A new but relatively simple processing study was conducted to investigate the microstructure-property relationships of alumina/aluminium titanate (AAT) composites. The objectives of this study were: (a) to develop a process for fabricating AAT and β-spodumene modified AAT composites using a solid-state reaction method and functionally-graded AAT using an infiltration technique, and (b) to evaluate the effects of dispersed aluminium titanate (AT) on the phase relations, microstructure and mechanical properties of alumina-based composites. The study has revealed that the processing procedures played an important rule in the microstructural development of AAT composites. The microstructure and properties of AAT composites have been found to be strongly influenced by the presence of dispersed AT. The phase relations in the AAT system have been characterised by x-ray diffraction (XRD) and neutron diffraction (ND). Rietveld analysis showed that the AT content increased in proportion with the amount of rutile added. The dynamic ND study showed that AT commenced to form at ~1310°C The presence of AT caused a reduction of hardness but an improvement in fracture toughness. In addition, the presence of AT hindered the processes or kinetics of sintering and densification. The use of β-spodumene has been investigated as a liquid-phase-sintering aid for the densification of AAT composites. XRD, ND, differential thermal analysis (DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Vickers indentation were used to characterise the effect of β-spodumene on the phase relations, densification, microstructure and mechanical properties of AAT composites. The presence of β-spodumene was found to have a profound influence on the phase relations, densification, microstructure and properties of AAT composites. / The addition of β-spodumene caused a small reduction of AT content and a commensurate increase of alumina phase. Functionally-graded AAT composites have been successfully synthesised through infiltration of porous alumina preform with a solution containing TiCl4. The infiltration kinetics of liquid into porous alumina preform has also been investigated and modelled. It was found that the infiltration rate equation proposed by Washburn was proven to be suitable for describing the kinetics of infiltration in terms of preform sintering temperature, viscosity, and multiple infiltrations. The influence of applied pressure was consistent with the model proposed by Travitzky and Shlayen, where the applied pressure enhanced the rate of infiltration. Pre-sintering of alumina preform at 900, 1000 and 1100°C for 2 h resulted in different rates of infiltration which may be attributed to a varying degree in tortuosity of the pore channels. The graded composition character of functionally-graded AAT composites has been determined by XRD and grazing incidence synchrotron diffraction (GISRD). Graded compositions from Rietveld refinement analysis showed that the concentration of AT decreased with depth. In contrast, the α-A12O3 content increased with depth. Microstructural examination by SEM showed that the content of AT grains was the most abundant near the surface and decreased gradually with an increase in depth. The hardness results showed that FGM had a soft graded-region (AT rich) but hard non-graded alumina region. / The lower hardness in the graded region can be attributed to the presence of intrinsically soft AT phase. The presence of graded AT caused a considerable improvement in damage tolerance. The isothermal decomposition of AT at 1100°C both in air and vacuum has been studied. Both ex-situ and in-situ studies have been conducted to examine the effect of environment on the decomposition behaviour of AT. The addition of MgO was effective in enhancing the thermal stability of AT against decomposition both in air and in vacuum.

The grades of steel used for automotive bodies are interstitial free steel grades and titanium stabilized ultra-low carbon steel grades. During the manufacturing of these grades, the addition of titanium in liquid steel is achieved in the steel refining units and may cause processing problems. Titanium reacts with the dissolved aluminum and oxygen to form complex solid aluminum titanate type micro-particles (inclusions). During the flow of titanium alloyed steel grades containing solid inclusions (such as aluminum titanate and alumina type inclusions), the clog accompanied by steel skull can be formed at the submerged entry nozzle between the tundish and the mold. To reduce the effects of aluminum titanate type inclusions, they can be either modified or removed. The current study focused on the removal of Al2O3, TiO2, and Al2TiO5 inclusions by dissolving them in slag in the temperature range of 1430 – 1600 °C using a high-temperature confocal scanning laser microscope. In this technique, a single particle (inclusion) is placed on the surface of a solid slag, and the inclusion-slag system is heated to steelmaking temperatures. The dynamic changes in inclusion size are measured to determine dissolution kinetics and mechanism. This work has developed a complex oxide particle synthesis technique and provides the first-ever kinetic data for removal of aluminum titanate inclusions into steelmaking slags. It is found that Al2O3 inclusions have a slower dissolution rate than that of Al2TiO5 inclusions followed by TiO2 inclusions. The rate-controlling steps are investigated using a shrinking core model. It is shown that the rate-controlling step for dissolution of both Al2O3 and Al2TiO5 inclusion types is the mass transfer of alumina. Evidence in support of this finding is the particle-slag interface characterization by line scan analysis and calculated diffusivity values being inversely proportional to the viscosity of slag. The dissolution path of aluminum titanate is proposed in the following steps. First, aluminum titanate dissociates into alumina, titanium oxide and oxygen while slag penetrates through the particle. In the next step, the alumina and titanium oxide dissolves in slag, and the oxygen leaves the system. The existence of gas bubbles enhances the overall rate of Al2TiO5 dissolution. The current work establishes a detailed understanding of the dissolution of Al-Ti-O type inclusions in steelmaking slags. This knowledge will inform steelmakers on which inclusions of different chemistry can be removed preferably and develop strategies on better slag design to produce superior quality steel with reduced operational downtime. / Thesis / Doctor of Philosophy (PhD)

Cette thèse avait pour objectif de mettre en place et d’appliquer les techniques de mesure de champs de déplacements et de déformations (corrélation d’images numériques CIN) pour caractériser le comportement mécanique non linéaire de matériaux réfractaires. L’étude a été réalisée sur différents types de matériaux présentant des degrés variables de flexibilité : un matériau modèle monophasé à base de titanate d’aluminium (TA VF) et des matériaux industriels multi-phasés à base de magnésie. La flexibilité dans le cas du TA VF est obtenue grâce à l’anisotropie de la dilatation thermique entre les trois axes cristallographiques, et dans le cas des matériaux industriels grâce à la différence de coefficients de dilatation entre les agrégats de spinelle et la matrice magnésienne. Ces matériaux industriels ayant une déformation à rupture plus faible, la technique de corrélation d’images a dû être optimisée en ajustant au mieux les conditions expérimentales.La CIN et la méthode de suivi de marqueurs ont permis de mettre en évidence le caractère dissymétrique du comportement mécanique en flexion du TA VF entre la zone de l’éprouvette sollicitée en traction et celle en compression et d’investiguer le déplacement relatif des rouleaux du dispositif de flexion. Cette dissymétrie de comportement engendre un déplacement progressif de la fibre neutre au fur et à mesure que la charge appliquée augmente. Cette technique a ensuite été étendue à d’autres essais tels que l’essai brésilien et le Wedge Splitting appliqués aux matériaux industriels magnésiens. La CIN a ainsi permis d’illustrer les mécanismes de rupture (initiation et propagation de fissures) et de mettre en évidence la présence de phénomènes de « crack branching » obtenus grâce au réseau initial de microfissures volontairement généré au sein du matériau par différentiel de dilatation entre phases dans le but d’améliorer sa résistance aux chocs thermiques. Enfin, à partir des champs de déplacements obtenus par corrélation d’images, la méthode de recalage par éléments finis a été développée et utilisée pour déterminer l’évolution des propriétés élastiques du matériau pendant l’essai. / The present thesis aimed to apply digital image correlation (DIC) used for kinematic fields’ measurements as a support for the experimental characterization of refractory materials with specific non-linear behaviour. Model and industrial materials with different degrees of flexibility were studied. The first type of materials was a single phase model flexible aluminium titanate material (AT VF) developed for academic purposes by improving the grain growth. Its non-linear mechanical behaviour was obtained thanks to the thermal expansion mismatch of its grains according to the different crystallographic axis. The second one is multi-phased magnesia based industrial materials, whose flexibility is less accentuated, and for which the non-linear mechanical behaviour is obtained thanks to the thermal expansion coefficients mismatch between spinel aggregates and magnesia matrix. In order to apply the optical methods on these materials which exhibit lower strain-to-rupture, it was necessary to optimize the accuracy of these techniques by improving experimental conditions.In the case of AT VF, DIC and mark tracking method have been applied on four-points bending test at room temperature to underline the material asymmetric mechanical behaviour which induces a significant shift of the neutral fibre and to evaluate the relative displacement of rolls. The application of DIC has been extended to other experimental testing method such as Brazilian and Wedge Splitting test using the multi-phased magnesia based materials. This highlighted fracture mechanisms (crack occurrence and propagation) and the presence of crack branching phenomenon promoted thanks to an initial micro-cracks network voluntary introduced by thermal expansion mismatch between the different phases so as to improve their thermal shock resistance. From displacement experimentally obtained by DIC, a finite element method updating (FEMU-U) has been developed to determine material properties.

Les filtres céramiques représentent une solution efficace pour capturer et retenir les particules carbonées émises par les moteurs automobiles Diesel. En cas de choc thermique dû à une régénération sévère, la résistance thermomécanique de ces filtres est primordiale pour assurer une bonne efficacité de filtration pendant toute la durée de vie du véhicule. Pour cette raison, la conception de filtres à particules Diesel à base de titanate d'aluminium est une innovation prometteuse au sein de la gamme du groupe Saint-Gobain. A température ambiante comme à haute température, les caractérisations des comportements mécaniques et à la propagation de fissure du titanate d'aluminium sont les objectifs principaux de ces travaux de thèse. Basée sur différents essais mécaniques analysés par corrélation d'images 2D et 3D, une méthodologie d'identification est ainsi développée et appliquée sur la céramique à base de titanate d'aluminium pour les filtres à particules. Tout d'abord, des essais de flexion effectués à température ambiante mettent en évidence le comportement endommageable de cette céramique microfissurée fortement poreuse. Des fonctions de forme spécifiques à la flexion quatre points sont construites pour mesurer, par corrélation d'images 2D, la cinématique globale et la position de l'axe neutre. Une loi d'endommagement est identifiée pour représenter la dissymétrie entre les comportements en traction et en compression. Cette approche d'identification est appliquée à haute température, où le comportement mécanique du matériau est non-linéaire en raison du réseau de microfissures et de la viscosité de la phase secondaire. Une seconde approche de corrélation d'images 2D, basée sur les séries de Williams, est appliquée pour analyser des essais de flexion entaillée et étudie la fissuration quasi-fragile du matériau à température ambiante. Les différents modes d'endommagement sont quantifiés énergétiquement à travers l'application d'une méthode de corrélation d'images, basée sur la méthode de l'écart à l'équilibre. A haute température, la propagation de fissure apparaît également comme quasi-fragile, entre autres en raison d'importants mécanismes de renforcements vers 800°C. Parallèlement, l'essai de double-torsion est analysé car il permet de contrôler la propagation de fissures sur de longues distances. Un prototype est conçu pour réaliser des essais in situ dans un tomographe. Par corrélation d'images 3D, l'évolution du front curviligne de la fissure est observée dans l'épaisseur du matériau. Avec une simulation X-FEM, la répartition des facteurs d'intensité des contraintes le long du front de fissure est calculée pour en expliquer sa propagation. Ces travaux ont permis de caractériser les fortes déformabilité et résistance à la propagation de fissure du matériau à haute température. Ces propriétés jouent un rôle clef dans la résistance thermomécanique des filtres à particules Diesel à base de titanate d'aluminium. / Ceramic filters are an efficient solution to capture and retain the carbon particulates that are emitted by Diesel engines. In case of thermal shock due to a severe regeneration, the thermomechanical resistance of these filters is essential to ensure high filtration efficiency during the whole life time of the vehicle. For this reason, the conception of filters made of aluminium titanate is a promising innovation for the group Saint-Gobain. The main objective of this thesis is the characterization of mechanical and fracture behaviours, at both room and high temperature. To reach these goals, integrated techniques of Digital Image Correlation (DIC) present a strong potential to measure displacement fields, analyze tests and identify mechanical properties. Based on different mechanical tests analyzed by 2D and 3D-DIC, an identification methodology is developed and applied on the porous ceramic made of aluminium titanate for Diesel particulate filters. First, bending tests at room temperature highlight the damageable behaviour of this microcracked ceramic. Some specific basis functions for bending tests are built to measure by 2D-DIC the global kinematics and the neutral axis position. A damage law is identified to describe the asymmetry between behaviours in tension and compression. This identification approach is also applied at high temperature, where the mechanical behaviour is non-linear because of the microcracks and the silicate secondary phase. A second approach of 2D-DIC, based on the Williams series, is applied to analyze notched bending tests and to identify the parameters governing the quasi-brittle fracture of the material at room temperature. The energies dissipated by the different damage modes are quantified thanks to a third 2D-DIC method based on the equilibrium gap method. At high temperature, the behaviour is also non-brittle, because of numerous toughening mechanisms near 800°C, among others reasons The double-torsion test is also analyzed since it enables to control the propagation of long cracks for thin and brittle specimens. A prototype is built to perform in situ tests analyzed by tomography X. Using 3D-DIC, it is possible to observe the evolution of the curvilinear crack front in the specimen thickness. Thanks to a X-FEM simulation, the stress intensity factors are calculated along the crack front to explain its propagation. These works have highlighted the important deformability and crack propagation resistance of this material at high temperature. These two properties might be the main reasons for the high thermomechanical resistance of Diesel particulate filters made of aluminium titanate. The identified laws at high temperature can be used for numerical simulations of filters during severe regenerations. More generally, techniques used in these works present a strong interest for the development of new ceramics made of aluminium titanate for filtration applications.