La problématique énoncée par l’utilisation de matériaux composites C/C denses implique la connaissance et la maîtrise des processus de dégradation auxquels ils sont soumis. L’utilisation de moyens de caractérisation in-situ de ces voies de dégradation constitue alors un atout considérable pour leur anticipation. Ainsi, l’utilisation de la MEBE en Température associée à une caractérisation cristallographique par MET et une confrontation ex-situ par Analyse thermogravimétrique a abouti à l’obtention de lois cinétiques caractérisant la propagation de l’oxydation dans toutes les directions de l’espace. A la suite de cette étape expérimentale, une approche numérique basée sur l’utilisation d’algorithmes de Monte-Carlo Cinétique, a alors été mise en place pour modéliser ces observations tant sur le plan atomique avec la modélisation de la loi cinétique d’oxydation linéique, que meso et macroscopique par la simulation de la loi cinétique de perte de masse dans le cas particulier du HOPG. / The problem stated by the use of composites C / C dense implies knowledge and control of degradation processes to which they are subjected. The use of in-situ characterization of these means of degradation pathways then is a considerable asset for their advance. Thus, the use of ESEM in temperature associated with a crystallographic characterization by TEM and ex situ confrontation by thermogravimetric analysis resulted in obtaining kinetic laws characterizing the propagation of oxidation in all directions. Following this experimental stage, a numerical approach based on the use of algorithms Kinetic Monte-Carlo, was then introduced to model these observations both at the atomic level with the modeling of the oxidation kinetics law linear, as meso-and macro-simulation by the kinetic law of mass loss in the case of HOPG.

Les travaux présentés dans ce mémoire se concentrent sur la compréhension, la description et enfin la modélisation de la décomposition des matériaux d’aménagement ou d’ameublement d’usage courant (principalement des polymères naturels et de synthèse) sous l’effet de la chaleur. Ce champ de la recherche n’est pas nouveau, et de nombreux modèles existent à ce jour (le plus souvent des modèles d’Arrhénius associés à diverses fonctions cinétiques). Toutefois, contrairement aux développements liés à la description de la cinétique chimique en phase gazeuse, la plupart des modèles exploités à ce jour pour la phase solide souffrent généralement d’une justification théorique insuffisante. De plus, des essais, en particulier à petite échelle, laissent apparaître des comportements qui, au-delà de ne pas être prédits par les modèles existant, viennent de surcroît invalider certaines de leurs hypothèses sous-jacentes. Le contexte des travaux est plus précisément celui de la décomposition anaérobie des solides, à petite échelle, pour des masses de l’ordre du milligramme, pour se concentrer à la fois sur la cinétique de perte de masse et, dans une moindre mesure, sur les transferts thermiques dans la phase condensée. Le travail est articulé autour de trois volets principaux qui forment chacun un chapitre du présent ouvrage. Le premier concerne la réalisation de nombreux essais à l’analyseur thermogravimétrique (ATG), sur la base de plans d’expérience. Le but est d’une part de déterminer les variables d’influence de la décomposition thermique et, d’autre part, d’identifier les écarts de comportement par rapport aux prédictions de certains modèles existant dans la littérature. Le résultat majeur de cette campagne est l’absence de convergence en masse des essais, même pour des masses expérimentales très faibles. De même, les effets de la vitesse de chauffage et de la dilution en phase solide ont été explorés, mettant ainsi en avant des comportements très éloignés des prédictions théoriques. Le second concerne la modélisation de la décomposition thermique d’un matériau soumis un essai à l’analyseur thermogravimétrique et la mise en évidence des problématiques liées aux transferts thermiques au sein du matériau. Il a été démontré que les conditions aux limites de Dirichlet, usuellement utilisées pour décrire ce dispositif, ne sont pas adaptées pour reproduire les spécificités liées au dispositif expérimental. Le troisième volet a consisté à construire un modèle cinétique issu d’hypothèses liées à la phase solide. Ce modèle est basé dans un premier temps sur les travaux d’Eyring concernant la théorie du complexe activé. Par la suite, l’exploitation du formalisme thermodynamique lié au complexe activé a permis de proposer une formulation nouvelle, dite « hors approximation d’Ellingham », pour décrire la décomposition des matériaux sous l’effet de la température. Ce modèle a été comparé à deux modèles usuels, dits (A, E, 1) et (A,E,n), et conduit à de meilleures modélisations pour les mécanismes mono-réactionnels. Enfin, les perspectives de ce travail concernent, en premier lieu, une meilleure caractérisation des conditions aux limites thermiques au sein d’un analyseur thermogravimétrique, afin de reproduire numériquement les essais réalisés. En second lieu, il apparaît comme pertinent d’étendre le modèle développé à des mécanismes multi-réactionnels, afin d’augmenter ses capacités prédictives pour les applications visées / The work presented in this thesis focuses on understanding, describing and finally modelling the degradation, under heat exposure, of commonly used furnishing materials (mainly natural or synthetic polymers). This is not a new research field, as many models exist nowadays (such as Arrhenius models associated with varied kinetics functions). However, unlike for development related to gas phase chemical kinetics, most current solid phase chemical kinetics related models suffer from insufficient theoretical backgrounds. Moreover, laboratory experiments, more precisely small scale ones, reveal some behaviours, that are not only unpredicted by current model, but also invalidate some of the underlying assumptions these models are based on. This work context is more precisely related to solid anaerobic decomposition, at small scale, for mass in the range of one milligram, in order to focus on both mass loss kinetics and, to a lesser extent, on thermal transfer in solid phase. This work was structured into three main sections, each of them being a chapter of this thesis. First part concerns numerous experiments based on experimental plans and performed with a thermogravimetric analyzer (TGA). This aims at, on the one hand, determining most influent variables on thermal decomposition, and, on the other hand, identifying behaviour discrepancies between experimental data and predictions of current models available in the literature. Test campaign main result is that there is no mass convergence with TGA, even for very low masses. In addition, the effect of both heating rate and solid phase dilution were explored. This led to some behaviours significantly different from theoretical predictions. Second part concerns the modelling of material thermal degradation in a TGA analysis. It also highlights problems related to heat transfer inside solid material. It is demonstrated in this work that Dirichlet boundary conditions, which are usually used to describe TGA device, are not adequate to reproduce such experimental specificities. Third and last part is dedicated to the elaboration of a kinetic model relying on assumptions specific to the solid phase. First and foremost this model is on based on Eyring’s work on transition state theory. Then exploring thermodynamic formalism related to transition state allowed the formulation of a new model of thermal degradation called “outside Ellingham assumption”. This model is compared to two commonly used ones, so-called (A, E, 1) and (A, E, n) and led to best prediction for single reaction mechanisms. Finally, the prospects inspired by this work concern, first, a better characterisation of thermal boundary condition in TGA, in order to be able to reproduce experiments by modelling. Secondly, it may be relevant to extend the develop model to multiple reaction mechanisms, in order to increase its predictive capabilities for the targeted applications

In this study thermal and mechanical properties and chemical structure of four differentpolymers (PE, PP, polyASA and PVC) were investigated to find out if the recycled polymershad the same properties and can be used in the same applications as the virgins or not.FT-IR was used for investigation of chemical structure. TGA, DSC and thermal stability wereused to compare the thermal properties. Tensile test also used to examine the mechanicalproperties.All the tests showed the recycling process is not done completely well. The differences inresults for virgins and recycled samples are the reasons which verified this claim.The results obtained from this study clarifying that the amount of stabilizer in the recycledpolymers were considerably less than the amount in virgins, means that the company had notadded enough stabilizer during the recycling process.

En vue de la réduction des problèmes engendrés par les phénomènes de retrait-gonflement des sols dans la dépression de la Lama au Sud du Bénin, nous avons entrepris des recherches dans le but de maîtriser le comportement de ces sols. Six échantillons de sols fins dont quatre argileux de cette région ont été prélevés. Différents essais ont été réalisés : une caractérisation macroscopique concernant les propriétés mécaniques et géotechniques et les essais microscopiques prenant en compte les analyses chimiques, thermiques, minéralogiques et microstructurales. Les sols étudiés sont constitués de différents minéraux argileux. Celle à structure fibreuse est à l'origine d’un comportement macroscopique particulier décelé par l’essai de gonflement libre. Les essais ont confirmé le fort potentiel de gonflement et de retrait de certains sols qui sont donc à l'origine des fortes dégradations rencontrées.Les résultats montrent que les sols traités se distinguent par les performances mécaniques acquises et peuvent être utilisés à différents niveaux de la chaussée selon leur teneur en liant.Les différentes méthodes utilisées ont révélé des facettes particulières de l'étude de traitement des sols fins. Principalement, nous avons noté que les informations apportées par les observations au Microscope Electronique à Balayage, les analyses thermiques et les analyses de Diffraction aux Rayons X ont permis de compléter l’analyse des résultats géotechniques. En somme, les méthodes de caractérisation géotechnique permettent d’avoir une idée générale du potentiel de gonflement, mais pour les études d’envergure, la réalisation d’études microscopiques est primordiale. / To help reduce the problems caused by phenomena due to the shrink-swell soil in the depression of the Lama in southern Benin, we have undertaken research in order to control the behavior of these soils. Six soil samples, including four clay from this area were taken. Different types of tests were performed: a macroscopic characterization concerning mainly mechanical and geotechnical properties and microscopic tests taking into account the chemical, thermal, microstructural and mineralogical analysis. The soils studied consist of different clay minerals. The fibrous structure is at the origin of a particular macroscopic behavior detected by the free swell test. The tests confirmed the potential for swelling and shrinking of some soils that are causing heavy damage.Three soils treated with different contents at Binder Hydraulic Road, were subjected to several tests. The results show that these soils are distinguished by the acquired mechanical performance and may be used at different levels of the floor according to binder content.Also, the different methods revealed specific facets of fine soil treatment study. Mainly, we noted that the information provided by the observations scanning electron microscope, thermal analysis and the analysis of diffraction X-Ray are very important and helped complete the analysis of geotechnical results for soil treatment. In sum, geotechnical characterization methods used to get a general idea of the swelling potential, but for large-scale studies, conducting microscopic studies is paramount.

Les nanotubes de carbone (NTCs) sont des charges particulièrement intéressantes car ils présentent des facteurs de forme (longueur/diamètre) très élevés. Cependant, le développement de ces applications à haute valeur ajoutée a été freiné par les problèmes de mise en oeuvre des NTCs (résultant de la difficulté de les disperser dans un milieu polymère) et par la formation d'agrégats de nanotubes en " fagots ", ne permettant pas l'obtention de mélanges homogènes. La solution réside dans la fonctionnalisation des nanotubes avec des chaînes polymères afin de réduire l'effet des interactions entre NTCs et d'assurer une meilleure comptabilisation avec le polymère hôte au cours du mélange. Ici, nous nous sommes intéressés à la fonctionnalisation des nanotubes de carbone par des polyoléfines en utilisant une procédure de greffage radicalaire de type " grafting onto ".

In this study, we were particularly interested in looking at the possibility that cross metathesis of olefins in melt phase could be used to produce polydimethylsiloxane (PDMS) modified polypropylene (PP). The intention of this project was also to study and quantify relationships among the main experimental factors in the reaction: temperature, catalyst concentration and molar ratio of PP to PDMS, through a 2-level factorial statistical design. In order to examine if PP-PDMS copolymers were synthesized in the melt phase, measurement of the chemical, physical and viscoelastic properties of the synthesized copolymers was necessary. Techniques including proton (¹H)-nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), rheometry and scanning electron microscopy (SEM), were all used to characterize the synthesized copolymers. ¹H NMR measurements confirmed the presence of PDMS in the copolymers. They also provided a quantitative measurement of PP to PDMS molar ratio in copolymers by determining the integration of PP PDMS repeating unit signals in NMR spectra. Compared to virgin PP, a lower melting enthalpy of the PP phase in the copolymer was observed from DSC results. This implied that the PDMS component influenced the thermal behavior of the PP crystalline phase in the copolymers. Moreover, TGA measurements indicated that a higher thermal stability was obtained for PP-PDMS copolymers than that for virgin PP wax and this was expected since PDMS is known for its excellent stability at high temperature. Rheological analysis showed that the presence of PDMS in the copolymers gave lower complex viscosities and loss moduli, but higher storage moduli than those for virgin PP. Furthermore, the morphology of copolymers was examined by SEM and elemental analysis at the surface using an energy dispersive X-ray (EDX) analyzer on the SEM. It was found that micrographs of copolymers showed round domains on the surface, which were not observed in virgin PP wax and those round segments were confirmed to contain silicon. Torque values used in a batch mixer for polymerizations and the remaining weight % of copolymers at 350°C were used to conduct statistical analysis, through which models used to describe the relationships between experimental factors and these physical responses were determined.

A new generation of compact and highly efficient power production and propulsion technologies are critically needed in enabling NASAs long-term goals. Nuclear fission power technologies as part of project Prometheus are in development to meet this need. Proposed reactor concepts utilize a combination of refractory metals and stainless steels. One such refractory alloy, Niobium 1% Zirconium (Nb-1Zr), will be used because of its strength at high temperatures, neutron absorption properties, and resistance to corrosion by liquid alkali metals. One potential problem in using Nb-1Zr is that it undergoes rapid high temperature oxidation, even in low oxygen concentrations. Long-term oxidation of the niobium matrix can significantly deteriorate the mechanical properties of the alloy. This thesis reports on experimental studies of the high temperature interaction of 316 stainless steel (316 SS) and Nb-1Zr under prototypic space fission reactor operating conditions. Specifically, how the high temperature oxidation rate of Nb-1Zr changes when in contact with 316 SS at low external oxygen concentrations. The objective of the project is to determine if transport of gaseous contaminants, such as oxygen, will occur when Nb-1Zr is in contact with 316 SS, thereby increasing the oxidation rate and degrading material properties. Experiments were preformed in a realistic non-nuclear environment at the appropriate operating conditions. Thermal Gravimetric Analysis techniques were used to quantify results. Coupons of Nb-1Zr and Nb-1Zr in contact with 316 SS foil are subjected to flowing argon with oxygen concentrations between 4-15ppm and heated to a temperature of 500, 750, and 1000oC for 2 to 10 hours. Experiments were conducted at the Early Flight Fission Test Facility at NASA Marshall Space Flight Center. The experimental results indicate that a complex oxidation process, which depends greatly on temperature and oxygen concentration, occurs at the expected operating conditions. Non-linear regression techniques were applied to experimental data in order to derive correlations for the approximate oxidation rate of Nb-1Zr and Nb-1Zr in contact with 316 SS as a function of time, temperature, and oxygen concentration.

The objective of this study is to investigate the influence of sulfur compounds (S and Na2S) for powdered activated carbon derived from carbon black of pyrolyzed waste tires (CPBAC). Besides, this study investigated the distribution of impregnated sulfur in the inner pores of activated carbon and its effected on the specific surface area and pore size distribution. This study investigated the fundamental mechanisms by analysis of thermodynamic properties and to establish the kinetic models for the adsorption/desorption of HgCl2 by/from sulfur impregnated CBPAC. Furthermore, this study investigated the adsorptive and desorption capacity of HgCl2 onto CPBAC via thermogravimetric analysis (TGA). Experimental results indicated that the specific surface area of sulfur impregnated CBPAC with elemental S (S0) was larger than sulfur impregnated CBPAC with Na2S. Besides, the sulfur content of sulfur impregnated CBPAC increased with increasing the surface area of CBPAC under the same impregnated temperature. And, the adsorptive capacity of CBPAC increased with the increase of influent HgCl2 concentration and surface area of the activated carbon. According to the experimental results of the adsorption capacity under the differential sulfur content, its indicated that the affection of sulfur content for adsorption capacity of HgCl2 was much than HgCl2 concentration and surface area of the activated carbon. The desorption energys were 266 and 282 kJ/mole for HgCl2 desorption from saturated CBPAC-S0 and CBPAC-Na2S, respectively. The results showed the process of HgCl2 adsorption onto CBPAC was in favor of a physisorbed state of HgCl2 at the adsorption temperature of 150 oC but the process of HgCl2 adsorption onto CBPAC which impregated was in favor of a chemisorbed state of HgCl2 at the adsorption of 150 oC. The value of ∆G for CBPAC at the adsorption temperature of 30 ~150 oC were ranged from -15.28 kJ/mole to -26.63 kJ/mole. The value of ∆G for CBPAC-S0 at the adsorption temperature of 30~150 oC ranged from -23.45 kJ/mole to -32.09 kJ/mole. The value of ∆G for CBPAC-Na2S at the adsorption temperature of 30~150 oC ranged from -22.84 kJ/mole to -32.72 kJ/mole. The results showed negative values of ∆G confirmed the feasibility of adsorption process and the spontaneous nature for the adsorption of HgCl2. The value of ∆H for CBPAC at the adsorption temperature of 30 ~150 oC ranged from -35.58 kJ/mole to -35.82 kJ/mole. The value of ∆H for CBPAC-S0 at the adsorption temperature of 30 ~150 oC ranged from -38.07 kJ/mole to -52.49 kJ/mole. The value of ∆H for CBPAC-Na2S at the adsorption temperature of 30~150 oC was -37.45 kJ/mole to -53.12 kJ/mole. A negative ∆H suggested that the adsorption of HgCl2 is an exothermic process. Besides, the adsorptive behavior of HgCl2 for two activated carbons (CBPAC-Na2S and CBPAC-S0) at high temperature (110 ¢J and 150 ¢J ) was the same chemical reaction mechanism due to the same ∆H. Besides, the results of model simulation indicated that modified adsorption kinetic model based on pore diffusion scheme developed in this study could successfully simulate the transport and adsorption of HgCl2 by considering the chemical reaction within the inner pores of carbon grains at 150 oC.

Allyl methacrylate, AMA was polymerized by chemical initiator and by &amp / #947 / -radiation under different conditions. The polymer obtained is mostly gel type with some soluble fractions at lower conversions. Arrhenius activation energy is 82.3 kJ/mol for chemical initiated polymerization. The polymer was characterized by FT-IR, NMR, DSC, TGA, XPS, XRD, DLS, and MS methods. It was found that about 98-99% of allyl side groups retained as pendant even after completion of the polymerization, while 1-2% may give crosslinking and/or cyclization that yields lactones and anhydrides. The spectroscopic and thermal results of the work showed that the reaction is not cyclopolymerization, but may have end group cyclization. Molecular weight of 1.1x106 was measured by DLS. Therefore, insolubility is due to the high molecular weight of polymer, even in the early stage of polymerization rather than crosslinking. The Tg of PAMA was observed as 94&ordm / C before curing, upon curing at 150-200&ordm / C, Tg increased to 211&ordm / C as measured by DSC. The thermal treatment of polymer at about 350&ordm / C gave anhydride by linkage type degradation, following side group cyclization. The XPS analysis showed the presence of radical fragments of AIBN and CCl4 associated with oligomers. The MS and TGA thermograms showed two or three stage degradations depending on solubility. The first stage was mostly linkage type degradation for the fragmentation of pendant allyl groups at 225-350&ordm / C. In the second stage, at 395-515&ordm / C, the degradation is random scission and depolymerization.

The total amount of plastic wastes produced by our society has been growing rapidly. The low biodegradability of these wastes creates a serious environmental problem that is directing the governments and environmental agencies to take serious measures to solve the problem of the plastic wastes. Landfilling or incineration of these wastes are not the right solutions, because the former has the danger of leaching and soil impregnation of its degradation products and the latter produce air pollution problems due to the possible emissions of toxic and acid gases. An alternative approach to the solution of problem caused by these wastes is the recycling of them by chemical recovery. In this method, the waste plastics are thermally non-catalytically or catalytically degraded into gases and oils. In this study, pure and aluminum containing ordered mesoporous materials MCM-type and SBA-type, were synthesized using different aluminum sources and aluminum loadings in order to be tested in catalytic degradation of polypropylene. These catalysts, except aluminum containing SBA-type catalysts, were synthesized by hydrothermal synthesis method. Aluminum containing SBA-type catalysts were synthesized by impregnation method. Tetraethyl orthosilicate was used as the Si source and aluminum nitrate, aluminum sulphate and aluminum isopropoxide were used as the Al source. It was observed that these materials had high surface areas and exhibited Type IV isotherms. In MCM-type materials, the aluminum incorporated more effectively into the structure at low concentrations but not effectively at high concentrations. On the other hand, in SBA-type catalysts, the aluminum incorporation into structure was very effective. 27Al MAS NMR spectra of the catalysts exhibited a mixture of tetrahedral and octahedral aluminum. TEM images showed well-ordered hexagonal arrays of mesopores. As an initial step, the activation energy value of polypropylene pyrolysis reaction in the presence of synthesized catalysts was determined by the help of a thermal analyzer and these TGA results showed a marked reduction in the degradation temperature. In the case of using aluminum containing MCM-type materials, the activation energy values decreased to about 68-126 kJ/mol. On the other hand, when aluminum containing SBA-type catalysts were used, the activation energy values decreased from 172 kJ/mol to a value in the range of 51 &ndash / 89 kJ/mol. Heavier molecules degraded into lighter hydrocarbons in the presence of catalysts and they gave high ethylene selectivity among the gaseous products. Additionally, butane selectivity increased with the use of catalysts. SBA-type catalysts showed higher selectivity to lighter hydrocarbons (&lt / C14). C7 selectivity among the liquid products was high when aluminum isopropoxide was used in the synthesis of catalysts and C18 selectivity increased significantly when aluminum nitrate was used in the synthesis of MCM-type catalysts.