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Proust, Vanessa
Universite de Montpellier, Ecole doctorale Sciences Chimiques Balard, Institut Europeen des Membranes - IEM, unite de recherche UMR 5635, 300 Av. du Professeur Emile Jeanbrau, Montpellier (France); Direction Generale de l'Armement - DGA (France); Centre National de la Recherche Scientifique - CNRS (France)2016
Universite de Montpellier, Ecole doctorale Sciences Chimiques Balard, Institut Europeen des Membranes - IEM, unite de recherche UMR 5635, 300 Av. du Professeur Emile Jeanbrau, Montpellier (France); Direction Generale de l'Armement - DGA (France); Centre National de la Recherche Scientifique - CNRS (France)2016
AbstractAbstract
[en] In the present work, the Polymer Derived Ceramics (PDCs) route has been investigated to prepare silicon carbide (SiC), silicon carbonitride (SiCN) and silicon nitride (Si3N4) matrix (nano)composites in which transition metal-containing (nano)phases (Ti or Zr) are distributed. This approach has been applied to produce bulk materials. In the first chapter, we develop a literature review on the definition and the different types of nanocomposites, the different strategies to prepare them with a particular focus on the PDCs route and the targeted applications in the nuclear and concentrating solar system energy field. In a second chapter, the synthesis experimental protocols and the various methods to characterize the materials at each step of their preparation have been described. The third chapter focuses on the Si-C-Ti compositional system which displays potential to be used in the fuel cladding of the 4. generation of nuclear fission reactor. The precursors are prepared by mixing titanium (Ti)-based nanofillers and a hyperbranched polycarbosilane named ally-hydrido-polycarbosilanes (AHPCS) to be cast into a green compact then pyrolyzed to generate bulk (nano)composites which represent multiphase materials according to the composition of the nanofillers. In particular, the active behavior of Ti nanopowders into the AHPCS significantly limit the volume shrinkage of the polymer during its pyrolysis at 1000 deg. C under argon to form (nano)composites composed of titanium carbide, titanium silicide and silicon carbide phases. Their structure has been investigated in details and a preliminary study on helium implantation has been done on these materials. In the chapter IV, we considered the same system. Here, our objective was to focus on the chemistry of preceramic polymers to prepare single-source precursors called poly-titano-carbosilanes. We investigated their chemistry and structure by solid-state NMR as well as their pyrolysis behavior by thermogravimetric analyses up to 1000 deg. C under argon. Amorphous materials were generated at 1000 deg. C. Titanium carbide nanocrystals precipitated during a further heat-treatment up to 1600 deg. C in a silicon carbide matrix. Dense pieces were prepared by warm-pressing of poly-titano-carbosilanes followed by pyrolysis of the green compact. Helium implantation tests have been done and compared with the results gained in chapter 3. In the fifth chapter, we followed the same strategy, with a more fundamental aspect, for (nano)composites prepared in the Si-N-M-(C) (M=Ti, Zr). The effect of the poly-metallo-carbosilane formulation on the (nano)composite properties has been investigated by solid-state NMR analysis, thermogravimetric analysis and X-ray diffraction. The structural evolution of these materials has been investigated up to 1600 deg. C under ammonia and nitrogen atmosphere. The final materials represent nanocomposites of the type nc-TiN/a-Si3N4 with nc, nanocrystals and a being amorphous after a pyrolysis at 1400 deg. C. By increasing the temperature up to 1600 deg. C, the matrix crystallized. The effect of zirconium instead of titanium has been investigated. A preliminary study on the potential of these materials as solar absorber for concentrating solar power (CSP) is reported. (author)
[fr]
Dans le cadre de ce travail, une methode chimique, la voie 'polymere preceramique', a ete mise en oeuvre pour generer des (nano)composites ceramiques a matrice de carbure, carbonitrure et nitrure de silicium et contenant des (nano)cristaux a base de metaux de transition (Ti ou Zr). Ces materiaux ont ete prepares sous forme d'objets massifs. Cette these consiste tout d'abord en un premier chapitre de bibliographie decrivant les (nano)composites, la methode de preparation mise en oeuvre dans ce manuscrit ainsi que les materiaux vises et leur application, principalement dans le domaine de l'energie nucleaire et solaire a concentration. L'etude consiste dans un deuxieme chapitre a decrire les methodes de synthese mises en jeu dans notre etude ainsi que les differentes techniques de caracterisation mises en oeuvre pour caracteriser les precurseurs de depart, les materiaux au cours de leur elaboration et les materiaux finaux. Le chapitre III s'est interesse a l'elaboration des (nano)composites autour du systeme Si-C-Ti, pouvant notamment entrer dans la composition de gaines a combustible au sein des reacteurs nucleaires a fission de generation IV. Ces materiaux ont ete elabores a partir de melanges de nanopoudres a base de titane et d'un polycarbosilane hyperbranche, l'allylhydridopolycarbosilane (AHPCS). Les nanopoudres a base de titane jouent le role de charges passives/actives dans l'AHPCS pour s'opposer au retrait volumique que subit le polymere lorsque celui-ci est pyrolyse sous argon a 1000 deg. C. Des objets massifs sont elabores par moulage. Une etude detaillee du comportement a la pyrolyse des differentes formulations est faite et les materiaux finaux ont ete caracterises structuralement. Une etude preliminaire en implantation helium de ces materiaux est realisee. Dans le chapitre IV, nous nous sommes interesses au meme systeme en travaillant plus particulierement la chimie de polymeres preceramiques. L'objectif a ete de synthetiser des polymeres dit a 'source unique' (=polytitanocarbosilanes) qui, par des traitements thermiques appropries, conduisent a des (nano)composites dans lesquels des nanocristaux de carbure de titane (nc-TiC) sont disperses dans une phase amorphe ou cristallisee de carbure de silicium sans phases secondaires comme dans l'approche detaillee au chapitre III. Ces polymeres ont ete synthetises pour etre adaptes a la conception d'objets massifs par compactage a chaud puis traitement thermique des compacts polymeres. Les materiaux finaux ont alors ete caracterises par differentes techniques afin de selectionner les parametres operatoires, allant de la synthese des polymeres a leur conversion en ceramique, conduisant aux (nano)composites souhaites (e.g. matrice amorphe de carbure de silicium) avec les proprietes visees (e.g. comportement sous implantation helium). Dans un cinquieme chapitre, l'etude est plus fondamentale et vise a suivre la meme demarche de chimiste que le chapitre IV pour synthetiser des polymetallo(carbo)silazanes qui sont des precurseurs des systemes carbonitrures et nitrures de type Si-N-M-(C) (M = Ti, Zr). Une etude de l'effet de la nature du polymere sur les proprietes des (nano)composites est notamment entreprise par RMN du solide, analyse thermogravimetrique et diffraction des rayons X. Une etude preliminaire d'application de ces materiaux en energie solaire a concentration est proposee. (auteur)Original Title
Elaboration de nanocomposites ceramiques carbures/nitrures a partir de polymeres
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14 Jan 2016; 266 p; 383 refs.; Available from the INIS Liaison Officer for France, see the INIS website for current contact and E-mail addresses; These de Doctorat, Specialite: Chimie et physico-chimie des materiaux
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Miscellaneous
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Thesis/Dissertation
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CARBIDES, CARBON COMPOUNDS, CHEMICAL ANALYSIS, CHEMICAL REACTIONS, COHERENT SCATTERING, DECOMPOSITION, DIFFRACTION, ELEMENTS, FABRICATION, FLUIDS, GASES, GRAVIMETRIC ANALYSIS, HYDRIDES, HYDROGEN COMPOUNDS, MATERIALS, NANOMATERIALS, NITRIDES, NITROGEN COMPOUNDS, NONMETALS, ORGANIC COMPOUNDS, ORGANIC SILICON COMPOUNDS, PARTICLES, PNICTIDES, POWDERS, QUANTITATIVE CHEMICAL ANALYSIS, RARE GASES, SCATTERING, SILICON COMPOUNDS, THERMAL ANALYSIS, THERMOCHEMICAL PROCESSES, TITANIUM COMPOUNDS, TRANSITION ELEMENT COMPOUNDS
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