Per- and polyfluoroalkyl substances (PFASs) have drawn great attention recently, due to their environmental persistence, potential toxicity and global distribution. PFAS is a large family of substances, characterized by a perflourinated carbon chain and a functional group. All PFASs are synthetic and have been widely used since the 1950s due to their unique properties of being both hydrophobic and oleophobic, making them useful for many industries. To be able to predict the fate of PFASs in the environment and to obtain detailed understanding of the transport processes, their partitioning behavior between soil particles and water depending on a range of parameters must be investigated. The aims of this study was to investigate the effects of pH, cation composition, functional group and perfluorocarbon chain length on sorption of PFASs to soil particles, by batch sorption experiment in laboratory scale. The laboratory-scale experiments were combined with modelling of the net charge to evaluate if net charge is a good predictor for sorption of PFASs to soil particles. 14 PFASs of varying length and functional groups were studied (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTeDA, PFBS, PFHxS, PFOS and FOSA). The effect on sorption of Na+, Ca2+ (two different concentrations) and Al3+ were investigated at pH-range 3-6. Modelling of net charge was carried out in the geochemical model Visual MINTEQ. The soil had 45% organic carbon content. The adsorption of PFASs was strongly correlated with perfluorocarbon chain length, showing a stronger adsorption to particles with increasing perfluorocarbon chain length (i.e. more hydrophobic). The relation between sorption (represented by the distribution coefficient log Kd) and perfluorocarbon chain length was linear for all PFSAs and C3 to C10 PFCAs. The PFSAs (sulfonate functional group) sorbed stronger to soil particles than the PFCAs (carboxylic functional group), and FOSA (sulfonamide functional group) sorbed the strongest. For most PFCAs, (C5-C13) there was a trend of decreasing log Kd (i.e. decreased sorption) with increasing pH, due to pH-dependent changes of the soil particle surfaces. For short and intermediate perfluorocarbon chain length PFCAs (C5-C8) and for PFHxS among the PFSAs, cations had a clear effect on sorption. Aluminium ions (trivalent, Al(NO3)3) had the largest effect, followed by calcium (divalent, Ca(NO3)2) where higher concentration resulted in stronger sorption. Sodium (univalent, NaNO3) had the least influence on sorption. The net charge modelled with Visual MINTEQ takes into account many parameters (including pH) that affect the surface charge and sorption of PFASs to soil particles. When comparing log Kd for the different PFASs with pH and net negative charge, net charge was a better predictor of sorption of PFASs to soil particles than solution pH alone. / Per- och polyfluoroalkylsubstanser (PFAS:er) har dragit stor uppmärksamhet till sig på senare tid, på grund av deras persistenta egenskaper, potentiella toxicitet och globala utbredning. PFAS är en stor grupp ämnen, kännetecknad av en perflourinerad kolkedja och en funktionell grupp. Alla PFAS är syntetiska och har använts i stor utsträckning sedan 1950-talet på grund av deras unika egenskaper av att vara både vatten- och fettavstötande, vilket gör dem användbara för många industriella tillämpningar. För att kunna förutsäga var dessa föroreningars hamnar i miljön och få mer detaljerad förstående för transportprocesserna, måste deras fördelningbeteende mellan jordpartiklar och vattenundersökas för en rad olika parametrar. Syftet med denna studie var att undersöka effekterna av förändrat pH, katjonsammansättning, funktionell grupp och perfluorkolkedjelängd på sorption av PFAS:er till jordpartiklar. Detta gjordes med sorptionsexperiment i laboratorieskala. Laboratorieexperimentet kompletterades med modellering av nettoladdning, för att se huruvida detta väl kunde förklara sorptionen till jordpartiklar. 14 PFAS:er av varierande längd och med tre olika funktionella grupper studerades (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTeDA, PFBS, PFHxS, PFOS och FOSA). Effekten på sorption av Na+, Ca2+ (två olika koncentrationer) och Al3+ undersöktes vid pH-intervallet 3-6. Modellering av nettoladdning utfördes i den geokemiska modellen Visual MINTEQ. Jorden som användes hade en halt av organiskt kol på 45%. Adsorptionen av PFAS:er var starkt positivt korrelerad med kedjelängden på de perfluorinerade kolkedjan. Ju längre kolkedja (dvs. mer hydrofob), desto starkare adsorption till partiklar. Relationen mellan sorptionen (här uttryckt som partitioneringskofficienten log Kd) och kedjelängd var linjär för alla PFSA och för C3 till C10 för PFCA. PFSA (sulfonat) adsorberade starkare än PFCA (karboxyl), och FOSA (sulfonamid) adsorberades starkast. För de flesta PFCA, (C5-C13) fanns en allmän trend där log Kd (dvs. sorption) minskade med ökande pH, på grund av pH-beroende förändringar på jordpartiklarna. För korta och medellånga PFCA (C5-C8) och för PFHxS hade katjonsammansättningen en tydlig effekt på sorptionen. Aluminiumjoner (trevärd, Al(NO3)3) hade den största effekten, följt av kalcium (tvåvärd, Ca(NO3)2) där den högre koncentrationen resulterade i starkare sorption. Natrium (envärd, NaNO3) hade minst påverkan på sorptionen till jordpartiklar. Visual MINTEQ tar hänsyn till många parametrar (inklusive pH), när nettoladdningen på jordpartiklarnas yta räknas ut. När log Kd för olika PFAS:er jämfördes med endera pH eller negativ nettoladdning, drogs slutsatsen att nettoladdning korrelerade bättre med sorption än pH.

The Jupiter Icy Moons Explorer is a planetary exploration mission that aims to study the moons of Jupiter in the planet’s vast magnetosphere. Among the various instruments on board is the Particle Environment Package (PEP), that is led by the Swedish Institute of Space Physics (IRF) in Kiruna. The Jovian plasma Dynamics and Composition analyzer (JDC) is one of six sensors within PEP and focuses on the characterization of positive ions. To be able to measure their three-dimensional distribution and composition, in-situ and in high time resolution, JDC has to cover a large field of view of 2π sr, for the desired energy range, in just a couple of seconds. An electrostatic analyzer within the sensor determines the energy per charge of such particles and a time-of-flight mass spectrometer measures their mass per charge. Constraints on weight and the radiation environment of Jupiter drive the design of the sensor: small and lightweight to allow extra shielding, but still large enough to accomplish measurements in the harsh radiation environment of Jupiter. This work focuses on a new type of compact, electrostatic analyzer using spherical wedges and the start signal generation for the time-of-flight measurement using new venetian blind-type surfaces. Simulations on the electrostatic analyzer showed that the most promising design is a hybrid variant, using an inner shell with spherical wedges and a spheroidal outer shell. A prototype sensor was built and tested with successful results. A reflectron-type time-of-flight cell measures the time it takes for a particle to pass a linear electric field. The time measurement has to be very accurate and requires that all ions enter the reflectron from the same start position. Commonly this is achieved with thin carbon foils of some nanometer thickness to provide a very accurate start position. Upon impact and after leaving a foil, ions generate secondary electrons that act as start signals for the time measurement. Foils require a substantial pre-acceleration of several kilovolts for the ions to penetrate the foil, thus increasing the size and mass of the instrument. When incident ions are reflected at grazing angles from a surface, secondary electrons are released in the same way as with foils. To increase position accuracy during this reflection process, venetian blind-type start surfaces are investigated, where many smaller surfaces replace a large flat surface. The most promising sample was found to be micro pore optics, that were initially designed to focus gamma rays. In several experiments it could be shown that micro pore optics show good reflection properties when used as start surfaces in the time-of-flight measurement. Both improvements allow a more compact and lightweight sensor that can be better shielded against the harsh radiation environment in Jupiter’s system. Jupiter hosts the strongest radiation environment in the solar system, that could kill an unprotected human thousand times over. / JUICE, PEP

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Due to size effects, the microtechnologies that are used to manufacture micro-sensors, allowed a drastic reduction of electrical power consumption. This feature contributed to the emergence of the concept of autonomous sensors, which have the ability to take the energy needed for their operation from the environment where they are located. Among the different energy sources, our choice was made on ambient mechanical vibrations. The electromechanical conversion is done within a transducer integrated with a micromechanical structure. In this work, we have designed and fabricated an electrostatic transducer based on silicon-glass technology, which required the development of a dedicated deep etching process. The device was tested experimentally and we have obtained a conversion of mechanical energy into electrical energy, corresponding to a power of 61 nW, with a device whose surface area is only 66 mm². This device is the first miniaturized silicon converter based on electrostatic transduction which does not use an electret

Microelectromechanical systems (MEMS) devices have been increasing in popularity for radio frequency (RF) and microwave communication systems due to the ability of MEMS devices to improve the performance of these circuits and systems. This interdisciplinary field combines the aspects of lithographic fabrication, mechanics, materials science, and RF/microwave circuit technology to produce moving structures with feature dimensions on the micron scale (micro-structures). MEMS technology has been used to improve switches, varactors, and inductors to name a few specific examples. Most MEMS devices have been fabricated using planar micro fabrication techniques that are similar to current integrated circuit (IC) fabrication techniques. These techniques limit the thickness of individual layers to a few microns, and restrict the structures to have planar and not vertical features. One micro fabrication technology that has not seen much application to microwave MEMS devices is LIGA, a German acronym for X-ray lithography, electroforming, and moulding. LIGA uses X-ray lithography to produce very tall structures (hundreds of microns) with excellent structural quality, and with lateral feature sizes smaller than a micron. These unique properties have led to an increased interest in LIGA for the development of high performance microwave devices, particularly as operating frequencies increase and physical device size decreases. Existing work using LIGA for microwave devices has concentrated on statically operating structures such as transmission lines, filters, couplers, and antennas. This research uses these unique fabrication capabilities to develop dynamically operating microwave devices with high frequency performance. This thesis documents the design, fabrication and testing of LIGA-MEMS variable capacitors that exploit the vertical dimension. Also included are methods to improve both the reliable fabrication and operation of these devices as well as material property characterization. Variable capacitors can be found in systems such as voltage-controlled oscillators, filters, impedance matching networks and phase shifters. Important figures-of-merit for these devices include the quality factor (Q), tuning range and tuning voltage. Two different types of variable capacitors are presented, a pull-away design and a design based on the principle of leveraged bending. The pull-away style variable capacitors were found to have high Q-factors, especially the devices fabricated using a thick gold device layer. As an example, the small gold half capacitance electrode design features a Q-factor of 95 at an operating frequency of 5.6 GHz and a tuning ratio of 1.36:1 with a tuning voltage range of 0 to 7.8 V. The design based on leveraged bending significantly improves the tuning ratio to a value of 1.9:1 while still maintaining a high Q-factor similar to those found in the pull-away style designs. A further increase in tuning ratio to a value of approximately 2.7:1 would be possible, based on simulated results, by simply changing the angle of the capacitance electrode in the layout. To improve device performance and fabrication reliability, modifications were made to both the fabrication process and the device layout. In the fabrication process the exposure step, electroplating step, and the etching process were modified to improve the quality of the resulting devices. In the layout, anti-stiction measures were introduced that reduce the contact area during collapse. To improve device characterization as well as the feedback link between simulation and fabrication, a set of test structures called VM-TEST was developed to accurately determine the important mechanical material properties of thick electroplated layers. These structures utilize the measurement of the pull-in voltage in cantilever and fixed-fixed beams, along with measured structure dimensions, to accurately extract the mechanical properties. Both nickel and gold test structures were analyzed with extracted Young’s modulus values of 186.2 and 60.8 GPa respectively. Also presented is a study of the gap shape in cantilever and fixed-fixed beams that significantly reduces the pull-in voltage while still maintaining a required maximum actuator displacement. It was shown that in the case of cantilever beam actuators, an approximately 40% reduction in pull-in voltage is possible, and in the case of fixed-fixed beam actuators, an approximately 30% reduction is possible by simply varying the shape of the gap between the beam and actuator electrode. These results can be used to significantly reduce the pull-in voltage of future designs. These promising results show that the LIGA fabrication process is capable of producing high performance dynamically operating RF MEMS devices, by exploiting the vertical dimension, not typically performed in most existing RF MEMS designs.

Cette étude vise à une meilleure compréhension des phénomènes rencontrés en filtration des aérosols nanométriques, c’est-à-dire inférieurs à 100 nm, neutres et/ou chargés. Pour ce faire, trois différents types de média ont été étudiés : des grilles, en acier et matières synthétiques, des filtres non tissés, en fibres de verre ou polymériques, et des lits granulaires, constitués de billes d’acier ou de zéolithe. Il ressort des résultats expérimentaux obtenus que quel que soit le média testé, l’efficacité de collecte des particules augmente lorsque le diamètre de l’aérosol diminue, et ce jusque 4 nm. Ceci entre en contradiction avec l’approche théorique dite du rebond thermique, développée par Wang et Kasper en 1991, selon laquelle l’efficacité de collecte serait susceptible de diminuer en-dessous de 10 nm. La vérification des calculs de Wang et Kasper permet d’expliquer cette incohérence, et montre, à partir de valeurs plus réalistes de l’énergie d’adhésion particule-fibre, que si le rebond thermique existe, celui-ci ne pourra se manifester qu’en-dessous de 1 nm, au mieux. Ainsi, les perméances expérimentales des différents médias testés ont pu être modélisées en tenant compte des mécanismes de collecte par diffusion et/ou par effets électrostatiques. Une étude originale sur les performances, dans le domaine nanométrique, de filtres en fibres de verre intentionnellement percés complète ce travail. Pour un même média fibreux, la perméance augmente avec le diamètre de perforation réalisée. Par ailleurs, pour une taille de perforation donnée, la perméance devient indépendante du diamètre des particules en-dessous d’une taille limite, fonction de la dimension de la perforation. Il a enfin été mis en évidence que la baisse d’efficacité est d’autant plus importante que la résistance à l’écoulement de l’air du filtre est importante. Un modèle semi-empirique, fondé sur la différenciation du flux d’aérosol traversant la fuite du flux traversant le matelas fibreux résiduel du filtre, permet de bien représenter ces états de fait / This study aims to better understand the mechanisms encountered in nanoparticles aerosol filtration, the particles being charged or not. Three different types of media were studied: stainless steel or synthetics wire screens, unwoven filters in glass or polymer fibres, and at last, granular beds made from steel or zeolite balls. Experimental results show that, whatever the media, collection efficiency increases as the particle diameter decreases down to 4 nm. This point conflicts with the so-called thermal rebound effect developed by Wang and Kasper in 1991, according to which collection efficiency could decrease below 10 nm. The checking of Wang and Kasper’s calculations enables to explain this discrepancy and shows from more probable particle-to-fibre adhesion energy values that if thermal rebound phenomenon exists, it would only be measurable below 1 nm. Then, experimental points can be modelled from both diffusion and electrostatic forces collection mechanisms. An investigation on the filtration behaviour of fibreglass filters in the nanometric domain when intentionally-pierced with calibrated needles completes the above-mentioned works. For a same media, penetration increases as the leak diameter does. On the other hand, for a given hole size, penetration becomes independent of the particle diameter below a critical scale, which is a function of the leak diameter. It was lastly shown that the efficiency of a pierced media decreases all the more that its air flow resistance is higher. A semi-empirical model based on the differentiation between the aerosol flow across the leak and the one through the residual fibrous bed of the filter enables to well represent these points

Le présent travail est destiné à acquérir un ensemble de données expérimentales et quantitatives cohérentes sur le comportement physico-chimique d'un système constitué d'un polysaccharide linéaire, flexible et chimiquement fonctionnalisé en groupements carboxyliques, le carboxyméthyl-dextrane (CMD) et d'un milieu ionique comportant des cations d'affinité variée pour ces fonctions : Na+, Ca2+ et Cd2+. La densité de sites et leur constante de dissociation - complexation ont été déterminées par titrage potentiométrique avec des électrodes spécifiques (proton et cadmium). Les propriétés électro-hydrodynamiques et les transitions conformationnelles ont été étudiées en combinant la conductimétrie, l'électrophorèse, la diffusion dynamique de lumière et la viscosimétrie. Enfin, la stabilité colloïdale en relation avec les interactions intermoléculaires a été étudiée par turbidimétrie et diffusion dynamique de lumière. En présence d'ions monovalents, le comportement du CMD, typique d’une particule microgel molle, est déterminé par la force ionique et la concentration en polysaccharide. A basse force ionique, le CMD est en condition de bon solvant lorsqu'il est peu concentré tandis que le recouvrement des doubles-couches électriques autour des macromolécules détermine les propriétés électro-hydrodynamiques du CMD en régime concentré. A haute salinité, les interactions électrostatiques intramoléculaires et interparticulaires sont négligeables, et la macromolécule a un comportement caractéristique de polymère en mauvais solvant à haute fraction volumique. En présence de cations divalents, le calcium, et plus encore le cadmium, entrent en compétition avec le proton pour l’occupation des sites carboxyliques, ce qui s’accompagne par une réorganisation locale des chaînes polymères. A haute force ionique, la taille élevée des agrégats, la vitesse initiale d'agrégation élevée, ainsi que la persistance d'une forte turbidité au maximum d'effet, suggèrent que les agrégats sont formés en régime de type agrégation limitée par la diffusion des particules (DLA) / The present work focused on the acquisition of experimental and quantitative data on the physico-chemical properties of a linear, flexible and chemically functionalized polysaccharide by carboxymethyl grafting, yielding carboxymethyldextran macromolecules (CMD) and an aqueous electrolyte containing various ions Na+, Ca2+ et Cd2+ with different chemical affinity for these chemical functions. Charge density and complexation – dissociation constants have been evaluated using specific electrodes-based potentiometric titration. The electro-hydrodynamic properties and the conformational transitions were examined through electrical conductivity increment measurements, electrophoresis, dynamic light scattering and viscosimetry. Also, colloidal stability has been investigated by means of turbidimetry and dynamic light scattering. In the presence of monovalent ions, the behaviour of CMD, typically that of a soft microgel particle, is strongly depending on ionic strength and polysaccharide content. For low ionic strengths and in dilute regime, CMD is in situation of good solvent while in concentrated regime, overlapping double layers that develop around macromolecules governs the electro-hydrodynamic features of CMD. For sufficiently high ionic strengths, intermolecular and intramolecular electrostatic interactions are nearly suppressed, and CMD behaves as a polymer in bad solvent upon increase of its concentration in the medium. In the presence of divalent ions, calcium ions and cadmium ions are in competition with hydronium ions to occupy the carboxylic sites, and this situation is concomitantly accompanied by local reorganization of polymer chains. The large size of formed clusters, the high initial aggregation rate and the increased turbidity all suggest that aggregates are generated according to a diffusion limited aggregation (DLA) type of mechanism

Des couches fonctionnelles hybrides organiques/inorganiques ont été générées à une interface solide/liquide à l’aide d’une nouvelle technique de fabrication ascendante (bottomup) dénommée Croissance de Couche à partir d’une Surface (Surface Grown Layers - SgL)grâce à une modulation très fine de l’interaction électrostatique entre nano-objets decharges opposés en fonction de la force ionique de la dispersion aqueuse. Différents nanoparticules/tubes à la fois cationiques et anioniques et très stables vis-à-vis d’un environnement fortement salin ont été développés. La complexation électrostatique entre ces nanomatériaux a été étudiée en solution et près d’une interface au travers du concept de “transition de dessalage”. Dans un deuxième temps la croissance de couches hybrides à partird’un substrat a été étudiée en comparant l’approche SgL et la méthode classique d’adsorption séquentielle couche par couche (Layer by layer - LbL). Des expériences préliminaires ont montré le potentiel de cette approche dans le développement de substrats fonctionnels. / In this manuscript, one-step bottom-up fabrication of “smart organic-inorganic hybridfunctional layers” at a liquid/solid interface were fabricated via a novel surfacefunctionalization pathway termed as “Surface Grown Hybrid Functional Layers” or SgLthrough fine tuning of electrostatic interaction between “highly stable” and oppositelycharged nanomaterials as a function of ionic strength of the dispersion. Cationic and anionicnanomaterials based on different hybrid nanoparticles/nanotubes that are very stable towardshigh saline environment have been formulated. The electrostatic complexation between theseoppositely charged nanomaterials has been studied in bulk and at an interface through theconcept of “desalting transition” pathway. In a second step, the growth of functional hybridlayers directly from a substrate via the novel SgL approach was then compared with theconventional Layer-by-Layer approach (LbL). Finally the preliminary experiments haveshown the potential applications of generated functional surfaces.

The Magnetospheric Multiscale mission led by NASA has been designed to study the micro-physics of Magnetic Reconnection in Earth's magnetosphere by using four identical spacecrafts with instruments with high temporal and spatial resolutions. Among these instruments are the Dual Ion Spectrometers (DIS) engineered to measure the 3D distribution of ion flux in space. The detector assembly of the DIS consists of Micro-Channel Plates (MCP) mounted in Chevron configuration. Centre d'Etude Spatiale des Rayonnements (CESR), Toulouse is responsible for the provision and testing of all fifty MCP pairs for this mission. The goal of the work was to participate in the testing and characterization of the first prototype of the MCPs. It was achieved by understanding the working and characteristics of the MCPs in general and getting familiar with the detector assembly of the DIS i.e. the MCP pair and the detector circuit board in particular. To perform the testing, it was necessary to understand the testing system as well. These topics are described in this report along with the testing procedure and the data analysis. The testing procedure was developed eventually after facing several problems during the testing. MCP pair characteristics like pulse height distributions, gain, resistance and the MCP operating voltages for the mission were determined on analyzing the data. Crosstalk was found in the circuit board of the detector assembly and has also been discussed. / Validerat; 20101217 (root)

Ce travail porte sur l’étude de mésophases lamellaires lyotropes qui contiennent des polymères hydrosolubles confinés dans les lamelles d’eau de l’empilement. L’effet du polymère confiné sur la stabilité de la structure lamellaire est en particulier étudié grâce à une mesure directe des interactions entre les membranes de tensioactif grâce la technique du Surface Force Apparatus (SFA). Les systèmes étudiés sont des fluides complexes et très visqueux ce qui a donné lieu au développement d’une nouvelle méthode pour analyser les données collectées. En l’absence de polymère dissous dans l’empilement lamellaire, la valeur du module de compressibilité élastique mesurée est remarquablement interprétée avec la théorie électrostatique corrigée des corrélations des contre-ions. En présence de polymère, au fur et à mesure que les macromolécules remplacent le contenu en eau, le module élastique de compressibilité de l’empilement lamellaire chute,signature d’une interaction attractive due à la présence des macromolécules. Néanmoins, les développements théoriques proposés ne parviennent pas à interpréter quantitativement cette décroissance. De plus, des comportements très intéressants et inattendus ont été mis en évidence lors de l’approche d’un point critique : la présence de dislocations de très grands vecteurs de Burgers à grande séparation ainsi que des phénomènes d’avalanches. En particulier, des énergies de nucléation de dislocation ont pu être extraites. / This work deals with lyotropic lamellar mesophases which contain confined hydrosoluble polymers in the water layers of the stack. In particular the effect of confined polymers on the stability of the lamellar structure is investigated through a direct measurement of the interactions between the surfactant membranes thanks to the Surface Force Apparatus (SFA) technique. The investigated systems are complex fluids and samples are extremely viscous, this is why a new procedure for analyzing the collected data has been developed. In the absence of dissolved polymer in the lamellar stack, the measured value of the elastic compressibility modulus is remarkably interpreted with the electrostatic interaction corrected from the counterions correlations. In the presence of polymer, as long as the macromolecules replace the water content the elastic compressibilitymodulus of the lamellar stack decreases, evidencing an attractive interaction due to the macromolecules. Nevertheless, the proposed theoretical developments fail to quantitatively interpret this drop. Moreover, very interesting and unexpected phenomena have been evidenced on the approach of one critical point: dislocations of large Burgers vectors at large separations and avalanche phenomena. In particular dislocation nucleation energies have been extracted.