The chemistry of ceramic glazes

The development of ideas and theories concerning the structure of glazes, as one of the glassy materials, are reviewed in the general introduction. The raw materials and the manufacturing process for glazes are described (Chapter One). A number of new vanadyl(IV) dipyridylamine and tripyrldylamine complexes have been prepared, various spectroscopic techniques are used in the investigation of the vanadyl ion in a weak ligand field, the situation of those found in a glaze environment (Chapter Three). In glaze recipes containing silica, potash feldspar, china clay, MO(M= Ca, Sr, Sa, Ti and Zn) and NiO, the ligand field theory is used in the elucidation of the effect of M (in MO) on the absorption spectra and coordination behaviour of Ni(II) in glazes. The magnetic and visible spectral results are reviewed in terms of Dietzel's idea of field strength of M and also in terms of Shteinberg's theory of glaze structure. X-ray diffraction is used for the identification of various species that formed after the firing process of glazes (Chapter Four). In Chapter Five, [] Mossbauer spectroscopy, supplemented by E.S.R., X-ray and visible spectral measurements are used in the investigation of iron in a glaze composition similar to that used in Chapter Four. The Mossbauer results are used in following the influence of; M in MO (M= Sr, Ca and Ba), oxides of titanium(IV) and vanadium(V ), and firing conditions on the chemistry of iron. Generally the iron(II) and iron(III) in the fired glazes are in octahedral sites although there are a range of similar, though not identical environments. A quite noticable influence of M (in MO) on the resonance line width is seen. In one case evidence is found for iron(IV) in an iron/vanadium glaze. E.S.R. of vanadium containing glazes indicate that vanadium is present as V02+ in a highly distorted tetragonal environment .

The microstructure of the Irish stock market

This is the first paper to examine the microstructure of the Irish Stock Market empirically and is motivated by the adoption, on June 7th of Xetra the modern pan European auction trading system. Prior to this the exchange utilized an antiquated floor based system. This change was an important event for the market as a rich literature exists to suggest that the trading system exerts a strong influence over the behavior of security returns. We apply the ICSS algorithm of Inclan and Tiao (1994) to discover whether the change to the trading system caused a shift in unconditional volatility at the time Xetra was introduced. Because the trading mechanism can influence volatility in a number of ways we also estimate the partial adjustment coefficients of the Amihud and Mendelson (1987) model prior and subsequent to the introduction of Xetra. Although we find no evidence of volatility changes associated with the introduction of Xetra we do find evidence of an increase in the speed of adjustment (JEL: G15).

The microstructure of the foreign exchange market:the determinants of bid-ask spreads in the foreign exchange market

The purpose of this thesis is to shed more light in the FX market microstructure by examining the determinants of bid-ask spread for three currencies pairs, the US dollar/Japanese yen, the British pound/US dollar and the Euro/US dollar in different time zones. I examine the commonality in liquidity with the elaboration of FX market microstructure variables in financial centres across the world (New York, London, Tokyo) based on the quotes of three exchange rate currency pairs over a ten-year period. I use GARCH (1,1) specifications, ICSS algorithm, and vector autoregression analysis to examine the effect of trading activity, exchange rate volatility and inventory holding costs on both quoted and relative spreads. ICSS algorithm results show that intraday spread series are much less volatile compared to the intraday exchange rate series as the number of change points obtained from ICSS algorithm is considerably lower. GARCH (1,1) estimation results of daily and intraday bid-ask spreads, show that the explanatory variables work better when I use higher frequency data (intraday results) however, their explanatory power is significantly lower compared to the results based on the daily sample. This suggests that although daily spreads and intraday spreads have some common determinants there are other factors that determine the behaviour of spreads at high frequencies. VAR results show that there are some differences in the behaviour of the variables at high frequencies compared to the results from the daily sample. A shock in the number of quote revisions has more effect on the spread when short term trading intervals are considered (intra-day) compared to its own shocks. When longer trading intervals are considered (daily) then the shocks in the spread have more effect on the future spread. In other words, trading activity is more informative about the future spread when intra-day trading is considered while past spread is more informative about the future spread when daily trading is considered

The cutting performance of sialon ceramic tools

The thesis deals with a research programme in which the cutting performance of a new generation of ceramic cutting tool material is evaluated using the turning process. In part one, the performance of commercial Kyon 2000 sialon ceramic inserts is studied when machining a hardened alloy steel under a wide range of cutting conditions. The aim is to formulate a pattern of machining behaviour in which tool wear is related to a theoretical interpretation of the temperatures and stresses generated by the chip-tool interaction. The work involves a correlation of wear measurement and metallographic examination of the wear area with the measurable cutting data. Four main tool failure modes are recognised: (a) flank and crater wear (b) grooving wear (c) deformation wear and (d) brittle failure Results indicate catastrophic edge breakdown under certain conditions. Accordingly in part two, the edge geometry is modified to give a double rake tool; a negative/positive combination. The results are reported for a range of workpiece materials under orthogonal cutting conditions. Significant improvements in the cutting performance are achieved. The improvements are explained by a study of process parameters; cutting forces, chip thickness ratio, chip contact length, temperature distribution, stress distribution and chip formation. In part three, improvements in tool performance are shown to arise when the edge chamfer on a single rake tool is modified. Under optimum edge chamfer conditions a substantial increase in tool life is obtained compared with the commercial cutting geometry.

Polymer modified cement: hydration microstructure and diffusion properties

Investigations concentrated on the styrene butadiene rubber (SBR) latex and formulations included standard carboxylated and special carboxylated latexes. The aqueous component, containing the stabilisers and antifoaming agent but not the polymer solids, was also used. For comparison, limited investigations were carried out using other polymer types e.g. acrylic, ethylene-vinyl acetate (EVA), and redispersible powders rather than emulsions. The major findings were: 1) All latex systems investigated acted as retarders for cement hydration. The extent of retardation depends on the type of polymer. The mechanism for cement hydration may be changed, and excessive retardation influences properties. 2) Polymer modified cements exhibited either similar or coarser pore structures compared with unmodified cements. Results suggest that polymer mainly exists in a mixture of cement hydrates and polymer phase. Very little evidence was found for the formation of a distinct polymer film phase. 3) During the first few days of curing the polymer solids are removed from the pore solution and concentrations of OH-, Na+ and K+ are reduced. These observations are probably a result of polymer-cement surface interactions since there was no evidence of any chemical reactions or degradation of the polymer. 4) Improved diffusional resistance of modified cements depends on the ability to achieve adequate workability at low w/c ratio, rather than modification of matrix structure.

The relationship between fracture toughness and microstructure in titanium alloys

Linear Elastic Fracture Mechanics has been used to study the microstructural factors controlling the strength and toughness of two alpha-beta, titanium alloys. Fracture toughness was found to be independent of orientation for alloy Ti/6A1/4-V, but orientation dependent for IMI 700, bend and tension specimens giving similar toughness values. Increasing the solution temperature led to the usual inverse relationship between strength and toughness, with toughness becoming a minimum as the beta transus was approached. The production of a double heat treated microstructure led to a 100% increase in toughness in the high strength alloy and a 20% increase in alloy Ti/6A1/4V, with little decrease in strength. The double heat treated microstruoture was produced by cooling from the beta field into the alpha beta field, followed. by conventional solution treatment and ageing. Forging above the beta transus led to an increase in toughness over alpha beta forging in the high strength alloy, but had little effect on the toughness of Ti/6A1/4V. Light and electron microscopy showed that the increased toughness resulted from the alpha phase being changed from mainly continuous to a discontinuous platelet form in a transformed beta matrix. Void formation occurred at the alpha-beta interface and crack propagation was via the interface or across the platelet depending on which process required the least energy. Varying the solution treatment temperature produced a varying interplatelet spacing and platelet thickness. The finest interplatelet spacing was associated with the highest toughness, since a higher applied stress was required to give the necessary stress concentration to initiate void formation. The thickest alpha platelet size gave the highest toughness which could be interpreted in terms of Krafftt's "process zone size" and the critical crack tip displacement criterion by Hahn and Rosenfield from an analysis by Goodier and Field.

An X-ray micro-fluorescence study to investigate the distribution of Al, Si, P and Ca ions in the surrounding soft tissue after implantation of a calcium phosphate-mullite ceramic composite in a rabbit animal model

Synthetic calcium phosphates, despite their bioactivity, are brittle. Calcium phosphate-mullite composites have been suggested as potential dental and bone replacement materials which exhibit increased toughness. Aluminium, present in mullite, has however been linked to bone demineralisation and neurotoxicity: it is therefore important to characterise the materials fully in order to understand their in vivo behaviour. The present work reports the compositional mapping of the interfacial region of a calcium phosphate-20 wt% mullite biocomposite/soft tissue interface, obtained from the samples implanted into the long bones of healthy rabbits according to standard protocols (ISO-10993) for up to 12 weeks. X-ray micro-fluorescence was used to map simultaneously the distribution of Al, P, Si and Ca across the ceramic-soft tissue interface. A well defined and sharp interface region was present between the ceramic and the surrounding soft tissue for each time period examined. The concentration of Al in the surrounding tissue was found to fall by two orders of magnitude, to the background level, within similar to 35 mu m of the implanted ceramic.

Size-dependent radiation tolerance in ion irradiated TiN/AlN nanolayer films

Interface effects on ion-irradiation tolerance properties are investigated in nanolayered TiN/AlN films with individual layer thickness varied from 5 nm to 50 nm, prepared by pulsed laser deposition. Evolution of the microstructure and hardness of the multilayer films are examined on the specimens before and after He ion-implantation to a fluence of 4 × 10 m at 50 keV. The suppression of amorphization in AlN layers and the reduction of radiation-induced softening are observed in all nanolayer films. A clear size-dependent radiation tolerance characteristic is observed in the nanolayer films, i.e., the samples with the optimum layer thickness from 10 nm to 20 nm show the best ion irradiation tolerance properties, and a critical layer thickness of more than 5 nm is necessary to prevent severe intermixing. This study suggests that both the interface characteristics and the critical length scale (layer thickness) contribute to the reduction of the radiation-induced damages in nitride-based ceramic materials. © 2013 Elsevier B.V. All rights reserved.

An investigation into the depandance of electrical properties on microstructure in polycrystalline barium titanate

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