Dans le domaine des matériaux de structure destinés à des applications thermomécaniques sous conditions extrêmes, les carbures métalliques et, plus particulièrement, ceux de la famille de métaux de transition (i.e. titane, zirconium, hafnium) sont de bons candidats étant donné la nature à la fois métallique et covalente de leurs liaisons. De plus, parmi les céramiques non-oxydes, le carbure de silicium est le plus employé dans la réalisation de composites particulaires du fait de son bon comportement à l’oxydation à haute température. Les composites de type SiC/ZrC seraient de bons candidats pour des applications à haute température dans des atmosphères oxydantes car ils sont susceptibles de développer des propriétés thermostructurales intéressantes. Cependant, l’élaboration de composites particulaires, avec un bon contrôle de la distribution respective des deux phases carbures au sein de la microstructure, n’est pas parfaitement maîtrisée. En particulier, l’amélioration ou l’optimisation des performances thermomécaniques de ces céramiques avancées, exige le contrôle de leur composition chimique à l’échelle atomique et de leur nanostructuration. L’approche « Precursor Derived Ceramics » (PDCs) permet notamment de moduler la composition du matériau à l’échelle moléculaire et d’obtenir des matériaux de formes diverses et complexes (nanomatériaux, fibres, dépôts, composites). Cette méthode, appliquée au système Si/C/Zr, est basée sur la synthèse de polymères précéramiques par chimie click et hydrosilylation. Des poudres ultrafines obtenues après le traitement thermique par spray pyrolyse laser des précurseurs pourront suivre des étapes ultimes de mise en forme, de consolidation et de densification. / In the field of structural materials for thermomechanical applications under extreme conditions, metal carbides, and more specifically, those of the transition metal family (i.e. titanium, zirconium, hafnium) are good candidates thanks to the nature of the both metallic and covalent bonds. Further, among the non-oxide ceramics, silicon carbide is the most used in the elaboration of particulate composites because of its good oxidation behavior at high temperature. SiC/ZrC composites would be good candidates for high temperature applications in oxidizing atmospheres thanks to their ability to develop interesting thermostructural properties. However, the development of particulate composites, with good control of the respective distribution of the two carbides phases in the microstructure is not well controlled. Particularly, improving or optimizing the thermomechanical performances of these advanced ceramics, requires to control the chemical composition at the atomic scale and their nanostructuration. The "Precursor Derived Ceramics" approach (PDCs) notably allows to modulate the composition of the material at the molecular level and to obtain materials of various and complex shapes (nanomaterials, fibers, deposits, composites). This method, applied to the Si/C/Zr system is based on the synthesis ofpreceramic polymers by click chemistry and hydrosilylation. Ultrafine powders obtained after laser spray pyrolysis heat treatment could be shaped, consolidated and densified.

Cette étude est orientée sur les céramiques réfractaires des métaux de transition, comme le carbure de titane et de zirconium, envisagées pour leurs caractéristiques de résistance en conditions extrêmes. Ces céramiques seraient soumises à différentes sources d'irradiation (les neutrons, les produits de fission, les désintégrations alpha) dans les futurs réacteurs de génération IV. Les rayonnements rencontrés en réacteur peuvent être simulés par des irradiations externes à l'aide d'accélérateurs de particules, en utilisant des ions variés dans une large gamme d'énergie. Ces instruments permettent de reproduire en conditions contrôlées l'endommagement subi par des les matériaux internes aux centrales nucléaires.Dans un tel contexte radiatif, deux processus majeurs gouvernent l'endommagement des matériaux: les collisions nucléaires induites par les irradiations avec des ions de faible énergie (comme les noyaux de recul) et les excitations électroniques intervenant dans les irradiations avec des ions de grande énergie (comme les produits de fission). La prédominance de l'un ou de l'autre de ces processus est reliée à la masse et à l'énergie de la particule accélérée. Pour comprendre la contribution de chaque effet dans les mécanismes d'endommagement des structures cristallines soumises à des irradiations, nous avons simulé des rayonnements impliquant, d'une part, des ions de basse énergie, i.e. de quelques MeV et, d'autre part, des ions de grande énergie, i.e. de quelques centaines de MeV. Les principaux objectifs de ce travail ont été: (i) d'étudier le comportement de ces deux carbures sous irradiation, (ii) de déterminer les modifications structurales, chimiques et mécaniques induites par les effets nucléaires et électroniques, (iii) de comprendre les mécanismes d'endommagement dans ces carbures dans le régime nucléaire et (iv) d'essayer d'expliquer les résultats expérimentaux par les calculs obtenus en simulation.Pour cela, différentes techniques de caractérisation ont été combinées afin d'expliquer le scénario de ces carbures sous irradiation avec comme référence, le carbure de silicium SiC très étudié par le passé. Ces techniques complémentaires sont: la spectrométrie de rétrodiffusion de Rutherford en mode canalisé (RBS-C), la diffraction des rayons X (DRX), la spectroscopie Raman, la microscopie électronique en transmission (MET) et la nanoindentation. La combinaison de ces techniques expérimentales ainsi que la simulation a permis de conforter nos résultats et les différentes hypothèses formulées. Nous avons pu établir ainsi un scénario pour ces deux types de carbures TiC et ZrC sous irradiation aux ions. / This study is focused on the ceramic refractory transition metals, such as titanium carbide and zirconium envisaged to their strength characteristics under extreme conditions. These ceramics are subject to various sources of radiation (neutrons, fission products, the alpha decays) in future generation reactors IV. Radiation encountered in the reactor can be simulated by external irradiation with particle accelerators, using various ions in a wide energy range. These instruments can reproduce in controlled conditions damage suffered by nuclear materials.In such radiative context, two major processes govern damages into the materials: nuclear collisions induced by irradiation with low energy ions (like the recoil nuclei) and electronic excitations involved in irradiation with high-energy ions (such as fission products). The predominance of one of these processes is connected to the mass and energy of the accelerated particle. To understand the contribution of each effect in the damage mechanisms of crystal structures subjected to irradiation, we simulated radiation involving, on the one hand, low energy ions, i.e. a few MeV and, secondly, high energy ions, i.e. a few hundred MeV. The main objectives of this work were: (i) to study the behavior of these two carbides under irradiation, (ii) determine the structural, chemical and mechanical changes induced by nuclear and electronic effects, (iii) understand the damage mechanisms in these carbides in the nuclear regime and (iv) to try to explain the experimental results obtained by simulation calculations.For this, various characterization techniques were combined to explain the scenario of these carbides under irradiation as a reference, the silicon carbide SiC extensively studied in the past. These additional techniques are: Rutherford Backscattering Spectrometry in channeling mode (RBS-C), the X-ray diffraction (XRD), Raman spectroscopy, Transmission Electron Microscopy (TEM) and nanoindentation. The combination of these experimental techniques and simulation helped to consolidate our results and various assumptions. We were able to establish a scenario for these two types of carbides TiC and ZrC under ion irradiation.

In this thesis,zirconium carbide (ZrC) layers were deposited on graphite substrates using a CVD reactor at temperatures ranging from 1250 °C to 1450 °C in steps of 50 °C. The deposited layers were characterised by XRD, Raman Spectroscopy and SEM.ZrCsamples were also prepared by spark plasma sintering (SPS), at 1700, 1900 and 2100 °C at 50 MPa for 10 minutes. The phase and microstructure after the sintering process were investigated by XRD and SEM. Iridium (Ir) thin films were deposited on these ZrCsamples and annealed in vacuum at temperatures of 600 and 800 °C for 2h. The phase composition, solid-state reactions and surface morphology were investigated by GIXRD and SEM. XRD was used to identify the phases present in the as-deposited and annealed samples. It showed that Ir2Zr was the initial phase formed at 600 °C. At temperature 800 °C IrZr formed. / Thesis (PhD (Physics))--University of Pretoria, 2019. / University of Pretoria / Physics / PhD (Physics) / Unrestricted

Transition metal carbides have great industrial importance with a wide area of applications. Unlike many ceramic materials which can be produced from raw materials found in nature, the refractory carbides generally do not exist in the natural state. Synthesis of these carbides is costly and exacting. Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. Understanding how the experimental conditions affect the microstructure and properties in reactive sputtering deposition process is still an area of intense research activity. Reactively sputtered zirconium carbide thin films were grown on (100) silicon substrate and the influence of substrate temperature on the properties of the films were investigated. The substrate temperature was varied from ambient to 500°C and partial pressures of the sputter gas and reactive gas (argon and methane) were optimised to obtain crystalline films. Structural characteristics showed that the films exhibit nanocomposite structure consisting of ZrC nanocrystallites embedded in amorphous carbon typically at lower growth temperature (TS < 300°C), and at higher growth temperatures film were highly textured. In addition, Films deposited at 325 °C showed a distinct increase in FWHM which had considerable effect on the mechanical properties of the film. Maximum hardness of 24.8 GPa was seen at 325ºC. The changes in atomic bonding structures, their relative fractions with respect to substrate temperature were discussed. We also report superhard nanocrystalline nanocomposite NbC thin film deposited on Si (100) under 500˚C growth temperature via reactive magnetron sputtering. The pronounced nano hardness and modulus value of 42 GPa and 267 GPa at 40/60 C/Nb ratio were found to be strongly dependent on the grain size and higher percentage of carbide content. HRTEM studies further confirm the formation of nanocomposite structure with nanocrystalline grains embedded in amorphous matrix. The influence of vapour incidence angle (α= 0˚ to 75˚) on optimized ZrC and NbC thin films were investigated by depositing films in Oblique angle deposition geometry (OAD). The anisotropic growth rate of crystallographic planes and the mechanism of development of micro structural features in OAD of carbide films have been investigated. XRD and pole figure measurements indicated that the films grown at higher growth temperatures (800°C) exhibited higher degree of preferred orientation coupled with larger crystallite size whereas the films deposited at room temperature displayed random polycrystalline nature. The strong increase in porosity with increase in deposition angle with distinctly separated nanometer sized columns resulted in lowering of hardness and reduced modulus value. The film with zero incidence angle exhibited a maximum hardness and reduced modulus of 28 GPa and 223 GPa respectively. On the other hand, NbC films deposited with OAD, remained to be polycrystalline in nature with less intense peaks and also exhibited loss of preferential orientation indicating lower crystal quality with increase in vapor deposition angle. It is apparent that variation in crystallographic texture coupled with sculptured nanostructures are solely material dependent properties. Nano metric modulated ZrC/NbC superlattice multilayer structure performance has been evaluated for structural stability and hardness enhancement. Multilayers present superlattice effect in XRD patterns, which are attributed to the precise periodical stacking of crystalline monolayers also confirmed by cross section FESEM. X-ray photoelectron spectroscopy depth profile analysis was performed to get information on chemical composition of modulated layers and also to get an insight on the interface region. Hardness and modulus value of 43.2 GPa and 272 GPa was observed which is higher than individual monolayers response to mechanical loading. The enhanced hardness is possibly due to the inhibition of dislocation motion along the interface and also due to strain effects at the interface.

Release of metallic fission products from fully intact tri-structural isotropic (TRISO) fuel particles raises serious concern on the safety of high temperature gas-cooled reactors (HTGRs). In TRISO particles, SiC and/or ZrC coating is considered as the major barrier for the migration of the fission products. This thesis focuses on the migration mechanism study of Ag in SiC and Pd in ZrC.The mechanism of the migration of Ag in SiC is a long-lasting mystery. None of the currently existing models could satisfactorily explain the reported experimental facts. In this work, a new mechanism, termed as the “reaction-recrystallization” model, is proposed to explain the Ag migration behavior through SiC. Designed SiC/Ag diffusion couple experiments were carried out, and the results indicate that Ag migrates in SiC by the following three steps. First, Ag reacts with SiC to form an Ag-Si alloy (reaction). Second, carbon precipitates as a second phase and subsequently reacts with the Ag-Si alloy to form new β-SiC (recrystallization). Third, the Ag-Si alloy penetrates through the SiC layer by wetting its grain boundaries (migration). The validity of the proposed model was supported by thermodynamic calculations. (Chapter 3) The finding that SiC could be recrystallized in the presence of Ag inspires the idea of Ag-assisted crack healing in SiC. Cracks were intentionally generated by indenting the bulk SiC by a Vickers indenter. After vacuum annealing with Ag powder, the indent impressions were healed by newly-formed β-SiC grains with a recovery ratio of~ 60%. Median cracks were fully healed by both newly formed SiC and Ag-Si nodules. TEM observation reveals that the newly formed β-SiC layer is presented between the Ag-Si nodule and pristine SiC crack surface and smooths the tortuous crack surface. The above result is in potential to solve the problem of brittleness of SiC as a structural material. (Chapter 4)ZrC is considered as a candidate to replace SiC in TRISO fuel particles. The migration behavior of Pd in ZrC was investigated by designed Pd/ZrC diffusion couple experiments. It is found that ZrC reacts with Pd at temperatures higher than 600 °C to form Pd3Zr and amorphous carbon. The reaction kinetics parameters, i.e., the activation energy and the reaction order, along with the inter-diffusion coefficients of Zr and Pd, were calculated based on established models. These results provide preliminary explanation to the Pd migration in ZrC (Chapter 5).

Le présent document obéit à un plan strict inhérent à tous les manuscrits de thèsepassée en Validation des Acquis de l’Expérience (VAE). Après un CV détaillé ledocument présente tout d’abord un retour réflexif sur le parcours professionnel c'està-dire, une synthèse sur les taches effectuées d’un travail de type projet vers uneimplication de plus en plus forte vers un travail de recherche à proprement parlé. Aprèsce retour réflexif qui permet d’avoir une vue d’ensemble de la progression du parcours,une synthèse est proposée, non pas de la totalité des travaux, mais de trois domainesbien précis et représentatifs du parcours de recherche. Ce choix s’est fait en cherchantun fil d’Ariane qui est tout simplement la nature chimique de la céramique étudiée ;dans le présent document il s’agit de carbures et plus précisément de SiC, TiC, ZrC,HfC. Tout d’abord le travail sur les céramiques monolithiques pour les applicationsnucléaires est abordé puis, les applications spatiales avec la mise au point deprotections contre l’oxydation à partir de poudres revêtues enfin, le document s’achèvepar des travaux d’infiltration de céramiques à partir d’un matériau intermétallique oucomment il est possible de faire des céramiques ultra réfractaires à basse température.Ces travaux étant originaux ils ont fait l’objet de brevets et de publications qui serontabordés dans la troisième partie. / This document obeys a strict plan inherent in all PhD manuscripts passed in Validationof the Assets of Experiment (VAE). After a detailed resume this document first of all,presents a reflexive return on the career i.e., from a work of type project towards anincreasingly strong implication to a research task. After this reflexive return whichmakes it possible to have an overall picture of the progression of the course, asynthesis is proposed, not of total work, but of three fields quite precise andrepresentative of the course of research. This choice was done by seeking a wire ofARIANE which is the chemical nature of the studied ceramics; in this document it isabout carbides and more precisely about SiC, TiC, ZrC, HfC. First of all monolithicceramics for the nuclear applications is approached then, the space applications withthe elaborating of protections against oxidation made by core shell powders finally, thedocument is completed by ceramics infiltrations from an intermetallic material or howit is possible to make ultra refractory ceramics at low temperature. As these works areoriginal they were the object of patents and publications which will be approached inthe third part.

Zirconium- and titanium- based compounds (borides, carbides and nitrides) are of importance because of their attractive properties including: high melting temperature, high-temperature strength, high hardness, high elastic modulus and good wear-erosion-corrosion resistance. The ultra high temperature ceramics (UHTCs) - zirconium diboride (ZrB2) and zirconium carbide (ZrC) in combination with SiC are potential candidates for ultra-high temperature applications such as nose cones for re-entry vehicles and thermal protection systems, where temperature exceeds 2000°C. Titanium nitride (TiN) and titanium diboride (TiB2) composites have been considered for cutting tools, wear resistant parts etc. There are problems in the processing of these materials, as very high temperatures are required to produce dense composites. This problem can be overcome by the development of composites through reactive hot processing (RHP). In RHP, the composites are simultaneously synthesized and densified by application of pressure and temperatures that are relatively low compared to the melting points of individual components. There have been earlier studies on the fabrication of dense ZrB2-ZrC, ZrB2-SiC and TiN-TiB2 composites by the following methods: Pressureless sintering of preformed powders at high temperatures (1800-2300°C) with MoSi2, Ni, Cr, Fe additions Hot pressing of preformed powders at high temperatures (1700-2000°C) with additives like Ni, Si3N4, TiSi2, TaSi2, TaC Melt infiltration of Zr/Ti into B4C preform at 1800-1900°C to produce ZrB2-ZrC-Zr and TiB2-TiC composites RHP of Zr-B4C, Zr-Si-B4C and Ti-BN powder mixtures to produce ZrB2-ZrC, ZrB2-SiC and TiN-TiB2 powder mixtures at 1650-1900°C Spark plasma sintering of powder mixtures at 1800-2100°C There has been a lack of attention paid to the conditions under which ceramic composites can be produced by simple hot pressing (~50 MPa) with minimum amount of additives, which will not affect the mechanical properties of the composites. There has been no systematic study of microstructural evolution to be able to highlight the change in relative density (RD) with temperature during RHP by formation of sub-stoichiometric compounds, and liquid phase when a small amount of additive is used. The present study has been undertaken to establish the experimental conditions and densification mechanisms during RHP of Zr-B4C, Zr-B4C-Si and Ti-BN powder mixtures to yield (a) ZrB2-ZrC, (b) ZrB2-SiC, (c) ZrB2-ZrC-SiC and (d) TiN-TiB2 composites. The following reactions were used to produce the composites: (1) 3 Zr + B4C → 2 ZrB2 + ZrC (2) 3.5 Zr + B4C → 2 ZrB2 + 1.52rCx- 0.67 (3) (1+y) Zr + C → (1+y) ZrCx- 1/ (1+y) (y=0 to 1) (4) 2 Zr + B4C + Si → 2 ZrB2 + SiC (5) 2.5 Zr + B4C + 0.65 Si → 2 ZrB2 + 0.5 ZrCx + 0.65 SiC (6) 3.5 Zr + B4C + SiC → 2 ZrB2 + 1.5 ZrCx + SiC (5 to 15 vol%) (7) (3+y) Ti + 2 BN → (2+y) TiN1/(1+y) + TiB2 (y=0 to 0.5) (a) ZrB2-ZrC Composites: The effect of different particle sizes of B4C (60-240 μm, <74 μm and 10-20 μm) with Zr on the reaction and densification of composites has been studied. The role of Ni addition on reaction and densification of the composites has been attempted. The effect of excess Zr addition on the reaction and densification has also been studied. The RHP experiments were conducted under vacuum in the temperature range 1000-1600°C for 30 min without and with 1 wt% Ni at 40 MPa pressure. The RHP composites have been characterized by density measurements, x-ray diffraction for phase analysis and lattice parameter measurements, microstructural observation using optical and scanning electron microscopy. Selected samples have been analyzed by transmission electron microscopy. The hardness of the composites has also been measured. The results of the study on the effect of different particle sizes B4C and Ni addition on reaction and densification in the stoichiometric reaction mixture as follows. With the coarse B4C (60-240 μm and <74 μm) particles the temperature required are higher for completion of the reaction (1600°C and above). The microstructural observation showed that the material is densified even in the presence of unreacted B4C particles. The composite made with 10-20 μm B4C and 1 wt% Ni showed completion of the reaction at 1200°C, whereas composite made without Ni showed unreacted B4C (∼3 vol%) and the final densities of both the composites are similar (5.44 g/cm3). Increase in the temperature to 1400°C resulted in the completion of the reaction (without Ni) accompanied with a relative density (RD) of 95%. The composites produced with and without Ni at 1600°C had similar densities of 6.13 g/cm3 and 6.11 g/cm3 respectively (~97.3% RD). The Zr-Ni phase diagram suggests that the addition of Ni helps in formation of Zr-Ni liquid at ~960°C and leads to an increase in the reaction rate up to 1200°C. Once the reaction is completed, not enough Zr is available to maintain the liquid phase and further densification occurs through solid state sintering. The grain sizes of ZrB2 and ZrC phases after 1200°C are 0.4 μm and 0.3 μm, which are much lower than those reported in literature (2-10 μm), and may be the reason for reducing the densification temperature to 1600°C for stoichiometric ZrB2-ZrC composites. The effect of excess Zr (0.5 mol), over and above the stoichiometric Zr-B4C powder mixture, on reaction and densification of the composites is as follows. The formation of ZrB2 and ZrC phases with unreacted starting Zr and B4C is observed at 1000°C and with increase in temperature to 1200°C the reaction is completed. Since microstructural characterization reveals no indication of free Zr, it is concluded that the excess Zr is incorporated by the formation of non-stoichiometric ZrC (ZrCx-0.67). This observation is supported by lattice parameter measurements of ZrC in the stoichiometric and non-stoichiometric composites which are lower than those reported in the literature. X-ray microanalysis of ZrC grains in the stoichiometric and non-stoichiometric composites using transmission electron microscopy confirmed the presence of carbon deficiency. The composite produced at 1200°C showed the density of 6.1 g/cm3 (~97% RD), whereas addition of Ni produced 6.2 g/cm3 (~99% RD). The reduction in densification temperature for the non-stoichiometric composites is due to the presence of ZrCx even in the absence of Ni. The mechanism of densification of the composites at 1200°C is attributed to the lowering of critical resolved shear stress with increasing non-stoichimetry in the ZrC, which leads to plastic deformation during RHP. An additional mechanism may be enhanced diffusion through the structural point defects created in ZrC. The hardness of the composites are 20-22 GPa, which is higher than those of reported in literature due to the presence of a dense and fine grain microstructure in the present work. In order to verify the role of non-stoichiometric ZrC the study was extended to produce monolithic ZrC using various C/Zr ratios (0.5-1). Here again, stoichiometric ZrC does not densify even at 1600°C, whereas non-stoichiometric ZrC can be densified at 1200°C. (b) ZrB2-SiC Composites: Since ZrB2 and ZrC do not have good oxidation resistance unless they are reinforced with SiC, the present study has been extended to produce ZrB2-SiC (25 vol%) composites using Zr-Si-B4C powder mixtures. The samples produced at 1000°C showed the formation of ZrB2, ZrC and Zr-Si compounds with unreacted Zr and B4C and as the temperature is increased to 1200°C only ZrB2 and SiC remained. A fine grain (~0.5 μm) microstructure has been observed at 1200°C. During RHP, it was observed that the formations of ZrC, Si-rich phases and fine grain size at low temperatures was responsible for attaining the high relative density at a temperature of ~1600°C. The relative densities of the composites produced with 1 wt% Ni at 40 MPa, 1600°C for 30 min is 97% RD, where as composites without Ni showed a small amount of partially reacted B4C; extending the holding time to 60 min eliminated the B4C and produced 98% RD. The hardness of the composites is 18-20 GPa. (c) ZrB2-ZrC-SiC Composites: Since ZrC plays a crucial role in densification of ZrB2-ZrC and ZrB2-SiC composites, the study has been extended to reduce the processing temperature for ZrB2-ZrCx-SiC composites by two methods. In one of the methods, Si is added to the non-stoichiometric 2.5Zr-B4C powder mixture which is resulted in ZrB2-ZrCx-SiC (15 vol%) composites with ~98% RD at 1600°C. In another method, SiC particulates are added to the non-stoichiometric 3.5Zr-B4C powder mixture to yield ZrB2-ZrCx-SiCp (5-15 vol%) composites at 1400°C. The density of the 5 vol% SiC composite is 99.9%, whereas addition of 15 vol% SiC reduced the density to 95.5% RD. The mechanisms of densification of the composites are similar to those observed in ZrB2-ZrC composites. The hardness of the composites is 18-20GPa (d) TiN-TiB2 Composites: ZrB2, ZrC, TiB2, and TiN are members of the same class of transition metal borides, carbides and nitrides; however, their densification mechanisms appear to be different. In earlier work, the RHP of stoichiometric 3Ti-2BN powder mixtures yielded dense composite at 1400-1600°C with 1 wt% Ni addition, whereas composites without Ni required at least 1850°C. The major contributor to better densification at 1600°C (with Ni) appeared to be the formation of local Ni-Ti liquid phase at ~942°C (Ti-Ni phase diagram). The present work explores the additional role of non-stoichiometry in this system. It is shown that Ti excess can lead to a further lowering of the RHP temperature, but with a different mechanism compared to the Zr-B4C system. Excess Ti allows the transient alloy phase to remain above the liquidus for a longer time, thereby permitting the attainment of a higher relative density. However, eventually, the excess Ti is converted into a non-stoichiometric nitride. Thus, the volume fraction of a potentially low melting phase is not increased in the final composite by this addition. The contrast between these two systems suggests the existence of two classes of refractory materials for which densification may be greatly accelerated in the presence of non-stoichiometry, either through the ability to absorb a liquid-phase producing metal into a refractory and hard ceramic structure or greater deformability. Conclusions: The study on RHP of ZrB2-ZrC, ZrB2-SiC, ZrB2-ZrC-SiC and TiN-TiB2 composites led to the following conclusions: • It has been possible to densify the ZrB2-ZrC composites to ~97 % RD by RHP of stoichiometric Zr-B4C powder mixture with or without Ni addition. The role of B4C particle size is important to complete both reaction as well as densification. • Excess Zr (0.5 mol) to stoichiometric 3Zr-B4C powder mixtures produces dense ZrB2-ZrCx composite with 99% RD at 1200°C. The densification mechanisms in these non-stoichiometric composites are enhanced diffusion due to fine microstructural scale / stoichiometric vacancies and plastic deformation. • In the case of ZrB2-SiC composites, the formation of a fine microstructure, and intermediate ZrC and Zr-Si compounds at the early stages plays a major role in densification. • Starting with non-stoichiometric Zr-B4C powder mixture, the dense ZrB2-ZrCx-SiC composites can be produced with SiC particulates addition at 1400°C. • Non-stoichiometry in TiN and ZrC is route to the increased densification of composites through enhanced liquid phase sintering in TiN based composites that contain Ni and through plasticity of a carbon-deficient carbide in ZrC based composites.

Group IV transition metal carbides are promising materials for high temperature structural application, due to their unique sets of properties such as high melting temperature, high temperature strength, hardness, elastic modulus, wear and corrosion resistance, metal-like thermal and electrical conductivity and thermal shock resistance. This group includes zir-conium carbide, which, along with its composites, are potential candidates for applications such as nose cones for re-entry vehicle, engines, wear resistant parts and in nuclear fuel cladding. Such structural applications demand high strength material with minimal flaws, in order to achieve the required reliability. Attainment of high strength calls for fully dense material with as small a grain size as possible. Producing fully dense zirconium carbide requires very high temperature, which is a direct consequence of its high melting point. Higher processing temperatures increase grain size, thereby also causing a loss in strength, along with the increased cost. Therefore, there is always a driving force to produce such a material in fully densified form at as low a temperature as possible. There have been a number of studies on processing and densification of zirconium carbide. Pressureless sintering of zirconium carbide requires temperature of 2400oC-3000oC to reach reasonably high density. At such high temperatures, abnormal grain growth limits the final density, as pores get entrapped inside the grains. Hot pressing of zirconium carbide also requires upwards of 2000oC to reach high density and is the primary route to produce densified zirconium carbide product. Reactive hot pressing (RHP), is a relatively new processing approach. Here, the reaction between zirconium and carbon to produce zirconium carbide and the densification of the porous mass, occurs simultaneously. Study on reactive hot pressing of zirconium carbide have shown that, it is possible to achieve very high density at much lower temperatures 1600oC. Clearly, reactive processing is an exciting new technique to process zirconium carbide. However, there has been a lack of studies to understand why it provides better densification than conventional hot pressing. Such understanding is of paramount importance, as it can lead to better optimization of RHP and perhaps even lower the process temperature further. The objective of the present study is to understand the densification process in RHP of zirconium carbide through systematic and carefully designed experiments. A model of reactive hot pressing is also constructed to get more insight into the phenomenon. 0.1 Pressureless Reaction Sintering of Zirconium Car-bide Pressureless reaction sintering (RS) of zirconium carbide is studied to understand the role of stoichiometry and zirconium metal in densification. ZrC of four different stoichiometries are chosen for these sets of experiments which are conducted in vacuum at 1200oC and 1600oC for 1 hour to understand the role of stoichiometry. One sample of pure Zr is also sintered to elucidate the role of zirconium in densification. After reaction sintering, all the samples are characterized by density measurement, x-ray diffraction and microstructure, using scanning electron microscopy. After pressureless sintering at 1600oC, zirconium metal reaches the highest relative density of ~ 95%. Densification decreases monotonically with increasing stoichiometry. Zr+0.5C composition reaches the next best relative density (of 90%), while Zr+0.67C composition shows much lower densification. The other two compositions, Zr+0.8C and Zr+C, in contrast, display de-densification rather than densification. Since the pure zirconium sample reaches high density, it can, in principle, help in densification of the mixed powders before getting fully reacted. Non-stoichiometric carbides also exhibit higher diffusivity of carbon, which aids the densification and the greater the deviation from stoichiometry, the smaller the deleterious effects of de-densification from reaction. This troika of factors is responsible for the substantially better densification in non-stoichiometric carbide, compared to stoichiometric carbide. 0.2 Reactive Hot Pressing of Zirconium and Carbon Reactive hot pressing of zirconium carbide is explored with the emphasis on finding the underlying densification mechanism. The earlier proposed densification mechanism for RHP is the plastic flow of transient non-stoichiometric carbide. To differentiate the effect of transient phases from that of zirconium, RHP is carried out at 800oC. At this low temperature, transient phases cannot take part in plastic flow and subsequent densification. Thus, any densi cation at this temperature can be totally attributed to zirconium and the role of zirconium thus can be separated from that of transient phases. A combination of RHP and RS experiments are carried out at 1200oC to better understand the phenomenon. Again, ZrC carbide of four different stoichiometries are investigated in this RHP study. After RHP at 800oC, all the four different ZrC compositions reached more than 90% RD through plastic flow of the Zr leading to a continuous matrix with embedded graphite particles. Since the reaction remains incomplete at this temperature, it is clear that Zirconium alone is responsible for enabling densification at such a low temperature. It is therefore argued that any unreacted Zr would, at higher temperature, be able to drive densification even more. Thus, zirconium does not only participate in densification; it is a dominant factor enabling low temperature densification. Pressureless reaction sintering at 1200oC following the RHP at 800oC, results in de-densi fication, as the reaction between zirconium and carbon occurs with significant volume shrinkage. Since such shrinkage increases with stoichiometry of the carbide, the higher stoichiometry carbides are more susceptible to de-densification. RHP at 1200oC, mostly completes the reaction, but only ZrC0:5 reaches near theoretical density. Thus, the final density of the fully reacted mixture is arrived at through a combination of processes in which the more stoichiometric carbides suffer from not only the smaller metal content but also a greater volume shrinkage during reaction. Thus, ZrC0:5 reaches 99% RD whereas ZrC reaches only 85% RD. The interplay between these two processes may be controlled by a two step RHP begin-ning at 800oC followed by a ramp up to 1200oC. The higher RD achieved at 800 C results in a higher final density for all the four compositions. Thus, two step RHP is a novel way to get better densification in RHP of zirconium carbide. 0.3 Hot Pressing of Zirconium Carbide Powders of Different Stoichiometry In the literature, densification in RHP is mostly attributed to the presence of transient non-stoichiometric carbides. To examine this hypothesis, ZrC of three different stoichiometries are prepared and then subjected to hot pressing at the same temperature and pressure as the previous RHP experiments (i.e. 1200oC and 40MPa for 30 min). After the hot pressing experiments, ZrC0:5 composition shows significant densification (95% RD), whereas ZrC0:67 composition shows very limited densification (70% RD) and ZrC composition shows little or no densification (50% RD). Evidently, the transient phase formed with stoichiometry close to ZrC0:5 can certainly contribute substantially to densification. But for the more carbon-rich compositions, the transient phases do not appear to play a significant role and the benefit of RHP, wherein ZrC can reach 90% RD, must come from the contribution of metal plasticity. 0.4 Reactive Hot Pressing of Zirconium and Zirconium Carbide Two limiting factors for densification during RHP are, de-densification (courtesy of the reaction) and the gradual increase in volume fraction of a rigid, non-sintering phase. To investigate the role of these factors further, two compositions of mixed metal and carbide powders, namely Zr+ZrC and 0.5Zr+ZrC, are subjected to RHP. When reaction is complete, the compositions after RHP will correspond to ZrC0:5 and ZrC0:67, respectively, but with the following difference with respect to the metal-carbon mixtures investigated earlier: these new compositions do not experience de-densification due to reaction and they contain significantly more amount of hard phase (53 and 69%) in the starting composition than their zirconium and carbon mixture counterparts i.e. Zr+0.5C and Zr+0.67C (16 and 20%). These two compositions are subjected to the same process schedules, i.e., RHP at 800oC, pressureless reaction sintering at 1200oC following RHP at 800oC and two step 800oC and 1200oC RHP. After 800oC RHP, Zr+ZrC and 0.5Zr+ZrC compositions reach much lower density than Zr+0.5C and Zr+0.67C compositions as a direct consequence of the larger amount of hard phase hindering densification at the lower temperature. After the 1200oC pressureless sintering following the RHP at 1200oC, the RD of Zr+ZrC and 0.5Zr+ZrC compositions increase (which is opposite to the behaviour of Zr+0.5C and Zr+0.67C com-positions) as they do not su er from reaction derived de-densification. After two step RHP, Zr+ZrC and 0.5Zr+ZrC compositions reach a final RD that is higher than the Zr+0.5C and Zr+0.67C compositions, even though after the first RHP at 800oC, they were much less densified. Thus, the absence of de-densification during reaction is able to more than compensate for the increase in hard phase content. 0.5 Reactive Hot Pressing: Low temperature process-ing route Based on the major factors of densification identified earlier, it was investigated whether RHP temperatures could be brought down further while being supplemented by a free sintering step to complete the reaction without de-densification. From a practical standpoint, such a process would allow dense products to be made by hot pressing with low temperature dies and fixtures while carrying out a more economical pressureless sintering at higher temperatures Therefore, Metal-carbide mixtures, Zr+ZrC and Ti+ZrC, are chosen, along with a temperature of 900 C which is above the allotropic phase transformation temperature for Zr around 880oC, thereby utilizing a zirconium phase that is softer than the hexagonal Zr. For completion of reaction, pressureless reaction sintering is done at 1300oC and 1400oC. It is found that after 1400oC reaction sintering, both the compositions reach almost full density and the Ti+ZrC composition also shows a higher hardness (13 vs 10 GPa) than the Zr+ZrC composition, due to the formation of a binary carbide with consequent solid solution hardening. 0.6 Effect of Particle Size on Reactive Hot Pressing During RHP, premature exhaustion of zirconium by reaction can limit densification. One way to have better densification is to slow down the reaction, so that significant amount of densification takes place before the metal zirconium is exhausted. One way to reduce reaction rates is to increase particle size. Larger particles are expected to slow down the reaction without affecting sintering, as densification is controlled by power law creep of Zr which is grain size independent. Because of lack of availability of Zr with different particle sizes, two different graphite particle sizes, i.e. 7-10 m and 50-60 m, were studied and it was shown that after 1200oC RHP, indeed the larger particle size improves densification. 0.7 Modelling of Reactive Hot Pressing Reactive hot pressing is a complicated phenomenon, and to get an insight and also to optimize the parameters, the availability of a computational model is of paramount importance. Keeping that in mind, a model of RHP has been constructed based on four different parts, namely: 1. Densification of zirconium under pressure 2. Reaction of zirconium and carbon 3. The constraint on sintering from a rigid phase and, finally, 4. The volume contraction during reaction. The model uses published data for the 4 steps and shows reasonable qualitative and quantitative agreement with the experimental results. Further experiments are done with the model to optimize the processing parameters. Results from the virtual experiments consolidates our earlier conviction gained from experimental results, by showing zirconium is the principal factor in densification and exhaustion of zirconium coupled with reaction derived de-densification prevent the higher stoichiometric carbide from achieving full densification. It also shows, RHP gives best densification when reaction is 70-80% complete. So two step RHP where the first RHP will only complete the reaction 70-80%, and a final RHP at temperature which will complete the reaction, will possibly be the way to achieve best densification. 0.8 Conclusions The study on RHP of zirconium carbide led to the following conclusions: • Zirconium plays the most crucial role in densification. • Transient phases only play a role when the final stoichiometry of RHPed carbide is close to that of ZrC0:5. • De-densification from reaction prevents higher stoichiometric carbide from reaching full densification. • Two step RHP, with one RHP at lower temperature at which reaction will remain incomplete, and the other at higher temperature to complete the reaction, yields best densification. • For lower stoichiometric carbide (ZrC0:5,ZrC0:67), full densification can be achieved at 1200oC. For higher stoichiometric carbide, even though large amount of densification upward of 90% RD is achieved at 1200oC, full densification will be out of reach. • RHP shows better densification than conventional hot pressing for all stoichiometries.