O carbeto de boro é um material sintético com ligações químicas essencialmente covalentes, tem um alto ponto de fusão só é sinterizável em elevada temperatura. Possui excepcional dureza, baixa densidade, resistência a abrasão, elevada velocidade sônica e boas propriedades mecânicas, características ideais para as aplicações balísticas. Tem como principal característica a alta seção de choque para nêutrons térmicos para aplicações nucleares. O presente trabalho teve por objetivo avaliar as propriedades mecânicas do carbeto de boro, pela introdução de diferentes teores de diboreto de titânio, pela reação in situ com pós de carbeto de titânio, e adição do carbono durante a sinterização, em forno resistivo sem pressão e prensagem isostática a quente dos componentes cerâmicos. Em menores temperaturas valores obtidos da densidade teórica para o carbeto de boro puro, foram alcançados com o emprego do aditivo. Os resultados obtidos na sinterização mostram a eficiência da introdução do carbeto de titânio para o aumento da densificação do material. Com percentuais de 20% de carbeto de titânio, obteve-se os máximos valores para microdureza (HV) de 35 GPa e tenacidade a fratura (KlC) de 3,16 MPa.m1/2. Comprovadamente a dificuldade de sinterização em elevadas temperaturas, para maior densificação, de componentes cerâmicos de carbeto de boro pode ser minimizada com a introdução de percentuais de carbeto de titânio. / Boron Carbide is a synthetic material with essentially covalent chemical bonds with high fusion point. The main characteristics are: it is sintered at high temperature, high hardness, low density, abrasion resistant, high sonic velocity, good mechanical properties and high neutron absorption cross section (10BxC, x>4). Those features are ideal for ballistics applications. The aim of this study was to evaluate the changes in mechanical properties of Boron Carbide with different concentration of Titanium Diboride by reaction in situ with TiC powders. The addition of carbon during sintering without pressure and hot isostatic pressing of ceramic components was studied. At low temperatures, the nearly values for the theoretical density for pure Boron Carbide were obtained only with the use of additives. In sintering, the use of TiC increased Boron Carbide density. At concentrations up to 20% of TiC, the maximum values for hardness (HV) and fracture toughness (KlC) were obtained. With the introduction of different levels of additive, the difficulty of sintering at high temperatures was minimized and the density of ceramic components was maximized.

O carbeto de boro é um material sintético com ligações químicas essencialmente covalentes, tem um alto ponto de fusão só é sinterizável em elevada temperatura. Possui excepcional dureza, baixa densidade, resistência a abrasão, elevada velocidade sônica e boas propriedades mecânicas, características ideais para as aplicações balísticas. Tem como principal característica a alta seção de choque para nêutrons térmicos para aplicações nucleares. O presente trabalho teve por objetivo avaliar as propriedades mecânicas do carbeto de boro, pela introdução de diferentes teores de diboreto de titânio, pela reação in situ com pós de carbeto de titânio, e adição do carbono durante a sinterização, em forno resistivo sem pressão e prensagem isostática a quente dos componentes cerâmicos. Em menores temperaturas valores obtidos da densidade teórica para o carbeto de boro puro, foram alcançados com o emprego do aditivo. Os resultados obtidos na sinterização mostram a eficiência da introdução do carbeto de titânio para o aumento da densificação do material. Com percentuais de 20% de carbeto de titânio, obteve-se os máximos valores para microdureza (HV) de 35 GPa e tenacidade a fratura (KlC) de 3,16 MPa.m1/2. Comprovadamente a dificuldade de sinterização em elevadas temperaturas, para maior densificação, de componentes cerâmicos de carbeto de boro pode ser minimizada com a introdução de percentuais de carbeto de titânio. / Boron Carbide is a synthetic material with essentially covalent chemical bonds with high fusion point. The main characteristics are: it is sintered at high temperature, high hardness, low density, abrasion resistant, high sonic velocity, good mechanical properties and high neutron absorption cross section (10BxC, x>4). Those features are ideal for ballistics applications. The aim of this study was to evaluate the changes in mechanical properties of Boron Carbide with different concentration of Titanium Diboride by reaction in situ with TiC powders. The addition of carbon during sintering without pressure and hot isostatic pressing of ceramic components was studied. At low temperatures, the nearly values for the theoretical density for pure Boron Carbide were obtained only with the use of additives. In sintering, the use of TiC increased Boron Carbide density. At concentrations up to 20% of TiC, the maximum values for hardness (HV) and fracture toughness (KlC) were obtained. With the introduction of different levels of additive, the difficulty of sintering at high temperatures was minimized and the density of ceramic components was maximized.

Boron carbide is produced in a heat resistance furnace using boric oxide and petroleum coke as the raw materials. In this process, a large current is passed through the graphite rod located at the center of the cylindrical furnace, which is surrounded by the coke and boron oxide mixture. Heat generated due to resistance heating is responsible for the reaction of boron oxide with coke which results in the formation of boron carbide. The whole process is highly energy intensive and inefficient in terms of the production of boron carbide. Only 15% charge gets converted into boron carbide. The aim of the present work is to develop a mathematical model for this batch process and validate the model with experiments and to optimize the operating parameters to increase the productivity. To mathematically model the process and understand the influence of various operating parameters on the productivity, existing simple one-dimensional (1-D) mathematical model in radial direction is modified first. Two-dimensional (2-D) model can represent the process better; therefore in second stage of the project a 2-D mathematical model is also developed. For both, 1-D and 2-D models, coupled heat and mass balance equations are solved using finite volume technique. Both the models have been tested for time step and grid size independency. The kinetics of the reaction is represented using nucleation growth mechanism. Conduction, convection and radiation terms are considered in the formulation of heat transfer equation. Fraction of boron carbide formed and temperature profiles in the radial direction are obtained computationally. Experiments were conducted on a previously developed experimental setup consisting of heat resistance furnace, a power supply unit and electrode cooling device. The heating furnace is made of stainless steel body with high temperature ceramic wool insulation. In order to validate the mathematical model, experiments are performed in various conditions. Temperatures are measured at various locations in the furnace and samples are collected from the various locations (both in radial and angular directions) in the furnace for chemical analysis. Also, many experimental data are used from the previous work to validate the computed results. For temperatures measurement, pyrometer, C, B and K type thermocouple were used. It is observed that results obtained from both the models (1-D and 2-D) are in reasonable agreement with the experimental results. Once the models are validated with the experiments, sensitivity analysis of various parameters such as power supply, initial percentage of B4C in the charge, composition of the charge, and various modes of power supply, on the process is performed. It is found that linear power supply mode, presence of B4C in the initial mixture and increase in power supply give better productivity (fraction reacted). In order to have more confidence in the developed models, the parameters of one the computed results in the sensitivity analysis parameters are chosen (in present case, linear power supply is chosen) to perform the experiment. Results obtained from the experiment performed under the same simulated conditions as computed results are found in excellent match with each other.

Die Arbeit beschäftigt sich mit der Weiterentwicklung des verdämmten Druckversuches zur Bestimmung experimenteller Daten an verschiedenen Keramik- und Glassorten. Die untersuchten Materialien (Al2O3, TiB2, B4C, Floatglas, schweres Flintglas) lagen in Form von Fragmenten (Bruchstücken) vor und wurden aus realen Impaktexperimenten wiedergewonnen. Zusätzlich wurden thermisch vorgeschädigte Aluminiumoxidzylinder in die Betrachtungen einbezogen. Daten granulierter bzw. vorgeschädigter spröder Materialien sind von besonderem Interesse für Finite Element Rechnungen, um beispielsweise experimentell sehr aufwendige Beschußversuche rechnerisch zu simulieren.Als Untersuchungsmethode wurde der verdämmte Druckversuch verwendet und sowohl an quasistatische als auch an schlagdynamische Belastungsbedingungen angepaßt. Außerdem wurden die entwickelten Testaufbauten für sehr hohe hydrostatische Drücke optimiert. In den quasistatischen Experimenten konnten damit Drücke von 380 MPa bis 1960 MPa und in den dynamischen Versuchen von 495 MPa bis 2060 MPa erreicht werden. Im Ergebnis wurden mechanische Kennwerte der granulierten bzw. vorgeschädigten Materialien ermittelt (Restfestigkeit, Verdichtungsverhalten) und deren Schädigungsgrad vor und nach den Versuchen bestimmt (Rasterelektronenmikroskopie und Messung der spezifischen Oberfläche). Die vielversprechenden Resultate der verschiedenen Keramiken und Gläser wurden verglichen und die Materialien im Hinblick auf ihr Energieaufnahmevermögen unter schlagartiger Belastung bewertet.

This thesis gives a comprehensive characterization of lightweight non-oxide ceramic materials for ballistic applications, an overview of production technologies and processing of boron carbide B4C and its ceramic-based composites. A framework for evaluating the ballistic resistance of the material based on mechanical properties is shown there. It can be used in experiments without normalized equipment. The experiments including B4C + Si, B4C + Ti composites, and application of Spark plasma sintering (SPS) were designed according to outputs from the theoretical part. The volume fractions of Si, Ti dopants were optimized based on ongoing chemical reactions during sintering. The obtained samples were subjects of mechanical testing which results were compared to identify the ideal ratio of matrix and reinforcement. As the best suited material for ballistic protection, B4C + 1,0 obj. % reaches these values of parameters; hardness = 3502 ± 122 HV1; fracture toughness KIC = 2,97 ± 0,03 MPam^0,5.

The mechanical properties of boron carbide (B4C) with 10 and 20 vol% particulate inclusions of commercially available nano-sized alpha-phase silicon carbide (a-SiC) or micron-sized titanium diboride (TiB2) were investigated so as to produce a fine-grained material with high hardness, toughness, and overall strength in order to increase the effectiveness of B4C as a structural ceramic, whose use in the field has been limited because of the extreme brittle nature of the material. Full density sintering of the ceramics (≥99% theoretical) was completed using the novel Plasma Pressure Compaction (P²C®) technique, which limited grain growth due to a reduced processing temperature and a significantly reduced consolidation time. The reinforced ceramic composites had particulate grains homogeneously distributed within the B4C matrix. X-ray diffraction patterns confirmed that the constituents did not interdiffuse. The four-point flexure strength for the monolithic B4C ceramic was found to be significantly larger than any recorded value found in scientific literature, and was most likely attributed to the fine-grained microstructure resulting from the P²C® processing. The mechanical properties of the nano-sized a-SiC-B4C ceramics showed a slight increase in the Chevron-notched four-point bend fracture toughness due to the crack deflection toughening mechanism. A slight decrease in the Vickers microhardness and the static elastic modulus values were also observed. A significant increase in the fracture toughness as well as a slight increase in the microhardness and elastic modulus of the micron-sized TiB2-B4C materials was found. The toughening mechanism of this composite was attributed to the slight chemical bond between the B4C matrix and the ultra-small, ultra-tough TiB2 particulates, which forced a propagating crack to completely rip apart the TiB2 reinforcing particles. This cleaving nature resulted in significant amounts of energy being absorbed by the micron-sized particulates. It was concluded that the composite with 20 vol% TiB2 allowed for the largest gain in toughness because it possessed the largest number of ultra small, ultra tough particulate-cracktip interactions.

Die Arbeit beschäftigt sich mit der Weiterentwicklung des verdämmten Druckversuches zur Bestimmung experimenteller Daten an verschiedenen Keramik- und Glassorten. Die untersuchten Materialien (Al2O3, TiB2, B4C, Floatglas, schweres Flintglas) lagen in Form von Fragmenten (Bruchstücken) vor und wurden aus realen Impaktexperimenten wiedergewonnen. Zusätzlich wurden thermisch vorgeschädigte Aluminiumoxidzylinder in die Betrachtungen einbezogen. Daten granulierter bzw. vorgeschädigter spröder Materialien sind von besonderem Interesse für Finite Element Rechnungen, um beispielsweise experimentell sehr aufwendige Beschußversuche rechnerisch zu simulieren.Als Untersuchungsmethode wurde der verdämmte Druckversuch verwendet und sowohl an quasistatische als auch an schlagdynamische Belastungsbedingungen angepaßt. Außerdem wurden die entwickelten Testaufbauten für sehr hohe hydrostatische Drücke optimiert. In den quasistatischen Experimenten konnten damit Drücke von 380 MPa bis 1960 MPa und in den dynamischen Versuchen von 495 MPa bis 2060 MPa erreicht werden. Im Ergebnis wurden mechanische Kennwerte der granulierten bzw. vorgeschädigten Materialien ermittelt (Restfestigkeit, Verdichtungsverhalten) und deren Schädigungsgrad vor und nach den Versuchen bestimmt (Rasterelektronenmikroskopie und Messung der spezifischen Oberfläche). Die vielversprechenden Resultate der verschiedenen Keramiken und Gläser wurden verglichen und die Materialien im Hinblick auf ihr Energieaufnahmevermögen unter schlagartiger Belastung bewertet.

Les matrices céramiques autocicatrisantes sont constituées d’une alternance de couches de SiC, B-C et Si-B-C, déposées par voie gazeuse (CVD). Les couches borées (Si)-B-C sont amorphes après élaboration et leur structure évolue à haute température (T ≥ 1000 °C). Diverses caractérisations (XRD, spectroscopie Raman, NMR, diffusion des neutrons, XANES) ont permis de préciser la structure locale des céramiques brutes d'élaboration. Celle-ci a par la suite été validée par des simulations par dynamique moléculaire ab initio. Elle est constituée de motifs icosaédriques, similaires à ceux de B4C, mais fautés et reliés entre eux par des environnements tétravalents CB4-xCx et trivalents BC3. Dans le cas des matériaux Si-B-C, cette même phase amorphe forme un continuum incluant des clusters de SiC. L’évolution structurale de ces céramiques sous atmosphère inerte a été étudiée en fonction de la température (1100°C ≤ T ≤ 1400 °C) et du temps (t ≤ 1 h). Le caractère métastable des matériaux induit une cinétique de réorganisation rapide. L'évolution structurale se traduit successivement, à T et t croissants, par l’apparition de carbone libre sp2, la cristallisation de B4C, ainsi que la croissance de nanocristallites de SiC dans les matériaux Si-B-C. Les propriétés mécaniques ont également été caractérisées à haute température à l’aide d’essais sur microcomposites Cf/(Si)-B-Cm. Les matériaux font preuve d’un comportement transitoire complexe et fortement dépendant de la température du fait de leur évolution structurale. / Self-healing matrices are composed of SiC, B-C and Si-B-C multilayers deposited by chemical vapour deposition (CVD). The boron-rich layers (Si)-B-C are amorphous in their as-deposited state but crystallize at high temperature (T ≥ 1000 °C). Various analyses (XRD, Raman spectroscopy, NMR, neutron diffraction, XANES) were used to characterize the local structure of the as-processed and heat-treated ceramics. The local structure of heat-treated ceramics was also confirmed by molecular dynamic ab initio simulations. The structure consists of icosahedral units as in B4C but faulted and connected with each other through tetrahedral CB4-XCX and trigonal BC3 sites. In Si-B-C ceramics, the same amorphous phase forms a continuum embedding SiC clusters. The structural evolution of the ceramics in inert atmosphere were studied as a function of temperature (1100°C ≤ T ≤ 1400 °C) and time (t ≤ 1 h). The metastability of the materials leads to fast kinetics of reorganization. When T and t increase, one observes successively the formation free-sp2 carbon, the crystallization of B4C and, in Si-B-C ceramics, the coarsening of the SiC nanocrystallites. The high temperature mechanical properties have also been assessed by tensile tests on Cf/(Si)-B-Cm microcomposites. The materials undergo a complex transient behaviour which is strongly temperature dependent due to the structural changes.

Mon activité de recherche fondamentale dans le groupe de théorie du Laboratoire des Solides Irradiés concerne l'étude des propriétés des matériaux d'intérêt pour le CEA, dans les domaines du nucléaire ou de la nanoélectronique. Elle a pour objectif d'atteindre une description théorique -sans paramètre ajustable- des processus contrôlant l'excitation électronique, ainsi que la relaxation -ou désexcitation- électronique, et couvre: - Les propriétés de la matière hors excitation - l'état fondamental; - Les propriétés de l'état excité, abordées sous l'angle de la spectroscopie pour les électrons de valence; - Les vibrations collectives des atomes, leur couplage avec les électrons, et leurs effets sur le transport électronique ou la relaxation électronique. Ces études requièrent un environnement de calcul intensif et l'accès aux ordinateurs du Grand Equipement National de Calcul Intensif GENCI. Dans ce manuscrit, est d'abord rappelé comment calculer la fonction diélectrique inverse en théorie de la fonctionnelle de la densité dépendante du temps, et quel est le lien avec la fonction de perte électronique observée. Des résultats théoriques sur la fonction diélectrique inverse dans des oxydes non corrélés représentés par le dioxyde de titane TiO$_2$ et la zircone ZrO$_2$ sont décrits. Ensuite sont donnés les principaux résultats théoriques pour les calculs de spectres d'absorption optique pour l'oxyde de cuivre Cu$_2$O et la zircone ZrO$_2$. J'y présente une nouvelle interprétation de travail sur le noyau permettant de modéliser les effets excitoniques en théorie de la fonctionnelle de la densité dépendante du temps. Enfin, les derniers calculs menés sur les carbures de bore sont rappelés.