Ceramics have been widely used for personnel and vehicle armour because of their desirable properties such as high hardness and low density. However the brittle nature associated with the ceramic materials, i.e. low toughness, reduces their ability to withstand multiple ballistic hits. The present work is focused on ceramic armour materials made from alumina and zirconia toughened alumina (ZTA). The effects of grain size and zirconia phase transformation toughening on the mechanical and high strain rate properties in both materials were investigated in detail. Alumina, 10%, 15% and 20% nano ZTA with 1.5 mol% yttria stabiliser were produced with various grain sizes. The processing of the materials started from suspension preparation, spray freeze drying of the suspension and die pressing to produce homogeneous green bodies with densities above 54%. Then, the green bodies were sintered using conventional single stage and/or two stage sintering to produce the samples with full density and a range of grain sizes (0.5 to 1.5 µm alumina grains and 60 to 300 nm zirconia grains). The effects of the processing conditions on the microstructures were studied and the optimum processing route for each sample was determined. The mechanical properties of the alumina and ZTA samples were investigated, including Vickers hardness, indentation toughness, 4-point bend strength and wear resistance. The results showed that, with an increasing amount of zirconia addition, evident increases of the toughness, strength and wear resistance properties were observed, whilst the hardness reduced slightly correspondingly. The effect of density and grain sizes on the hardness and toughness were studied as well: larger alumina grain size led to a higher hardness and negligible change in toughness, whilst the zirconia grain coarsening enhanced the phase transformation toughening effect and the samples displayed a higher toughness. In addition to the investigation of the mechanical properties, the alumina and nano ZTA samples were subjected to high strain rate testing, including split Hopkinson pressure bar (SHPB) (8-16 m/s) and gas gun impact testing (100-150 m/s). The high strain rate performances were compared in terms of their fracture behaviours, fragmentation process and fragment size distribution. Raman spectroscopy was used to measure the amount of zirconia phase transformation in ZTA samples after the high strain rate testing. The residual stress and dislocation density in alumina grains after testing were quantitatively measured using Cr3+ fluorescence spectroscopy. The results indicated that zirconia phase transformation can reduce the residual stress and dislocation densities in the ZTA samples, resulting in less damage, lower plastic deformation and less crack propagation. In addition, a nano zirconia material with 1.5 mol% yttria stabiliser (1.5YSZ) was subjected to a gas gun impact test with a very high impact speed (142 m/s); a deep projectile penetration was observed, due to the low hardness of the pure zirconia, whilst the sample stayed intact. The result further confirmed that the zirconia phase transformation toughening effect can improve the sample's high strain rate performance.

The effects of metastable tetragonal zirconia on the properties of Ordinary Portland Cement were observed during which the effect of crystallite size pH on the preparation solution, precursor salt, and the presence of co-precipitates, Fe(OH)3, SnO2 and SiO2 on the crystallization temperature, enthalpy and crystal structure, immediately following the crystallization exothermic burst phenomenon in ZrO2 were measured. Thermal analysis and x-ray methods were used to determine crystallite sizes and structures immediately following the exothermic burst. Comparisons were made for zirconias prepared from oxychloride, chloride and nitrate solutions. The existence of tetrameric hydroxidecontaining ions in oxychloride precursor is used to rationalise low values of crystallization enthalpy. The position of the crystallization temperature, Tmax was not dependent on crystallite size alone but also on the pH at which the gel was made, the surface pH after washing, and the presence of diluent oxides. Enthalpy v r1/2 and Tmax v (diluent vol)1/3 relationships indicate that surface coverage effects dominate a surface nucleated phenomenon. The data established for ZrO2 systems was used to develop tetragonal-ZrO2-SnO2 powders capable of improving the mechanical properties of Ordinary Portland Cement discs. The ZrO2-OPC discs were prepared by powder mixing, water hydration and uniaxial pressing. Vicat needle tests showed that tetragonal-ZrO2 increases the initial setting rate. Microscopy indicated that porosity distribution changes near to ZrO2 particles. Zirconia has also been introduced into OPC discs by vacuum infiltration methods developed for solutions and colloidal suspensions. Comparisons between OPC discs and the OPCtetragonal ZrO2 composites have been made on the basis of diametral compression strength, Young’s modulus, hardness and toughness (K1c), as estimated by the cracked indentation method. Bell-shaped curves are found for the way the mechanical properties are changed as a function of Zirconia content.

Les réfractaires électrofondus, qui constituent l’objet de ce travail, appartiennent au système alumine-zircone-silice. Ils sont obtenus par coulée dans des moules à des températures supérieures à 2000°C, rendant très difficile toute instrumentation. De nombreux phénomènes intrinsèques au matériau interviennent lors du refroidissement qui suit la coulée. Parmi ces derniers, cette recherche a essentiellement porté sur la transformation de phase (de tétragonale à monoclinique) de la zircone et aux phénomènes associés (gonflement, plasticité,…).A partir d’essais mécaniques à haute température réalisés en laboratoire, les lois de comportements thermiques et mécaniques ont été caractérisées et modélisées en cours de transformation de la zircone. La plasticité à très bas seuil de contrainte observée a, en particulier, été décrite par une vitesse de déformation dérivée du modèle de Leblond, une fonction de rendement de type Cam-clay sans consolidation et une fonction de rendement définissant l’avancement de la transformation en fonction de la température. Après implémentation dans un code de calcul par éléments finis et validation par confrontation avec des résultats d’essais sous contraintes multiaxiales, ce modèle a été assemblé aux autres composantes du comportement mécanique (fluage, élasticité,…), pour décrire l’ensemble des phénomènes thermomécaniques observés lors du refroidissement.Parallèlement, des coulées de blocs en laboratoire, instrumentées par des thermocouples et des capteurs d’émission acoustique, ont permis de reconstruire par simulation numérique l’évolution du champ de température à l’intérieur de la dalle au cours du refroidissement. L’enthalpie de solidification et celle associée à la transformation de phase, préalablement quantifiée par ATD, ont été prises en compte. L’application du modèle mécanique complet, associant toutes les composantes du comportement, a permis de calculer l’évolution du champ de contraintes généré par les gradients thermiques en fonction du temps et, en particulier, de mettre en évidence le rôle essentiel joué par la transformation de phase sur la relaxation des contraintes. / Fused-cast refractories, which are concerned by this work, belong to the alumina-zirconia-silica system. They are obtained by casting in molds at temperatures higher than 2000°C, that make very difficult any instrumentation. Many phenomena intrinsic to the material occur during cooling-down after casting. Among these latter, this research essentially focused on the phase transformation (from tetragonal to monoclinic) of zirconia and the associated phenomena (swelling, plasticity,...).From high temperature mechanical tests performed in laboratory, the thermal and mechanical behavior laws were characterized and modeled during the zirconia transformation. Plasticity at very low stress threshold was observed. A Leblond type model has been extended by introducing a Cam-clay yield function without consolidation. In this model, the progress of the transformation is controlled by the evolution of the temperature. This model was complemented by other components of the mechanical behavior (creep, elasticity, ...). It has been validated by experimental tests under multiaxial loadings that replicate the main thermomechanical phenomena observed during cooling.In parallel, blocks casted in laboratory conditions, instrumented with thermocouples and acoustic emission sensors, allowed a numerical simulation of the change in temperature field within the block during cooling-down. This simulation took into account the solidification enthalpy and the enthalpy associated to the phase transformation, previously quantified by DTA. The implementation of the complete mechanical model integrating all the behavior components led to a calculation of the stress field changes generated by thermal gradients as a function of time and, in particular, to highlight the essential role played by the phase transformation on stress relaxation.

The effects of metastable tetragonal zirconia on the properties of Ordinary Portland Cement were observed during which the effect of crystallite size pH on the preparation solution, precursor salt, and the presence of co-precipitates, Fe(OH)3, SnO2 and SiO2 on the crystallization temperature, enthalpy and crystal structure, immediately following the crystallization exothermic burst phenomenon in ZrO2 were measured. Thermal analysis and x-ray methods were used to determine crystallite sizes and structures immediately following the exothermic burst. Comparisons were made for zirconias prepared from oxychloride, chloride and nitrate solutions. The existence of tetrameric hydroxidecontaining ions in oxychloride precursor is used to rationalise low values of crystallization enthalpy. The position of the crystallization temperature, Tmax was not dependent on crystallite size alone but also on the pH at which the gel was made, the surface pH after washing, and the presence of diluent oxides. Enthalpy v r1/2 and Tmax v (diluent vol)1/3 relationships indicate that surface coverage effects dominate a surface nucleated phenomenon. The data established for ZrO2 systems was used to develop tetragonal-ZrO2-SnO2 powders capable of improving the mechanical properties of Ordinary Portland Cement discs. The ZrO2-OPC discs were prepared by powder mixing, water hydration and uniaxial pressing. Vicat needle tests showed that tetragonal-ZrO2 increases the initial setting rate. Microscopy indicated that porosity distribution changes near to ZrO2 particles. Zirconia has also been introduced into OPC discs by vacuum infiltration methods developed for solutions and colloidal suspensions. Comparisons between OPC discs and the OPCtetragonal ZrO2 composites have been made on the basis of diametral compression strength, Young’s modulus, hardness and toughness (K1c), as estimated by the cracked indentation method. Bell-shaped curves are found for the way the mechanical properties are changed as a function of Zirconia content.