Cellulose nanofibrils (CNFs) are nanoscale fibers of high aspect ratio that can be isolated from a wide variety of cellulosic sources, including wood and bacterial cellulose. With high strength despite of their low density, CNFs are a promising renewable building block for the preparation of nanostructured materials and composites. To fabricate CNF-based materials with improved inherent rheological and mechanical properties and additional new functionalities, it is essential to tailor the surface properties of individual CNFs. The surface structures control the interactions between CNFs and ultimately dictate the structure and macroscale properties of the bulk material. In this thesis we have demonstrated different approaches, ranging from non-covalent adsorption and covalent chemical modification to modification of cellulose biosynthesis, to tailor the structure and surface functionalities of CNFs for the fabrication of advanced materials. These materials possess enhanced properties such as water-redispersibility, water absorbency, dye adsorption capacity, antibacterial activity, and mechanical properties. In Paper I, CNFs were modified via the irreversible adsorption of carboxymethyl cellulose (CMC). The adsorption of small amounts of CMC onto the surface of CNFs prevented agglomeration and co-crystallization of the nanofibrils upon drying, and allowed the recovery of rheological and mechanical properties after redispersion of dried CNF samples. In Paper II, CNFs bearing permanent cationic charges were prepared through quaternization of wood pulp fibers followed by mechanical disintegration. The activation of the hydroxyl groups on pulp fibers by alkaline treatment was optimized prior to quaternization. This optimization resulted in individual CNFs with uniform width and tunable cationic charge densities. These cationic CNFs demonstrated ultrahigh water absorbency and high adsorption capacity for anionic dyes. In Paper III, via a similar approach as in Paper II, CNFs bearing polyethylene glycol (PEG) were prepared by covalently grafting PEG to carboxylated pulp fibers prior to mechanical disintegration. CNFs with a high surface chain density of PEG and a uniform width were oriented to produce macroscopic ribbons simply by mechanical stretching of the CNF hydrogel network before drying. The uniform grafted thin monolayer of PEG on the surface of individual CNFs prevented the agglomeration of CNFs and facilitated their alignment upon mechanical stretching, thus resulted in ribbons with ultrahigh tensile strength and modulus. These optically transparent ribbons also demonstrated interesting biaxial light scattering behavior. In Paper IV, bacterial cellulose (BC) was modified by the addition of chitin nanocrystals (ChNCs) into the growing culture medium of the bacteria Acetobacter aceti which secretes cellulose in the form of entangled nanofibers. This led to the in situ incorporation of ChNCs into the BC nanofibers network and resulted in BC/ChNC nanocomposites exhibiting bactericidal activity. Further, blending of BC nanofibers with ChNCs produced nanocomposite films with relatively lower tensile strength and modulus compared to the in situ cultivated ones. The bactericidal activity increased significantly with increasing amount of ChNCs for nanocomposites prepared by direct mixing of BC nanofibers and ChNCs. In Paper V, CNFs were isolated from suspension-cultured wild-type (WT) and cellulose-binding module (CBM) transformed tobacco BY-2 (Nicotiana tabacum L. cv bright yellow) cells. Results from strong sulfuric acid hydrolysis indicated that CNFs from transgenic cells overexpressing CBM consisted of longer cellulose nanocrystals compared to CNFs from WT cells. Nanopapers prepared from CNFs of transgenic cells demonstrated significantly enhanced toughness compared to CNFs of WT cells. / <p>QC 20141103</p> / CARBOMAT

This thesis addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO2 surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and about 1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multi-dimensional Boolean valued functions in three dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. The third topic is the formation of ripple structures on ion bombarded semiconductor surfaces treated in the first topic as the prepatterned substrate of the metallic deposition. This intriguing phenomenon has been known since the 1960s and various theoretical approaches have been explored. These previous models are discussed and a new non-linear model is formulated, based on the local atomic flow and associated density change in the near surface region. Within this framework ripple structures are shown to form without the necessity to invoke surface diffusion or large sputtering as important mechanisms. The model can also be extended to the case where sputtering is important and it is shown that in this case, certain "magic" angles can occur at which the ripple patterns are most clearly defined. The results including some analytic solutions of the nonlinear equation of motions are in very good agreement with experimental observation.

Modification of the surface chemistry of materials used as implants in biomedical applications affords the ability to control cell adhesion, prevent inflammation and enhance integration with the host. Titanium and its alloys are strong and lightweight thereby making them desirable for applications such as hip and knee replacements, dental implants, and cardiac pacemaker implants. However, the lifetime of these implants is often limited by poor incorporation into the surrounding bone which results in loosening and wear. In order to overcome these limitations we have studied the modification of titanium substrates with a self-assembled monolayer that can be used to perform surface-initiated atom transfer radical polymerization (SI-ATRP) of a monomer to afford polymer brushes that effectively prevent the adhesion of cells. In addition, the polymer brushes afford the ability to tether a peptide sequence. Specific peptides containing adhesion sequences have been tethered to the polymer brushes. The resulting surfaces promote cell adhesion and osteoblast differentiation, thereby increasing bone tissue formation around the implant resulting in better incorporation of the implant.

A reactive-ionic functional group was incorporated into the structure of fiber finishes and colorants to provide high-yield add-on and permanency. The reactive-ionic group consists of a moderately strained, cyclic ammonium group which undergoes ionic assembly on the surface of negatively charged substrates. The ionic bond is then converted to a covalent bond at elevated temperatures via a ring-opening reaction. A reactive-ionic alkyl (wax) finish was prepared from octadecanol and N-phenyl pyrrolidine then applied to a glass slide to provide a permanent, hydrophobic surface with an average contact angle increase of approximately 40°. A reactive-ionic fluorinated finish was prepared from 1H,1H,2H,2H-perfluoro-1-octanol and N-phenyl pyrrolidine and after application served as a permanent, non-wetting, anti-stain finish for nylon carpet. A reactive-ionic chromophore (dye) was prepared from C.I. Disperse Red 1 and quinuclidine. The reactive-ionic dye was applied to cellophane and nylon films and bleached cotton, nylon and silk fabrics. The percent exhaustion for a 1% owf dyeing of silk fabric was measured to be 98% using visible light absorbance spectrophotometry. K/S values obtained from reflectance spectrophotometric measurements of a 1% owf dyeing of nylon 6,6 fabric showed a 6% color loss after solvent extraction, indicating that the dyeing was indeed permanent.

Les nanoparticules seront sans doute les outils diagnostiques et thérapeutiques de demain. Si ellessont magnétiques, elles sont promises à des applications telles que le renforcement du contraste enIRM, la thermothérapie et la libération contrôlée de médicaments. Les nanomatériaux La1-xSrxMnO3ont été sélectionnés car leur température de Curie (TC) peut être ajustée dans la gamme detempérature thérapeutique. Des particules calibrées en taille et désagrégées ont été élaborées par leprocédé glycine-nitrate (GNP). Les caractérisations chimiques et structurales ont permis de mieuxcomprendre les résultats contradictoires de la littérature concernant la soi-disant dépendance de TCavec la taille des nanoparticules. L’adaptabilité de ces nanoparticules pour des applications enhyperthermie ou en IRM a été confirmée. Enfin, la capacité des nanoparticules à s’échauffer a étéutilisée pour réticuler autour d’elles une couronne de macromolécules thermosensibles selon leconcept nouveau de chimie localement stimulée. / Nanoparticles may be the next generation of diagnostic and therapeutic tools. If they are magnetic,they are dedicated to applications such as MRI contrast agent, thermotherapy and controlled drugrelease. La1-xSrxMnO3 nanoparticles were selected because their Curie temperature (TC) may be tunedwithin the range of therapeutic temperature. Size sorted and disaggregated particles weresynthesized by the Glycine-Nitrate Process. Chemical and structural characterizations allowed abetter understanding of conflicting results found in the literature about the particle size-dependenceof TC. The possibility to use these nanoparticles for hyperthermia and MRI applications has beenconfirmed. Finally, their ability to heat has been used to crosslink thermosensitive macromoleculesall around them according to the new concept of locally stimulated chemistry.

Ce travail de thèse porte sur l'élaboration de particules de polymère magnétiques capables de capter et relarguer différents microorganismes par des interactions électrostatiques non spécifiques. Des nanoparticules d'oxyde de fer cationiques stabilisées par des contre-ions nitrate ont été synthétisées par coprécipitation de sels de fer. La surface de la maghémite obtenue a été modifiée par voie sol-gel avec un organosilane présentant une fonction méthacrylate pour permettre son incorporation covalente dans des particules de latex par des réactions de copolymérisation. Ces particules ont été obtenues par polymérisation radicalaire en dispersion, en émulsion ou en miniémulsion du méthacrylate de méthyle ou du styrène, conduite en présence de maghémite. Les interactions entre celle-ci et le stabilisant rendent difficile la formation de latex magnétiques par polymérisation en dispersion. En revanche, la polymérisation en (mini-)émulsion permet, selon la technique de dispersion des oxydes de fer utilisée avant polymérisation, l'obtention de particules de latex de 140 à 650 nm, dont la fraction magnétique varie entre 2 et 37 % et contient jusqu'à 91 % de maghémite. La distribution de taille est toutefois large. Les particules magnétiques ainsi obtenues ont été ensuite fonctionnalisées directement au cours de la polymérisation en émulsion par l'introduction de co-monomères chargés, de polyélectrolytes ou de polyamphotères réamorçables. Ces deux derniers types de polymère sont obtenus par polymérisation RAFT. Leur capacité de capture/relargage a été évaluée sur des systèmes modèles à base de silice. Les polyamphotères donnent de bons résultats sur de nombreux microorganismes / This thesis describes the synthesis of magnetic latexes which are able to capture and release various microorganisms via non-specific and electrostatic interactions. Cationic iron oxide nanoparticles stabilized by nitrate counterions were synthesized by the co-precipitation of iron salts in water. The surface of the asobtained maghemite was then modified by a sol-gel process using a methacrylate-functionalized organosilane, in order to incorporate the iron oxide nanoparticles into latex particles by copolymerization reactions. Magnetic particles were obtained by dispersion, emulsion or miniemulsion polymerization of styrene or methyl methacrylate, performed in the presence of iron oxide. Due to the interaction between the stabilizers and iron oxides, dispersion polymerization was not a suitable approach. On the other hand, (mini-)emulsion polymerization led to a large range of particle diameters (140 – 650 nm), according to the process used to disperse iron oxides prior to the polymerization. These latexes contained between 2 and 37 % of magnetic particles, incorporating up to 91% of iron oxide. But the size distribution remained quite broad in all cases. The functionalization of the as-prepared magnetic particles was then undertaken by the introduction of either a charged co-monomer or polyelectrolytes or polyampholytes reactivable during the polymerization process. These kinds of polymers were synthesized by RAFT polymerization. Their ability to capture and release microorganisms was tested on silica-based model systems. Polyampholytes displayed good results on several microorganisms

No description available.

Cette thèse, réalisée en partenariat avec deux industriels, a pour objectif de mettre au point une voie de valorisation matière des résines phénoplastes (bakélite) issues de gisement de déchets plastiques. En effet, ce type de résine (thermodurcissable) n’est pour l’instant pas valorisé en fin de vie et finit en enfouissement. Pour répondre aux attentes législatives (directive DEEE, mais aussi VHU dans l’automobile), qui imposent un quota de recyclage (réutilisation et valorisation matière) et de valorisation énergétique minimum pour les déchets en fin de vie, il parait important de développer des procédés de régénération de ces plastiques ainsi que de trouver des domaines d’application pour leur utilisation en tant que matière première secondaire.Enedis, dans le cadre du déploiement de ces nouveaux compteurs électriques, collecte les anciens compteurs et équipements installés et cherche une solution de recyclage adaptée. Une partie de ce gisement important de déchets est constituée de plastiques de tous types en mélange, et en particulier de bakélite. Le travail de cette thèse s’est concentré sur le traitement et la régénération de ce gisement.Dans un premier temps, un schéma de démantèlement et de tri de ce gisement varié a été mis en place. Il est basé sur une étude des matières présentes dans le gisement, en particulier plastiques. La présence d’additifs est également évaluée, en particulier celle de substances contrôlées comme les retardateurs de flamme halogénés, le cadmium, etc. L’objectif était d’optimiser le procédé de séparation des matières en vue d’obtenir des gisements de matières régénérées de pureté suffisante pour le réemploi, tout en limitant la présence d’additifs contrôlés pour respecter les concentrations maximales légales.Pour valoriser les résines phénoplastes issues de ce gisement, la voie envisagée consiste à réutiliser cette matière sous forme de charges incorporées au sein de matrices thermoplastiques (éventuellement régénérées). Pour ce faire, une étude de la transformation de la bakélite par broyage pour obtenir un produit de granulométrie très fine (micronisation) a été réalisée. La distribution granulométrique, la morphologie et son état physico-chimique de surface ont été évaluées en fonction des paramètres du procédé. Après incorporation à différents taux de charge dans des matrices thermoplastiques, les propriétés mécaniques en quasi-statique et dynamique des composites ont été évaluées. La fonctionnalisation des charges/matrices et l’incorporation d’agents compatibilisants ont permis d’améliorer la cohésion des interfaces. Une modélisation par homogénéisation a été réalisée pour rendre compte de l’influence des différentes variables sur la tenue mécanique des composites.Le comportement au feu des composites formulés a également été étudié. Du fait de la stabilité thermique élevée de la bakélite et du taux de char important formé lors de sa combustion, il est envisagé d’utiliser les charges phénoplastes comme donneur de carbone dans la formulation d’un système retardateur de flamme intumescent. Des additifs appropriés, comme une source d’acide et un agent gonflant, seront évalués pour la formulation du système. / The main goal of this PhD project, born from a partnership between EMA, APR2 and Enedis, was to develop a material recycling solution for phenolic molding compound (PMC, or Bakelite). Indeed, these types of thermoset material are hardly valorized and end up in landfill, mostly because of the lack of technically and economically viable solutions for recycling.Phenolic molding compound material are present in large amount in End of Life (EOL) electrical meter waste stream. Therefore, Enedis committed to find a valorisation scheme for these materials. This PhD work is aimed to develop a recycling process for PMC issued from this waste stream.Firstly, a dismantlement and sorting scheme was designed. It is based on the study of the waste stream material composition – in particular the plastic stream. The presence of regulated substances (such as halogenated flame retardant, etc.) in plastic formulations was assessed. The objective was to optimize the separation process to recover materials with a high degree of purity.The proposed recycling solution consists in using the PMC as a functional filler in a thermoplastic matrix. To do so, a comminution scheme was developed to reduce the size of the PMC part. The particle size distribution, morphology and surface chemistry of the obtained products were characterized. Quasi-static and dynamic mechanical properties of composite materials incorporating micronized PMC were determined. Various coupling schemes were studied in order to increase the adhesion between filler and matrix. The mechanical behaviour of the composite materials was also modelized using finite element methods.The fire behaviour of the composite material incorporating PMC filler was also studied. Because of the high thermal stability and high char yield of phenolic molding compound, its potential use as a carbon donor in intumescent flame retardant formulations was finally assessed.

This thesis is focused on the description of selected deposition methods of thin films using low-temperature plasma. Currently, many various technologies of thin films are developed and there are many applications in various industrial sectors. This thesis first gives a brief overview of deposition methods, plasma behavior during deposition and subsequent description of the selected methods of application due to the physical and chemical processes. They also discussed the advantages and disadvantages of the described coating technologies, and several examples of their use. The thesis should thus contribute to the overall view of modern coating technologies, their development and use currently, or possible use in the future.

Ce travail porte sur les propriétés des nanocristaux de cellulose, leur modification de surface et le développement de matériaux avancés. Diverses approches sont utilisées sur ces substrats nanométriques visant à modifier leurs propriétés de surface et étendre leur utilisation dans des applications très sophistiquées, telles que la postsulfation et la désulfatation, le greffage et l'adsorption de polymères, l’oxydation sélective, le greffage moléculaire et l'inclusion "hôte-invité". Sur la base de modifications de surface, l'analyse des propriétés (pour différents taux de groupements sulfates) et divers nanomatériaux dérivés des nanocristaux de cellulose sont étudiés et préparés, notamment des nanocristaux sulfatés à différents taux, des nanocomposites extrudés, des éponges biocomposites et des hydrogels supramoléculaires. L'effet d’un gradient de groupements sulfates sur la chimie de surface, la morphologie et les propriétés physiques des nanocristaux de cellulose est discuté et notamment quatre modèles de section transversale sont comparés pour la détermination de la mesure du degré de substitution surfacique des nanocristaux de cellulose. Une stratégie nouvelle de protection impliquant une double couche polymère et la compatibilisation physique et/ou chimique des nanocristaux de cellulose est proposée afin de promouvoir à la fois la stabilité thermique des nanoparticules et la compatibilité des nanocristaux avec des matrices polymères non polaires au cours de la mise en forme par extrusion. En participant àla réticulation pour la construction de matériaux avancés, des nanocristaux de cellulose sélectivement oxydés (et de la cellulose microfibrillée oxydée pour comparaison) sont introduits dans de l'alginate pour développer des éponges biocomposites présentant une meilleure stabilité mécanique et une meilleure stabilité structurelle. Grâce à la conception intelligente par inclusion 'hôte-invité' in situ entre des nanocristaux de cellulose chimiquement modifiés et la cyclodextrine,deux polysaccharides hydrophiles sont combinés dans des hydrogels supramoléculaires pour l'administration de médicaments. En un mot, cette thèse contribue à l’avancée des nanocristaux de cellulose dans les domaines de l'analyse des propriétés et le développement des applications. / The present work focuses on the properties of cellulose nanocrystals, their surface modification and development of advanced materials. Diverse approaches are employed on these nanoscaled substrates aiming to modify their surface properties and extend their use in highly sophisticated applications, such as postsulfation and desulfation, polymer grafting and adsorption, selective oxidation, molecular grafting, and ‘host-guest' inclusion. On the basis of surface modifications, properties analysis (for different sulfate group contents) and various nanomaterials derived from cellulose nanocrystals are investigated and prepared, including gradient sulfated nanocrystals, extruded nanocomposites, biocomposite sponges, and supramolecular hydrogels. The effect of gradient degrees of sulfate groups on cellulose nanocrystals to surface chemistry, morphology and physical properties are discussed, particularly four cross-section models are compared for the determination of the surface degree of substitution on cellulose nanocrystals. A novel strategy involving a double-polymer-layer shield and physical and/or chemical compatibilization of cellulose nanocrystals is proposed, in order to realize both improvement of thermal stability and promotion of compatibility for nanocrystals with non-polar polymeric matrices during processing by melt-extrusion. With the idea of participating as crosslinking aid for the construction of advanced materials, selectively oxidized cellulose nanocrystals (with oxidized microfibrillated cellulose as comparison) are introduced in alginate for the development of biocomposite sponges with improved mechanical stability or structural stability. Through the smart design of in situ ‘host−guest' inclusion between chemically modified cellulose nanocrystals and cyclodextrin, two hydrophilic polysaccharides are combined in supramolecular hydrogels for use as drug delivery. In a word, this dissertation contributes to the advances of cellulose nanocrystals in the topics of property analysis and application development.