On the long list of solid-state hydrogen storage materials, magnesium hydride stands out for its relatively high hydrogen storage capacity of 7.7 wt%, combined with the low cost and abundance of magnesium. For practical applications however, issues such as the slow kinetics and the high stability of magnesium hydride must be resolved in order to reduce the potential operating temperatures of a magnesium-based solid-state hydrogen storage system. Catalysis has been widely used to improve the hydrogen storage kinetics and thin film techniques have been used to explore novel structures and combinations of materials in order to improve both the kinetics and thermodynamics of hydrogen storage in magnesium. The original contribution to knowledge of this work lies in the study and understanding of the evolution of a range of novel thin film multilayer coatings and the effect of the structure, structural evolution and materials on the hydrogen storage properties of these materials, each consisting of 150 layers of magnesium, < 20 nm thick, separated by < 3 nm thick layers of a nickel-rich, iron-based transition metal mix, chromium and vanadium. The samples, as well as a non-catalysed control sample, were produced by means of magnetron-assisted physical vapour deposition and delaminated from the substrate for volumetric, gravimetric and calorimetric hydrogen cycling measurements. The coatings were analysed both before and after hydrogen cycling to understand the structural evolution of the coatings from highly structured thin film multilayers to flaky thin film particles containing finely distributed nano-crystalline catalyst particles. The formation of the intermetallic Mg2Ni in one of the samples was found to be beneficial for the hydrogenation kinetics, whilst the dehydrogenation kinetics were found to be affected mostly by the nano-crystalline transition metal phases that formed in the catalysed samples during hydrogen cycling. This resulted in hydrogenation and dehydrogenation of magnesium hydride in less than 4 and 13 minutes at 250°C with activation energies as low as 60.6 ± 2.5 kJ mol-1.

Government regulation of industrial hazards is examined in the context of the economic and technical processes of industrial development. Technical problems and costs of control are considered as factors in both the formation and impact of regulation. This thesis focuses on an historical case-study of the regulation of the hazard to painting workers from the use of lead pigments in paint. A regulatory strategy based on the prohibition of lead paints gained initial acceptance within the British state in 1911, but was subsequently rejected in favour of a strategy that allowed continued use of lead paint subject to hygiene precautions. The development of paint technology and its determinants, including concern about health hazards, are analysed, focusing on the innovation and diffusion into the paint industry of the major white pigments: white lead (PbC03 .PB(OH)2)and its substitutes. The process of regulatory development is examined, and the protracted and polarised regulatory d~bate contrasted to the prevailing 'consensual' methods of workplace regulation. The rejection of prohibition is analysed in terms of the different political and technical resources of those groups in conflict over this policy. This highlights the problems of consensus formation around such a strategy, and demonstrates certain constraints on state regulatory activity, particularly regarding industrial development. Member-states of the International Labour Organisation agreed to introduce partial prohibition of lead paint in 1921. Whether this was implemented is related to the economic importance of lead and non-lead metal and pigment industries to a nation. An analysis is made of the control of lead poisoning. The rate of control is related to the economic and technological trajectory of the regulated industry. Technical and organisational characteristics are considered as well as regulatory factors which range from voluntary compliance and informal pressures to direct legal requirements. The implications of this case-study for the analysis of the development and impacts of regulation are assessed.

The development of cobalt molybdenum and cobalt tungsten brush plating electrolytes is described. Their optimum compositions and operating conditions for commercial applications have been determined. The effects of composition, pH, applied voltage, stylus speed and pressure upon deposit composition and efficiency have been investigated. Transmission and Scanning Electron Microscopy have been employed to study the cobalt alloy deposits produced. Evaluation of the wear resistant properties of the cobalt alloys developed in this work was carried out in the laboratory using a pin and disc technique and a simulated hot forging test, and by industrial trials involving the "on site" plating of hot forging dies and cold pressing tools. It was concluded that the electrolytes developed in tl1is work enabled cobalt alloys containing 6% Mo or 8% W to be deposited at 17-20V. Brush plated cobalt deposits possessed a mixed CPU and FCC crystallographic structure at room temperature. The application of 13µm of either of the cobalt alloys resulted in improved wear performance in both pin and disc and simulated hot forging tests. The results of the industrial trials indicated that by the use of these alloys, the life of hot forging dies may be increased by 20-100%. A commercial forging organisation is using electrolytes developed in this work to coat dies prior to forging nimonic alloys. Reductions in forging temperature and improved forging qualities have been reported. Cold pressing tools coated with the alloys showed a reduced tendency to "pick-up" and scoring of the pressed panels. Reports of a reduced need for lubrication of panels before pressing have also been received.

No description available.

The objectives of this research programme were to examine the influence of manufacturing and processing parameters on the environmental stability of aqueous acrylic based latices and to also extend the programme to an assessment of the behaviour of various stabiliser types suitable to such materials through either end-group modification or direct in-situ addition. During the research programme a number of physical and chemical techniques were assessed to routinely characterise and monitor the photochemical and thermal degradation of acrylic latices. These were based on emulsion polymerised formulations of methyl methacrylate and butyl acrylate. In the first instance, acrylic latices based on different formulations were chosen as homopolymers and copolymers. Here the nature of impurities and oxidation products generated during various stages of their manufacture have to be characterised and inter-related to their influence on subsequent environmental degradation. This involved the use of reflectance FT-IR spectroscopy to show functional group changes together with colourimetric U.V. analysis to determine photochemical generation of hydroperoxides. The early chemical changes and their subsequent influence on the physical and chemical properties of the latices during the later stages of environmental degradation were found to exhibit a close inter-relationship. In this regard the formation and the manufacturing temperatures and periods were crucial. Thermal methods of analysis were also used to characterise differences in the properties of the latices before and during thermal and photochemical oxidation. The nature of the residual persulphate initiator and the compositions of the latices in terms of end group modification were important parameters. De-esterification and hydroperoxide formation were found to be important processes during latex degradation while the use of low levels of co-monomer addition. such as methacrylic acicL to the emulsion reaction gave latices with improved light stability. Subsequent aspects of the research programme involved a detailed investigation into the behaviour and performance of various stabiliser types and formulations. Thus, while coreactive hindered piperidine stabilisers was found to be effective, the incorporation of simple terminal dialkyl acrylamide/methacrylaroide groups were also found to be effective. The efficiency of dialkylamide groups operating through a sacrificial mechanism is discussed. The influence of these processing operations on subsequent stabiliser activity provides valuable information on the mode of action of these stabilisers in such complex media. Further work involved a study into the effect of fluorinated methacrylates used in emulsion polymerised formulations. Here, the presence of residual starting materials in the monomer was found to have a detrimental effect in terms of photostability. Subsequent analysis of acrylic resins, based on solution polymerised formulations of methyl methacrylate and fluorinated methacrylates, was undertaken. The influence of reactive stabiliser types on these resins was important and to improve stabiliser perfonnance, synergistic stabiliser formulations were studied. This project will provide important fundamental information on the behaviour of active chromophores produced during the manufacturing process and hopefully resuh in the development of monitoring methodologies to establish paint quality.

No description available.

The practical advantages of thermal spray coatings like high deposition rates, low cost and tribological properties of high wear resistance have enabled these coatings to become an integral part of aircraft and automobile industry. Recent advancements in thermal spraying techniques like high particle speed and temperature call for new applications for these coatings. This experimental study addresses the Rolling Contact Fatigue performance of thermal spray coatings deposited by a variety of techniques like High Velocity Oxy-Fuel (HVOF), Detonation Gun (D-Gun) and Plasma spraying. RCF tests were conducted using a modified four ball machine in conventional steel ball bearing and hybrid ceramic bearing configurations. Tribological conditions during the RCF tests were varied by changing the test lubricant and the lubrication mechanism, contact load and shape of the drive coated rolling element to vary the roll/slip ratio. RCF tests were analyzed on the basis of the performance, coating failures using surface and subsurface observations, and residual stress studies. Experimental and theoretical studies of the ball kinematics have also been included. These tests revealed that the performance of the coated rolling elements was dependent upon the coating and the substrate properties. The coating thickness, substrate hardness, tribological conditions during the test, coating and substrate material as well as the coating process and the substrate preparation significantly affect the coating performance and the failure modes. Three different failure modes of these coatings have been discussed along with the changes in the near surface residual stress behaviour of the coated rolling elements.

The preparation, type and stability of emulsions stabilised solely by solid silica particles has been investigated in detail using a combination of conductivity, stability, light diffraction, optical microscopy and contact angle measurements. The wettability of the particles in situ at the oil-water interface plays a major role in such systems. The stability of aqueous colloidal dispersions in the presence of various electrolytes and over a range of pH is shown to be important in determining the stability of toluene-in-water emulsions formed from them. Partial flocculation of the silica dispersions enhances the emulsion stability whereas strong flocculation results in unstable emulsions. Inversion of emulsion type occurs via two mechanisms. Catastrophic inversion of water-in-oil emulsions stabilised by hydrophobic silica particles occurs upon increasing the volume fraction of water in the system. Transitional inversion of emulsions at fixed volume fraction of water has been achieved by varying the mass fraction of hydrophilic (or hydrophobic) particles in systems containing particle mixtures. Neither inversion mechanism exhibits hysteresis, in contrast to surfactant-stabilised systems. The energy of attachment of a particle to the oil-water interface is shown to be dependent on the contact angle and the interfacial tension. The contact angle was varied by changing the hydrophobicity of the silica particles. Particles of intermediate hydrophobicity were most effective at stabilising emulsions which is thought to be due to the contact angle at the oil-water interface being close to 90°. The interfacial tension was affected by changing the nature of the oil phase or by'replacing water with various polar liquids. Undecanol-water emulsions stabilised by silica particles of intermediate hydrophobicity break down via gel formation followed by coalescence. The wettability of the silica surface was varied in situ by varying the pH of the aqueous phase. Increasing the pH causes dissociation of silanol groups, which increases the affinity of the particles for the aqueous phase. The type and stability of emulsions and the contact angle of an aqueous drop under toluene on hydrophobically modified glass slides were measured as a function of pH. The results are modelled using simple theory. The wettability of hydrophobic pigment surfaces is dependent on the type and concentration of added surfactant. The findings are discussed in terms of surfactant adsorption at the relevant interfaces.

No description available.

No description available.