Spectroscopic studies of field-induced electron emission from isolated microstructures

A detailed investigation has been undertaken into the field induced electron emission (FIEE) mechanism that occurs at microscopically localised `sites' on uncoated and dielectric coated metallic electrodes. These processes have been investigated using two dedicated experimental systems that were developed for this study. The first is a novel combined photo/field emission microscope, which employs a UV source to stimulate photo-electrons from the sample surface in order to generate a topographical image. This system utilises an electrostatic lens column to provide identical optical properties under the different operating conditions required for purely topographical and combined photo/field imaging. The system has been demonstrated to have a resolution approaching 1m. Emission images have been obtained from carbon emission sites using this system to reveal that emission may occur from the edge triple junction or from the bulk of the carbon particle. An existing UHV electron spectrometer has been extensively rebuilt to incorporate a computer control and data acquisition system, improved sample handling and manipulation and a specimen heating stage. Details are given of a comprehensive study into the effects of sample heating on the emission process under conditions of both bulk and transient heating. Similar studies were also performed under conditions of both zero and high applied field. These show that the properties of emission sites are strongly temperature and field dependent thus indicating that the emission process is `non-metallic' in nature. The results have been shown to be consistent with an existing hot electron emission model.

Hypercoiling and hydrophobically associating polymers : interfacial synthesis, surface properties and pharmaceutical applications

The objective of the work described was to identify and synthesize a range of biodegradable hypercoiling or hydrophobically associating polymers to mimic natural apoproteins, such as those found in lung surfactant or plasma apolipoproteins. Stirred interfacial polymerization was used to synthesize potentially biodegradable aromatic polyamides (Mw of 12,000-26,000) based on L-Iysine, L-Iysine ethyl ester, L-ornithine and DL-diaminopropionic acid, by reaction with isophthaloyl chloride. A similar technique was used to synthesize aliphatic polyamides based on L-Iysine ethyl ester and either adipoyl chloride or glutaryl chloride resulting in the synthesis of poly(lysine ethyl ester adipamide) [PLETESA] or poly(lysine ethyl ester glutaramide) (Mw of 126,000 and 26,000, respectively). PLETESA was found to be soluble in both polar and non-polar solvents and the hydrophobic/hydrophilic balance could be modified by partial saponification (66-75%) of the ethyl ester side chains. Surface or interfacial tension/pH profiles were used to assess the conformation of both the poly(isophthalamides) and partially saponified PLETESA in aqueous solution. The results demonstrated that a loss of charge from the polymer was accompanied by an initial fall in surface activity, followed by a rise in activity, and ultimately, by polymer precipitation. These observations were explained by a collapse of the polymer chains into non-surface active intramolecular coils, followed by a transition to an amphipathic conformation, and finally to a collapsed hydrophobe. 2-Dimensional NMR analysis of polymer conformation in polar and non-polar solvents revealed intramolecular associations between the hydrophobic groups within partially saponified PLETESA. Unsaponified PLETESA appeared to form a coiled structure in polar solvents where the ethyl ester side chains were contained within the polymer coil. The implications of the secondary structure of PLETESA and potential biomedical applications are discussed.

Acanthamoebal surface properties and the modulation of phagocytosis

The surface nature of Acanthamoeba trophozoites and cysts was investigated with respect to cell surface charge, hydrophobicity and surface carbohydrate composition. Particulate microelectrophoresis revealed a marked negative charge for both morphological forms, though less for cyst surfaces. Hydrophobicity was determined by adhesion to n-hexadecane and indicated a relatively low hydrophobic nature of both forms, though less so for cysts. Surface carbohydrate composition was studied by the use of fluorescent lectins and flow cytometry, using a ligand-receptor approach for further in depth analysis of binding of particular lectins. These studies showed trophozoite and cyst surfaces to be rich in N-acetylglucosamine, N-acteylneuraminic acid, mannose and glucose, with the addition of N-acetylgalactosamine on cysts. The importance of such surface properties was investigated with respect to phagocytosis of polystyrene latex microspheres, of different surface types and size. Investigations into the optimum conditions of uptake of beads indicated a preference for a medium devoid of nutrients, such as saline, though temperature was not a factor. An amoebal predilection for beads of lower charge and greater hydrophobicity was demonstrated. Furthermore, a preference for the largest bead size used (2.0 m) was observed. The influence of either Con A or mannose or glucose on bead association was apparently limited. The fate of foreign DNA ingested by Acanthamoeba appeared to indicate that such DNA was destroyed, as it could not be detected following extraction procedures and PCR amplification.

The effect of care solutions on the bulk and surface properties of soft contact lenses

Purpose: Soft contact lenses for continuous wear require the use of cleaning regimes which utilise hydrogen peroxide systems or multipurpose cleaning solutions (MPS). The compositions of MPS are becoming increasingly complex and often include disinfectants, cleaning agents, preservatives, wetting agents, demulcents, chelating and buffering agents. Recent research on solution–lens interactions has focused on specific ocular parameters such as corneal staining. However the effect of a solution on the lens, particularly silicone hydrogel lenses, itself has received less attention. The purpose of this work was to establish and understand the effects that care solutions have on selected bulk and surface material properties. Methods: Selected bulk and surface properties of each material (etafilcon A, vifilcon A, balafilcon A, senofilcon A, lotrafilcon A and lotrafilcon B, galyfilcon A) were measured after a 24 h soak in a variety of care solutions. Additionally the lenses were soaked for 24 h in hyperosmolar (680 mOsm L-1) and hyposmolar (170 mOsm L-1) PBS. A bulk property parameter the total diameter (TD) was measured using an Optimec contact lens analyser. The surface property related CoF of soaked lenses was measured on a nano-tribometer with conditions of load 30 mN, at a distance of 20 mm and speed 30 mm/min. Results: In terms of bulk properties, change is related to the EWC of the lens, the higher the EWC of the lens the greater the TD changes. Silicone hydrogel lenses have EWCs of <47% and little or no TD changes were observed; lotrafilcon A exhibited no change irrespective of the cleaning solution. Conventional contact lenses have higher EWCs (58% for etafilcon A and 55% for vifilcon A) and the TD was seen to change to a greater extent, for example the etafilcon A material in ReNu MPS had an increase to 14.45± 0.07 mm from the cited 14.2 mm. Other lenses increased or decreased in TD depending on the solution used. The osmolarity of the solution although important is not the only factor governing change in the TD, for example soaking senofilcon A in hyperosmolar PBS (680 mOsm L-1) for 24 h increased the TD of the lens (+0.25 ± 0.07 mm), however when the same lens type was soaked for 24 h in a MPS with a lower osmolarity there was a similar effect. Biotribology measurements demonstrated that some solution–lens combinations can reduce the CoF by 55%, when compared with biotribology with the native packing solution. An increase in the CoF was observed for other solution–lens combinations. Conclusions: There is a dramatic difference in bulk and surface performance of specific lens materials with particular care solutions. Individual components of the care solutions have effects on the bulk and surface properties of contact lenses. The affects are not as great with the silicone hydrogel as compared with conventional hydrogels.

Caking behaviour of spray-dried milk powders:using scanning probe microscopy to study nanoscale surface properties and material composition

Spray drying is widely used to manufacture many powdered products, with the drying process parameters having significant influence over the final powder's surface properties and propensity for unwanted caking. In most cases caking experiments are performed on bulk powders, but especially in multi-component powders, it is often difficult to interpret these results, where interaction effects between particles can be complex. Here the technique of scanning probe microscopy is used to characterize the nanoscale properties of spray dried model milk powders in order to investigate the surface properties of the powders.

The influence of defects on the electron-transfer and magnetic properties of RbxMn[Fe(CN)6]y·zH2O

The synthesis and detailed characterization of a few samples of the compound RbMn[Fe(CN)]·zHO are described. The composition of the materials significantly depends on the applied preparative conditions. Analysis of spectroscopic results (FTIR, Raman, Fe Mössbauer, XPS) and X-ray powder-diffraction data yielded a further assessment of the difference in structural features in terms of the amount of Fe(CN)6 vacancies and the associated number of water molecules. The characteristic individual magnetic behavior, as well as the metal-to-metal charge-transfer capabilities of the various samples, could be related to significant changes within the structures that appear to be associated with the synthetic method used.

The relation between physical properties of the anterior eye and ocular surface temperature

PURPOSE. To examine the relation between ocular surface temperature (OST) assessed by dynamic thermal imaging and physical parameters of the anterior eye in normal subjects. METHODS. Dynamic ocular thermography (ThermoTracer 7102MX) was used to record body temperature and continuous ocular surface temperature for 8 s after a blink in the right eyes of 25 subjects. Corneal thickness, corneal curvature, and anterior chamber depth (ACD) were assessed using Orbscan II; noninvasive tear break-up time (NIBUT) was assessed using the tearscope; slit lamp photography was used to record tear meniscus height (TMH) and objective bulbar redness. RESULTS. Initial OST after a blink was significantly correlated only with body temperature (r = 0.80, p < 0.0005), NIBUT (r = -0.68, p < 0.005) and corneal curvature (r = -0.40, p = 0.05). A regression model containing all the variables accounted for 70% (p = 0.002) of the variance in OST, of which NIBUT (29%, p = 0.004), and body temperature (18%, p = 0.005) contributed significantly. CONCLUSIONS. The results support previous theoretical models that OST radiation is principally related to the tear film; and demonstrate that it is less related to other characteristics such as corneal thickness, corneal curvature, and anterior chamber depth. © 2007 American Academy of Optometry.

Mechanical properties and the evolution of matrix molecules in PTFE upon irradiation with MeV alpha particles

The morphology, chemical composition, and mechanical properties in the surface region of α-irradiated polytetrafluoroethylene (PTFE) have been examined and compared to unirradiated specimens. Samples were irradiated with 5.5 MeV 4He2+ ions from a tandem accelerator to doses between 1 × 106 and 5 × 1010 Rad. Static time-of-flight secondary ion mass spectrometry (ToF-SIMS), using a 20 keV C60+ source, was employed to probe chemical changes as a function of a dose. Chemical images and high resolution spectra were collected and analyzed to reveal the effects of a particle radiation on the chemical structure. Residual gas analysis (RGA) was utilized to monitor the evolution of volatile species during vacuum irradiation of the samples. Scanning electron microscopy (SEM) was used to observe the morphological variation of samples with increasing a particle dose, and nanoindentation was engaged to determine the hardness and elastic modulus as a function of a dose. The data show that PTFE nominally retains its innate chemical structure and morphology at a doses <109 Rad. At α doses ≥109 Rad the polymer matrix experiences increased chemical degradation and morphological roughening which are accompanied by increased hardness and declining elasticity. At  α doses >1010 Rad the polymer matrix suffers severe chemical degradation and material loss. Chemical degradation is observed in ToF-SIMS by detection of ions that are indicative of fragmentation, unsaturation, and functionalization of molecules in the PTFE matrix. The mass spectra also expose the subtle trends of crosslinking within the α-irradiated polymer matrix. ToF-SIMS images support the assertion that chemical degradation is the result of a particle irradiation and show morphological roughening of the sample with increased a dose. High resolution SEM images more clearly illustrate the morphological roughening and the mass loss that accompanies high doses of a particles. RGA confirms the supposition that the outcome of chemical degradation in the PTFE matrix with continuing irradiation is evolution of volatile species resulting in morphological roughening and mass loss. Finally, we reveal and discuss relationships between chemical structure and mechanical properties such as hardness and elastic modulus.

Microstructural study of aluminide surface coatings on single crystal nickel base superalloy substrates

Aluminide diffusion coatings are frequently employed to enhance the oxidation resistance of nickel base superalloys. However, there is a concern that the presence of an aluminide coating could influence the properties of the coated superalloy, especially in respect of fatigue behaviour. To understand the nature of the effects of surface coatings on the fatigue properties of superalloys, an understanding of microstructural development within both the coating and the coating/substrate interfacial zone during high temperature fatigue testing is necessary. This paper is concerned with microstructural changes in aluminide diffusion coatings on single crystal γ′ strengthened superalloy substrates during the course of high temperature fatigue testing. The 'edge on' transmission electron microscopy technique is employed to study cross-sections of two stage (aluminization plus diffusion treatment) coated superalloy samples. The paper examines the degradation of the coating produced by phase transformations induced by loss of aluminum from the coating and/or aging of the coating. Aluminum removal both by interdiffusion with the substrate and by oxidation of the coating surface is considered. Microstructural development in the portion of the substrate influenced by interdiffusion with the coating is also discussed.