L’objectif général de ma thèse est de développer une modélisation spatialisée à l’échelle d’un versant, afin de mieux rendre compte des principales voies de transfert des pesticides dans les terrains agricoles. Je cherche à adopter une approche simplifiée, mais qui permet néanmoins de représenter les discontinuités existantes (parcelles, fossés, talus … etc). En effet, on souhaite pouvoir quantifier les mécanismes du transfert des pesticides en prenant en compte l’influence des éléments du paysage (parcelles, fossés, bandes enherbées …etc) sur la partition des transferts d’eau et de pesticides en surface et en subsurface. On s’appuie pour ce développement sur les données acquises sur le bassin versant expérimental de la Morcille (69), qui servent à fournir des ordres de grandeur et un cadre pour tester la pertinence des développements effectués. Une synthèse bibliographique sur les processus en jeu et les modèles existants a conduit au choix de la plateforme de modélisation hydrologique CMF, développée à l’université de Giessen (Kraft, 2012). Cette dernière permet une modélisation orientée objet d’un système hydrologique (colonne de sol, versant, bassin versant ...etc) et propose une grande variété d’équations physiques pour la représentation des processus hydrologiques. Le travail est mené sur trois étapes, une première consiste à l’évaluation du comportement de la plateforme et la validation de sa réponse via la comparaison dans un premier temps via un modèle 1D suite à une comparaison avec Hydrus1D. Dans un second temps, nous avons mené des simulations en 2D en comparant avec le modèle Cathy en se basant sur les travaux de Sulis et al. (2010) et avec Hydrus2D (Simunek et al., 1999 & Simunek et al., 2001) sur un versant inspiré du versant expérimental de la Morcille. La deuxième étape consiste à la prise en compte des écoulements préférentiels dans certains types de sol structurés, nous paraît nécessaire pour une meilleure représentation des processus en jeu. La représentation du transfert préférentiel des produits phytosanitaires via les macropores vers la ressource en eau représente encore un défi pour la recherche. L’approche à double perméabilité (DP) choisie contient le développant d’une nouvelle fonction d’infiltration dans les macropores. Notre modèle DP contient également deux fonctions alternatives d’échange matrice-macropores ; la première est proportionnelle à la différence des teneurs en eau des deux compartiments du sol (Philip, 1968). La deuxième fonction d’échange est une onde diffusante basée sur l’approche présentée par van Genuchten (1993). La dernière partie de la thèse consiste en la modélisation des solutés suivant successivement les deux approches : simple porosité et double perméabilité, en considérant le transport des solutés par convection et une adsorption linéaire. La validation de notre approche de modélisation est menée en comparant avec les simulations d’Hydrus1D/2D. / The aim of my thesis is to develop a spatial scale modeling of a catchment, to better reflect the main pathways of pesticides in agricultural lands. We are looking to adopt a simplified approach, yet it allows to represent the existing discontinuities (plots, ditches, embankments ... etc). Indeed, we wish to quantify the mechanisms of transfer of pesticides taking into account the influence of landscape features (patches, ditches, grass strips ... etc) on the partition of water transfers and pesticides in surface and subsurface. It relies for this development on the acquired data on the experimental watershed Morcille (69), which serve to provide orders of magnitude and a framework to test the relevance of business developments. A literature review on the processes involved and the existing models led to the choice of hydrological modeling framework CMF, developed at the University of Giessen (Kraft, 2012). CMF allows for object oriented modeling of a hydrologic system (soil column, slope, watershed etc.) and offers a wide variety of physical equations for the representation of hydrological processes. The work is conducted in three steps, the first involves assessing the behavior of CMF and validating its response via the comparison initially via a 1D model following a comparison with Hydrus1D. Secondly, we conducted 2D simulations comparing with the Cathy model based on the work of Sulis et al. (2010) and Hydrus2D (Simunek et al., 1999 & Simunek et al., 2001) on a hillslope inspired from the experimental slope of Morcille. The second step is to take account of preferential flow in certain types of structured soil, seems necessary for better representation of the processes. The representation of the preferential transfer of pesticides through macropores to water resources is still a research challenge. The dual permeability approach (DP) contains selected developing the infiltration of a new function in the macropores. Our DP model also contains two alternative exchange functions matrix-macropores; the first one is proportional to the difference of the water contents of the two compartments of the soil (Philip, 1968). The second exchange function is a diffusing wave based on the approach outlined by van Genuchten (1993). The last part of the thesis consists in the modeling of solutes successively following two approaches: single dual porosity and permeability, considering the convective transport of solutes and a linear adsorption. The validation of our modeling approach is conducted by comparing with the Hydrus1D / 2D simulations.

Lorsque les verres bioactifs entrent en contact avec des tissus vivants, une série de réactions physico-chimiques (dissolution, précipitation...) ont lieu à l’interface matériau / os, et conduisent à la formation d’une couche phosphocalcique, dont la composition est proche de la phase minérale de l’os (hydroxyapatite). La couche d’apatite sert de site de minéralisation pour les cellules osseuses, ce qui permet in fine un lien intime entre le verre bioactif et les tissus osseux. Ce lien est caractéristique de la bioactivité, qui peut être modulée via plusieurs paramètres du verre comme la composition en éléments majeurs et traces ou les propriétés texturales (surface spécifique, porosité).Dans ce contexte, nous avons élaboré des verres bioactifs dans des systèmes binaires (SiO2-CaO) et ternaires (SiO2-CaO-P2O5). Ces verres ont été dopés en ions zinc et magnésium via la voie sol-gel. Grâce à l'emploi de tensioactifs, nous avons obtenu des verres mésostructurés. Enfin, en utilisant des méthodes dites « d’opale inverse », des verres à macroporosité organisée ont été synthétisés. L'influence de ces paramètres sur la réactivité des verres au contact d’un milieu biologique (DMEM) a principalement été étudiée par des techniques utilisant des microfaisceaux d'ions. L'émission X induite par particules chargées (PIXE) combinée à la spectrométrie de rétrodiffusion Rutherford (RBS) a en effet démontré des effets évidents sur la cinétique, l'amplitude et la distribution spatiale des réactions physico-chimiques. / When bioactive glasses are in contact with living tissues, several physico-chemical reactions (dissolution, precipitation…) take place at the material / bone interface, and lead to the formation of a phosphocalcic layer, whose composition is close to the mineral phase of the bone (hydroxyapatite). The apatite layer is used as a mineralization site for bone cells and finally allows an intimate bond between the bioactive glass and osseous tissues. This bond is typical of bioactivity, which can be modulated through several parameters of the glass, like composition in major and trace elements or textural properties (specific surface, porosity).In this context, we elaborated bioactive glasses in binary (SiO2-CaO) and ternary (SiO2-CaO-P2O5) systems. Glasses have been doped with zinc and magnesium ions through the sol-gel route. Thanks to the use of surfactants, we obtained mesostructured glasses. Finally, by using inverse opal method, organized macroporous glasses have been synthesized. The influence of these parameters on the reactivity of glasses in contact with a biological medium (DMEM) has been mainly studied by techniques using micro-ion beams. The X-ray emission induced by charged particles (PIXE) combined with Rutherford backscattering spectrometry (RBS) has indeed demonstrated clear effects on the kinetics, the amplitude, and the spatial distribution of the physico-chemical reactions.

This article combines a systematic literature review on the fabrication of macroporous α-Al2O3 with increased specific surface area with recent results from our group. Publications claiming the fabrication of α-Al2O3 with high specific surface areas (HSSA) are comprehensively assessed and critically reviewed. An account of all major routes towards HSSA α-Al2O3 is given, including hydrothermal methods, pore protection approaches, dopants, anodically oxidized alumina membranes, and sol-gel syntheses. Furthermore, limitations of these routes are disclosed, as thermodynamic calculations suggest that γ-Al2O3 may be the more stable alumina modification for ABET > 175 m2/g. In fact, the highest specific surface area unobjectionably reported to date for α-Al2O3 amounts to 16–24 m2/g and was attained via a sol-gel process. In a second part, we report on some of our own results, including a novel sol-gel synthesis, designated as mutual cross-hydrolysis. Besides, the Mn-assisted α-transition appears to be a promising approach for some alumina materials, whereas pore protection by carbon filling kinetically inhibits the formation of α-Al2O3 seeds. These experimental results are substantiated by attempts to theoretically calculate and predict the specific surface areas of both porous materials and nanopowders.

Made available in DSpace on 2017-07-25T19:30:02Z (GMT). No. of bitstreams: 1 Andre Carlos Auler.pdf: 1218277 bytes, checksum: aedcd75095720ba4b41e7ad48e647731 (MD5) Previous issue date: 2014-07-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Liming is the practice used to correct soil acidity and its reaction is dependent on the mode of application of the lime. The addition of lime to the soil with the tilling is an alternative for increasing his reaction. However, tillage alters its structure and processes occurring in it. The aim of this study was to evaluate the influence of liming of liming in three modes of application of limestone (on the surface, incorporated with plowing and harrowing and subsoiling and disking) on the physico-hydrical attributes of a Dystrudept. For this, an experiment was installed in the field with banded design, with treatments in a factorial arrangement (3 × 2). Treatments formed from the combination of two rates of lime (0 and 15 Mg ha-1) and three modes of application of limestone (on the surface, incorporate with plowing and harrowing and subsoiling and harrowing). Undisturbed and disturbed soil samples were collected at 0-0.10 and 0.10-0.20 m layers between plant rows of corn 18 months after installation of the experiment. The water-dispersed clay (WDC), flocculation degree (FD), bulk density (BD), total porosity (TP), water retention curves, pore size distribution curve, particle size and soil chemical properties were determined order to diagnose the effects of liming the soil studied. Liming effects on the physico-hydrical attributes of the soil were restricted to 0-0.10 m layer. The WDC and the FD were influenced by tillage, but not by liming. When liming was performed on the surface, there was a reduction of the DB and increased TP. In all modes of application of limestone, liming increased water retention and altered the distribution of pores. To conclude, the changes in physico-hydrical attributes of the soil were mostly due to the increase of pH and replacement of aluminum by calcium and magnesium in the exchange complex. / A calagem é a prática empregada na correção da acidez do solo e sua reação depende do modo de aplicação do corretivo. A incorporação de calcário com o revolvimento do solo é uma alternativa para o aumento da reação. Porém, a mobilização do solo altera a sua estrutura e os processos que nela ocorrem. O objetivo deste trabalho foi avaliar a influência da calagem em três modos de aplicação do calcário (na superfície, incorporada com aração e gradagem e com subsolagem e gradagem) nos atributos físico-hídricos de um CAMBISSOLO HÁPLICO Alumínico. Para isso, instalou-se um experimento em campo com delineamento em faixas, com tratamentos em arranjo fatorial (3 × 2). Os tratamentos constituíam-se da combinação de duas doses de calcário (0 e 15 Mg ha-1) e três modos de aplicação do calcário (na superfície, incorporado com aração e gradagem e subsolagem e gradagem). Amostras indeformadas e deformadas de solo nas camadas 0-0,10 e 0,10-0,20 m foram coletadas nas entrelinhas da cultura do milho 18 meses após a instalação do experimento. Foram avaliados os teores de argila dispersa em água (ADA), grau de floculação (GF), densidade do solo (Ds), porosidade total (Pt), curvas de retenção de água, curva de distribuição de poros, granulometria e atributos químicos do solo. Os efeitos da calagem sobre os atributos físico-hídricos do solo foram restritos à camada 0-0,10 m. A ADA e o GF foram influenciados pelo modo de aplicação do calcário, mas não pela calagem. Quando a calagem foi realizada na superfície, ocorreu redução da DS e aumento da Pt. Em todos os modos de aplicação do calcário, a calagem aumentou a retenção de água e alterou a distribuição de poros. Concluiu-se que as alterações nos atributos físico-hídricos do solo foram em sua maioria decorrentes do aumento do pH e da substituição do alumínio por cálcio e magnésio no complexo de troca.

Depuis plus d’une cinquantaine d’années, de formidables avancées ont été initiées dans le domaine de l’ingénierie tissulaire cutanée menant à la reconstruction in vitro de substituts de peau. La plupart sont des substituts dermiques destinés à être utilisés comme aide à la cicatrisation des plaies aigües et chroniques en complément des traitements de greffes conventionnels ainsi que pour l’augmentation des tissus mous. Bien qu’un nombre croissant de patients aient pu bénéficier de ces matrices dermiques, leur application clinique reste encore restreinte, en raison de leur coût élevé mais également à cause de résultats cicatriciels parfois peu satisfaisants. Par conséquent, il reste un défi de taille, celui de développer des substituts dermiques stimulant activement la cicatrisation, présentant un faible coût de production, sans propriétés antigéniques et possédant des propriétés mécaniques adaptées. Dans ce cadre, les hydrogels à base de fibrine constituent des candidats prometteurs, en particulier en raison du rôle central de cette protéine dans la cicatrisation. Le principal inconvénient est qu’à concentration physiologique, ces hydrogels sont faibles mécaniquement, ce qui les rend difficilement manipulables. L’objectif de cette thèse a été la mise au point ainsi que la caractérisation de différents hydrogels destinés à être utilisés comme substituts dermiques. Ces derniers présentent l’avantage d’associer les propriétés biologiques de la fibrine avec les propriétés mécaniques d’un polymère synthétique, le polyéthylène glycol dans une architecture de réseaux interpénétrés de polymères (RIP). Les résultats obtenus ont permis : - de confirmer les propriétés physico-chimiques des RIP développés initialement par nos collaborateurs de l’université de Cergy-Pontoise, - de valider en trois étapes (in vitro, ex vivo puis in vivo) la biocompatibilité de ces nouvelles matrices, destinées à être utilisées comme supports de culture 2D et pour l’augmentation des tissus mous, - d’élaborer et de caractériser des matrices macroporeuses, optimisées pour la culture 3D de fibroblastes de dermes humains. / Over the past five decades, we assisted in extraordinary advances in the field of skin tissue engineering which led to the in vitro reconstruction of a wide range of skin substitutes. Most of them are dermal substitutes: Their clinical application ranges from treating acute and chronic wounds to soft tissue augmentation. Although increasing numbers of patients have been treated with dermal substitutes, their clinical application has been limited by their substantial cost and some poor healing outcomes. Hence, there is still a challenge to produce a dermal substitute which enhance sufficiently wound healing. To this end, the substitute should exhibit suitable properties for enabling the repair process. Other requirements such as excellent biocompatibility, minimal antigenicity, ease to handle and cost-effective production are also essential. In this context, fibrin hydrogels constitute promising candidates for skin tissue engineering since fibrin fibers form a physiological and provisional backbone during wound healing. However, the poor mechanical properties of fibrin-based hydrogels at physiological concentration are an obstacle to their use. In this study, our aim was to design and characterize mechanically reinforced fibrin-based hydrogels by combining the intrinsic properties of a fibrin network with the mechanical features of a polyethylene glycol network using an interpenetrating polymer network (IPN) architecture. They are intended to be used as dermal scaffolds. The results obtained in this thesis: - Confirmed the suitable physico-chemical properties of IPN, first developed by our partner of the University of Cergy-Pontoise. - Validated their biocompatibility using a three-step approach (in vitro, ex vivo and in vivo assays). - Led to the synthesis and characterization of a new type of fibrin-based macroporous matrices, optimized for 3D dermal fibroblast culture.

Nous avons étudié la conductivité thermique de particules de silice mésoporeuse organisée de type SBA-15 de morphologie bâtonnet et présentant trois états d’agrégation : non agrégées (morphologie A), agrégées en macrostructures fibreuses homogènes en taille (morphologie B) et agrégées en macrostructures fibreuses hétérogènes en taille (morphologie C). Ces trois types de morphologie ont subi un traitement thermique post-synthèse à des températures variables allant de 150 °C jusqu’à 900 °C. Les mesures de conductivité thermique ont été effectuées sur ces trois morphologies. Il s’est avéré que la morphologie B est la plus isolante par rapport aux deux autres morphologies. De plus, le traitement thermique post-synthèse à 300 °C est optimal pour avoir des caractéristiques texturales très importantes, ainsi qu’une meilleure performance en isolation thermique (23 mW.m-1.K-1 pour la poudre, 30 mW.m-1.K-1 pour le monolithe). Dans le cas de la morphologie B, nous avons modifié l’interconnexion entre les mésopores cylindriques réguliers qui caractérisent la SBA-15; soit la présence ou non de microporosité, voire de mésoporosité, en variant la température de l’étape de synthèse dite de vieillissement de 36 à 130 °C. Il apparait que la température de vieillissement à 130 °C améliore la performance d’isolation thermique (22 mW.m-1.K-1). Des pastilles de la SBA-15 de morphologie B en été élaborées par ajout de liants de deux types : organique avec la carboxyméthylcellulose, et inorganique avec une silice colloïdale. En ajoutant ces deux types de liants, les propriétés mécaniques sont un peu améliorées, cependant la performance d’isolation thermique diminue notablement. / We have studied the thermal conductivity of rod-shaped particles of ordered mesoporous silica (OMS) SBA-15 type with three states of aggregation: non aggregated (morphology A), aggregated in fibrous macrostructures homogeneous in size (morphology B) and aggregated in fibrous macrostructures heterogeneous in size (morphology C). These three types of morphology were heat treated at temperatures from 150 °C to 900 °C. The thermal conductivity measurements were performed on these three morphologies in powder form or monoliths (assembly of particles or aggregates). It has been found that the morphology B is more insulating compared to the two other morphologies. In addition, the post-synthesis heat treatment at 300 °C is optimum for obtaining important textural characteristics (specific surface area and pore volume), and a better thermal insulation performance (23 mW.m-1 K-1. for the powder and 30 mW.m-1.K-1 for the monolith). For morphology B, we have changed the interconnection between regular cylindrical mesopores of SBA-15 by varying the synthesis temperature during the aging step from 36 to 130 °C. It appears that the aging temperature at 130 °C, where the connection between the cylindrical mesopores is realized by mesopores, improves the performance of thermal insulation (22 mW.m-1.K-1). Monoliths of OMS SBA-15 type with morphology B were prepared by adding two kinds of binders: organic with carboxymethylcellulose (CMC), and inorganic with a colloidal silica (Ludox AS40). By adding these two kinds of binders, the mechanical properties of the SBA-15 with morphology B are improved, but the thermal insulation performance decreases considerably.

Macroporous ceramic materials have found widespread technological application ranging from particulate filters in diesel engines, tissue engineering scaffolds, and as support materials in carbon capture processes. This thesis demonstrates how the pore space of macroporous alumina can be manipulated, analysed in three-dimensions (3D) using visualisation techniques, and functionalised with a CO2-adsorbing material. A novel method was developed to produce macroporous alumina materials: by combining sacrificial templating with thermally expandable polymeric microspheres and gel-casting of an alumina suspension. This method offers a versatile production of macroporous ceramics in which the level of porosity and the pore size distribution can easily be altered by varying the amount and type of spheres. The permeability to fluid flow could be regulated by controlling the connectivity of the pore space and the size of the smallest constrictions between the pores. Sacrificial templating with particle-coated expandable spheres significantly increased the fraction of isolated pore clusters and reduced both the sizes and the numbers of connections between neighbouring pores, compared to templating with un-coated spheres. The macroporous alumina materials were characterised with X-ray micro-computed tomography (μ-CT). The 3D data-sets obtained by X-ray μ-CT were used to calculate the spatial variation in porosity, the throat and pore size distributions and to calculate the permeability to fluid flow. The throat and pore size distributions were also able to be accurately quantified in only one extrusion and intrusion cycle with water-based porosimetry; a relatively novel and simple characterisation technique. The pore walls of the macroporous alumina materials were also coated with zeolite films by a colloidal processing technique. The CO2-uptake of the coated alumina materials and of hierarchically porous monoliths of zeolites was evaluated and compared. / As the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Submitted. Paper 4: Accepted. Paper 5: Manuscript. Paper 6: Submitted.

Lors de la conservation des vins en bouteilles, des réactions d’oxydation prématurées peuvent se produire et les propriétés barrières à l’oxygène de l’obturateur en liège sont souvent mises en cause. À l’heure actuelle, aucune étude n’a permis de déterminer la structure interne du liège ou l’effet de l’hydratation sur ses propriétés mécaniques. Quant aux propriétés barrières à l’oxygène, l’étape limitante au transfert reste indéterminée ainsi que l’effet de la compression et le rôle de l’interface verre/liège. L’étude de la structure interne du liège par imagerie a permis de visualiser la macroporosité du matériau et de conclure que pour les qualités de liège étudiées, les lenticelles ne sont pas interconnectées. La caractérisation des propriétés mécaniques du liège a montré que le module de Young n’était pas affecté pour une humidité relative < 50 %. En milieu plus humide, ce dernier diminue à cause de la formation de clusters de molécules d’eau entre les chaines de polymères constituants les parois cellulaires. En comparant le comportement du liège brut avec celui d’autres obturateurs, un effet de la taille des particules de liège et du ratio liège/additifs utilisés dans ces obturateurs, a également été mis en évidence. Au regard du mécanisme de transfert de gaz, les mécanismes en jeu et en particulier l’étape limitante ont été clairement déterminés : il s’agit de la diffusion au travers des parois cellulaires selon la loi de Fick. L’effet de la compression du bouchon ne modifie pas significativement le transfert d’oxygène tandis que le rôle de l’interface verre/liège semble gouverner les transferts de gaz de l’extérieur vers l’intérieur de la bouteille. / During the post bottling aging, premature oxidation reactions could occur and the oxygen barrier properties of the stopper are often pointed out. Nowadays, the internal structure of this material or the effect of hydration on its mechanical properties are still undetermined. Moreover, regarding the barrier properties, the limiting step of the oxygen transfer was not yet fully understood as well as the effect of compression or the role of the glass/cork interface in a bottleneck. The study of the internal structure of cork stopper allowed us to visualize the macroporosity of the material and conclude that there is no interconnectivity between lenticels, for the two qualities studied. The effect of hydration on the mechanical properties of cork was also investigated. The results shown that the rigidity of the material was not significantly affected for relative humidity < 50 %. Above this hydration level, the Young’s moduli decrease due to clusters formation of water molecules. Comparing the natural cork behavior to other stoppers, an effect of the particle size and the ratio cork/additives used in these stoppers was also highlighted. Regarding the transport mechanism of gas through cork, the limiting step was clearly determined: it’s the diffusion through the cell wall according to a Fickian mechanism. The compression of the stopper does not have a significant impact on the effective diffusion coefficient of oxygen. However, the role of the glass/cork interface is really important and seems to govern the gas transfer from the surrounding atmosphere into the bottle.