Soy flour (SF), a by-product of the soybean oil extraction processing, was investigated for its application in soy-polypropylene composites for interior automotive applications. The emphasis of this work was the understanding of this new type of filler material and the contribution of its major constituents to its thermal stability and impact properties. For this reason, reference materials were selected to represent the protein (soy protein isolate (SPI)) and carbohydrate (soy hulls (SH)) constituents of the soy flour. Additional materials were also investigated: the residue obtained after the protein removal from the soy flour which was called insoluble soy (IS), and the remaining liquid solution after acid precipitation of the proteins, containing mostly sugars and minerals, which was called soluble sugar extract (SSE). Two treatments, potassium permanganate and autoclave, were analyzed for their potential to modify the properties of the soy composite materials. An acid treatment with sulfuric acid conducted on soy flour was also considered. The soy materials were studied by thermogravimetric analysis (TGA) under isothermal (in air) and dynamic (in nitrogen) conditions. SPI had the highest thermal stability and SSE the lowest thermal stability for the early stage of the heating process. Those two materials had the highest amount of residual mass at the end of the dynamic TGA in nitrogen. The two treatments showed minimal effect on the isothermal thermal stability of the soy materials at 200 ??C. A minor improvement was observed for the autoclave treated soy materials. Fourier transformed infrared (FTIR) spectroscopy indicated that the chemical surface composition differed according to type of the soy materials but no difference could be observed for the treatments within one type of soy material. Contact angle analysis and surface energy estimation indicated differences of the surface hydrophobicity of the soy materials according to type of material and treatment. The initial water contact angle ranged from 57 ?? for SF to 85 ?? for SH. The rate of water absorption increased dramatically after the autoclave treatment for IS and SPI. Both materials showed the highest increase in the polar surface energy fraction. In general, the major change of the surface energy was associated with change of the polar fraction. After KMnO4 treatment, the polar surface energy of SF, IS and SPI decreased while SH showed a slight increase after KMnO4 treatment. A relationship between protein content and polar surface energy was observed and seen to be more pronounced when high protein containing soy materials were treated with KMnO4 and autoclave. Based on the polar surface energy results, the most suitable soy materials for polypropylene compounding are SPI (KMnO4), SH, and IS (KMnO4) because their polar surface energy are the lowest which should make them more compatible with non-polar polymers such as polypropylene. The soy materials were compounded as 30 wt-% material loading with an injection moulding grade polypropylene blend for different combinations of soy material treatment and coupling agents. Notched Izod impact and flexural strength as well as flexural modulus estimates indicated that the mechanical properties of the autoclaved SF decreased when compared to untreated soy flour while the potassium permanganate treated SF improved in impact and flexural properties. Combinations of the two treatments and two selected (maleic anhydride grafted polypropylene) coupling agents showed improved impact and flexural properties for the autoclaved soy flour but decreased properties for the potassium permanganate treated soy flour. Scanning electron microscopy of the fractured section, obtained after impact testing of the composite material, revealed different crack propagation mechanisms for the treated SF. Autoclaved SF had a poor interface with large gaps between the material and the polypropylene matrix. After the addition of a maleic anhydride coupling agent to the autoclaved SF and polypropylene formulation, the SF was fully embedded in the polymer matrix. Potassium permanganate treated SF showed partial bonding between the material and the polymer matrix but some of the material showed poor bonding to the matrix. The acid treated SF showed cracks through the dispersed phase and completely broken components that did not bind to the polypropylene matrix. In conclusion, the two most promising soy materials in terms of impact and flexural properties improvement of soy polypropylene composites were potassium permanganate treated SF and the autoclaved SF combined with maleic anhydride coupling agent formulation.

The content of this master’s thesis are methods of pretreatment and coating of the surface of PET to produce conductive copper structure and quality control. Thesis also includes theoretical analysis of these methods. Physical and chemical techniques of surface pretreatment methods are discussed in the theoretical part as well as methods making surface of substrate conductive, the subsequent galvanic copper plating and quality control of coating and testing of the adhesion between layers. The experimental part focuses on two methods of the polymer material surface pretreatments. The properties of these pretreatments were evaluated by using the atomic force microscopy and detection of surface energy by wetting and contact angle measurements. The surface is making conductive with cathode sputtering and electrochemical coating of copper. Adhesion of layers is tested mainly with scratch test and other methods. The results of these sub-operations are used for the realization of multi-layer conductive structures.

La génération de surfaces présentant des nanostructurations de surface variées et modulables est l’objectif principal de ce travail. L’auto-assemblage de copolymères à bloc ou de nanoparticules d’or a été privilégié, et nécessite pour se faire de moduler finement les interactions aux interfaces substrat/ matériaux déposés. Dans une première partie, un dispositif expérimental de greffage de silane alkyle en voie vapeur est décrit. Cette technique de greffage permet d’aboutir à des surfaces fonctionnalisées soit de façon homogène, soit de façon graduelle et ce, avec un ou deux silanes (substrat respectivement mono ou bi-composant). La robustesse, la simplicité et la flexibilité de notre procédé ont été démontrés par des caractérisations physico-chimique (mesure des propriétés de mouillabilité), chimique (spectroscopie de photoélectrons X) ainsi que par analyse topographique (microscopie à force atomique). Dans une deuxième partie, l’influence des interactions aux interfaces substrat / film sur l’auto-assemblage de copolymères à bloc PS-b-PMMA a été mise en évidence par AFM. A partir des substrats de silicium homogènes en énergie de surface, il a été possible de moduler la nanostructuration sur différents échantillons et à partir des surfaces fonctionnalisées graduellement, cette variation de nanostructuration a pu être obtenue sur un même substrat. Par l’utilisation de copolymère à bloc PS-b-PI, il est par ailleurs possible de générer des films nanostructurés sans préfonctionnalisation du substrat, sans recuit et ce quelle que soit l’épaisseur du film. Dans une troisième partie, l’influence des interactions aux interfaces sur l’assemblage capillaire/convectif dirigé de nanoparticules d’or a été démontré par microscopie à champ sombre. La nature chimique et la densité de greffage des silanes ainsi que la dimension des échantillons ont été modulées pour mettre en évidence le rôle de ces paramètres sur l’assemblage de ces particules. Cette étude montre que les interactions aux interfaces contrôlent l’assemblage des entités chimiques organiques et inorganiques et donc la nanostructuration de surface qui en résulte. / The purpose of this work is to develop a methodology based on the control of interactions at substrate/deposited material interfaces in order to achieve well-defined structures at the nanoscale (nanostructuration). In particular, silane molecules were grafted onto planar substrates to adjust the physico-chemical interactions in order to consequently control block copolymers / gold nanoparticles self-assemblies. The first part describes the experimental set-up developed to graft alkyl silanes through vapor phase strategy. The modification can be finely tuned such that homogeneously or gradually functionalized surfaces with either one or two silanes (or- or two-component substrate, respectively) are obtained. The versatility and simplicity of our process were demonstrated by wettability measurements, X-ray photoelectron spectroscopy and microscopic analysis (AFM) performed on these different surfaces. The second part points out the influence of grafting density and polarity on block copolymers self-assembly. PS-b-PMMA films were first used. With using homogeneously-modified substrates, it has been demonstrated that block copolymers self-assembly depends on substrate surface chemistry, and different cases (dewetting, wetting, parallel or perpendicular orientation of nanodomains) were achieved as a function of the grafting density of silanes on the substrate. Using gradually-modified surface, these different nanostructures were obtained on one unique sample. Moreover, by using appropriate deposition conditions with another block copolymer (PS-b-PI), well-oriented nanostructured films were obtained without pre-functionalization or annealing, regardless of film thickness. In the third part influence of surface chemistry on gold nanoparticles deposited through capillary/convective assembly is investigated and characterized by dark field microscopy. The careful selection of silane in conjunction with appropriate grafting density are adjusted in order to emphasize the impact of these parameters on the assembly process and therefore on the surface nanostructures. This study demonstrates that the control of interfacial interactions dictates the self-assembly of organic or inorganic materials deposited on a planar substrate.

Today there is growing interest within the construction sector to increase the proportion of biobased building materials made from renewable resources. By-products or residuals from wood processing could in this case be valuable resources for manufacturing new types of biocomposites. An important research question related to wood-based biocomposites is how to characterise molecular interactions between the different components in the composite. The hygroscopic character of wood and its water sorption properties are also crucial. Thermal modification (or heat treatment) of wood results in a number of enhanced properties such as reduced hygroscopicity and improved dimensional stability as well as increased resistance to microbiological decay. In this thesis, surface characteristics of thermally modified wood components (often called wood fibres or particles) and influencing effects from moisture sorption have been analysed using a number of material characterisation techniques. The aim is to increase the understanding in how to design efficient material combinations for the use of such wood components in biocomposites. The specific objective was to study surface energy characteristics of thermally modified spruce (Picea abies Karst.) under influences of water vapour sorption. An effort was also made to establish a link between surface energy and surface chemical composition. The surface energy of both thermally modified and unmodified wood components were studied at different surface coverages using inverse gas chromatography (IGC), providing information about the heterogeneity of the surface energy. The water vapour sorption behaviour of the wood components was studied using the dynamic vapour sorption (DVS) method, and their surface chemical composition was studied by means of X-ray photoelectron spectroscopy (XPS). Additionally, the morphology of the wood components was studied with scanning electron microscopy (SEM). The IGC analysis indicated a more heterogeneous surface energy character of the thermally modified wood compared with the unmodified wood. An increase of the dispersive surface energy due to exposure to an increased relative humidity (RH) from 0% to 75% RH at 30 ˚C was also indicated for the modified samples. The DVS analysis indicated an increase in equilibrium moisture content (EMC) in adsorption due to the exposure to 75% RH. Furthermore, the XPS results indicated a decrease of extractable and a relative increase of non-extractable compounds due to the exposure, valid for both the modified and the unmodified wood. The property changes due to the increased RH condition and also due to the thermal modification are suggested to be related to alterations in the amount of accessible hydroxyl groups in the wood surface. Recommendations for future work and implications of the results could be related to knowledge-based tailoring of new compatible and durable material combinations, for example when using thermally modified wood components in new types of biocomposites for outdoor applications. / <p>Forskningsfinansiärer och strategiska forskningsprojekt:</p><p>Nils och Dorthi Troëdssons forskningsfond (Projektnr 793/12 Hydro-termo-mekanisk modifiering av trä).</p><p> KTH Royal Institute of Technology.</p><p> COST Action FP0904.</p><p> KK-Stiftelsen.</p><p>Stiftelsen för strategiskt forskning (SSF). QC 20150908</p>

This master thesis presents a theoretical investigation of the energy and stability of interfaces in iron-carbide compounds, specifically focusing on the α-Fe/Cr7C3 system. The study aims to fill the gap in knowledge regarding the surface energetics of these interfaces using Density Functional Theory (DFT). Six different α-Fe/Cr7C3 interfaceswere constructed α-Fe(001)/Cr7C3(024), α-Fe(001)/Cr7C3(202), α-Fe(001)/Cr7C3(040),α-Fe(110)/Cr7C3(024), α-Fe(110)/Cr7C3(202) and α-Fe(110)/Cr7C3(040). Due to limited computational resources, only one of them was computationally analyzed to determine its interfacial energy value. The results revealed that the interfacial energy of the α-Fe(001)/Cr7C3(040) interface falls within the range of incoherent interfaces, indicating its stability. The computed interfacial energy values ranged from 0.94 to 3.39 J/m2, consistent with similar studies on other iron interfaces. The simulations also identified minimum and local minimum points in the interface energy curve, representing stable configurations at specific interface separation distances. The presence of a minimum point at an interface separation value of d = 1.3551 Å with an interfacial energy of 0.94 J/m2 indicates the most stable configuration, while a local minimum point at d = 2.27 Å with an interfacial energy of 2.12 J/m2 suggests another stable configuration for the interface. The conclusion that the computations were correctly performed with an interfacial energy value of 0.94 J/m2 for the most stable configuration at a supercell length (aSupercell ) of 22.23 Å is drawn. The findings of this research have significant implications for future investigations and applications. Firstly, this study fills the gap of the unresearched ferrite-carbide interfaces with theoretical data. Secondly, the knowledge gained from studying these interfaces contributes to understanding hydrogen interactions, which is fundamental for the transition towards a hydrogen economy. Additionally, the incoherent nature of the interface introduces challenges in understanding material behavior and properties, necessitating further investigations for designing efficient systems. Future work includes experimental validation of the α-Fe/Cr7C3 interface to compare the theoretical and experimental energies and stability. Investigating the remaining interfaces and examining the effects of introducing hydrogen atoms in these interfaces, along with calculating the corresponding hydrogen trapping energies, are important research areas. Further advancements in understanding these interfaces can be achieved through interface engineering, multiscale modeling, and studying other iron-carbide systems. / Detta examensarbete presenterar en teoretisk undersökning av energin och stabiliteten hos gränssnitt i järnkarbidföreningar och fokuserar specifikt på α-Fe/Cr7C3-systemet. Studien syftar till att fylla kunskaps tomrummet gällande ytegenskaperna hos dessa gränssnitt genom användning av densitetsfunktionalteori (DFT). Sex olika α-Fe/Cr7C3-gränssnitt konstruerades α-Fe(001)/Cr7C3(024), α-Fe(001)/Cr7C3(202), α-Fe(001)/Cr7C3(040), α-Fe(110)/Cr7C3(024), α-Fe(110)/Cr7C3(202) och α-Fe(110)/Cr7C3(040). På grund av begränsade beräkningsresurser analyserades endast ett av dem för att bestämma dess gränssnittsenergivärde. Resultaten visade att gränssnittsenergin för α-Fe(001)/Cr7C3(040)- gränssnittet ligger inom intervallet för inkoherenta gränssnitt, vilket indikerar dess stabilitet. De beräknade gränssnittsenergivärdena varierade mellan 0,94 och 3,39 J/m2 , vilket är i linje med liknande studier där järngränssnitt studeras. Minimi och lokala minimipunkter i gränssnittets energikurva, vilket representerar stabila konfigurationer vid specifika avstånd mellan gränssnittet. Förekomsten av en minimipunkt vid ett gränssnittsavstånd på d = 1,35 Å med en gränssnittsenergi på 0,94 J/m2 indikerar den mest stabila konfigurationen, medan en lokal minimipunkt vid d = 2,27 Å med en gränssnittsenergi på 2,12 J/m2 antyder en annan stabil konfiguration för gränssnittet. Slutsatsen dras att beräkningarna utfördes korrekt med ett gränssnittsenergivärde på 0,94 J/m2 för den mest stabila konfigurationen vid en supercellslängd (aSupercell) på 22,23 Å. Fynden från denna forskning har betydande implikationer för framtida undersökningar och tillämpningar. För det första fyller denna studie kunskapsgapet gällande de otillräckligt utforskade ferrit-karbidgränssnitten med teoretisk data. För det andra bidrar den erhållna kunskapen från studiet av dessa gränssnitt till förståelsen av väteinteraktioner, vilket är grundläggande för övergången till en väteekonomi. Dessutom innebär gränssnittets inkoherenta natur utmaningar när det gäller att förstå materialbeteende och egenskaper, vilket kräver ytterligare undersökningar för att utforma effektiva system. Framtida arbete inkluderar experimentell validering av gränssnittet mellan α-Fe/Cr7C3 för att jämföra teoretiska och experimentella energier och stabilitet. Att undersöka återstående gränssnitt och undersöka effekterna av att introducera väteatomer i dessa gränssnitt och beräkna motsvarande vätefällningsenergier är viktiga forskningsområden. Gränssnittsdesign, flerskalig modellering och studier av andra järnkarbid-system kan ytterligare främja förståelsen av dessa gränssnitt.

La région boréale arctique (RBA) couvre une vaste étendue qui lui confère un rôle important dans le système climatique mondial, par ses échanges d'énergie et de matière avec l'atmosphère. La température de l'air dans la région boréale arctique a augmenté à des taux disproportionnés par rapport à la moyenne mondiale, entraînant des changements dans la composition et la structure de la végétation. La RBA comprend l'écotone de la forêt boréale et de la toundra (EFT), qui s'étend sur plus de 10,000 km à travers l'hémisphère nord. La structure et la composition de la végétation varient considérablement à travers l’EFT. Du sud au nord, les arbres deviennent plus courts, plus dispersés et finalement absents. Ce gradient entraîne des variations dans la balance énergétique de surface. Ainsi, des changements dans la composition et la structure de la végétation dans l’EFT pourraient influencer le climat régional futur de ces régions. Ces changements régionaux pourraient se répercuter sur le climat mondial en interagissant avec le cycle du carbone par des changements dans les régimes de perturbations et la profondeur de la couche limite atmosphérique. L'objectif de cette étude était de développer un état des lieux de la variation latitudinale des interactions entre la surface et l’atmosphère et du climat régional à travers l’EFT dans le nord-ouest du Canada. Nous avons utilisé des mesures de covariance des turbulences provenant d’une forêt subarctique en marge de l’EFT et d’une toundra minérale caractérisant l’EFT du nord-ouest du Canada afin de quantifier les différences journalière et saisonnières des échanges d'énergie. Quatre paramètres de surface (albédo, conductance aérodynamique, conductance de surface et facteur de découplage) ont été examinés dans le but d’expliquer les différences dans la balance énergétique de surface. Des observations par radiosonde basées sur des campagnes de terrain et une expérience de modélisation de la couche limite atmosphérique ont été réalisées afin de discuter des conséquences potentielles des changements de végétation sur la dynamique de la couche limite atmosphérique (hauteur, température, humidité) et ses implications pour le climat régional. La forêt subarctique a démontré une meilleure capacité à transférer la chaleur vers l’atmosphère et une plus grande résistance à l'évapotranspiration, se traduisant par des conditions atmosphériques plus chaudes et sèches, spécialement au printemps. En été et automne, une conductance de surface plus élevée sur le site de la toundra s’est traduite par à une plus grande proportion de l'énergie utilisée pour humidifier l'atmosphère, résultant en une couche atmosphérique moins épaisse et un refroidissement régional du climat. La caractérisation des interactions entre la surface et l’atmosphère à travers l’EFT contribuera à améliorer les prédictions des effets des changements de végétation en cours sur le climat régional dans la région boréale arctique. / Considering its vast extent, the Arctic-boreal region (ABR) plays an important role in the global climate system through its exchange of energy and matter with the atmosphere. Air temperature across the ABR has been increasing at a higher rate compared to the global average and has led to changes in vegetation composition and structure across the ABR. The ABR includes the forest-tundra ecotone (FTE), spanning more than 10,000 km across the northern hemisphere. As the world’s longest transition zone, the FTE separates the boreal and Arctic biomes over a width of only a few tens to hundreds of kilometers. Vegetation composition and structure varies considerably across the FTE as trees become, from south to north, shorter and more stunted, sparser, and eventually, absent. The associated latitudinal gradient in surface properties results in corresponding latitudinal variations in the energy balance. Thus, changes in the latitudinal variation in surface properties and energy exchanges within the atmospheric boundary layer (ABL) may affect future regional climate across the FTE. The goal of this study was to develop a baseline understanding of the latitudinal variation in surface-atmosphere interactions and atmospheric boundary layer dynamics across the FTE in northwestern Canada. We used paired eddy covariance measurements of surface energy fluxes and supporting environmental measurements at a subarctic woodland (‘woodland’) and a mineral upland tundra site (‘tundra’) to quantify differences in daily and seasonal differences in woodland and tundra properties and energy exchanges. Four bulk surface parameters (albedo, aerodynamic conductance, surface conductance, and decoupling factor) were examined to explain drivers of those differences. Campaign-based radiosonde observations and numerical experiments using an ABL model were used to examine the impacts of a sparse tree cover on ABL dynamics (height, temperature, humidity) and their implications for surface climate compared to treeless tundra. The sparse tree cover at the woodland site showed an enhanced ability to transfer heat into the atmosphere and a higher resistance to evapotranspiration compared to tundra, leading to warmer and drier conditions especially in late winter and spring. In summer and fall, higher bulk surface conductance at the tundra site led to more energy being used to moisten the atmosphere, resulting in a shallower ABL and regional cooling of the atmosphere. Refined characterization of land surface-atmosphere interactions across the FTE will help to project the effect of ongoing vegetation changes on regional climate in the circumpolar Arctic-boreal region.