The contextual evaluation of research on sexually explicit materials

This thesis criticises many psychological experiments on 'pornography' which attempt to demonstrate how 'pornography' causes and/or equals rape. It challenges simplistic definitions of 'pornography', arguing that sexually explicit materials (SEM) are constructed and interpreted in a number of different ways; and demonstrates that how, when and where materials are depicted or viewed will influence perceptions and reactions. In addition, it opposes the overreliance on male undergraduates as participants in 'porn' research. Theories of feminist psychology and reflexivity are used throughout the thesis, and provide a detailed contextual framework in a complex area. Results from a number of interlinking studies which use a variety of methodological approaches (focus groups, questionnaires and content analysis), indicate how contextual issues are omitted in much existing research on SEM. These include the views and experiences participants' hold prior to completing SEM studies; their opinions about those who 'use' 'pornography'; their understanding of key terms linked with SEM (eg: pornography and erotica); and discussions of sexual magazines aimed at male and female audiences. Participants' reactions to images and texts associated with SEM presented in different contexts are discussed. Three main conclusions are drawn from this thesis. Firstly, images deemed 'pornographic' differ through historical and cultural periods' and political, economic and social climates, so 'experimental' approaches may not always be the most appropriate research tool. Secondly, there is not one definition, source, or factor which may be named 'pornography'; and thirdly the context and presentation of materials influence how images are perceived and reacted to. The thesis argues a number of factors influence view of 'pornography', suggesting SEM may be 'in the eye of the beholder'.

Nitrogen implantation of tool steels and engineering coatings

Ion implantation modifies the surface composition and properties of materials by bombardment with high energy ions. The low temperature of the process ensures the avoidance of distortion and degradation of the surface or bulk mechanical properties of components. In the present work nitrogen ion implantation at 90 keV and doses above 1017 ions/cm2 has been carried out on AISI M2, D2 and 420 steels and engineering coatings such as hard chromium, electroless Ni-P and a brush plated Co-W alloy. Evaluation of wear and frictional properties of these materials was performed with a lubricated Falex wear test at high loads up to 900 N and a dry pin-on-disc apparatus at loads up to 40 N. It was found that nitrogen implantation reduced the wear of AISI 420 stainless steel by a factor of 2.5 under high load lubricated conditions and by a factor of 5.5 in low load dry testing. Lower but significant reductions in wear were achieved for AISI M2 and D2 steels. Wear resistance of coating materials was improved by up to 4 times in lubricated wear of hard Cr coatings implanted at the optimum dose but lower improvements were obtained for the Co-W alloy coating. However, hardened electroless Ni-P coatings showed no enhancement in wear properties. The benefits obtained in wear behaviour for the above materials were generally accompanied by a significant decrease in the running-in friction. Nitrogen implantation hardened the surface of steels and Cr and Co-W coatings. An ultra-microhardness technique showed that the true hardness of implanted layers was greater than the values obtained by conventional micro-hardness methods, which often result in penetration below the implanted depth. Scanning electron microscopy revealed that implantation reduced the ploughing effect during wear and a change in wear mechanism from an abrasive-adhesive type to a mild oxidative mode was evident. Retention of nitrogen after implantation was studied by Nuclear Reaction Analysis and Auger Electron Spectroscopy. It was shown that maximum nitrogen retention occurs in hard Cr coatings and AISI 420 stainless steel, which explains the improvements obtained in wear resistance and hardness. X-ray photoelectron spectroscopy on these materials revealed that nitrogen is almost entirely bound to Cr, forming chromium nitrides. It was concluded that nitrogen implantation at 90 keV and doses above 3x1017 ions/cm2 produced the most significant improvements in mechanical properties in materials containing nitride formers by precipitation strengthening, improving the load bearing capacity of the surface and changing the wear mechanism from adhesive-abrasive to oxidative.

A rationale for the optimisation by computer methods of the efficient use of metals and materials

The aim of the research project was to gain d complete and accurate accounting of the needs and deficiencies of materials selection and design data, with particular attention given to the feasibility of a computerised materials selection system that would include application analysis, property data and screening techniques. The project also investigates and integrates the three major aspects of materials resources, materials selection and materials recycling. Consideration of the materials resource base suggests that, though our discovery potential has increased, geologic availability is the ultimate determinant and several metals may well become scarce at the same time, thus compounding the problem of substitution. With around 2- to 20- million units of engineering materials data, the use of a computer is the only logical answer for scientific selection of materials. The system developed at Aston is used for data storage, mathematical computation and output. The system enables programs to be run in batch and interactive (on-line) mode. The program with modification can also handle such variables as quantity of mineral resources, energy cost of materials and depletion and utilisation rates of strateqic materials. The work also carries out an in-depth study of copper recycling in the U.K. and concludes that, somewhere in the region of 2 million tonnes of copper is missing from the recycling cycle. It also sets out guidelines on product design and conservation policies from the recyclability point of view.

Microstructural degradation of aluminide coatings on single crystal nickel based superalloys during high temperature exposure

An investigation, employing edge-on transmission electron microscopy, of the microstructure of aluminide diffusion coatings on a single crystal y' strengthened nickel base super alloy is reported. An examination has been made of the effect of postcoating exposure at 1100°C on the stability of the coating matrix, a B2 type phase, nominally NiAl. Precipitation in the coating is considered with respect to both decomposition of the B2 matrix to other Ni-Al (plus titanium) phases and the formation of chromium bearing precipitates. A comparison is drawn with behaviour at lower temperatures (850-950°C). © 1995 The Institute of Materials.

Precipitation of chromium containing phases in aluminide coated nickel-base superalloy single crystals

The precipitation of chromium-containing phases, in both the B2 type β-phase coating matrix (nominally NiAl) and the substrate of high-activity-pack-aluminized single crystals of a nickel-base superalloy, is considered in this paper. An ‘edge-on’ transmission electron microscopy (TEM) technique is employed to examine the precipitation of M23X6, σ, α-Cr and other phases after coating and diffusion treatment and subsequent post-coating treatment at 850 and 950 °C. Initial precipitation is dominated by the formation of M23X6 in both the coating and substrate, however, in the case of single-crystal substrates the formation of this carbon-rich phase is not sustained. M23X6 precipitation is superceded by the formation of coherent precipitates of the α-Cr phase which effectively retains the basis but removes the superlattice of the β-matrix. Extensive precipitation of α-Cr has the effect of changing the balance of chromium to molybdenum in solution in the β-phase and further precipitation is dominated by Σ-phase intermetallics and other Cr-Mo-containing phases.

In vitro bioactivity of titanium-doped bioglass

Previous studies have suggested that incorporating relatively small quantities of titanium dioxide into bioactive glasses may result in an increase in bioactivity and hydroxyapatite formation. The present work therefore investigated the in vitro bioactivity of a titanium doped bioglass and compared the results with 45S5 bioglass. Apatite formation was evaluated for bioglass and Ti-bioglass in the presence and absence of foetal calf serum. Scanning electron microscopy (SEM) images were used to evaluate the surface development and energy dispersive X-ray measurements provided information on the elemental ratios. X-ray diffraction spectra confirmed the presence of apatite formation. Cell viability was assessed for bone marrow stromal cells under direct and indirect contact conditions and cell adhesion was assessed using SEM. © 2014 Springer Science+Business Media.

Synthesis and characterization of nanoporous phospho-tungstate organic-inorganic hybrid materials

Nanoporous phospho-tungstate organic-inorganic hybrid materials have been synthesized from sodium tungstate and mono-n-dodecyl phosphate (MDP), which was used as both surfactant and phosphorus precursor. These hybrid materials were thoroughly characterized by N2 adsorption, elemental analysis, powder XRD, FTIR, Raman, TG, TEM and XPS and possess lamellar structures with interlayer spacings of 3.2 nm. A plausible method for formation of hybrid materials comprised of lacunary Keggin anions and micelles of surfactants is proposed. © The Royal Society of Chemistry 2008.

Scavenging of halogen in recycling of halogen-based polymer materials

Pyrolytic recycling of materials for electronics and automotive is attractive because of the possibility of recovery of fuel and of precious metals from printed circuit. Due to the complexity of their composition an appropriate pre-treatment has to be performed in order to limit the evolution of dangerous halogen containing compounds which strongly impair the fuel quality. An advantageous pyrolysis approach implies the attempt of mineralisation of the organic bromine to the not volatile and harmless inorganic form using strong bases such as NaOH and KOH to reduce the amount of volatile and increasing the residue. The char stability is greatly variable depending on the substrate. Mg(OH)2 and Ca(OH)2 behave in a similar manner but to a lower extent. Carbonates and reducing agent such as LiAlH have been tested as well and their ability to scavenge bromine is discussed in terms of effectiveness and mechanism.

Green preparation of tuneable carbon-silica composite materials from wastes

Bio-oil has successfully been utilized to prepare carbon-silica composites (CSCs) from mesoporous silicas, such as SBA-15, MCM-41, KIT-6 and MMSBA frameworks. These CSCs comprise a thin film of carbon dispersed over the silica matrix and exhibit porosity similar to the parent silica. The surface properties of the resulting materials can be simply tuned by the variation of preparation temperatures leading to a continuum of functionalities ranging from polar hydroxyl rich surfaces to carbonaceous aromatic surfaces, as reflected in solid state NMR, XPS and DRIFT analysis. N2 porosimetry, TEM and SEM images demonstrate that the composites still possess similar ordered mesostructures to the parent silica sample. The modification mechanism is also proposed: silica samples are impregnated with bio-oils (generated from the pyrolysis of waste paper) until the pores are filled, followed by the carbonization at a series of temperatures. Increasing temperature leads to the formation of a carbonaceous layer over the silica surface. The complex mixture of compounds within the bio-oil (including those molecules containing alcohols, aliphatics, carbonyls and aromatics) gives rise to the functionality of the CSCs.

Synergistic synthesis of quasi-monocrystal CdS nanoboxes with high-energy facets

Hollow nanostructures with a highly oriented lattice structure and active facets are promising for catalytic applications, while their preparation via traditional approaches contains multiple steps and is time and energy consuming. Here, we demonstrate a new one-step strategy involving two complementary reactions which promote each other; it is capable of producing unique hollow nanoparticles. Specifically, we apply synergic cooperation of cation exchange and chemical etching to attack PbS nanosized cubes (NCs) and produce CdS quasi-monocrystal nanoboxes (QMNBs) which possess the smallest dimensions reported so far, a metastable zinc-blende phase, a large specific surface area, and particularly high-energy {100} facets directly visualized by aberration-corrected scanning transmission electron microscopy. These properties in combination allow the nanoboxes to acquire exceptional photocatalytic activities. As an extension of the approach, we use the same strategy to prepare Co9S8 and Cu7.2S4 single-crystal hollow nanooctahedrons (SCHNOs) successfully. Hence, the synergic reaction synthesis strategy exhibits great potential in engineering unique nanostructures with superior properties.

Catalytic applications of waste derived materials

Sustainability has become a watchword and guiding principle for modern society, and with it a growing appreciation that anthropogenic 'waste', in all its manifold forms, can offer a valuable source of energy, construction materials, chemicals and high value functional products. In the context of chemical transformations, waste materials not only provide alternative renewable feedstocks, but also a resource from which to create catalysts. Such waste-derived heterogeneous catalysts serve to improve the overall energy and atom-efficiency of existing and novel chemical processes. This review outlines key chemical transformations for which waste-derived heterogeneous catalysts have been developed, spanning biomass conversion to environmental remediation, and their benefits and disadvantages relative to conventional catalytic technologies.

The development of biomaterials for contact lens applications:effects of wear modality on materials design

The successful design of polymers for contact lens applications depends on the ability to provide a balance of properties appropriate to the ocular environment. Principal relevant aspects of the anterior eye are the tear film, eyelid and cornea, which govern the requirements for surface properties, modulus and oxygen permeability, respectively. Permeability requirements and the developing view of the needs of the cornea, in terms of oxygen consumption and the particular roles of fluorine and silicon in the design of silicone hydrogels, which have proved to be the most successful family of materials for this demanding application, are discussed. The contact lens field is complicated by the fact that contact lenses are used in a range of wear modalities, the extremes of which can conveniently be classified as lenses that are disposed of at the end of a single period of daily wear and those used for 30. days of successive day-and-night periods, frequently referred to as extended or continuous wear. As silicone hydrogels developed, in the decade following their launch there has been a progressive trend in properties taking both modulus and water content closer to those of conventional hydrogels. This is particularly evident in the family of daily disposable contact lenses that have appeared since 2008.

Site specific growth of metal catalyzed silica nanowires for biological and chemical sensing

In this research the integration of nanostructures and micro-scale devices was investigated using silica nanowires to develop a simple yet robust nanomanufacturing technique for improving the detection parameters of chemical and biological sensors. This has been achieved with the use of a dielectric barrier layer, to restrict nanowire growth to site-specific locations which has removed the need for post growth processing, by making it possible to place nanostructures on pre-pattern substrates. Nanowires were synthesized using the Vapor-Liquid-Solid growth method. Process parameters (temperature and time) and manufacturing aspects (structural integrity and biocompatibility) were investigated. Silica nanowires were observed experimentally to determine how their physical and chemical properties could be tuned for integration into existing sensing structures. Growth kinetic experiments performed using gold and palladium catalysts at 1050°C for 60 minutes in an open-tube furnace yielded dense and consistent silica nanowire growth. This consistent growth led to the development of growth model fitting, through use of the Maximum Likelihood Estimation (MLE) and Bayesian hierarchical modeling. Transmission electron microscopy studies revealed the nanowires to be amorphous and X-ray diffraction confirmed the composition to be SiO2 . Silica nanowires were monitored in epithelial breast cancer media using Impedance spectroscopy, to test biocompatibility, due to potential in vivo use as a diagnostic aid. It was found that palladium catalyzed silica nanowires were toxic to breast cancer cells, however, nanowires were inert at 1μg/mL concentrations. Additionally a method for direct nanowire integration was developed that allowed for silica nanowires to be grown directly into interdigitated sensing structures. This technique eliminates the need for physical nanowire transfer thus preserving nanowire structure and performance integrity and further reduces fabrication cost. Successful nanowire integration was physically verified using Scanning electron microscopy and confirmed electrically using Electrochemical Impedance Spectroscopy of immobilized Prostate Specific Antigens (PSA). The experiments performed above serve as a guideline to addressing the metallurgic challenges in nanoscale integration of materials with varying composition and to understanding the effects of nanomaterials on biological structures that come in contact with the human body.

The role of impurities in the shape, structure and physical properties of semiconducting oxide nanostructures grown by thermal evaporation

A thermal evaporation method developed in the research group enables to grow and design several morphologies of semiconducting oxide nanostructures, such as Ga_2O_3, GeO_2 or Sb_2O_3, among others, and some ternary oxide compounds (ZnGa_2O_4, Zn_2GeO_4). In order to tailor physical properties, a successful doping of these nanostructures is required. However, for nanostructured materials, doping may affect not only their physical properties, but also their morphology during the thermal growth process. In this paper, we will show some examples of how the addition of impurities may result into the formation of complex structures, or changes in the structural phase of the material. In particular, we will consider the addition of Sn and Cr impurities into the precursors used to grow Ga_2O_3, Zn_2GeO_4 and Sb_2O_3 nanowires, nanorods or complex nanostructures, such as crossing wires or hierarchical structures. Structural and optical properties were assessed by electron microscopy (SEM and TEM), confocal microscopy, spatially resolved cathodoluminescence (CL), photoluminescence, and Raman spectroscopies. The growth mechanisms, the luminescence bands and the optical confinement in the obtained oxide nanostructures will be discussed. In particular, some of these nanostructures have been found to be of interest as optical microcavities. These nanomaterials may have applications in optical sensing and energy devices.

Tubular micro- and nanostructures of TCO materials grown by a vapor-solid method

Microtubes and rods with nanopipes of transparent conductive oxides (TCO), such as SnO_2, TiO_2, ZnO and In_2O_3, have been fabricated following a vapor-solid method which avoids the use of catalyst or templates. The morphology of the as-grown tubular structures varies as a function of the precursor powder and the parameters employed during the thermal treatments carried out under a controlled argon flow. These materials have been also doped with different elements of technological interest (Cr, Er, Li, Zn, Sn). Energy Dispersive X-ray Spectroscopy (EDS) measurements show that the concentration of the dopants achieved by the vapor-solid method ranges from 0.5 to _3 at.%. Luminescence of the tubes has been analyzed, with special attention paid to the influence of the dopants on their optical properties. In this work, we summarize and discuss some of the processes involved not only in the anisotropic growth of these hollow micro and nanostructures, but also in their doping.