Boron carbide (B₄C) is a non-oxide ceramic in the same class of nonmetallic hard materials as silicon carbide and diamond. The high hardness, high elastic modulus and low density of B₄C make it a nearly ideal material for personnel and vehicular armor. B₄C plates formed via hot-pressing are currently issued to U.S. soldiers and have exhibited excellent performance; however, hot-pressed articles contain inherent processing defects and are limited to simple geometries such as low-curvature plates. Recent advances in the pressureless sintering of B₄C have produced theoretically-dense and complex-shape articles that also exhibit superior ballistic performance. However, the cost of this material is currently high due to the powder shape, size, and size distribution that are required, which limits the economic feasibility of producing such a product. Additionally, the low fracture toughness of pure boron carbide may have resulted in historically lower transition velocities (the projectile velocity range at which armor begins to fail) than competing silicon carbide ceramics in high-velocity long-rod tungsten penetrator tests. Lower fracture toughness also limits multi-hit protection capability. Consequently, these requirements motivated research into methods for improving the densification and fracture toughness of inexpensive boron carbide composites that could result in the development of a superior armor material that would also be cost-competitive with other high-performance ceramics. The primary objective of this research was to study the effect of titanium and carbon additives on the sintering and mechanical properties of inexpensive B₄C powders. The boron carbide powder examined in this study was a submicron (0.6 μm median particle size) boron carbide powder produced by H.C. Starck GmbH via a jet milling process. A carbon source in the form ofphenolic resin, and titanium additives in the form of 32 nm and 0.9 μm TiO₂ powders were selected. Parametric studies of sintering behavior were performed via high-temperature dilatometry in order to measure the in-situ sample contraction and thereby measure the influence of the additives and their amounts on the overall densification rate. Additionally, broad composition and sintering/post-HIPing studies followed by characterization and mechanical testing elucidated the effects of these additives on sample densification, microstructure development, and mechanical properties such as Vickers hardness and microindentation fracture toughness. Based upon this research, a process has been developed for the sintering of boron carbide that yielded end products with high relative densities (i.e., 100%, or theoretical density), microstructures with a fine (∼2-3 μm) grain size, and high Vickers microindentation hardness values. In addition to possessing these improved physical properties, the costs of producing this material were substantially lower (by a factor of 5 or more) than recently patented work on the pressureless sintering and post-HIPing of phase-pure boron carbide powder. This recently patented work developed out of our laboratory utilized an optimized powder distribution and yielded samples with high relative densities and high hardness values. The current work employed the use of titanium and carbon additives in specific ratios to activate the sintering of boron carbide powder possessing an approximately mono-modal particle size distribution. Upon heating to high temperatures, these additives produced fine-scale TiO ₂ and graphite inclusions that served to hinder grain growth and substantially improve overall sintered and post-HIPed densities when added in sufficient concentrations. The fine boron carbide grain size manifested as a result of these second phase inclusions caused a substantial increase in hardness; the highest hardness specimen yielded a hardness value (2884.5 kg/mm²) approaching that of phase-pure and theoretically-dense boron carbide (2939 kg/mm²). Additionally, the same high-hardness composition exhibited a noticeably higher fracture toughness (3.04 MPa•m¹/²) compared to phase-pure boron carbide (2.42 MPa• m¹/²), representing a 25.6% improvement. A potential consequence of this study would be the development of a superior armor material that is sufficiently affordable, allowing it to be incorporated into the general soldier’s armor chassis.

Le développement de céramiques légères à hautes performances mécaniques et à bas coût à base de silico-alumineux, suscite un intérêt grandissant dans divers domaines d’application tels que la protection balistique. Dans ce contexte, l’objectif de ce travail a été de développer un matériau innovant susceptible de rivaliser avec les protections balistiques en alumine ou en carbure. Plusieurs voies ont été explorées. Une étude approfondie des compositions de silico-alumineux a permis d’obtenir des matériaux présentant un meilleur compromis masse volumique / module d’Young, et dont le principal avantage est d’utiliser des procédés d’élaboration conventionnels (pressage, coulage sous pression) ainsi que les fours dédiés à la cuisson de la porcelaine par frittage naturel. Afin de renforcer la dureté de surface, des dépôts de carbures ont été réalisés à l’aide d’un protocole qui a permis une bonne accroche du carbure sur le substrat tout en conservant un traitement thermique conventionnel de consolidation. Enfin, des architectures lamellaires ont également été élaborées afin de maximiser les phénomènes de dissipation d’énergie. En bénéficiant d’un différentiel d’expansion thermique entre deux compositions de silico-alumineux, l’apparition de contraintes thermiques résiduelles au refroidissement de l’étape de frittage a permis d’augmenter la valeur de contrainte à la rupture des matériaux à architectures lamellaires de plus de 60%. / The development of lightweight alumino-silicate based ceramics exhibiting high mechanical performances and low cost, shows a growing interest in various application areas such as ballistic protection. In this context, the aims of this study is the development of innovative materials corresponding to competitive ballistic protection comparing to carbide or alumina materials. Several ways were explored. A thorough study of alumino-silicate compositions has allowed to obtain materials with a best compromise density / Young's modulus, the main advantage is the ability to use conventional methods of preparation (pressing, die-casting) and conventional kilns used for the firing of porcelain. To improve the surface hardness, carbide coatings were performed. The original protocol developed leads to carbide coating with good adhesion on the substrate using a traditional thermal treatment method. Finally, lamellar architectures of materials were developed to increase the energy dissipation of failure. Thanks to a differential thermal expansion between the two compositions of alumino-silicates, the occurrence of residual thermal stresses in lamellar materials has increased the average stress of failure values of more than 60%.