Lithium-aluminium casting alloys and their associated metal-mould reactions

Aluminium - lithium alloys are specialist alloys used exclusively by the aerospace industry. They have properties that are favourable to the production of modern military aircraft. The addition of approximately 2.5 percent lithium to aluminium increases the strength characteristics of the new alloys by 10 percent. The same addition has the added advantage of decreasing the density of the resulting alloy by a similar percentage. The disadvantages associated with this alloy are primarily price and castability. The addition of 2.5 weight percent lithium to aluminium results in a price increase of 100% explaining the aerospace exclusivity. The processability of the alloys is restricted to ingot casting and wrought treatment but for complex components precision casting is required. Casting the alloys into sand and investment moulds creates a metal - mould reaction, the consequences of which are intolerable in the production of military hardware. The primary object of this project was to investigate and characterise the reactions occurring between the newly poured metal and surface of the mould and to propose a method of counteracting the metal - mould reaction. The constituents of standard sand and investment moulds were pyrolised with lithium metal in order to simplify the complex in-mould reaction and the products were studied by the solid state techniques of powder X-Ray diffraction and magic angle spinning nuclear magnetic resonance spectroscopy. The results of this study showed that the order of reaction was: Organic reagents> > Silicate reagents> Non silicate reagents Alphaset and Betaset were the two organic binders used to prepare the sand moulds throughout this project. Studies were carried out to characterise these resins in order to determine the factors involved in their reaction with lithium. Analysis revealed that during the curing process the phenolic hydroxide groups are not reacted out and that a redox reaction takes place between these hydroxides and the lithium in the molten alloys. Casting experiments carried out to assess the protection afforded by various hydroxide protecting agents showed that modern effective, protecting chemicals such as bis-trimethyl silyl acetamide and hexamethyldisilazane did not inhibit the metal - mould reaction to a sufficiently high standard and that tri-methylchlorosilane was consistently the best performer. Tri-methyl chlorosilane has a simple functionalizing mechanism compared to other hydroxide protecting reagents and this factor is responsible for its superior inhibiting qualities. Comparative studies of 6Li and 7Li N.M.R. spectra (M.A.S. and `off angle') establish that, for solid state (and even solution) analytical purposes 6Li is the preferred nucleus. 6Li M.A.S.N.M.R. spectra were obtained for thermally treated laponite clay. At temperatures below 800oC both dehydrated and rehydrated samples were considered. The data are consistent with mobility of lithium ions from the trioctahedral clay sites at 600oC. The superior resolution achievable in 6Li M.A.S.N.M.R. is demonstrated in the analysis of a microwave prepared lithium exchanged clay where 6Li spectroscopy revelaed two lithium sites in comparison to 7Li M.A.S.N.M.R. which gave only a single lithium resonance.

myo-inositol pentakisphosphates. Structure, biological occurrence and phosphorylation to myo-inositol hexakisphosphate

1. Standard and high-performance anion-exchange-chromatographic techniques have been used to purify myo-[3H]inositol pentakisphosphates from various myo-[3H]inositol-prelabelled cells. Slime mould (Dictyostelium discoideum) contained 8 microM-myo-[3H]inositol 1,3,4,5,6-pentakisphosphate 16 microM-myo-[3H]inositol 1,2,3,4,6-pentakisphosphate and 36 microM-D-myo-[3H]inositol 1,2,4,5,6-pentakisphosphate [calculated intracellular concentrations; Stephens & Irvine (1990) Nature (London) 346 580-583]; germinating mung-bean (Phaseolus aureus) seedlings contained both D- and L-myo-[3H]inositol 1,2,4,5,6-pentakisphosphate (which was characterized by 31P and two-dimensional proton n.m.r.) and D- and/or L-myo-[3H]inositol 1,2,3,4,5-pentakisphosphate; HL60 cells contained myo-[3H]inositol 1,3,4,5,6-pentakisphosphate (in a 500-fold excess over the other species), myo-[3H]inositol 1,2,3,4,6-pentakisphosphate and D- and/or L-myo-[3H]inositol 1,2,4,5,6-pentakisphosphate; and NG-115-401L-C3 cells contained myo-[3H]inositol 1,3,4,5,6-pentakisphosphate (in a 100-fold excess over the other species), D- and/or L-myo-[3H]inositol 1,2,4,5,6-pentakisphosphate, myo-[3H]inositol 1,2,3,4,6-pentakisphosphate and D- and/or L-myo-[3H]inositol 1,2,3,4,5-pentakisphosphate. 2. Multiple soluble ATP-dependent myo-inositol pentakisphosphate kinase activities have been detected in slime mould, rat brain and germinating mung-bean seedling homogenates. In slime-mould cytosolic fractions, the three myo-inositol pentakisphosphates that were present in intact slime moulds could be phosphorylated to myo-[3H]inositol hexakisphosphate: the relative first-order rate constants for these reactions were, in the order listed above, 1:8:31 respectively (with first-order rate constants in the intact cell of 0.1, 0.8 and 3.1 s-1, assuming a cytosolic protein concentration of 50 mg/ml), and the Km values of the activities for their respective inositol phosphate substrates (in the presence of 5 mM-ATP) were 1.6 microM, 3.8 microM and 1.4 microM. At least two forms of myo-inositol pentakisphosphate kinase activity could be resolved from a slime-mould cytosolic fraction by both pharmacological and chromatographic criteria. Rat brain cytosol and a soluble fraction derived from germinating mung-bean seedlings could phosphorylate myo-inositol D/L-1,2,4,5,6-, D/L-1,2,3,4,5-, 1,2,3,4,6- and 1,3,4,5,6-pentakisphosphates to myo-inositol hexakisphosphate: the relative first-order rate constants were 57:27:77:1 respectively for brain cytosol (with first-order rate constants in the intact cell of 0.0041, 0.0019, 0.0056 and 0.000073 s-1 respectively, assuming a cytosolic protein concentration of 50 mg/ml) and 1:11:12:33 respectively for mung-bean cytosol (with first-order rate constants in a supernatant fraction with a protein concentration of 10 mg/ml of 0.0002, 0.0022, 0.0024 and 0.0066 s-1 respectively).

La critique du nationalisme de la "Semaine Sociale de Bordeaux" à la "Lutte pour la civilisation et la philosophie de la paix"

Over a long period the philosopher, Maurice Blondel, was an outspoken critic of exaggerated nationalism. The series of articles that appeared in 1909-10 in the Annales de philosophie chrétienne under the title of « La Semaine sociale de Bordeaux », and later were published in book form, contained a philosophically and theologically motivated critique of the early support shown by French Catholics for the doctrinaire nationalism of Charles Maurras. In 1928 Blondel returned to a critique of this same nationalism in his detailed article « Patrie et Humanité ». But the further criticism of nationalism contained in parts of his book Lutte pour la civilisation et philosophie de la paix, which was published in 1939 (and anew in 1947 in a slightly revised edition), was of a different order, being focused on the nationalism associated with what Blondel termed totalitarisme in its then German or Nazi form. Despite this record, it would be a mistake to assume that Blondel was an internationalist fitting clearly into the Briand mould. After the First World War Blondel favoured the hard-line foreign policy advocated by Poincaré and Foch, in particular over the future of the Rhineland. And he remained a conservative Catholic. His book of 1939 denounced not only totalitarisme in both its Nazi and Soviet forms, but also, on an opposing front, liberalism in the social and economic sphere. As to the deleterious effect of nationalism on international relations, he was an advocate of strengthening international law, notably the corpus of law emanating from The Hague. Maurice Blondel was greatly admired by Robert Schuman, the prominent French foreign minister under the Fourth Republic and a key figure for post-war European integration.

A naturally shaped silicone ventricle evaluated in a mock circulation loop: a preliminary study

Mock circulation loops are used to evaluate the performance of cardiac assist devices prior to animal and clinical testing. A compressible, translucent silicone ventricle chamber that mimics the exact size, shape and motion of a failing heart is desired to assist in flow visualization studies around inflow cannulae during VAD support. The aim of this study was therefore to design and construct a naturally shaped flexible left ventricle and evaluate its performance in a mock circulation loop. The ventricle shape was constructed by the use of CT images taken from a patient experiencing cardiomyopathic heart failure and used to create a 3D image and subsequent mould to produce a silicone ventricle. Different cardiac conditions were successfully simulated to validate the ventricle performance, including rest, left heart failure and VAD support.

Consumer brand equity : a model for the measurement, analysis and evaluation of consumer perceived value

The topic of my research is consumer brand equity (CBE). My thesis is that the success or otherwise of a brand is better viewed from the consumers’ perspective. I specifically focus on consumers as a unique group of stakeholders whose involvement with brands is crucial to the overall success of branding strategy. To this end, this research examines the constellation of ideas on brand equity that have hitherto been offered by various scholars. Through a systematic integration of the concepts and practices identified but these scholars (concepts and practices such as: competitiveness, consumer searching, consumer behaviour, brand image, brand relevance, consumer perceived value, etc.), this research identifies CBE as a construct that is shaped, directed and made valuable by the beliefs, attitudes and the subjective preferences of consumers. This is done by examining the criteria on the basis of which the consumers evaluate brands and make brand purchase decisions. Understanding the criteria by which consumers evaluate brands is crucial for several reasons. First, as the basis upon which consumers select brands changes with consumption norms and technology, understanding the consumer choice process will help in formulating branding strategy. Secondly, an understanding of these criteria will help in formulating a creative and innovative agenda for ‘new brand’ propositions. Thirdly, it will also influence firms’ ability to simulate and mould the plasticity of demand for existing brands. In examining these three issues, this thesis presents a comprehensive account of CBE. This is because the first issue raised in the preceding paragraph deals with the content of CBE. The second issue addresses the problem of how to develop a reliable and valid measuring instrument for CBE. The third issue examines the structural and statistical relationships between the factors of CBE and the consequences of CBE on consumer perceived value (CPV). Using LISREL-SIMPLIS 8.30, the study finds direct and significant influential links between consumer brand equity and consumer value perception.

Computer aided design and manufacture for three dimensional milling

Advances in both computer technology and the necessary mathematical models capable of capturing the geometry of arbitarily shaped objects has led to the development in this thesis of a surface generation package called 'IBSCURF' aimed at providing a more economically viable solution to free-form surface manufacture. A suit of computer programs written in FORTRAN 77 has been developed to provide computer aids for every aspect of work in designing and machining free-form surfaces. A vector-valued parametric method was used for shape description and a lofting technique employed for the construction of the surface. The development of the package 'IBSCURF' consists of two phases. The first deals with CAD. The design process commences in defining the cross-sections which are represented by uniform B-spline curves as approximations to give polygons. The order of the curve and the position and number of the polygon vertices can be used as parameters for the modification to achieve the required curves. When the definitions of the sectional curves is complete, the surface is interpolated over them by cubic cardinal splines. To use the CAD function of the package to design a mould for a plastic handle, a mathematical model was developed. To facilitate the integration of design and machining using the mathematical representation of the surface, the second phase of the package is concerned with CAM which enables the generation of tool offset positions for ball-nosed cutters and a general post-processor has been developed which automatically generates NC tape programs for any CNC milling machine. The two phases of these programs have been successfully implemented, as a CAD/CAM package for free-form surfaces on the VAX 11/750 super-minicomputer with graphics facilities for displaying drawings interactively on the terminal screen. The development of this package has been beneficial in all aspects of design and machining of free form surfaces.

Defects in steel investment castings

A general investigation was performed, in an industrial environment, of the major types of defect specific to investment castings in steel. As a result of this work three types of metallurgical defect were selected for further study. In the first of these, defects in austenitic stainless steel castings were found to result from deoxidation by-products. As a result of metallographic investigation and the statistical analysis of experimental data, evidence was found to support the hypothesis that the other two classes of defects - in martensite stainless and low alloy steels -both resulted from internal or grain boundary oxidation of the chromium alloy constituent This was often found to be followed by reaction between the metal oxides and the ceramic mould material. On the basis of this study, proposals are made for a more fundamental investigation of the mechanisms involved and interim suggestions are given for methods of ameliorating the effect in an industrial situation.

A systematic approach to establish fundamental principles of computer applications packages design

This work attempts to create a systemic design framework for man-machine interfaces which is self consistent, compatible with other concepts, and applicable to real situations. This is tackled by examining the current architecture of computer applications packages. The treatment in the main is philosophical and theoretical and analyses the origins, assumptions and current practice of the design of applications packages. It proposes that the present form of packages is fundamentally contradictory to the notion of packaging itself. This is because as an indivisible ready-to-implement solution, current package architecture displays the following major disadvantages. First, it creates problems as a result of user-package interactions, in which the designer tries to mould all potential individual users, no matter how diverse they are, into one model. This is worsened by the minute provision, if any, of important properties such as flexibility, independence and impartiality. Second, it displays rigid structure that reduces the variety and/or multi-use of the component parts of such a package. Third, it dictates specific hardware and software configurations which probably results in reducing the number of degrees of freedom of its user. Fourth, it increases the dependence of its user upon its supplier through inadequate documentation and understanding of the package. Fifth, it tends to cause a degeneration of the expertise of design of the data processing practitioners. In view of this understanding an alternative methodological design framework which is both consistent with systems approach and the role of a package in its likely context is proposed. The proposition is based upon an extension of the identified concept of the hierarchy of holons* which facilitates the examination of the complex relationships of a package with its two principal environments. First, the user characteristics and his decision making practice and procedures; implying an examination of the user's M.I.S. network. Second, the software environment and its influence upon a package regarding support, control and operation of the package. The framework is built gradually as discussion advances around the central theme of a compatible M.I.S., software and model design. This leads to the formation of the alternative package architecture that is based upon the design of a number of independent, self-contained small parts. Such is believed to constitute the nucleus around which not only packages can be more effectively designed, but is also applicable to many man-machine systems design.

A production planning system for plastic footwear in a seasonal market

Modern injection-moulding machinery which produces several, pairs of plastic footwear at a time brought increased production planning problems to a factory. The demand for its footwear is seasonal but the company's manning policy keeps a fairly constant production level thus determining the aggregate stock. Production planning must therefore be done within the limitations of a specified total stock. The thesis proposes a new production planning system with four subsystems. These are sales forecasting, resource planning, and two levels of production scheduling: (a) aggregate decisions concerning the 'manufacturing group' (group of products) to be produced in each machine each week, and (b) detailed decisions concerning the products within a manufacturing group to be scheduled into each mould-place. The detailed scheduling is least dependent on improvements elsewhere so the sub-systems were tackled in reverse order. The thesis concentrates on the production scheduling sub-systems which will provide most. of the benefits. The aggregate scheduling solution depends principally on the aggregate stocks of each manufacturing group and their division into 'safety stocks' (to prevent shortages) and 'freestocks' (to permit batch production). The problem is too complex for exact solution but a good heuristic solution, which has yet to be implemented, is provided by minimising graphically immediate plus expected future costs. The detailed problem splits into determining the optimal safety stocks and batch quantities given the appropriate aggregate stocks. It.is found that the optimal safety stocks are proportional to the demand. The ideal batch quantities are based on a modified, formula for the Economic Batch Quantity and the product schedule is created week by week using a priority system which schedules to minimise expected future costs. This algorithm performs almost optimally. The detailed scheduling solution was implemented and achieved the target savings for the whole project in favourable circumstances. Future plans include full implementation.

Preservation of York Minster historic limestone by hydrophobic surface coatings

Magnesian limestone is a key construction component of many historic buildings that is under constant attack from environmental pollutants notably by oxides of sulfur via acid rain, particulate matter sulfate and gaseous SO 2 emissions. Hydrophobic surface coatings offer a potential route to protect existing stonework in cultural heritage sites, however, many available coatings act by blocking the stone microstructure, preventing it from 'breathing' and promoting mould growth and salt efflorescence. Here we report on a conformal surface modification method using self-assembled monolayers of naturally sourced free fatty acids combined with sub-monolayer fluorinated alkyl silanes to generate hydrophobic (HP) and super hydrophobic (SHP) coatings on calcite. We demonstrate the efficacy of these HP and SHP surface coatings for increasing limestone resistance to sulfation, and thus retarding gypsum formation under SO/H O and model acid rain environments. SHP treatment of 19th century stone from York Minster suppresses sulfuric acid permeation.

Modelling a biochemical reaction with computational fluid dynamics

Earlier investigations (Cartland Glover et al., 2004) into the use of computational fluid dynamics (CFD) for the modelling of gas-liquid and gas-liquid-solid flow allowed a simple biochemical reaction model to be implemented. A single plane mesh was used to represent the transport and reaction of molasses, the mould Aspergillus niger and citric acid in a bubble column with a height to diameter aspect ratio of 20:1. Two specific growth rates were used to examine the impact that biomass growth had on the local solids concentration and the effect this had on the local hydrodynamics of the bubble column.

Learning from a deceptively spacious policy discourse

Networked Learning, e-Learning and Technology Enhanced Learning have each been defined in different ways, as people's understanding about technology in education has developed. Yet each could also be considered as a terminology competing for a contested conceptual space. Theoretically this can be a ‘fertile trans-disciplinary ground for represented disciplines to affect and potentially be re-orientated by others’ (Parchoma and Keefer, 2012), as differing perspectives on terminology and subject disciplines yield new understandings. Yet when used in government policy texts to describe connections between humans, learning and technology, terms tend to become fixed in less fertile positions linguistically. A deceptively spacious policy discourse that suggests people are free to make choices conceals an economically-based assumption that implementing new technologies, in themselves, determines learning. Yet it actually narrows choices open to people as one route is repeatedly in the foreground and humans are not visibly involved in it. An impression that the effective use of technology for endless improvement is inevitable cuts off critical social interactions and new knowledge for multiple understandings of technology in people's lives. This paper explores some findings from a corpus-based Critical Discourse Analysis of UK policy for educational technology during the last 15 years, to help to illuminate the choices made. This is important when through political economy, hierarchical or dominant neoliberal logic promotes a single ‘universal model’ of technology in education, without reference to a wider social context (Rustin, 2013). Discourse matters, because it can ‘mould identities’ (Massey, 2013) in narrow, objective economically-based terms which 'colonise discourses of democracy and student-centredness' (Greener and Perriton, 2005:67). This undermines subjective social, political, material and relational (Jones, 2012: 3) contexts for those learning when humans are omitted. Critically confronting these structures is not considered a negative activity. Whilst deterministic discourse for educational technology may leave people unconsciously restricted, I argue that, through a close analysis, it offers a deceptively spacious theoretical tool for debate about the wider social and economic context of educational technology. Methodologically it provides insights about ways technology, language and learning intersect across disciplinary borders (Giroux, 1992), as powerful, mutually constitutive elements, ever-present in networked learning situations. In sharing a replicable approach for linguistic analysis of policy discourse I hope to contribute to visions others have for a broader theoretical underpinning for educational technology, as a developing field of networked knowledge and research (Conole and Oliver, 2002; Andrews, 2011).

Increases in renal ε-(γ-glutamyl)-lysine crosslinks result from compartment-specific changes in tissue transglutaminase in early experimental diabetic nephropathy:Pathologic implications

Diabetic nephropathy (DN) is characterized by an early, progressive expansion and sclerosis of the glomerular mesangium leading to glomerulosclerosis. This is associated with parallel fibrosis of the renal interstitium. In experimental renal scarring, the protein cross-linking enzyme, tissue transglutaminase (tTg), is up-regulated and externalized causing an increase in its crosslink product, e-(γ-glutamyl)-lysine, in the extracellular space. This potentially contributes to the extracellular matrix (ECM) accumulation central to tissue fibrosis by increasing deposition and inhibiting breakdown. We investigated if a similar mechanism may contribute to the ECM expansion characteristic of DN using the rat streptozotocin model over 120 days. Whole kidney e-(γ-glutamyl)-lysine (HPLC analysis) was significantly increased from Day 90 (+337%) and peaked at Day 120 (+650%) (p <0.05). Immunofluorescence showed this increase to be predominantly extracellular in the peritubular interstitial space, but also in individual glomeruli. Total kidney transglutaminase (Tg) was not elevated. However, using a Tg in situ activity assay, increased Tg was detected in both the extracellular interstitial space and glomeruli by Day 60, with a maximal 53% increase at Day 120 (p <0.05). Using a specific anti-tTg antibody, immunohistochemistry showed a similar increase in extracellular enzyme in the interstitium and glomeruli. To biochemically characterize glomerular changes, glomeruli were isolated by selective sieving. In line with whole kidney measurement, there was an increase in glomerular e-(γ-glutamyl) lysine (+ 361%); however, in the glomeruli this was associated with increases in Tg activity (+228%) and tTg antigen by Western blotting (+215%). Importantly, the ratio of glomerular e-(γ-glutamyl) lysine to hydroxyproline increased by 2.2-fold. In DN, changes in the kidney result in increased translocation of tTg to the extracellular environment where high Ca2+ and low GTP levels allow its activation. In the tubulointerstitium this is independent of increased tTg production, but dependent in the glomerulus. This leads to excessive ECM cross-linking, contributing to the renal fibrosis characteristic of progressive DN.