first trimester of pregnancy in ten cities across Canada between 2008 and 2011. Questionnaire data and biological samples were analyzed to assess the effect of two groups of compounds: persistent [perfluorinated compounds - perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorohexane sulfonate (PFHxS)-] and nonpersistent chemicals (Bisphenol A, Triclosan, and phthalates). In addition, this thesis aimed to examine the potential of the second to fourth finger digit ratio (2D:4D) as a sensitive-endocrine endpoint. To this end, anthropometric measurements were obtained in about 800 children and their mothers during the Early Childhood Biomonitoring and Neurodevelopment Study (MIREC-CD Plus), a MIREC follow-up conducted to measure growth and development up to age five. Overall, the results of this thesis have contributed to the evidence regarding the potential adverse effect of several environmental contaminants (ECs) on female fecundity as measured by TTP. In the first article, we found that PFOA and PFHxS were associated with diminished fecundity, supporting previous evidence that suggested a similar effect. In the second article, we assessed for the first time the effect of Triclosan on TTP, presenting evidence of delayed fecundity at the highest quartile of exposure. In addition, our findings agreed with those of the only study that has assessed the effect of Bisphenol A on female fecundity, and which showed no effect. Finally, we found some indication that female exposure to phthalates might be associated with a shorter TTP, although this finding did not reach statistical significance. With regard to the potential of the digit length ratio (2D:4D) as an endocrine-sensitive endpoint in women, our data do not support a strong association between 2D:4D and TTP. In children, we did not find an adverse impact of maternal smoking during pregnancy on children’s 2D:4D. Thus, our data do not support evidence to suggest that 2D:4D could be used as a potential reproductive endocrine-sensitive endpoint in women as measured by TTP, and in their offspring as measured by exposure to maternal smoking during the first trimester of pregnancy.

BACKGROUND: Perfluorinated compounds (PFCs) have been used as durable water and oil repellent treatments in clothing for more than 50 years. The reason for its popularity is related to the chemical structure, which also makes these compounds persistent in the environment. Numerous studies have shown negative environmental and health effects related to high concentrations of perfluorinated compounds in blood serum. Due to these studies, this paper aimed to find out if perfluorinated compounds could be replaced by non-perfluorinated without compromising performance related to water and oil repellency. METHODOLOGY: A reference sample impregnated with fluorocarbons was compared with the following non-perfluorinated treatments, aliphatic polyurethane (comb polymer) organic silicone and acid (comb polymer) and hydrocarbon (dendrimer). Impregnations were subjected to abrasion, UV-radiation and washing and after each destructive treatment; oil and water repellency tests were conducted. The environmental and health effect of all treatments were examined in a theoretical study. RESULTS: Due to difficulties with the impregnation process, comparable results could only be concluded with the perfluorinated and the hydrocarbon compound. The hydrocarbon was superior the perfluorinated compound to abrasion but for usage simulation methods that allowed chemical reactions, hence UV-radiation and washing, the fluorocarbons showed better resistance. CONCLUSION: Results show that the hydrocarbon treatment could replace perfluorinated treatments commercially when only water and not oil repellency is required. The alternative treatments in this study are not yet sufficiently examined with respect to environmental and health and can therefore not be called greener with certainty. / Program: Textilingenjörsutbildningen

Le but de cette thèse était de développer de nouveaux électrolytes polymères pour une application batteries lithium métal polymère. Le premier volet concerne le développement des réseaux semi-interpénétrés à base de POE et d'un polycondensat. Ces types d'électrolytes ont permis de d'améliorer les propriétés mécaniques et les conductivités à haute et basse température. L'ajout de NCC comme renfort sur ces réseaux semi-interpénétrés a permis d'atteindre propriétés physico-chimiques intéressantes et des durées de vie élevées. De plus l'hydrogénation du polycondensat permettant de moduler sont taux de réticulation a permis d'obtenir un électrolyte (en présence du LiTFSI) présentant des conductivités de 1S.cm-1 à 90°C pour un rapport O/Li=20 et O/Li=30 avec une tenue mécanique de 0,5MPa jusqu'à 100°C. Dans le second volet une série de sels de lithium à anion organique a été synthétisée et caractérisée. Ces sels de lithium présentent des bonnes stabilités électrochimiques, thermiques et des conductivités cationiques parfois plus élevées que LITFSI en milieu polymère. Le dernier volet concerne la synthèse et la caractérisation physico-chimique des nouveaux ionomères perfluoré. Ces nouveaux ionomères à conduction cationique unipolaire sont obtenus à partir de monomères aromatiques porteurs de fonctions ioniques ayant une forte aptitude à la dissociation et des nombres de transport cationique proche de 1 à 70°C. / The aim of this thesis was to develop new polymer electrolytes for application of lithium metal polymer batteries. The first part concerns the development of semi-interpenetrating networks based on POE and a polycondensat. These types of electrolytes made it possible to improve the mechanical properties and conductivity at high and low temperatures. The addition of NCC as a reinforcement on the semi-interpenetrating network has led to interesting physicochemical properties and high cycle life for batteries.The partial hydrogenation of the polycondensat allowing the modulation of the reticulation ratio has allow to elaborate as an electrolyte (in the presence of LiTFSI) exhibiting 1S.cm-1 conductivities at 90 ° C for a ratio O/Li=20 and O/Li=30 with a mechanical strength of 0.5MPa to 100 ° C. In the second part a range of lithium with organic anion was synthesized and characterized. These lithium salts show good electrochemical and thermal stability, whereas ionics conductivities are sometimes higher than LiTFSI in polymer medium. The last part concerns the synthesis and physicochemical characterization of new perfluorinated ionomers. These new cationic ionomers with a unipolar conduction are obtained from aromatic monomers carriers ionic functional having a high ability to dissociation and cation transport numbers close to 1 at 70 ° C.

The most important substances of the group of perfluorinated compounds are perfluorooctyl sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorooctane sulphonamide (FOSA). Perfluorinated compounds have special physical and chemical properties, which make them valuable for usage in different industrial branches. These properties, which make them so useful are also the reason, why they are so harmful for the environment. The target of theoretical part of the diploma thesis was processing of literature searche on the topic: Evaluation of environmental load by perfluorinated compounds. In the experimental part was developed and optimized a method that was used for the identification and quantification of selected pollutants contained in real soil samples.

The City of Cape Town's (CoCT) wastewater management system discharges effluent from households, industries and other sources into the Atlantic Ocean through deep-water marine outfalls in Green Point, Camps Bay and Hout Bay. At total capacity, these three outfalls discharge 55.3 megalitres (Ml) into marine receiving environments daily. With minimal pre-treatment that amounts to screening and sieving, this results in microbial and chemical pollution of the sea (including chemicals of emerging concern), marine organisms, recreational beaches, and Marine Protected Areas (MPAs). This research focuses on contestations over evidence of that pollution in Hout Bay. The study documents the work of independent scientists seeking to provide evidence of coastal pollution obtained via microbial and chemical analyses of water (coastal and inland) and marine organisms (Mytilus galloprovincialis) samples. It also presents accounts of pollution obtained via ethnographic research with local residents, fishers, frequent water users and river activists who have observed and experienced poor coastal water quality. However, the form of evidence that is considered and informs decision-making processes by the CoCT has consistently sought to invalidate these forms of evidence, from both independent scientists and the public. Debates around knowledge of water and contests over evidence that highlight the entanglements of science, politics, and ways of knowing make visible a consistent pattern in coastal water-quality governance by the City, which results in inaction regarding the ever-growing issue of coastal pollution in Cape Town.

Today there are many uncertainties in the form of a lack of knowledge about perfluorinated and polyfluorinated substances (PFAS) regarding long-term risks to health and the environment, there is no efficacy data for many environments. The fluorocarbon bond is the strongest chemical bond, which means that PFAS can be transported long distances, for example through water streams and into the atmosphere. If surface water and groundwater are contaminated by PFAS, people are at risk of exposure to PFAS through the drinking water. It is therefore important to investigate and identify what difficulties and opportunities the municipalities see in their work to influence and reduce the occurrence of PFAS in drinking water with PFAS in water revenues and drinking water. The purpose of the study is to map what Halmstad, Linköping and Uppsala municipality see for difficulties and opportunities in their work on influencing and reducing the occurrence of PFAS in drinking water and how the result relates to scientific research about national environmental management. We have chosen to do a qualitative interview with an analysis of the interview using previous research on national environmental management about actions, cooperation and policy, directives, guidelines, and legislation. Some of the conclusions the study came to where that the municipalities see similar difficulties and opportunities in working with PFAS and have similar ways of working with PFAS. But there are still some differences and similarities in what they see for difficulties and opportunities in their work with PFAS. Difficulties that have been identified are inadequate or unclear guidelines, directives, legislation and insufficient limit values. It is also a difficulty that the municipalities do not know where all sources of PFAS pollution come from. Opportunities that have been identified are collaborations, knowing where certain parts of PFAS's pollution come from. One possibility that exists is to influence certain polluting activities by means of distribution routes, to submit activities to improve purification methods and to set requirements for sampling and remediation. / Det finns idag många osäkerheter i form av bristande kunskap om perfluorerade och polyfluorerade ämnen (PFAS) när det gäller långsiktiga risker mot hälsa och miljö, det saknas effektdata för många miljöer. Fluor-kol-bindningen är den starkaste kemiska bindningen vilket leder till att PFAS kan transporteras långa vägar, genom till exempel vattenströmmar och i atmosfären. Om ytvatten och grundvatten blir förorenat av PFAS så riskerar människor att exponeras för PFAS genom dricksvattnet. Det är därför av vikt att undersöka och identifiera vad för svårigheter och möjligheter kommunerna ser med sitt arbete med att påverka och minska förekomsten av PFAS i dricksvatten med PFAS i vattentäkter och dricksvatten. Syftet med studien är att kartlägga vad Halmstad, Linköping och Uppsala kommun, ser för svårigheter och möjligheter i sitt arbete med att påverka och minska förekomsten av PFAS i dricksvatten och hur resultatet förhåller sig till vetenskaplig forskning om nationell miljömanagement. Vi har valt att göra en kvalitativ intervju med en analys av intervjun med hjälp av tidigare forskning om nationell miljömanagement med avseende på åtgärder, samarbete och direktiv, riktlinjer och lagstiftning. Några av slutsatserna studien kom fram till var att kommunerna ser liknande svårigheter och möjligheter i arbetet med PFAS och har liknande sätt att arbeta med PFAS på. Men det finns ändå en del skillnader och likheter i vad de ser för svårigheter och möjligheter i deras arbete med PFAS. Svårigheter som har identifierats är otillräckliga eller otydliga riktlinjer, direktiv, lagstiftning och otillräckliga gränsvärden. Det är även en svårighet att kommunerna inte vet vart alla källor av PFAS-föroreningar kommer från. Möjligheter som har identifierats är samarbeten, att veta vart vissa delar av PFAS föroreningar kommer från. En möjlighet som finns är att påverka vissa förorenande verksamheter genom spridningsvägar, förelägga verksamheter att förbättra reningsmetoder och sätta krav på provtagning och sanering.