La famille de matériaux polymériques 1D de type [Fe(Rtrz)3]Ax présente un phénomène detransition de spin, i.e. une modification réversible de la configuration électronique de l’ionmétallique pilotée par un stimulus (P, T, hv). Pour ces matériaux les caractéristiques detransition sont proches des pré-requis pour des applications technologiques. Ce travail, basésur des investigations par diffraction X aux frontières des possibilités, présente pour lapremière fois une description fiable des propriétés structurales de ces matériauxpolymériques aux différentes échelles (atomique à microscopique). D’une part l’originalitédes comportements structuraux observés est mise en relation avec les propriétés detransition de spin et d’autre part des aspects nouveaux tels que la fatigabilité, l’influence dela pression ou les morphologies des domaines cohérents sont explorés. Ces résultatsapportent des éléments essentiels à la compréhension et à la poursuite du développementde ces matériaux. / The 1D polymeric materials family of type [Fe(Rtrz)3]Ax exhibit a spin transitionphenomenon, i.e. a reversible modification of the electronic configuration of a metallic iondriven by a stimulus (P, T, hv). For these materials the transition characteristics are close tothe pre-requisite for technological applications. This work, based on X-ray diffractioninvestigations close to the limit of possibilities, presents for the first time a reliabledescription of the structural properties of these polymeric materials with different scales(atomic to microscopic). On one hand the original structural behavior observed is relatedwith the properties of the spin transition and on the other hand new aspects such as fatigue,the influence of pressure or morphologies of domain size are explored. These results provideessential elements for the understanding and the further development of these materials.

This research has been performed in the framework of the Virtuhcon project, which intends to virtualize high temperature conversion processes. Coal gasification is one of these processes, which is nowadays considered as a promising technology for the chemical industry. This study is devoted to the coal char physical structure, which is one of the most important parameters influencing coal gasification reaction. First, this study presents the extensive literature review of the char physical structure role during its conversion. Collection of the char structural properties as well as their changes during char conversion are shown and discussed. Literature review is followed by the experimental investigations. Chars prepared from two brown coals (Lusatian and Rhenish) were gasified in a laboratory scale fluidized bed reactor in CO2 at temperatures of 800, 850, 900, and 950 °C and atmospheric pressure. Char samples were gasified completely as well as partially in order to evaluate the reaction kinetics and char structural changes during the reaction, respectively. Complete gasification curves were evaluated by different methods, including application of three gasification models (the Random Pore Model, the Volume Reaction Model, and the Shrinking Reaction Model), instantaneous reaction rate approach as well as the self-developed surface-related reaction rate approach. The results of different approaches were compared. This study also presents a comprehensive methodology to analyze coal char physical structure. The variety of measurement techniques (gas physical adsorption, mercury porosimetry, helium pycnometry, SEM, etc.) were applied to assess structural properties of the char, such as specific surface area, particle density, porosity, pore size and shape, structure morphology, etc. Problems associated with the choice of a proper measurement technique and the comparability of the data delivered by different techniques were discussed. The main objective of the study was to link char structural changes to the char gasification kinetics. The specific task of this thesis was to investigate pore size in relation to their availability for the reaction. As such, specific surface areas of pores of different sizes (from sub-micro to mesopores) were correlated to the instantaneous reaction rates. Both chars exhibit similar trends in their structural changes during gasification, although the absolute values differ, especially with respect to the pores of microscale. Furthermore, structural changes were caused not only by the reaction but also by the influence of the heat treatment, especially at the earlier stages of the reaction. The most reasonable correlation has been achieved between the instantaneous reaction rate and the specific surface area of mesopores. Sub-micro- and micropores did not govern the gasification reaction under given conditions. Finally, kinetic parameters derived from different evaluation methods were reapplied in order to test their ability to predict the experimental data. Each of the method has its advantages and disadvantages as used for the kinetic evaluation. The results of this study represent a substantive base of the experimentally derived data concerning physical structure and morphology of coal char. The findings can be used in numerical and simulation studies for development, validation, and improvement of the models which consider coal particle as a reactive porous solid.

Aujourd'hui, un grand nombre de nouvelles molécules peuvent être synthétisées à partir de la biomasse. Les tensioactifs dérivés de sucre sont notamment considérés comme une alternative aux tensioactifs fossiles en raison de leur biodégradabilité et de leur biocompatibilité. Cependant, les études associant la caractérisation physico-chimique et les propriétés biologiques de ce type de tensio-actifs sont limitées. Il est ainsi difficile de prédire les propriétés d'un tensioactif à partir de sa structure chimique. L'établissement d'une méthodologie permettant de relier la structure des surfactants à leurs propriétés apparait pertinent. Dans ce travail, quatre surfactants dérivés de sucre ayant chacun une chaîne C8 liée à une tête glucose ou maltose par un groupe amide ont été caractérisés par leurs propriétés tensio-actives dans différentes solutions (eau et milieu biologique). Leurs interactions avec des protéines ont également été analysées. Concernant l'évaluation des propriétés biologiques, des tests de cytotoxicité/irritation ont été effectués sur trois modèles in-vitro : 1) modèle cellulaire 20 (cellules L929 cultivées en monocouche), Il) modèle cellulaire 30 (cellules L929 cultivées dans un gel de collagène), Ill) épiderme humain reconstitué. Les résultats indiquent que les quatre surfactants synthétisés présentent de bonnes propriétés tensio-actives et trois d'entre eux sont moins cytotoxiques que des tensioactifs de référence. Plusieurs hypothèses permettant de relier la structure chimique des molécules à leurs propriétés physico-chimiques et biologiques ont été proposées. Des travaux futurs permettront d'enrichir la base de données sur les relations structure-propriétés des tensioactifs issus de la biomasse, et de l'utiliser pour synthétiser des surfactants présentant des propriétés adaptées aux applications envisagées. / Nowadays, a wide variety of new molecules can derive from biomass. Among them, the family of sugar-based surfactants, which are considered as alternatives to fossil-based surfactants, due to their relatively high biodegradability and biocompatibility, exhibit interesting properties both in terms of their self-assembly and their ability to induce biological responses. In the study, for the purpose to analyse these properties, different methodologies have been established. In this work, physico-chemistry and cellular biology methodologies are associated to analyse the properties of pre-selected molecules characterized by gradua) structure modifications. Firstly, we have screened synthesized sugar-based surfactants according to their solubility and their ability to reduce surface tension of water. Four pre-selected molecules, with a C8 chain linked to a glucose or maltose head through an amide functional group, either under the form of carbamoyl (carbohydrate scaffold bearing the carbonyl) or alkylcarboxamide (the alkyl chain bearing the carbonyl), were then dissolved in water/ cell culture media for surface tension measurements. Their behaviors in solutions were characterized by Krafft points, Critical Micellar Concentrations or self-assembling properties through different methods. To evaluate the cytotoxic/ irritant effects of these molecules on cells and tissues, 3 in-vitro models were established: I) 2D cell culture mode! (L929 cell monolayer) II) 3D ce!! culture mode! (L929 cells embedded in collagen gel) and III) Reconstituted human epidermis (differentiated human keratinocytes). Corresponding experiments were carried out on these models with increasing complexity. Results show that the synthesized sugar-based surfactants, GlulamideC8, Glu6amideC8, Glu6amideC8' and MallamideC8 can reduce the surface tension of water solution to the came level as standard surfactants (Tween 20 and Hecameg). In the meantime, GlulamideC8, Glu6amideC8' and MallamideC8 present Iess cytotoxicity effects on L929 cells both in the monolayer model and the 3D mode! than Tween 20 and Hecameg. All synthesized and standard surfactants (GlulamideC8, Glu6amideC8, Gu6amideC8', MallamideC8, Tween 20 and Hecameg) have no significant cytotoxic/ irritant effects on reconstituted human epidermis at 1000 ig/mL after 48 h of topical application. Discussions have been made according to the results of experiments to establish possible structures/ physico-chemical properties - cytotoxicity relationships of these surfactants.

This research has been performed in the framework of the Virtuhcon project, which intends to virtualize high temperature conversion processes. Coal gasification is one of these processes, which is nowadays considered as a promising technology for the chemical industry. This study is devoted to the coal char physical structure, which is one of the most important parameters influencing coal gasification reaction. First, this study presents the extensive literature review of the char physical structure role during its conversion. Collection of the char structural properties as well as their changes during char conversion are shown and discussed. Literature review is followed by the experimental investigations. Chars prepared from two brown coals (Lusatian and Rhenish) were gasified in a laboratory scale fluidized bed reactor in CO2 at temperatures of 800, 850, 900, and 950 °C and atmospheric pressure. Char samples were gasified completely as well as partially in order to evaluate the reaction kinetics and char structural changes during the reaction, respectively. Complete gasification curves were evaluated by different methods, including application of three gasification models (the Random Pore Model, the Volume Reaction Model, and the Shrinking Reaction Model), instantaneous reaction rate approach as well as the self-developed surface-related reaction rate approach. The results of different approaches were compared. This study also presents a comprehensive methodology to analyze coal char physical structure. The variety of measurement techniques (gas physical adsorption, mercury porosimetry, helium pycnometry, SEM, etc.) were applied to assess structural properties of the char, such as specific surface area, particle density, porosity, pore size and shape, structure morphology, etc. Problems associated with the choice of a proper measurement technique and the comparability of the data delivered by different techniques were discussed. The main objective of the study was to link char structural changes to the char gasification kinetics. The specific task of this thesis was to investigate pore size in relation to their availability for the reaction. As such, specific surface areas of pores of different sizes (from sub-micro to mesopores) were correlated to the instantaneous reaction rates. Both chars exhibit similar trends in their structural changes during gasification, although the absolute values differ, especially with respect to the pores of microscale. Furthermore, structural changes were caused not only by the reaction but also by the influence of the heat treatment, especially at the earlier stages of the reaction. The most reasonable correlation has been achieved between the instantaneous reaction rate and the specific surface area of mesopores. Sub-micro- and micropores did not govern the gasification reaction under given conditions. Finally, kinetic parameters derived from different evaluation methods were reapplied in order to test their ability to predict the experimental data. Each of the method has its advantages and disadvantages as used for the kinetic evaluation. The results of this study represent a substantive base of the experimentally derived data concerning physical structure and morphology of coal char. The findings can be used in numerical and simulation studies for development, validation, and improvement of the models which consider coal particle as a reactive porous solid.

Traumatic rupture of the anterior cruciate ligament (ACL) can cause local destabilization and loss of mobility. Reconstruction using engineered ACL grafts is rarely successful due to sub-optimal material choice and mechanical performance. Thus, the presented work demonstrates the fabrication of various embroidered single- and bi-component scaffolds made of two commercially available monofilament threads (polydioxanone, poly(lactic acid-co-ɛ- caprolactone)) as well as a novel melt spun poly(L-lactic acid) multifilament and their mechanical analysis by tensile tests and under cyclic loading. Selected scaffolds, adjusted by material composition and textile parameters, revealed a load–strain behavior comparable to native lapin ACL tissue exhibiting a sufficient amount of elastic deformation within the toe-region of 1.7%, scaffold stiffness of 123 N/mm and adequate maximum tensile load (300 N) and strain (20%). Therefore, the design of resorbable embroidered bi-component scaffolds represents a promising approach to replace artificial non-resorbable ligament grafts and allows for innovative tissue engineering strategies.

For fiber-reinforced plastic composites, fiber-matrix adhesion is a significant aspect of composite properties. While conventional lightweight structures are always aiming for high fiber-matrix adhesion, innovative and unconventional functional constructions require different concepts. The research work treating adaptive fiber-reinforced plastic composites with shape memory alloy wires presented here uses the approach of actuators freely movable within the composite. This is supposed to prevent mechanical tensions in the interfaces of actuator and composite structure, which would otherwise cause damages of the composite. This work examines hybrid yarns based on friction spinning technology, with shape memory alloy wires as their core component as well as glass fibers, and partly polypropylene, as their sheath component. Additionally, the surface properties of the shape memory alloy wires being used are modified by sanding and coating. The results of a characterization by pull-out testing clearly show that a coating of the shape memory alloy wires with an abherent causes considerable decrease in adhesion and friction in the interface and leads to the mobility of the shape memory alloy wires in the later composite. An even greater effect is attained by sheathing the hybrid yarns in an additional layer of polypropylene, compacting the yarn cross-section. Thus, the pull-out force could be reduced to 35–40% of the reference structure.

Le travail présenté porte sur la rhéologie, la mise en forme et la caractérisation de matériaux biocomposites de nouvelles générations pour des applications orthopédiques. Dans le cadre de cette étude, des biocomposites poly (D,L-lactide) (PDLLA)/bioverres ont été élaborés par extrusion bivis sous atmosphère inerte. Les bioverres différent par la nature de leur traitement thermique et leur morphologie. La première partie a été consacrée à l’étude de l’état de la dispersion des bioverres dans la matrice polymère. Nous avons montré que l’homogénéité de cette dispersion dépend, d’une part de la structure, de la morphologie, du taux volumique des charges et d’autre part des paramètres du procédé (cisaillement, température,…). Le comportement rhéologique des suspensions a été étudié à l’état fondu ainsi qu’à l’état solide. Un accent particulier a été porté sur l’étude de l’influence du taux des bioverres, de leur taille moyenne et plus particulièrement de leur traitement thermique. Les masses molaires de PDLLA extrait des composites élaborés ont été évaluées par chromatographie d’exclusion stérique (CES). Enfin, la qualité de la dispersion des charges, en termes de distance inter-particulaire et taille moyenne, a été étudiée par microscopie électronique à balayage (MEB) et analyses d’image. Il a été montré que l’utilisation de bioverres non traités thermiquement lors de la mise en forme de composites à haute température provoque la dégradation de la matrice. Aussi, on assiste à une réduction des masses molaires. Les propriétés viscoélastiques et les propriétés mécaniques sont altérées à leur tour. Cette dégradation a été étudiée par spectroscopie infrarouge (IRTF) et par analyse thermogravimétrique (ATG). Les origines et mécanismes sous-jacents de cette dégradation ont été proposés. Il est démontré pour la première fois que la présente dégradation du PDLLA peut être atténuée par l’emploi de différentes charges céramiques à propriétés spécifiques. En outre, l’utilisation de ces bioverres a permis l’obtention d’une dispersion homogène au sein de la matrice. L’analyse des propriétés rhéologiques de tels matériaux et leur modélisation a permis de mettre en évidence les interactions matrice-charges. La deuxième partie de l’étude a porté sur l’élaboration des biocomposites multicouches à gradient de propriétés par coextrusion. Ces multicouches présentent, d’une part, des propriétés variables selon le type de traitement et de composition du bioverre actif. D’autre part, le gradient de propriété a été également réalisé en faisant varier les paramètres expérimentaux relatifs au procédé de coextrusion. Les matériaux finaux, ainsi obtenus, présentent de très bonnes propriétés cohésives avec une bioactivité maîtrisée et contrôlée. / Bioactive and biodegradable composites have gained increasing importance in the orthopedic field as bone replacement materials and as scaffolds for tissue engineering. In this study, biocomposites based on poly(D,L-lactide) (PDLLA) and bioactive glass fillers were prepared by a twin screw extrusion under Argon inert gas with various filler contents, thermal treatments and particle sizes. The processing conditions were monitored to produce composites with well controlled physico-chemical, mechanical and dispersive properties. The aim of the present work is to gain a fundamental understanding of the relationships between structure, processing conditions and final properties of these biocomposites. The dispersion state of fillers was characterized by SEM. It was highlighted that the inclusion of non treated bioglass in PDLLA under elevated temperatures resulted in a decrease of molar mass. This degradation of the matrix leads to a reduction of the viscoelastic and mechanical properties of the composites. The origin and mechanisms of this degradation were probed using a Fourier Transform Infrared (FTIR) spectroscopy. The optimization of their processing allows a better control of this drastic loss of properties. Furthermore, the demonstration had been done that the present degradation of PDLLA matrix can be attenuated using a different glass ceramics with a special size and thermally treated. The rheological behaviour in linear and non linear viscoelasticity of the controlled PDLLA/BG suspensions has been assessed in both solid and molten state. Hence, their experimental rheological behaviour was compared to the theoretical suspension models. Finally, the effects of volume fraction, particle size and thermal treatment on the mechanical properties have been also investigated and discussed. The obtained results corroborate the rheological and physic-chemical ones. Finally, the multilayer structures with various amounts and treatments of BG fillers were obtained by a designed scale lab coextrusion machines. The gradient of properties has been obtained and improved cohesion properties between the neighboring were highlighted. Their bioactivity was finally demonstrated. At last, no residual stress inside the multilayers can be observed. This observation explains the conservation of the initial shape of those implants, without nor deformation neither relaxation, during the simulation of the chirurgical implantation in SBF.

<p> Radical species are essential in modern chemistry. In addition to fundamental chemistry, their unique chemical bonding and distinct physicochemical features serve critical functions in materials science in the form of organic electronics. Due to their high reactivity, radicals of the main group element are often transient. In recent years, remarkably stable radicals are often stabilized by π-delocalization, sterically demanding side groups, carbenes, and weakly coordinating anions. The impacts of modifications such as electron-donating, electron-withdrawing, and end-capping on the spin density distribution and thermodynamic and kinetic stability of archetypal radical-driven processes such as dimerization are not well understood. This dissertation aims to track the perturbation of spin density from EDG and EWG modifications, provide mechanistic insight into the radical-initiated reactions of conjugated radical cations, and establish correlations between molecular design and thermochemical properties and their resulting kinetic stability by computationally evaluating these characteristics against experimental data. The disclosed connections give useful new recommendations for the rational design of thermodynamically and kinetically stable novel materials.</p>

La Spectroscopie par Effet Tunnel Inélastique (IETS) avec un Microscope à Effet Tunnel (STM) est une nouvelle technique de spectroscopie vibrationnelle, qui permet de caractériser des propriétés très fines de molécules adsorbées sur des surfaces métalliques. Des règles de selection d’excitation vibrationnelle basées sur la symétrie ont été proposées, cependant, elles ne semblent pas exhaustives pour expliquer la totalité du mécanisme et des facteurs en jeu; elles ne sont pas directement transposables pour les propriétés d'un adsorbat et sont lourdes d'utilisation. Le but de cette thèse est donc d'améliorer ces règles de selection par une étude théorique. Un protocole de simulation de l'IETS a été développé, paramétré, et évalué, puis appliqué pour calculer des spectres IETS pour différentes petites molécules, qui sont systématiquement liées, sur une surface de cuivre. Des principes additifs de l'IETS ont été developpés, notamment concernant l’extension dans le vide de l’état de tunnel, l'activation/ quench sélectif de certains modes du aux propriétés électroniques de certains fragments moléculaires, et l'application de certaines règles d'addition de signaux IETS. De plus, des empreintes vibrationnelles par des signaux IETS ont été determinées pour permettre de différentier entre les orientations des adsorbats, la nature chimique des atomes et les isomères de structures. Une stratégie simple utilisant les propriétés de distribution de la densité électronique de la molécule isolée pour prédire les activités IETS sans des couts importants de calculs a aussi été développée. Cette expertise a été utilisée pour rationaliser et interpréter les mesures expérimentales des spectres IETS pour des métalloporphyrines et métallophtalocyanines adsorbées. Ces études sont les premières études IETS pour des molécules aussi larges et complexes. L'approche expérimentale a permis de déterminer les limitations actuelles des simulations IETS. Les défauts associés à l'identification ont été résolus en faisant des simulations d'images STM complémentaires. / Inelastic Electron Tunneling Spectroscopy (IETS) with the Scanning Tunneling Microscope (STM) is a novel vibrational spectroscopy technique that permits to characterize very subtle properties of molecules adsorbed on metallic surfaces. Its proposed symmetry-based propensity selection rules, however, fail to fully capture its exact mechanism and influencing factors; are not directly retraceable to an adsorbate property and are cumbersome. In this thesis, a theoretical approach was taken to improve them. An IETS simulation protocol has been developed, parameterized and benchmarked, and consequently used to calculate IETS spectra for a set of systematically related small molecules on copper surfaces. Extending IETS principles were deduced that refer to the tunneling state’s vacuum extension, the selective activating/quenching of certain types of modes due to the moieties’ electronic properties, and the applicability of a sum rule of IETS signals. Also, fingerprinting IETS-signals that enable discrimination between adsorbate orientations, the chemical nature of atoms and structural isomers were determined and a strategy using straightforward electronic density distribution properties of the isolated molecule to predict IETS activity without (large) computational cost was developed. This expertise was used to rationalize and interpret experimentally measured IETS spectra for adsorbed metalloporphyrins and metallophthalocyanines, being the first IETS studies of this large size. This experimental approach permitted to determine the current limitations of IETS-simulations. The associated identification shortcomings were resolved by conducting complementary STM-image simulations.