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Modern societies produce large quantities of municipal solid waste (MSW), which is commonly disposed of by incineration. This has several advantages: it reduces the waste’s volume and sterilizes it while also enabling energy recovery. However, MSW incineration has some notable disadvantages, the most widely debated of which is probably the production and release of persistent organic pollutants (POP) such as polychlorinated dibenzofurans (PCDF), dibenzo-p-dioxins (PCDD), biphenyls (PCB) and naphthalenes (PCN). Of the 210 PCDF and PCDD congeners, 17 are toxic, with hormone-disrupting and carcinogenic properties. Twelve of the 209 PCB congeners and at least 2 of the 75 PCN also exhibit such properties. These POP form in the post-combustion zones of MSW incineration plants and are removed from the flue gas using filtering devices that trap them in the fly ash This thesis concerns the formation and degradation of POP in processes related to MSW incineration. The first paper describes a case study in which PCDD were forming in filters designed to remove them from flue gases, causing emission-related issues in a full-scale MSW incineration plant. It was shown that the PCDD formation was probably due to chlorophenol condensation on the filters’ surfaces. The second paper describes the validation of a cooling probe designed to prevent POP formation during high temperature (>450 °C) flue gas sampling. The results obtained also confirmed that PCDF and PCDD formation takes place at temperatures below 600 °C. In the third paper, three different fly ashes were subjected to thermal treatment under an inert atmosphere in a rotary kiln and in sealed ampoules at 400 °C. The concentrations, degrees of chlorination and congener profiles of the POP in the treated ashes and emitted gases were compared to those for the untreated ashes. The trends observed for PCDF mirrored those for PCN, while the trends for PCDD closely resembled those for PCB. The PCDF congener profiles of the kiln ash were similar regardless of the initial ash composition, suggesting that the mechanisms of PCDF formation were similar in all cases. The fourth paper describes the surface characterization of the three fly ashes studied in paper three by SEM, EDX, XPS and XRD. In addition, the thermal desorption and subsequent degradation of POP from the ashes was studied at temperatures of 300-900 °C. The composition of the gases released as the temperature increased differed between the ashes and depended on their composition. Doping experiments using isotopically labelled PCDF and PCDD suggests that PCDD desorbed at lower temperatures than PCDF. This thesis examines several problems relating to POP formation during MSW incineration, from sampling to the ultimate fate of incineration residues. The results obtained illustrate the wide range of processes that contribute to thermal POP formation and degradation during and after MSW incineration. / Förbränning av hushållssopor är en vanlig metod för att hantera ett växande avfallsproblem. Metoden har flera fördelar, såsom minskning av volym och vikt, sterilisering och energiåtervinning. Sopförbränning har dock vissa nackdelar och det mest debatterade är sannolikt utsläpp av persistenta organiska föroreningar (POPs) som polyklorerad dibensofuran (PCDF), dibenso-p-dioxin (PCDD), bifenyl (PCB) och naftalen (PCN). Det finns totalt 210 PCDF- och PCDD- kongener, med mellan ett till åtta klor på kolskelettet, varav 17 är giftiga med hormonstörande och cancerframkallande egenskaper. Även tolv av totalt 209 PCB-kongener samt minst två av totalt 75 PCN-kongener uppvisar liknande egenskaper. Dessa klorerade organiska föroreningar bildas då rökgaserna kyls ner i sopförbränningsanläggningarna och avlägsnas från rökgaserna med hjälp av filter och hamnar i flygaskan. Denna avhandling handlar om bildning och nedbrytning av POPs i sopförbränningsrelaterade processer.   Den första artikeln är en fallstudie där PCDD bildas i filtren i en fullskalig sopförbränningsanläggning. Bildningen ledde till förhöjda halter organiska föroreningar i rökgaserna, vilket ledde till ökade utsläpp. Den funna bildningsvägen för PCDD i filtren befanns sannolikt bero på kondensation av klorfenoler på filterytorna. Den andra artikeln är en valideringsstudie av en kylprob avsedd att användas vid rökgasprovtagning vid hög temperatur (> 450 °C) för att undvika bildning av POPs under provtagningen. Studien bekräftade att majoriteten av PCDF- och PCDD- bildning i rökgaser från sopförbränning sker vid temperaturer under 600 °C. I den tredje artikeln berättas om behandling av tre olika flygaskor från olika sopförbränningsanläggningar. Askorna behandlades vid 400 °C i inert atmosfär i både en roterugn och i förseglade ampuller. De resulterande koncentrationerna, kloreringsgraderna och kongenprofilerna av de organiska föroreningarna jämfördes. Likheter hittades mellan PCDF och PCN, medan PCDD och PCB betedde sig på ett annat sätt. Studien fann också att PCDF kongenprofiler i aska som behandlats i roterugnen liknade varandra, oberoende av askornas sammansättning, vilket tyder på en liknande bildningsväg. För den fjärde artikeln, genomfördes ytkarakterisering (SEM, EDX, XPS och XRD) på de tre flygaskorna från artikel tre som sedan hettades upp från 30 °C till 900 °C i vacuum. Det som frigjordes på grund av uppvärmningen samt nedbrytningsprodukter från askorna studerades med hjälp av masspektrometri och infraröd spektroskopi. Studien fann att de gaser som frigjordes när temperaturen ökade skilde mellan askorna, beroende på deras sammansättning. Studien fann också att när aska dopad med isotopmärkt PCDF och PCDD utsattes för samma behandling, frigjordes PCDD vid lägre temperatur än PCDF. Denna avhandling berör flera aspekter av problematiken kring klorerade organiska föroreningar som bildas vid sopförbränning, från provtagning till hur man ska hantera flygaskan. Avhandlingen belyser även olika typer av bildning och nedbrytning av POPs i varma processer kopplade till sopförbränning.

In der vorliegenden Arbeit wurden das Wachstum und die Oberflächenstruktur von definier-ten V2O3-, V2O5- und MoO3-Filmen auf Au(111) sowie deren Einsatz als Modellsysteme zur Untersuchung von Elementarreaktionen auf Vanadiumoxid- und Molybdänoxid-basierten selektiven Oxidationskatalysatoren untersucht. Im Falle von V2O3(0001) befindet sich an der Oberfläche der Filme eine Lage von Vanadylgruppen, welche kein Bestandteil der Kristall-struktur sind. Die O Atome der Vanadylgruppen können durch Elektronenbeschuss definiert entfernt werden, wodurch eine partiell oder vollständig V-terminierte Oberfläche erzeugt werden kann. Der Grad der Oberflächenreduktion wird durch die Elektronendosis festgelegt. Dieses ermöglicht eine Untersuchung des Einflusses der Vanadylgruppen und der unterkoor-dinierten V-Ionen auf die Reaktivität der Modellkatalysatoren. Die Präparation von defektar-men V2O5(001)- und MoO3(010)-Filmen ist erstmals in der vorliegenden Arbeit dokumen-tiert. Diese Filme wurden mittels Oxidation in einer Hochdruckzelle bei einem Sauerstoffdruck von 50 mbar hergestellt. Anders als in vielen Publikationen berichtet sind diese hochkristallinen Schichten unter UHV-Bedingungen weitgehend reduktionsbeständig. Oberflächenverunreinigungen und Defekte scheinen aber einen großen Einfluss auf die Redu-zierbarkeit zu haben. Die von den Strukturen der regulären Oxide abweichenden Strukturen der Koinzidenzgitter von V2O5- und MoO3-Monolagen werden durch die Wechselwirkung mit der Au(111)-Unterlage stabilisiert, was vermutlich durch die einfache Verschiebbarkeit von Koordinationseinheiten in V und Mo-Oxiden erleichtert wird. Für beide Oxide beginnt das Wachstum regulärer Oxidstrukturen erst nach Vollendung der zweiten Lage. Die für geträgerte V2O5-Katalysatoren häufig vorgebrachte Annahme, dass V2O5-Kristallkeimbildung direkt auf einer Monolage stattfindet, sollte somit mit Vorsicht betrachtet werden. / The growth and the surface structure of well-ordered V2O3, V2O5 and MoO3 thin films have been investigated in this work. These films are seen as model systems for the study of ele-mentary reaction steps occurring on vanadia and molybdena-based selective oxidation cata-lysts. It is shown that well-ordered V2O3(0001) thin films can be prepared on Au(111). The films are terminated by vanadyl groups which are not part of the V2O3 bulk structure. Elec-tron irradiation specifically removes the oxygen atoms of the vanadyl groups, resulting in a V-terminated surface. The fraction of removed vanadyl groups is controlled by the electron dose. Such surfaces constitute interesting models to probe the relative role of both the vanadyl groups and the undercoordinated V ions at the surface of vanadia catalysts. The growth of well-ordered V2O5(001) and MoO3(010) thin films containing few point defects is reported here for the first time. These films were grown on Au(111) by oxidation under 50 mbar O2 in a dedicated high pressure cell. Contrary to some of the results found in the literature, the films are not easily reduced by annealing in UHV. This evidences the contribution of radiation and surface contamination in some of the reported thermal reduction experiments. The growth of ultrathin V2O5 and MoO3 layers on Au(111) results in formation of interface-specific monolayer structures. These layers are coincidence lattices and they do not correspond to any known oxide bulk structure. They are assumed to be stabilized by electronic interaction with Au(111). Their formation illustrates the polymorphic character and the ease of coordination units rearrangement which are characteristic of both oxides. The formation of a second layer apparently precedes the growth of bulk-like crystallites for both oxides. This observation is at odds with a common assumption that crystals nucleate as soon as a monolayer is formed dur-ing the preparation of supported vanadia catalysts.

The aim of this research was to find a suitable alternative medium of scarce freshwater for textile dyeing, and to recycle and reuse the dyebath using a combined coagulation/flocculation and novel filter media. Simulated seawater (SSW) was tested as the alternative dyeing medium with a salt concentration of 3.5% where NaCl was the major component. Fibre/dye systems of wool/acid and metal complex, wool/reactive, polyester/disperse, nylon/acid and metal complex, and acrylic/cationicdyes were tested in simulated seawater and the performances of dyed fabric were compared to conventional dyeing system of distilled water (DSW). The study found that commercial dyeing processes were robust and can be practically transferable into the seawater medium. The dye exhaustions, build-up, colour characteristics, and fastness to wash, cross-staining, rub and light were satisfactory within the dye ranges studied, which covers commercially available monochromatic Red, Yellow and Blue at light, medium and deep shades. Although SEM micrographs didn't show any presence of salt, a typical wash-off process of 1gL-1 with a non-ionic detergent at 70°C was sufficient to remove any salt that could be present on the surface or sub-surface of the dyed fabric. At room temperature, some acid and metal complex dyes were only partially soluble in SSW but this improved with gentle heating and addition of levelling agents. At dyeing temperatures near the boil, these dyes were completely soluble. A saturation limit was found to be existed for acrylic dyeing of cationic dyes over 1.0% o.m.f. depth. Although ionic interaction was the dominant mechanism for dyeing of wool, nylon and acrylic fibre with acid, metal complex and cationic dyes, the adsorption in highly saline dyebath most likely depended on the combined effects of ionic and physical/hydrophobic interaction. The resultant effect was higher dye exhaustion and consequently higher colour difference in SSW for some dyes. Reactive dyes were known to be sensitive to hardness of water but this study confirmed that reactive dye could be an alternative for deep dyeing for wool fibre in SSW. Reactive dyeing of wool followed a similar mechanism of gradual phase transfer as was observed for disperse dyeing of hydrophobic fibres over 3.0% o.m.f. depth. In contrast disperse dyeing of polyester produced consistent results for all dyes but some black dyeings produced superior colour strength in SSW. The build-up of colour in SSW compared to DSW can be different depending on the application level. To improve permeate flux by reducing membrane fouling, a number of surface modification were carried out to introduce fluorine based functional groups. Gaseous fluorination, fluorocarbon finish (FC) and plasma polymerisation were performed to introduce hydrophilic and oleophobic properties on supplied Azurtex membrane. The fluorinated Azurtex media exhibited increased wettability although it was not directly proportional to an increase in the fluorination level and treatment time. The water and oil repellency of FC and plasma treated filter media provided a reasonable level of repellency while the contact angle remained in the range of 130 to 145°. Pre-fluorination of filter media before FC treatment didn't change the water and oil repellency. Surface characterisation of Azurtex media was performed with ATR-FTIR, XPS and SEM. An increased level of fluorination at 10%F2 and prolonged exposure showed a degradation of the surface along with colour change. The fluorinated, FC treated and plasma polymerised membrane showed a typical C-F stretching vibration in the region of 1100-1350 cm-1 and weakly at 400-800cm-1. The XPS study showed a gradual increase in the -CF2 and -CF3 functionality signal intensities that resulted in imparting hydrophobicity The benchmarking of these modified Azurtex filter media against newly developed materials proved that plasma treatment improved the flow, reduced turbidity and provided an easy cake removal compared to fluorinated and FC finished filter media. Recycling of exhausted dyebath using a dual component coagulant/flocculant system of Pluspac 2000 and polyanionic Hydrosolanum protein derivative (HPSS) and microfiltration with Azurtex filter media was investigated. The process parameters such as pH and dosage of coagulants/flocculants were very critical during coagulation/flocculation for overall colour removal. The trial with model dye solution in SSW showed that the system worked in the saline environment with a relatively high concentration ratio of coagulant/flocculants but highly depends on the class and structure of dyes. Maximum colour removal was achieved for Lanaset Blue 2R and Sandolan Red MF-GRLN dye and was 89% and 61%, respectively, based on a ratio of 15:10 and 15:15 for PP2000: HPSS at pH 4.0 and 5.0, respectively. The reuse of the dyebath with combined physico-chemical and micro-filtration treatment was demonstrated to be feasible with wool/acid dye system. The colour profile of Lanaset Blue 2R and Sandolan Red MF-GRLN dyed fabrics up to 12th dyeing, with dyebath filtration undertaken after the 3rd /4th/5th reuse of the dyebath, remained comparable to dyeing in fresh baths. The colour strength, K/S, decreased after every filtration and the colour differences, DeltaE increased, but reversed in subsequent dyeing in reused dyebath. The wash and dry rub fastness of the dyed fabrics remained comparable and significant improvements in the abrasion resistance were observed.

ORMOCERR®s are organic-inorganic hybrid polymers. Since their material properties can be tailored precisely during synthesis, they are suitable for a wide range of applications in dielectric and optical microelectronics. This thesis reports on process development of ORMOCERR®s for Sequentially Build-Up (SBU) test vehicles, suitable for both electrical and optical interconnect. Furthermore, this work includes materials characterization, such as refractive index studies (system B59:V32), optical loss measurements (systems B59:V32 and B59:B66), and surface characterization through contact angle measurement and surface energy estimation (systems B59:V32 and B59:B66). Process development for a high-frequency test vehicle was performed applying a newly developed dielectric material of the ORMOCER® class. Dielectric layers in a total thickness of 80 μm were build-up on a common FR4 substrate, applying photolithographic processes and moderate process temperatures of below 433 K. The loss tangent and the permittivity of the material were measured to be 0.024 (loss tangent) and 3.05 (permittivity) over the entire frequency range 10 GHz to 40 GHz. The compatibility of the material to standard processes of the PCB industry was proven. Furthermore, a possibility for cost reduction in high-frequency MCM applications was shown, through the possibility of using low-cost substrates. The concept of a “flexible manufacture approach” for large-area panel optical backplane interconnects was introduced. Here, a 101.6 mm x 101.6 mm photolithographic mask is to be stepped-out over a large-area panel substrate (up to 609.6 mm x 609.6 mm). The goal is to be able to create a large amount of continuous and unique waveguide patterns over the whole area with a small portfolio of masks, thus being able to minimize excess costs. In practice continuous waveguide patterns were created over an area of 204.8 mm x 204.8 mm on a large-are panel (609.6 mm x 609.6 mm), using a large-are mask aligner and a 101.6 mm x 101.6 mm waveguide mask. The optical loss of the waveguides was measured to be 0.6 dB/cm (B59:V32 material system, λ =850 nm). In connection to the large-area panel project a re-evaluation on the optical power budget needed for high bit rate optical interconnects was performed. This work was mainly based on literature surveys of optical waveguide materials, planar optical amplifiers, light coupling structures, and planar light-routing structures. It was shown that optical amplification is necessary at certain places on realistically routed optical backplanes to boost the optical signal. Therefore, the concept of a flip-chip mountable optical amplifier (FOWA) device, based on planar optical waveguide amplifiers and Semiconductor Optical Amplifiers, was developed. The device’s design allows an independent manufacturing to the rest of the board and a mounting at key-positions using standard pick and place technology. Additionally, it was observed that most of the amplifier research is focused on the wavelength of 1310 nm and 1550 nm, whereas optical backplane applications are targeting the 830 nm range. During SBU processing of waveguide structures was discovered a de-wetting phenomenon of B59 resin on a cured B59:B66 and B59:V32 surface, respectively. Good wetting behavior could be achieved by adding small amounts of B66 or V32, respectively, to the B59. Surface tension estimations on various compositions of the systems B59:B66 and B59:V32 could not directly be correlated to the de-wetting phenomenon. Furthermore, the optical loss properties of B59 were only affected to a minor degree by adding B66 or V32. The process route proposed is an efficient alternative to processes including surface activations steps, thus opening possibilities for large-area processing in PCB industry, where surface activation steps, such as plasma activation or silanization, are not available. The process development, materials characterization, and reviews presented provide a basis for further research on processes for high-performance electro/optical backplane interconnects with focus on Large-Area Panel processing.

Le développement récent, dans le domaine de la santé, de lasers femtoseconde pompés par diode, délivrant des impulsions de forte énergie et utilisés en chirurgie (en particulier en ophtalmologie), nous amene à chercher de nouveaux domaines d’application dans le secteur de la santé. En effet, la durée très brève de l’interaction laser avec la matière (de l’ordre de 10-15s) et les fortes intensités de radiation délivrées, permettent d’envisager une ablation tissulaire rapide avec des effets thermiques négligeables.Ce travail va un triple objectif:- Etudier la capacité d’ablation de l’émail dentaire et de la dentine avec un laser femto seconde,- Mesurer l’accroissement de température généré par l’interaction laser/tissus avec et sans spray d’air + eau, sachant qu’un accroissement de température au delà de 5.5°C engendre des dommages irréversibles (nécrose) du tissu pulpaire.- Mener une étude comparative de l’adhésion des matériaux de restauration composite sur les surfaces préparées par laser versus l’adhésion sur des surfaces dentinaires préparées de façon conventionnelle avec une fraise et une turbine. / Recent development has led to the commercialization of high power femtosecond lasers, opening a new perspective into the field of laser surgery. Due to the short laser – material interaction time and the very high radiation intensity achieved with this type of laser, the ablation of a wide range of materials can be achieved with negligible thermal effects.The present work aims at- Studying the ablation of dental enamel and dentin by femtosecond laser- Measuring the increase of pulpal temperature generated during the laser treatment without external cooling and with external cooling using an air jet and a combination of the air jet and water irrigation.- Comparing the adhesion of restorative materials to dentin surface treated by the laser and by the conventional drilling method with a burr.

BorgWarner located in Landskrona are developing components for the four-wheeldrive drivetrain that are being massed produced in the automotive industry. Thanks to Borg- Warner’s unique product’s properties they have achieved a worldwide leading position as a provider of systems for advanced four-wheeldrive drivetrain (all-wheel drivetrain). The assignment from the BorgWarner is to create a better understanding about when vibrations occur and what properties of a friction disc affect vibrations in the wet clutch. The goals of this thesis are to: Map system parameters like Surface topografy. Measure pressure distribution between the friction discs. Measure the Youngs modulus, also known as stiffness. It is not sure that a bad pressure distribution could cause vibrations in the wet clutch. The results from the topography explain the appearance of the pressure distribution. Varying stiffness means that the density of the material is also varying because the stiffness depends on the material composition. When forces are applied on the friction disc, it leads to varying deformation on samples. When the samples all deforms different, the result of the different deformation could be slanting surface. When a disc with non- parallel friction surface rotates it could generate vibration in the wet clutch.

Les nanoparticules de dioxyde de titane (TiO2) sont largement utilisées dans les cosmétiques, notamment dans les lotions solaires, pour leurs propriétés optiques intéressantes. Cependant, le TiO2 étant très réactif et potentiellement nocif pour les cellules cutanées, celui-ci est recouvert d’une couche de passivation composée d’espèces chimiques inertes. D’autres traitements de surface peuvent par la suite être appliqués afin de faciliter leur dispersion dans les cosmétiques. Ainsi, les nanoparticules de TiO2 de grades cosmétiques ont des chimies de surface variées qui leur confèrent des propriétés physicochimiques propres. Cependant, le comportement de ces particules lors de leur utilisation en émulsion cosmétique est peu connu. Lors de ce travail de thèse, plusieurs systèmes nanoparticules/émulsion ont été étudiés au cours de leur vieillissement accéléré et suivant les conditions d’utilisation. Tout d’abord, l’impact de deux nanoparticules de traitements de surface différents a été testé sur les mécanismes de (dé)stabilisation des émulsions solaires. Puis, les nanoparticules en émulsion ont été caractérisées au cours du temps et ont fait apparaitre des modifications chimiques rapides au niveau de leur surface. Celles-ci affectent les propriétés physicochimiques des surfaces et ont été prises en compte lors du suivi de l’impact de ces nanoparticules sur les bactéries à travers des protocoles imitant les conditions réelles d’exposition. / Nanoparticles of titanium dioxide (TiO2) are currently used in cosmetics, especially in sunscreens, because of their interesting optical properties. However, the TiO2 is really reactive and could promote the formation of dangerous species for the cutaneous cells. For that reason, these particles are passivated by the application of inert surface treatments. Other coatings could be added in order to improve the dispersion of nanoparticles in the emulsion. Hence, the cosmetic grades of TiO2-nanoparticles have diverse physicochemical surface properties and their behavior in cosmetic use is uncertain. In this work, nanoparticles/emulsion systems were studied during their accelerated aging, mimicking use conditions. First, the impact of two nanoparticles with different surface treatments were tested on the (de)stabilization mechanisms in emulsions. Then, the nanoparticles were characterized within the emulsions and highlighted quick surface modifications. As these changed the physicochemical surface properties of the nanoparticles, they were taken into account during the evaluation of the NP impact on cutaneous bacteria.

Les normes environnementales, en constante évolution, deviennent de plus en plus strictes pour réduire la présence de métaux et / ou composés organiques volatils dans l’environnement. Cette restriction constitue donc une préoccupation industrielle majeure dans le domaine des traitements de surface où les métaux sont prépondérants. Depuis peu le nickel a été placé en CMR (cancérogène, mutagène et reprotoxique) et appartient donc à la liste de produits à éviter. En conséquence, des alternatives au revêtement de nickel sont très sollicitées par les industriels afin de respecter l’environnement tout en gardant les mêmes performances de dépôts que le nickel (bonne résistance à la corrosion,…). Notre axe de recherche concerne la formulation et la caractérisation de dépôts électrolytiques d’alliages cuivre – étain considérés comme alternative au nickel. Une première partie porte sur les mécanisme d’électrodéposition des alliage cuivre étain en présence de gélatine et en milieu acide et sulfate. Une deuxième partie apporte des compléments d’informations sur les mécanismes mis en œuvre lors de l’électrodéposition des alliages CuSn. La gélatine, présent [Sic] dans l’électrolyte, modifie les revêtements CuSn élaborés identifiant un phénomène d’adsorption de substrat de platine. Un mode d’action de la gélatine suivant le modèle de Norde a été proposé. Cette étude s’oriente vers une application industrielle, c’est pourquoi une troisième partie est dédiée à l’élaboration et la caractérisation des revêtements CuSn sur différents substrats (laiton, acier / To date, nickel electrodeposition plays a key role in a variety of decorative, engineering and electroforming applications due to its costs that are maintained at an acceptable level, and their excellent functional properties (corrosion resistance…). Environmental constraints lead to increasingly severe regulations. […] This study focuses on the formulation of an acid and sulfate electrolyte. […] In the present study, deposition of Cu-Sn on platinum substrate was studied, and the role of gelatin at the interface was investigated. A phenomenon of gelatin adsorption is determined by different techniques of the characterization. The third part of this study deals with the electrodeposition of CuSn alloys on different substrates moving towards industrial application. The end goal is to identify optimum operating conditions based on gelatin action.