Non-metallic cold-cathode electron emission from composite metal-insulator microstructures

A detailed investigation has been undertaken into a field-induced electron emission (FIEE) mechanism that occurs at microscopically localised `sites' on uncoated, dielectric-coated and composite-coated metallic cathodes. An optical imaging technique has been used to observe and characterize the spatial and temporal behaviour of the populations of emission sites on these cathodes under various experimental conditions, e.g. pulsed-fields, gas environment etc. This study has shown that, for applied fields of 20MVm^-1, thin dielectric (750AA) and composite metal-insulator (MI) overlayers result in a dramatic increase in the total number of emission sites (typically 30cm^-2), and hence emission current. The emission process has been further investigated by a complementary electron spectroscopy technique which has revealed that the localised emission sites on these cathodes display field-dependent spectral shifts and half-widths, i.e. indicative of a `non-metallic' emission mechanism. Details are also given of a comprehensive investigation into the effects of the residual gas environment on the FIEE process from uncoated Cu-cathodes. This latter study has revealed that the well-known Gas Conditioning process can be performed with a wide range of gas species (e.g. O_2, N_2 etc), and furthermore, the degree of conditioning is influenced by both a `Voltage' and `Temperature' effect. These experimental findings have been shown to be particularly important to the technology of high-voltage vacuum-insulation and cold-cathode electron sources. The FIEE mechanism has been interpreted in terms of a hot-electron process that is associated with `electroformed' conducting channels in MI, MIM and MIMI surface microstructures.

The influence of non-metallic inclusions upon the properties of linepipe steels

The principal aim of this work was to determine the role of non-metallic inclusions in the process of hydrogen stepwise cracking (SWC). Additionally, the influence of inclusions upon the notch ductility of hydrogen charged (HC) and uncharged (UN) tensile specimens was examined. To obtain a basis for experiment a series of low carbon-manganese steels were prepared by induction melting. In order to produce variations in the composition, morphology, volume fraction, size and distribution of the inclusions the steel chemistry was adjusted prior to casting by additions of deoxidiser and Ca-Si injection. Sections of each ingot were hot rolled. Metallography, image analysis, mechanical tests and hydrogen SWC tests were then carried out. The volume fraction, morphology, and shape of inclusions influenced the tensile ductility of the steels. Marked anisotropy was found in the steels containing type II MnS inclusions at all rolling temperatures, whereas the fully Ca treated steel was isotropic. It was found that several inclusion parameters (projected length PL, mean free distance MFD, nearest-neighbour distance NND) correlated with fracture strain. An increase in inclusion volume fraction and/or the dimension of inclusions on a plane parallel to the plane of fracture led to a decrease in fracture strain. The inclusion parameters did not correlate with the fracture strains for the HC tensile specimens. However, large or clusters of inclusions acted as the principal sites for crack initiation. `Fisheyes' or areas of `flat' fracture were often found on these fracture surfaces. The criteria for SWC initiation was found to be either large inclusions or clusters of inclusions. As the PL of inclusions increased the probability of large SWCs occurring increased. SWC initiation at inclusions was believed to occur at a critical concentration of hydrogen. Factors which assisted the concentration of hydrogen at inclusions were discussed. None of the proposed mechanisms of hydrogen embrittlement could be identified as the single cause of SWC.

Cross-linking of collagen I by tissue transglutaminase provides a promising biomaterial for promoting bone healing

Transglutaminases (TGs) stabilize proteins by the formation of ε(γ-glutamyl)lysine cross-links. Here, we demonstrate that the cross-linking of collagen I (COL I) by tissue transglutaminase (TG2) causes an alteration in the morphology and rheological properties of the collagen fibers. Human osteoblasts (HOB) attach, spread, proliferate, differentiate and mineralize more rapidly on this cross-linked matrix compared to native collagen. When seeded on cross-linked COL I, HOB are more resistant to the loss of cell spreading by incubation with RGD containing peptides and with α1, α2 and β1 integrin blocking antibodies. Following adhesion on cross-linked collagen, HOB show increased phosphorylation of the focal adhesion kinase, and increased expression of β1 and β3 integrins. Addition of human bone morphogenetic protein to HOB seeded on TG2 cross-linked COL I enhanced the expression of the differentiation marker bone alkaline phosphatase when compared to cross-linked collagen alone. In summary, the use of TG2-modified COL I provides a promising new scaffold for promoting bone healing. © 2014 Springer-Verlag.

Fatigue in metallic alloys containing non-metallic particles

This paper examines the effects of non-metallic particles on fatigue performance and, in particular, their influence on fatigue crack propagation at high ΔK (Kmax) levels. The nature and properties of a number of common non-metallic particles found in Fe- and Al- based alloys are described, and consideration is given to the consequences of mismatch of physical and chemical properties between particle and matrix. Effects of particles on fatigue in conventional alloys are illustrated and compared with the behaviour of Al/SiCp MMC. The problems associated with developing particulate reinforced MMC with adequate fatigue crack growth resistance and toughness for structural applications are discussed. © 1991.

High-pressure XPS of crotyl alcohol selective oxidation over metallic and oxidized Pd(111)

Here, we report on the first application of high-pressure XPS (HP-XPS) to the surface catalyzed selective oxidation of a hydrocarbon over palladium, wherein the reactivity of metal and oxide surfaces in directing the oxidative dehydrogenation of crotyl alcohol (CrOH) to crotonaldehyde (CrHCO) is evaluated. Crotonaldehyde formation is disfavored over Pd(111) under all reaction conditions, with only crotyl alcohol decomposition observed. In contrast, 2D Pd5O4 and 3D PdO overlayers are able to selectively oxidize crotyl alcohol (1 mTorr) to crotonaldehyde in the presence of co-fed oxygen (140 mTorr) at temperatures as low as 40 °C. However, 2D Pd5O4 ultrathin films are unstable toward reduction by the alcohol at ambient temperature, whereas the 3D PdO oxide is able to sustain catalytic crotonaldehyde production even up to 150 °C. Co-fed oxygen is essential to stabilize palladium surface oxides toward in situ reduction by crotyl alcohol, with stability increasing with oxide film dimensionality.

Epitaxial growth and magnetic properties of half-metallic Fe3O4 on GaAs(100)

The growth and magnetic properties of epitaxial magnetite Fe3O4 on GaAs(100) have been studied by reflection high-energy electron diffraction, x-ray photoelectron spectroscopy, magneto-optical Kerr effect, and x-ray magnetic circular dichroism. The epitaxial Fe3O4 films were synthesized by in situ post growth annealing of ultrathin epitaxial Fe films at 500K in an oxygen partial pressure of 5×10−5mbar. The XMCD measurements show characteristic contributions from different sites of the ferrimagnetic magnetite unit cell, namely, Fetd3+, Feoh2+, and Feoh3+. The epitaxial relationship was found to be Fe3O4(100)⟨011⟩∕∕GaAs(100)⟨010⟩ with the unit cell of Fe3O4 rotated by 45° to match that of GaAs(100) substrate. The films show a uniaxial magnetic anisotropy in a thickness range of about 2.0–6.0nm with the easy axes along the [011] direction of the GaAs(100) substrate.

Involvement of tissue transglutaminase in the stabilisation of biomaterial/tissue interfaces important in medical devices

Tissue transglutaminase (tTG) has recently been established as a novel cell surface adhesion protein that binds with high affinity to fibronectin in the pericellular matrix. In this study, we have made use of this property to enhance the biocompatibility of poly(epsilon-caprolactone) (PCL), a biomaterial currently used in bone repair. Poly(epsilon-caprolactone) discs were first coated with fibronectin and then tTG. The surface localisation of the two proteins was confirmed using ELISA and the tTG shown to be active on the surface by incorporation of biotin cadaverine into the fibronectin coating. When human osteoblasts (HOBs) were seeded onto the coated polymer surfaces in serum free medium, the surface coated with fibronectin and then tTG showed an increase in the spreading of the cells as compared to the surface coated with fibronectin alone, when analysed using environmental scanning electron microscopy. The presence of tTG had no effect on HOB cell differentiation when analysed by determining alkaline phosphatase activity. The use of tTG as a novel adhesion protein in this way may therefore have considerable potential in forming a stable tissue/biomaterial interface for application in medical devices.

Biomaterial interactions with compromised tissue surfaces

This thesis is concerned with the nature of biomaterial interactions with compromised host tissue sites. Both ocular and dermal tissues can be wounded, following injury, disease or surgery, and consequently require the use of a biomaterial. Clear analogies exist between the cornea/tear film/contact lens and the dermal wound bed/wound fluid/skin adhesive wound dressing. The work described in this thesis builds upon established biochemistry to examine specific aspects of the interaction of biomaterials with compromised ocular and dermal tissue sites, with a particular focus on the role of vitronectin. Vitronectin is a prominent cell adhesion glycoprotein present in both tear fluid and wound fluid, and has a role in the regulation and upregulation of plasmin. The interaction of contact lenses with the cornea was assessed by a novel on-lens cell-based vitronectin assay technique. Vitronectin mapping showed that vitronectin-mediated cell adhesion to contact lens surfaces was due to the contact lens-corneal mechanical interaction rather than deposition out of the tear film. This deposition is associated predominantly with the peripheral region of the posterior contact lens surface. The locus of vitronectin deposition on the contact lens surface, which is affected by material modulus, is potentially an important factor in the generation of plasmin in the posterior tear film. Use of the vitronectin mapping technique on ex vivo bandage contact lenses revealed greater vitronectin-mediated cell adhesion to the contact lens surfaces in comparison to lenses worn in the healthy eye. The results suggest that vitronectin is more readily deposited from the impaired corneal tissue bed than the intact healthy tissue bed. Significantly, subjects with a deficient tear film were found to deposit high vitronectin-mediated cell adhesion levels to the BCL surface, thus highlighting the influence of the contact lens-tissue interaction upon deposition. Biomimetic principles imply that adhesive materials for wound applications, including hydrogels and hydrocolloids, should closely match the surface energy parameters of skin. The surface properties of hydrocolloid adhesives were found to be easily modified by contact with siliconised plastic release liners. In contrast, paper release liners did not significantly affect the adhesive surface properties. In order to characterise such materials in the actual wound environment, which is an extremely challenging task, preliminary considerations for the design of an artificial wound fluid model from an animal serum base were addressed.

Molecular detection using metallic nanowires with quantized conductance

This thesis studies the adsorption of molecules with different binding strengths onto copper nanowires with prestabilized conductance values fabricated by an electrochemical method. Since the diameters of these wires are comparable to the wavelength of conduction electrons the conductance of the nanowires is quantized, and the adsorption of even a few molecules onto atomically thin wires changes the conductance from integer values to fractional ones. These changes are proportional to the binding strength of the adsorbed molecules. The decrease in conductance is hypothesized to be caused by the scattering of the conduction electrons by the adsorbed molecules. The sensitivity of molecular adsorption-induced conductance change can be used for the development of a chemical sensor. The stabilized copper nanowires obtained in this thesis may also be used for other purposes, such as interconnecting conductors between nanodevices and digital switches in functional nanoelectronic circuitry.

Resonance fluorescence spectrum of a \Lambda-type quantum emitter close to a metallic nanoparticle

We theoretically study the resonance fluorescence spectrum of a three-level quantum emitter coupled to a spherical metallic nanoparticle. We consider the case that the quantum emitter is driven by a single laser field along one of the optical transitions. We show that the development of the spectrum depends on the relative orientation of the dipole moments of the optical transitions in relation to the metal nanoparticle. In addition, we demonstrate that the location and width of the peaks in the spectrum are strongly modified by the exciton-plasmon coupling and the laser detuning, allowing to achieve controlled strongly subnatural spectral line. A strong antibunching of the fluorescent photons along the undriven transition is also obtained. Our results may be used for creating a tunable source of photons which could be used for a probabilistic entanglement scheme in the field of quantum information processing.