The term nanoceramics is well known in the ceramic field for at least two decades. Even though there are many reports that nanoceramics are superior in terms of mechanical and other properties, no comprehensive and conclusive study on the grain size dependent variation in mechanical properties. So this study was an attempt to study the property variation with grain size and yttria content for a well known ceramic, yttria stabilised zirconia. High solids content but low viscosity YSZ nanosuspensions have been slip cast into -52% dense, very homogeneous green bodies in sizes up to 60 mm in diameter. Sintering cycles have been optimised using both hybrid and conventional two-step heating to yield densities >99.5% of theoretical whilst retaining a mean grain size of <100 nm. The sintered samples have been characterised for hardness, toughness, strength, wear resistance and hydrothermal ageing resistance. The results have been compared with that of a submicron zirconia ceramic prepared using a commercial powder. The strength of the nanoceramics has been found to be very similar to that of conventional submicron ceramics, viz. -10Pa, although the fracture mechanism was different. Two toughness measurement approaches have been used, indentation and surface crack in flexure. The results indicate that the nano 1.5YSZ ceramics may be best viewed as crack, or damage, initiation resistant rather than crack propagation resistant; indentation toughness measurements as high as 14.5 MPa m 112 were observed. Micro-Raman mapping was demonstrated to be a very effective technique to map the phase transformations in zirconia. The wear mechanism of nanozirconia has been observed to be different compared to that in conventional, submicron YSZ and the wear rates to be lower, particularly under wet conditions. In addition, and potentially most usefully, the nan03YSZ ceramics appear to be completely immune to hydrothermal ageing for up to 2 weeks at 245°C & 7 bar; conditions that see a conventional, commercial submicron ceramic disintegrate completely within 1 hour.

This thesis concerns the formation, sintering and humidity dependent electrical behaviour of the spinel ceramic material nickel germanate, Ni(_2)Ge0(_4).Ni(_2)Ge0(_4) has been prepared via the solid state reaction between NiO and GeO(_2) over a range of temperatures, and characterised using a number of techniques. The sintering behaviour of pressed pellets of Ni(_2)Ge0(_4) has also been investigated, together with a characterisation of the microstructure of the sintered bodies. Substitutional doping of Ni(_2)GeO(_4) with Li as a replacement for Ni is found to promote a high degree of shrinkage in the sintering process, probably due to the formation of a liquid phase. XRD revealed that even when 10 % of the Ni atoms were replaced with Li, no change in the crystal structure could be detected. A C. impedance spectroscopy of Ni(_2)Ge0(_4) samples was used to investigate the humidity sensitivity of this material. Equivalent circuit analysis, based on a network of resistors and constant phase elements, shows that the humidity sensitivity is due to conduction in a surface layer of water, in agreement with the models currently popular in the Uterature. Measurement of the water adsorption isotherm of Ni(_2)Ge0(_4) in pellet form indicates that a single monolayer of water is formed at around 20 %R(_H), with an approximately linear increase in water layer thickness up to around 80 %R(_H), after which capillary condensation causes a large increase in the volume of adsorbed water. The information gained on the thickness of this layer of water has been correlated with the resistance of the layer measured by impedance spectroscopy, and subsequently used to provide evidence for a model of the humidity sensitive conduction. The conduction in the surface layer is thought to be due to dissociation of the water, where the amount of dissociation is exponentially dependent on the humidity.

Cement-based materials are of importance in the construction of geothermal wells and high-temperature oil and gas wells. These materials fill the annulus between the well casing and the rock forming a protective layer, known as sealant, which is used primarily to secure and support the casing inside the well. In addition it prevents entry of unwanted fluids into the well and communication between formation fluids at different levels. These cement based sealants need to perform for many years at high temperatures and in severe chemical environments; conditions which can cause the material of the well-casing to degrade resulting in reduced strength and increased permeability. The aim of this study is to develop new materials which will have the potential properties (high strength and low permeability) for use as sealants in geothermal and deep, hot oil wells. In order to do this special cement slurries, based on the CaO−Al2O3−SiO2−H2O (CASH) hydroceramic system, have been synthesised over the temperature range 200 to 350 °C (i.e. the typical working temperature of these wells). The additives used in these cement slurries are silica flour and alumina. A detailed description of a suite of novel hydroceramic compositions over the temperature range 200 to 350 °C is given. X-ray diffraction has been used to determine the mineralogical composition and Rietveld refinement to quantify the known phases present at different temperatures. In addition the chemistry of some of the major phases present has been examined using electron probe microanalysis. Scanning electron microprobe and simulation software have been employed to study the crystal shape of these major minerals. The engineering properties of the hydroceramic materials are very important. A study of the compressive strength and permeability has been carried out over a range of temperature (200 to 350 °C). In addition permeability has been calculated using simulation software and the results compared with experimental values. Hydroceramic formulations with excellent strength and permeability measurements have been found. Some of these formulations have been tested for durability under simulated well conditions. These materials have been immersed into different brines for a certain period of time at temperatures between 200 to 300 °C. Some preliminary results regarding the changes in mineralogy in these samples are presented in this thesis. These experiments have been carried out at the Synchrotron Radiation Source (SRS) using tomographic energy-dispersive diffraction imaging (TEDII).

The research described in this dissertation follows on from the study made by Jewell (1980)into the effects of tensile reinforcement on the mechanical behaviour of sand. For this study Jewell used the direct shear test with reinforcement placed about the central plane as shown in fig. 1.1. The direct shear test was chosen for the following reasons. (1) The reinforcement variables could be better controlled and examined in a unit cell test than in modular field studies of soil reinforcement systems. (2) The pattern of deformation is similar to that experienced by soil in which a rupture band develops, with the principal axes of stress, strain and strain increment free to rotate as is the case in model and field structures. (3) The overall shear strength of the sample is measured directly at the boundaries of the apparatus. The direct shear tests were monitored by boundary measurements and internal measurements using a radiographic technique. The findings are outlined below with reference made to relevant observations by other researchers. 1) The optimum orientation for a relatively flexible steel grid was found to be approximately along the direction of principal tensile strains in the unreinforced sand, see fig.1.2. This indicated that the reinforcement functioned by limiting tensile strains in the sand. McGown et al. (1978) obtained a similar result for plane strain cell tests on sand containing a single layer of flexible reinforcement. However in both studies the reinforcement was observed to waken the sand. Jewell recognized weakening to occur when the steel grid was placed along the direction of principal compressive strains in the unreinforced sand. This was attributed to a reduction in vertical effective stress. McGown et al. observed weakening of the sand when the reinforcement orientation approached the rupture band which developed in the sand alone. This was recognized to be the direction of zero-extension in the unreinforced sand. The weakening was linked to a lower bond between soil and reinforcement than soil alone. 2) Internal strains determined by Jewell showed the tensile reinforcement modified strains in the sand over a well defined zone, see fig.1.3. This resulted in a significant rotation of principal axes of strain increment, with the bond of major strains which developed across the centre of the box in the unreinforced sand being prohibited from forming. This agreed with boundary measurements, indicating the reinforcement functioned by limiting tensile strains in the sand. Consequently a less favourable mode of failure took place. The limit of rotation of principal axes of strain increment was understood to be the alignment of a direction of zero-extension in the sand with the reinforcement. These findings agree with the ideas expressed by Basset and Last (1978) on the mode of action of tensile reinforcement, which in particular was related to the effect of tensile reinforcement on the strain field in a reinforced earth wall as shown in fig.1.4. 3) For efficient use of tensile reinforcement it was demonstrated that the bond with sand should be as high as possible. This could be achieved by roughening the surface. Alternatively, the bond was improved by introducing openings or apertures in the reinforcement, changing the shape to a grid. It appeared that the bond for a suitably proportioned grid could be as high as for a fully roughened surface. 4) The longitudinal stiffness of tensile reinforcement was observed to affect the magnitude and rate of increase in strength in the direct shear tests. The rupture strain of tensile reinforcement relative to maximum tensile strains of the soil, under the same operational stress conditions, have also been observed to influence the reinforcing effect in terms of its limiting behaviour, i.e. whether brittle or ductile (McGown, et al. 1978). With regards to the performance of reinforced earth walls, Al-Hussanini and Perry (1976) observed that steel reinforced strips produced a stiffer and stronger structure than a more extensible fabric reinforcement, even though surface roughness was less. The importance of reinforcement tensile stiffness is recognized in limit equilibrium designs for tensile reinforced soil structures by limiting the available reinforcement force to the tensile strains that can develop in the soil (e.g. Jewell 1985). For highly structured non-woven and composite geotextiles, McGown et al. (1982) demonstrated that the stress-strain behaviour can be significantly affected by soil confinement. Testing wider strips in isolation was not found to replicate the effects of soil confinement. Another factor which needs to be considered when assessing the tensile property of a polymer reinforcement is creep. McGown et al. (1984) illustrated an appropriate method of interpreting creep data using isochronous curves, which enable long term laboratory test data to be extrapolated to the design life of the soil structure. 5) The strain and hence stress fields in the reinforced direct shear tests have been shown to be complex and non-uniform. However Jewell successfully modelled the variation of reinforcing effect for tensile reinforcement at different orientations by using a simple limit equilibrium analysis, see fig.1.5. The effect of the tensile reinforcement force was represented as: - an increase in the normal effective stress acting on the central plane of the box due to the normal component of the force and - a reduction in the applied shear stress due to the parallel component of the force to the central plane. Subsequently this analysis has been applied to limit equilibrium design methods for reinforcing soil retaining walls and embankments, Jewell et al. 1984, and Jewell 1982 respectively. 6) A reduction in the reinforcing effect for individual reinforcement due to the presence of other reinforcement was observed in the shear box. This loss of efficiency of individual reinforcement was termed interference. Interference between tensile reinforcement has also been studied by Guilloux et al. (1979) for the pull-out resistance from soil. However interference between reinforcement has yet to be introduced into a limit equilibrium design method.

No description available.

To support the concept of environmentally friendly materials and sustainable development, the low-carbon cementitious materials have been extensively studied to reduce amount of CO2 emission to the atmosphere. One of the efforts is to promote alternative cementitious binders by utilizing abundant alumina-silicate wastes from the industrial sectors (e.g. fly ash or furnace slag), among which “Geopolymer (GP) cement” has received most attention as it can perform a wide variety of behaviours, in addition to cost reduction and less environmental impacts. The most common geopolymer production, fly ash-based, gained some strength with very slow rate at ambient temperature, while the strength is evidently improved when cured in high (above room) temperature, e.g. over 40°C. The major challenge is to step over the limitation of heat curing process and inconvenience in practice. In this study, the testing schemes of (i) GP manufacturing in various processes, (ii) inclusion of ordinary Portland cement (OPC) in GP mixture, called GeoPC and (iii) GeoPC manufactured with dry-mixing method, have been intensively investigated through mechanical testing (Setting time, Compressive strength and Internal heat measurement) and mechanism analysis (XRD, FTIR, SEM and EDXA) in order to develop the geopolymers, achieving reasonable strength without external sources of heat curing. It is found that the proposed (dry) mixing process could have generated intensive heat liberation which was observed as a comparable factor to heat curing from any other external sources, enhancing the curing regime of the mixture. The additional calcium content in the developed GeoPC system not only resulted in an improvement of an early strength by the extra precipitation of calcium compounds (C,N-A-S-H), but also provided a latent heat from the reaction of its high potential energy compounds (e.g. OPC or alkaline activators). The developments from these approaches could lead to geopolymer production to achieve reasonable strength in ambient curing temperature known as “Self-cured geopolymer cement”, without external heat, and hence provide construction industry viable technologies of applying geopolymers in on-site and off-site construction.

In this thesis Moore and Yeo's proposed mapping of the structural glass to the Ising spin glass in a random field is presented. In contrast to Random First Order Theory and Mode Coupling Theory, this mapping predicts that there should be no glass transition at finite temperature. However, a growing correlation length is predicted from the size of rearranging regions in the supercooled liquid, and from this a growing structural relaxation time is predicted. Also presented is a study of the propensity of binary fluids (i.e. fluids containing particles of two sizes) to phase separate into regions dominated by one type of particle only. Binary fluids like this are commonly used as model glass formers and the study shows that this phase separation behaviour is something that must be taken into account.The mapping relies on the use of replica theory and is therefore very opaque. Here a model is presented that may be mapped directly to a system of spins, and also prevents the process of phase separation from occurring in binary fluids. The system of spins produced in the mapping is then analysed through the use of an effective Hamiltonian, which is in the universality class of the Ising spin glass in a random field. The behaviour of the correlation length depends on the spin-spin coupling J and the strength of the random field h. The variation of these with packing fraction and temperature T is studied for a simple model, and the results extended to the full system. Finally a prediction is made for the critical exponents governing the correlation length and structural relaxation time.

Accurate prediction of long-term moisture expansion in fired clay ceramics requires finding a relationship between the reactivity of a ceramic material with moisture and time. Recently a (time)1/4 law has been proposed which provides a precise relationship between moisture expansion and mass gain in fired clay ceramics and time. However, mass gain studies rather than expansive strain studies provide a more accurate and fundamental measure of the reactivity of fired clay ceramics with moisture. The possibility of using the (time)1/4 law to describe rate of mass gain and consequently to predict moisture expansion in fired clay ceramics with time requires study of the effect of chemical composition and firing temperature on the linear dependence of mass gain on (time)1/4. Pure kaolinite as well as kaolinite mixed with controlled additions of alkali and alkaline-earth metals were employed in this study. These materials were fired at temperatures between 800°C and 1200°C. Mass gain due to the chemical combination of the fired materials with moisture was measured using a recording microbalance under tightly controlled environmental conditions of temperature and relative humidity. The mass gain results show that the (time)1/4 law can be used to obtain an accurate linear relationship between long-term mass gain and time at almost all firing temperatures and at all different compositions. The presence of alkali metals was found to strongly affect the chemical combination of fired clay ceramics with moisture and hence affect the rate of mass gain. On the other hand, alkaline earth metals were found to produce similar reaction kinetics to kaolinite alone. BET surface area and X-ray diffraction results confirm that there is a correlation between the reactivity with moisture and both the specific surface area and crystallinity of fired clay ceramics.

The microelectronics industry requires continuous advances due to ever-evolving technology and the corresponding need for higher density substrates with smaller features. Specifically, new dielectric materials with enhanced electrical properties are needed. At the same time, adhesion must be maintained in order to preserve package reliability and mechanical performance. As a result, this research investigates the use of thin glass sheets as an alternative substrate material as it offers a number of advantages including coefficient of thermal expansion similar to silicon, good dielectric properties and optical transparency to assist in the alignment of buried features. As part of this project it was necessary to deposit metallic coatings onto the glass sheets to create electrical tracks, pads and microvias. In order to meet these requirements, the metallisation of both smooth as received glass surfaces and surfaces roughened by laser machining using electroless copper and nickel deposition were investigated. This study resulted in a number of important conclusions about the roles of chemical bonding and mechanical anchoring in both the adhesion and catalyst adsorption, that are key factors in the electroless metallisation process.....

Les céramiques de type non-oxyde à base de silicium ont été très largement étudiées en raison deleurs incroyables propriétés thermostructurales généralement très supérieures à celles desmatériaux conventionnels. En particulier, les carbonitrures de bore et de silicium (SiBCN)proposent une grande fiabilité mécanique et sont stables jusqu’à des températures de l’ordre de2200 °C en raison de la faible mobilité atomique de leurs structures. Le développement de la voie« polymères précéramiques » s’est avéré primordial pour la réalisation de céramiques techniquesaux propriétés contrôlées. Au travers de la thermolyse des polymères, une large gamme decéramiques peut être obtenue à partir de précurseurs moléculaires en contrôlant à la fois lastructure de l’unité monomérique et le degré de polymérisation, mais aussi la procédure dethermolyse. La thermolyse directe des polymères est compatible avec plusieurs types detechniques de mise en forme et offre la possibilité de réaliser des structures et des objets deformes complexes. Le nanomoulage à partir d’un moule poreux et le co-assemblage d’unpolymère précéramique et d’un bloc copolymère sont deux voies largement empruntées pour laproduction de céramiques poreuses ordonnées. Ce manuscrit présente une étude sur l’élaborationde céramiques de type SiBCN mésoporeuses ordonnées selon la méthode du nanomoulage. Lamise en forme de ces poudres céramiques par frittage flash conduit alors à la fabrication demonolithes à porosité hiérarchisée. Une deuxième partie envisage également l’utilisation d’uncopolymère tribloc comme agent structurant pour la synthèse de matériaux mésoporeux ordonnésde type carbure de silicium. / SiC based non-oxide type ceramics have been largely studied due to high thermostructural properties.In particular, Silicoboron carbonitrides (SiBCN) display high mechanic reliability and stay stableuntil temperature such as 2200 °C due to a low atomic mobility in their structure. The developpementof the Polymer Derived Ceramics (PDCs) route played a major role in the production of technicalceramics with controlled properties. Through the thermolysis of preceramic polymers, a large rangeof ceramics can be obtained from molecular precursors while controlling at the same time themonomeric unit structure, the polymerization level but also the thermolysis process. Directthermolysis of polymers is compatible with many shaping techniques and offers the opportunity torealize complex shapes/structures. Nanocasting from a porous template and self-assembling of apreceramic polymer and multi-bloc copolymers are the main strategies leading to organized porousceramics. This document is about the fabrication of organized mesoporous SiBCN-type ceramics viananocasting. The shaping of such ceramic powders with the spark plasma sintering technique leads tomonoliths with hierarchical porosity. A second part considers the use of a commercial tri-blockcopolymer as structuring agent for the synthesis of SiC-type ordered materials.