This dissertation work focuses on the processability improvement of B4C, especially the compaction and sintering improvement of B4C by applying a Ni-B nanolayer coating on individual B4C particles. A modified electroless coating procedure was proposed and employed to coat nanometer Ni-B layer onto micron-sized B4C particles. The thickness was able to be tuned and controlled below 100 nm. Key parameters, including the amount of nickel source, the amount of the surface activation agent (PdCl2), the amount of the complexing agent (C2H8N2), and the addition rate of the reducing agent (NaBH4) were studied. When the targeted thickness was 5 nm, a continuous and uniform nanolayer coating was obtained with the optimal condition of individual parameter combined. Reduction of the as-coated B4C powder in a H2-Ar atmosphere was studied between 400-900C to reduce the surface oxides' Ni2O3 and B2O3. Reduction at 800C in hydrogen atmosphere was found to be the most effective condition to remove oxygen in the coating layer, with Ni2B as the reduction product. Compaction of the as-received, separated and uncoated, and separated with Ni-B coating B4C powders using uniaxial die compaction and combustion driven compaction (CDC) techniques was studied. CDC technique showed the advantage over the traditional uniaxial die compaction by yielding much higher green density and green strength (73% vs. 53.8% green density for the Ni-B coated B4C). Among compacts obtained from the same technique, Ni-B coated B4C compact yielded the densest packing with crack-free compact surface and the highest strength, demonstrating more bonding between B4C particles provided by Ni-B surface coating. Sintering of the Ni-B coated B4C in an Ar atmosphere between 1150 - 1600C with soaking time of 2 hrs and 10 hrs was studied. Liquid phase was found to form during the sintering process. Density measurement showed that the liquid phase Ni-B formed greatly facilitated B4C densification. Considerable density increase and inter-granular connection was achieved when sintered at 1600C for 10 hrs. The density enhancement by Ni-B coating was supported by transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS) examination which showed that there was B4C species diffusion into liquid Ni-B phase. This liquid phase enhanced the diffusion of B4C species and formed strong bonding between B4C grains by dissolving small B4C particles and sharp edge and corners of B4C particles. Strength test demonstrated that the Ni-B coating dramatically improved the strength of B4C compacts by yielding a much higher strength of the Ni-B coated samples than the uncoated samples (13.97 vs. 1.79 MPa for the uinaxial die compacted samples, 27.03 vs. 2.21 MPa for the CDC samples). Electrical conductivity Ni-B coated B4C samples was also shown to be improved with the electrical resistivity being reduced from infinite for pure B4C samples to 1.8Ã 10-3 Ω·m for the Ni-B coated samples. This research work has shown that with the Ni-B coating, B4C densification can start at a temperature as low as 1600C via a liquid phase sintering process. / Ph. D.

This thesis is a theoretical study of configurational disorder in icosahedral boron-rich solids, in particular boron carbide, including also the development of a methodological framework for treating configurational disorder in such materials, namely superatom-special quasirandom structure (SA-SQS). In terms of its practical implementations, the SA-SQS method is demonstrated to be capable of efficiently modeling configurational disorder in icosahedral boron-rich solids, whiles the thermodynamic stability as well as the properties of the configurationally disordered icosahedral boron-rich solids, modeled from the SA-SQS method, can be directly investigated, using the density functional theory (DFT). In case of boron carbide, especially B4C and B13C2 compositions, the SA-SQS method is used for modeling configurational disorder, arising from a high concentration of low-energy B/C substitutional defects. The results, obtained from the DFT-based calculations, demonstrate that configurational disorder of B and C atoms in boron carbide is not only thermodynamically favored at high temperature, but it also plays an important role in altering the properties of boron carbide − for example, restoration of higher rhombohedral symmetry of B4C, a metal-to-nonmetal transition and a drastic increase in the elastic moduli of B13C2. The configurational disorder can also explain large discrepancies, regarding the proper- ties of boron carbide, between experiments and previous theoretical calculations, having been a long standing controversial issue in the field of icosahedral boron- rich solids, as the calculated properties of the disordered boron carbides are found to be in qualitatively good agreement with those, observed in experiments. In order to investigate the configurational evolution of B4C as a function of temperature, beyond the SA-SQS level, a brute-force cluster-expansion method in combination with Monte Carlo simulations is implemented. The results demonstrate that configurational disorder in B4C indeed essentially takes place within the icosahedra in a way that justifies the focus on lowenergy defect patterns of the superatom picture. The investigation of the thermodynamic stability of icosahedral carbon-rich boron carbides beyond the believed solubility limit of carbon (20 at.% C) demonstrates that, apart from B4C generally addressed in the literature, B2.5C represented by B10Cp2(CC) is predicted to be thermodynamically stable with respect to B4C as well as pure boron and carbon under high pressure, ranging between 40 and 67 GPa, and also at elevated temperature. B2.5C is expected to be metastable at ambient pressure, as indicated by its dynamical and mechanical stabilities at 0 GPa. A possible synthesis route of B2.5C and a fingerprint for its characterization from the simulations of x-ray powder diffraction pattern are suggested. Besides modeling configurational disorder in boron carbide, the SA-SQS method also opens up for theoretical studies of new alloys between different icosahedral boron-rich solids − for example, (B6O)1−x(B13C2)x and B12(As1−xPx)2. As for the pseudo-binary (B6O)1−x(B13C2)x alloy, it is predicted to display a miscibility gap resulting in B6O-rich and either ordered or disordered B13C2-rich domains for intermediate global compositions at all temperatures up to melting points of the materials. However, some intermixing of B6O and B13C2 to form solid solutions is also predicted at high temperature. A noticeable mutual solubility of icosahedral B12As2 and B12P2 in each other to form B12(As1−xPx)2 disordered alloy is predicted even at room temperature, and a complete closure of a pseudo-binary miscibility gap is achieved at around 900 K. Apart from B12(As1−xPx)2, the thermodynamic stability of other compounds and alloys in the ternary B-As-P system is also investigated. For the binary B-As system, zincblende BAs is found to be thermodynamically unstable with respect to icosahedral B12As2 and gray arsenic at 0 K and increasingly so at higher temperature, indicating that BAs may merely exist as a metastable phase. This is in contrast to the binary B-P system, in which zinc-blende BP and icosahedral B12P2 are both predicted to be stable. Owing to the instability of BAs with respect to B12As2 and gray arsenic, only a tiny amount of BAs is predicted to be able to dissolve in BP to form BAs1−xPx disordered alloy at elevated temperature. For example, less than 5% BAs can dissolve in BP at 1000 K. As for the binary As-P system, As1−xPx disordered alloys are predicted at elevated temperature − for example, a disordered solid solution of up to ∼75% As in black phosphorus as well as a small solubility of ∼1% P in gray arsenic at 750 K, together with the presence of miscibility gaps. The thermodynamic stability of three different compositions of α-rhombohedral boron-like boron subnitride, having been proposed so far in the literature, is investigated. Those are, B6N, B13N2, and B38N6, represented respectively by B12(N-N), B12(NBN), and [B12(N-N)]0.33[B12(NBN)]0.67. It is found that, out of these sub- nitrides, only B38N6 is thermodynamically stable from 0 GPa up to ∼7.5 GPa, depending on the temperature, and is thus concluded as a stable composition of α-rhombohedral boron-like boron subnitride.

De nombreuses études ont montré la faisabilité de la fabrication de pièces composites en carbure de bore et de silicium par l’infiltration de silicium fondu dans une préforme poreuse en carbure de bore (Reaction bonding). Cette méthode permet l’obtention d'un composite fortement chargé en carbure de bore (phase qui nous intéresse pour les applications balistiques), sans pour autant avoir besoin de monter à des températures de frittage de plus de 2200°C (température habituellement utilisée pour fritter le B4C). Dans notre cas la température maximale est comprise entre 1400-1600°C. Cette thèse s’intéresse plus particulièrement à l’adaptation du procédé de « reaction bonding » au chauffage sous champ micro-ondes. Les micro-ondes sont particulièrement intéressantes en ce qui concerne la rapidité du cycle thermique et le chauffage préférentiel de certaines phases (dans le cas des multi-matériaux). Pour ce faire, plusieurs verrous technologiques ont dû être levés (travail sous atmosphère et sous champs électromagnétiques, température élevée, …). Les composites obtenus sont comparés à leurs équivalents en chauffage conventionnel. Des différences microstructurales ont été observées au niveau du SiC formé lors de la réaction. Cette thèse nous a donc permis de :-trouver des conditions de fabrication de pièces en carbure de bore par chauffage micro-ondes (Argon/Hydrogéné10%, légère surpression : 1.4 bars)-montrer que les propriétés mécaniques (dureté, module d’Young,…) obtenues en four micro-ondes sont équivalentes à celles obtenus en four conventionnel (dureté : 14-20GPa) -montrer d’importante différences microstructurales du carbure de silicium formé, entre les échantillons obtenus sous vide (four conventionnel) et ceux obtenus sous atmosphère contrôlée (micro-ondes et four conventionnel).-montrer que le passage à des plus grandes tailles est possible, il est même plus simple d’infiltrer de grandes pièces que de petites à cause de l’effet de la masse sur la réponse du matériau aux champs électromagnétiques des micro-ondes.Ces résultats sont très prometteurs pour des applications balistiques : fabrication de gilets pare-balles et blindages légers. / Many studies have shown the feasibility of processing silicon-boron carbide composite by infiltration of molten silicon through a porous preform made of boron carbide (Reaction Bonding Process). Using this method, the obtained composite contains a large amount of boron carbide, which is the hardest and the most interesting phase for ballistic application. In our developed process, the maximum processing temperature is 1600°C, which is far below the usual high temperature stage/pressure conditions commonly used to sinter B4C by conventional method (respectively 2200°C and40MPa). The main goal of this thesis is to develop a novel reaction bonded process based on microwave heating. Microwaves heating has many interesting features, including fast heating process, selective heating mechanism (in case of heating multi-materials) and volumetric heating distribution. . To fulfill our goal, many technological issues need to be addressed (working in controlled atmosphere and under microwave field, high temperature ...). This thesis reports the development of this novel process, and materials made from it, exhibit similar properties compared to those made conventionally. However, some microstructural differences were observed in SiC resulting phases. This thesis has allowed to-find out the boron carbide composite piece fabrication conditions in microwave cavity (Argon/Hydrogen10%, slight overpressure: 14bars)-show that mechanical properties (hardness, Young’s modulus…) obtained are comparable to those measured on conventionally reaction bonded produced materials. -show that formed SiC has some microstructural peculiarities, between vacuum samples (for conventional) and ones obtained in hydrogenous argon (using microwave).-show that it is possible to produce larger size piece (66mm of diameter). These results are shown to be promising for ballistic applications, including the fabrication of bulletproof jacket and light armor

Formation of hexagonal boron nitride (h-BN) by carbothermic reduction of B2O3 under nitrogen atmosphere at 1500oC was investigated. Reaction products were subjected to powder X-ray diffraction analysis, chemical analysis and were examined by SEM. B4C was found to exist in the reaction products of the experiments in which h-BN formation was not complete. One of the aims of this study was to investigate the role of B4C in the carbothermic production of h-BN. For this purpose, conversion reaction of B4C into h-BN was studied. B4C used in these experiments was produced in the same conditions that h-BN was formed, but under argon atmosphere. It was found that formation of h-BN from B4C&ndash / B2O3 mixtures was slower than activated C&ndash / B2O3 mixtures. It was concluded that B4C is not a necessary intermediate product in the carbothermic production of h-BN. Some additives are known to catalytically affect the h-BN formation. The second aim of this study was to examine the catalytic effect of some alkaline earth metal oxides and carbonates, some transition metal oxides and cupric nitrate. It was found that addition of 10wt% CaCO3 into the B2O3+C mixture was optimum for increasing the rate and yield of h-BN formation and decreasing the B4C amount in the products and that the reaction was complete in 2 hours. CaCO3 was observed to be effective in increasing the rate and grain size of the formed h-BN. Addition of cupric nitrate together with CaCO3 provided a further increase in the size of the h-BN grains.

Boron carbide nano-powders, singly-doped over a range of compositions, were pressurelessly-sintered at identical temperature and atmospheric conditions in a dif- ferential dilatometer to investigate sintering behavior. Samples that achieved relative densities greater than 93% of theoretical density were post-HIPed. Post-HIPing re- sulted in an increase in relative density as well as an increase in Vicker's hardness. To optimize the sintering behavior, nano-powders with multiple dopants were prepared based on the results of single dopant experiments. These powders were studied using the same heating schedule as the single dopant samples. The powder with optimized composition was selected, and 44.45 mm diameter disks were pressed to determine the effects of sample size. Powder composition #166 with Al, Ti, W and Mg additions was processed using di¢çerent methods in order to create defect-free green bodies after uniaxial press- ing. The 44.45 mm diameter compacts were heat-treated to remove organics and B₂O₃coatings on particles and then encapsulated in an evacuated fused silica am- pule. Encapsulated samples were HIPed at temperatures below the coarsening region observed in the dilatometric traces of multiply-doped nano-powders. The E-HIPed sample showed a relative density of 96% with a limited extent of nano-sized grain microstructure.

Submitted by Aelson Maciera (aelsoncm@terra.com.br) on 2017-08-16T18:44:54Z No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) / Approved for entry into archive by Ronildo Prado (bco.producao.intelectual@gmail.com) on 2018-01-30T17:35:55Z (GMT) No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) / Approved for entry into archive by Ronildo Prado (bco.producao.intelectual@gmail.com) on 2018-01-30T17:36:40Z (GMT) No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) / Made available in DSpace on 2018-01-30T17:44:12Z (GMT). No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) Previous issue date: 2017-03-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Sintering additives (AS) have great potential to be applied in refractory castables as they reduce the densification temperature of these products. Additionally, these components may induce the generation of a transient liquid phase in the microstructure at high temperatures, which can react with the other materials of the composition to give rise novel solid refractory phases. Considering these aspects, the present work evaluated the role of five different AS (boron oxide, boric acid, sodium borosilicate, magnesium borate and boron carbide) when added to alumina-based castable compositions containing hydratable alumina as binder. Based on the thermomechanical characterization, XRD analysis and the in situ elastic modulus measurement, boron carbide (B4C) have been selected as a promising AS because this material sped up the sintering process at lower temperatures and induced the aluminum borates formation due to the reaction between the liquid phase and the fine alumina contained in the castable matrix. Afterwards, the effects of B4C was evaluated in ultra-low calcium oxide castables bonded with: colloidal alumina (AC), hydratable alumina (AB) and/ or SioxX®-Zero (SZ). SZ-bonded materials (4 wt.%) had good performance at temperatures around 1100°C due to the mullite generation. On the another hand, castables containing AC as binder (4 wt.% of solids) and 0.5 wt.% of B4C are promising options to be used in working conditions between 600-815°C, whereas the same mixture without B4C could only be densified above 1100°C. Similar effect was observed when 1.0 wt.% B4C was added to SZ-containing castables as the aluminum borates generation allows these compositions to be used in working conditions around 815°C. Therefore, an appropriate AS selection for high-alumina castables with ultra-low CAC content has the potential to favour the earlier sintering of the refractory and improve its thermomechanical properties, which can fulfill the requirements of the petrochemical industry. / Os aditivos sinterizantes (AS) possuem potencial para serem aplicados em concretos refratários, pois diminuem a temperatura de densificação destes produtos. Adicionalmente, tais componentes podem atuar favorecendo a formação de líquidos transientes na microestrutura em altas temperaturas, os quais têm a capacidade de reagir com os outros constituintes da composição para formar novas fases refratárias. Diante desta possibilidade, neste trabalho foram avaliados os efeitos da adição de cinco fontes de boro como AS (óxido de boro, ácido bórico, borosilicato de sódio, borato de magnésio e carbeto de boro) em concretos de alta alumina contendo alumina hidratável como ligante. Baseado na caracterização das propriedades termomecânicas destes refratários, assim como nas análises de DRX e da avaliação do módulo elástico in situ, foi selecionado o carbeto de boro (B4C) como o AS promissor, pois este promoveu o início da sinterização dos concretos em temperaturas inferiores e induziu a formação de boratos de alumínio a partir da reação do líquido com a alumina da matriz dos concretos refratários. Posteriormente, avaliou-se o efeito da adição do B4C em concretos com ultra-baixo teor de óxido de cálcio e ligados com: alumina coloidal (AC), alumina hidratável (AB) e/ou SioxX®-Zero (SZ). Materiais ligados com SZ (4%-p) são promissores em temperaturas próximas a 1100°C devido à formação de mulita. Por outro lado, concretos contendo AC (4%-p de sólidos) e 0,5%-p B4C são indicados para condições de serviço entre 600-815°C, pois sem a fonte de boro densificaram apenas acima de 1100°C. Efeito similar foi observado quando adicionado 1,0%-p B4C no concreto contendo SZ, visto que também foram formados boratos de alumínio possibilitando sua utilização em condições de serviço próximas aos 815°C. Desta forma, realizando-se a correta seleção do AS adicionado em concretos de alta alumina com ultra-baixo teor de CAC, tem o potencial de aumentar a sinterabilidade do material e melhorar suas propriedades termomecânicas, podendo assim atender os requisitos da indústria petroquímica.

The aim of this study was to understand the processing – structure – property relationships in spark plasma sintered (SPS) boron carbide (B4C) and B4C-titanium diboride (TiB2) ceramic composites. SPS allowed for consolidation of both B4C and B4C-TiB2 composites without sintering additives, residual phases, e.g., graphite, and excessive grain growth due to long sintering times. A selection of composite compositions in 20% TiB2 feedstock powder increments from 0% to 100%, was sintered at 1900°C for 25 minutes hold time. A homogeneous B4C-TiB2 composite microstructure was determined with excellent distribution of TiB2 phase, while achieving ~99.5% theoretical density. An optimum B4C-23 vol.% TiB2 composite composition with low density of ~3.0 g/cm3 was determined that exhibited ~30-35% increase in hardness, fracture toughness, and flexural bend strength compared to commercial armor-grade B4C. This is a result of a) no residual graphitic carbon in the composites, b) interfacial microcrack toughening due to thermal expansion coefficient differences placing the B4C matrix in compression and TiB2 phase in tension, and c) TiB2 phase aids in crack deflection thereby increasing the amount of intergranular fracture. Collectively, the addition of TiB2 serves as a strengthening and toughening agent, and SPS shows promise for the manufacture of hybrid ceramic composites.

Metal matrix composites (MMCs) are emerging as advanced engineering materials for application in aerospace, defence, automotive and consumer industries (sports goods etc.). In MMCs, a metallic base material is reinforced with ceramic fiber, whisker or particulate in order to achieve a combination of properties not attainable by either constituent individually. Aluminium or its alloy is favoured as metallic matrix material because of its low density, easy fabricability and good engineering properties. In general, the benefits of aluminium metal matrix composites (AMCs) over unreinforced aluminium alloy are increased specific stiffness, improved wear resistance and decreased coefficient of thermal expansion. The conventional reinforcement materials for AMCs are SiC and AI2O3. In the present work, boron carbide (B4C) particles of average size 40μm were chosen as reinforcement because of its higher hardness (very close to diamond) than the conventional reinforcement like SiC, AI2O3 etc. and of its density (2.52 g cm"3) very close to Al alloy matrix. In addition, due to high neutron capture cross-section of 10B isotope, composites containing B4C particle reinforcement have the potential for use in nuclear reactors as neutron shielding and control rod material. Al-5%Mg alloy was chosen as matrix alloy to utilize the beneficial role of Mg in improving wettability between B4C particles and the alloy melt. (Al-5%Mg)-B4C composites containing 10 and 20 vol% B4C particles were fabricated. For the purpose of inter-comparison, unreinforced Al-5%Mg alloy was also prepared and characterized. The Stir Cast technique, commonly utilized for preparation of Al-SiC, was adapted in this investigation.The Composites thus prepared was subsequently hot extruded with the objective of homogenization and healing minor casting defects. Finally the unreinforced alloy and its composites were characterized in terms of their microstructure, mechanical and thermo-physical properties, sliding wear behaviour and neutron absorption characteristics. The microstructures of the composites were evaluated by both optical microscope and scanning electron microscope (SEM). The micrographs revealed a relatively uniform distribution of B4C particles and good interfacial integrity between matrix and B4C particles. The hot hardness in the range of 25°C to 500°C and indentation creep data in the range of 300°C to 400°C show that hot hardness and creep resistance of Al-Mg alloy is enhanced by the presence of B4C particles. Measurement of coefficient of thermal expansion (CTE) of composites and unreinforced alloy upto 450°C showed that CTE values decrease with increase in volume fraction of reinforcement. Compression tests at strain rates, 0.1, 10 and 100 s-1 in the temperature range 25 - 450 °C showed that the flow stress values of composites were, in general, greater than those of unreinforced alloy at all strain rates. These tests also depicted that the compressive strength increases with increase in volume fraction of reinforcements. True stress values of composites and unreinforced alloy has been found to be a strong function of temperature and strain rate. The kinetic analysis of elevated temperature plasticity of composites revealed higher stress exponent values compared to unreinforced alloy. Similarly, apparent activation energy values for hot deformation of composites were found to be higher than that of self-diffusion in Al-Mg alloy. Tensile test data revealed that the modulus and 0.2% proof stress of composites increase with increase in volume fraction of the reinforcements. Composites containing 10%BUC showed higher ultimate tensile strength values (UTS) compared to unreinforced alloy. However, composites with 20%B4C showed lower UTS compared to that of the unreinforced alloy. This could be attributed to increased level of stress concentration and high level of plastic constraint imposed by the reinforcing jparticles or due to the presence solidification-induced defects (pores and B4C agglomerates ). Sliding wear characteristics were evaluated at a speed of 1 m/s and at loads ranging from 0.5 to 3.5kg using a pin-on-disc set up. Results show that wear resistance of Al-5%Mg increases with the addition of B4C particles. Significant improvement in wear resistance of Al-5%Mg is achieved with the addition of 20% B4C particles. SEM examination of worn surfaces showed no pull-out of reinforcing particles even at the highest load of 3.5 kg, thus confirming good interfacial bonding between dispersed B4C particles and Al alloy matrix. The neutron radiography data proved that (Al-5%Mg)-B4C composites possess good neutron absorbing characteristics. From the experimental data evaluated in the "study, it may be concluded that (Al-5%Mg)-B4C composites could be a candidate material for neutron shielding and control rod application. The enhanced elevated temperature-strength and favourable neutron absorption characteristics of these composites are strong points in favour of this material.

Le carbure de bore B4C est envisagé en tant qu'absorbeur de neutrons dans les réacteurs nucléaires à neutrons rapides et à caloporteur sodium, RNR-Na, de génération IV. Cette filière de réacteur constitue aujourd'hui la référence pour l'avenir du nucléaire en France. Ainsi, un premier concept de réacteur RNR-Na, nommé ASTRID, devrait être construit aux alentours de 2025. L'objectif de notre étude est de comprendre, d'un point du vue fondamental, les effets induits par les irradiations aux ions, sur la structure cristallographique de B4C, dans différents domaines de pouvoirs d'arrêt. Pour cela, des échantillons de B4C, frittés par Spark Plasma Sintering (SPS) au SPCTS de Limoges, ont été irradiés par des ions de différentes natures et de différentes énergies, nous permettant de favoriser: (i) le pouvoir d'arrêt nucléaire Sn, afin d'induire un endommagement dit balistique dans le matériau, ou (ii) le pouvoir d'arrêt électronique Se, pour induire un endommagement dit électronique. Les irradiations en régime balistique ont été réalisées à l'aide d'ions C+, Ar+ et Au+ à des énergies inférieures au MeV, sur le VdG 4 MV de l'IPNL et auprès de la plateforme JANNuSOrsay. Les modifications structurales de B4C dans des gammes d'endommagement compris entre 0 et 9 dpa ont ainsi pu être étudiées. Les irradiations en régime électronique ont été effectuées par des ions S9+ et I9+ de 60 et 100 MeV sur l'accélérateur Tandem de l'IPNO. L'impact des excitations électroniques sur B4C à des pouvoirs d'arrêt électronique compris entre 4 et 15 keV.nm-1 a été déterminé. Afin d'étudier également les effets couplés de l'irradiation et de la température, toutes les irradiations ont été réalisées à température ambiante (RT), à 500°C et à 800 °C. Les caractérisations microstructurales des échantillons irradiés ont été effectuées principalement par microspectrométrie Raman au CEA Saclay et par Microscopie Electronique en Transmission (MET) in situ à JANNuS-Orsay. Nos études ont permis de mettre en évidence un seuil d'amorphisation du B4C dans les deux régimes d'endommagement à RT. En régime balistique, l'amorphisation du matériau est atteinte pour un taux de 9 dpa environ. En régime électronique, un pouvoir d'arrêt de 9 keV.nm-1 a permis de mettre en évidence une amorphisation du matériau induite par la formation de traces latentes nanométriques amorphes, et leur recouvrement à hautes fluences. De plus, nous avons également montré que la température permettait de limiter l'endommagement dès 500°C dans B4C, voire de l'inhiber presque totalement à 800°C / Boron carbide B4C is a material considered as neutron absorber for the Sodium Fast reactors SFR of the fourth generation. This type of reactor is the reference for the future of the nuclear technology in France. A first prototype of SFR, called ASTRID, should be built around 2025. The aim of this study is to understand, from a fundamental point of view, the effects induced by ion irradiation on the crystallographic structure of B4C, in different energy ranges. So, boron carbide samples were sintered by Spark Plasma Sintering (SPS) technique at the SPCTS laboratory in Limoges (France) and then irradiated with ions of different natures and energies, favoring: (i) the nuclear stopping power, creating ballistic damage in the material, or (ii) the electronic stopping power, creating mainly electronic damage. For the irradiations in the ballistic regime, we used C+, Ar+ and Au+ ions with energies below 1 MeV, on the accelerator VdG 4 MV of the IPNL and on the JANNuS-Orsay plateform. The structural modifications of B4C were studied between 0 and 9 dpa. The irradiations in electronic regime were performed with S9+ and I9+ ions with energies of 60 and 100MeV, at the 15 MV Tandem accelerator of the IPNO. The electronic excitations values corresponding to those conditions are ranging between 4 and 15 keV.nm-1. The irradiations were carried out at room temperature, 500°C and 800°C to study the coupled effects of temperature and irradiation. The structural characterizations of the samples after irradiation were performed by Raman spectrometry at CEA Saclay and by in situ Transmission Electron Microscopy at the JANNuS-Orsay facility. Our study demonstrated the existence of an amorphisation threshold in boron carbide in both irradiation regimes at room temperature. In the ballistic regime, the amorphisation of the material is reached around a value of 9 dpa. In the electronic regime, from a stopping power in between 9 and 10 keV.nm-1 an amorphisation process, induced by the formation of latent tracks and their overlapping at high fluences was observed. Moreover, at 500°C, we showed that the temperature slowed down the damage induced by the irradiation in B4C, and almost totally prevented it at 800°C

The popularity of graphene owing to its unique properties has triggered huge interest in other two-dimensional (2D) nanomaterials. Among them, silicene shows considerable promise for electronic devices due to the expected compatibility with silicon electronics. However, the high-end potential application of silicene in electronic devices is limited owing to the lack of an energy band gap. Hence, the principal objective of this research is to tune the electronic and magnetic properties of silicene related nanomaterials through first-principles models. I first explored the impact of edge functionalization and doping on the stabilities, electronic, and magnetic properties of silicene nanoribbons (SiNRs) and revealed that the modified structures indicate remarkable spin gapless semiconductor and half-metal behaviors. In order to open and tune a band gap in silicene, SiNRs were perforated with periodic nanoholes. It was found that the band gap varies based on the nanoribbon’s width, nanohole’s repeat periodicity, and nanohole’s position due to the quantum confinement effect. To continue to take advantage of quantum confinement, I also studied the electronic and magnetic properties of hydrogenated silicene nanoflakes (SiNFs). It was discovered that half-hydrogenated SiNFs produce a large spin moment that is directly proportional to the square of the flake’s size. Next, I studied the adsorption behavior of various gas molecules on SiNRs. Based on my results, the SiNR could serve as a highly sensitive gas sensor for CO and NH3 detection and a disposable gas sensor for NO, NO2, and SO2. I also considered adsorption behavior of toxic gas molecules on boron carbide (BC3) and found that unlike graphene, BC3 has good sensitivity to the gas molecules due to the presence of active B atoms. My findings divulged the promising potential of BC3 as a highly sensitive molecular sensor for NO and NH3 detection and a catalyst for NO2 dissociation. Finally, I scrutinized the interactions of CO2 with lithium-functionalized germanene. It was discovered that although a single CO2 molecule was weakly physisorbed on pristine germanene, a significant improvement on its adsorption energy was found by utilizing Li-functionalized germanene as the adsorbent. My results suggest that Li-functionalized germanene shows promise for CO2 capture.