A new strategy for selecting and evaluating physical solvents for gas absorption

This work describes how the physical properties of a solvent affect the design variables of a physical gas absorption process. The role of every property in determining the capital and the running cost of a process has been specified. Direct mathematical relationships have been formulated between every item of capital or running cost and the properties which are related to that item. The accuracy of the equations formulated has been checked by comparing their outcome with some actual design data. A good agreement has been found. The equations formulated may be used to evaluate on the basis of economics any suggested new solvents. A group of solvents were selected for evaluation. Their physical properties were estimated or collected as experimental data. The selected ones include three important solvents, the first is polyethylene glycol dimethyl ether (Selexol) which represents the currently most successful one, The other two solvents are acetonyl acetone (B2) and n-formyl morpholine which have been suggested previously as potential credible alternatives to the current ones. The important characteristics of: acetonyl acetone are its high solubility and its low viscosity, while the n-formyl morpholine is characterised by its low vapour pressure and its high selectivity. It was found that acetonyl acetone (B2) is the most attractive solvent for commercial applications particularly for process configurations that:include heat exchangers and strippers. The effect of the process configuration on the selected solvent was investigated in detail and it was found that there is no universal solvent which is the best for any process configuration, but that there is a best solvent for a given process configuration. In previous work, acetonyl acetone was suggested as a commercially promising physical solvent. That suggestion was not fully based on experimental measurement of all the physical properties. The viscosity of acetonyl acetone and its solubility at 1 atm were measured but the vapour pressure and the solubility of C02 and CH4 at high pressure were predicted. In this work, the solubilities of C02, CH4 and C3H8 in acetenyl acetone were measured for a partial pressure range of (2 ~ 22) bar at 25°C, The vapour pressure of this solvent was also measured, and the Antoine equation was formulated from tbe experimental data. The experimental data were found to be not In agreement with the predicted ones, so acetonyl acetone was re-evaluated according to the experimental data. It was found that this solvent can be recommended for further trials in a pilot plant study or for small scale commercial units.

The discretionary role of the line manager in inspiring work engagement and innovative behaviour:a study of social exchange and job resources in the public sector

This thesis is about the discretionary role of the line manager in inspiring the work engagement of staff and their resulting innovative behaviour examined through the lens of Social Exchange Theory (Blau, 1964) and the Job Demands-Resources theory (Bakker, Demerouti, Nachreiner & Schaufeli, 2001). The study is focused on a large British Public Sector organisation undergoing a major organisational shift in the way in which they operate as part of the public sector. It is often claimed that people do not leave organisations; they leave line managers (Kozlowski & Doherty, 1989). Regardless of the knowledge in the literature concerning the importance of the line manager in organisations (Purcell, 2003), the engagement literature in particular is lacking in the consideration of such a fundamental figure in organisational life. Further, the understanding of the black box of managerial discretion and its relationship to employee and organisation related outcomes would benefit from greater exploration (Purcell, 2003; Gerhart, 2005; Scott, et al, 2009). The purpose of this research is to address these gaps with relation to the innovative behaviour of employees in the public sector – an area that is not typically associated with the public sector (Bhatta, 2003; McGuire, Stoner & Mylona, 2008; Hughes, Moore & Kataria, 2011). The study is a CASE Award PhD thesis, requiring academic and practical elements to the research. The study is of one case organisation, focusing on one service characterised by a high level of adoption of Strategic Human Resource Management activities and operating in a rather unique manner for the public sector, having private sector competition for work. The study involved a mixed methods approach to data collection. Preliminary focus groups with 45 participants were conducted, followed by an ethnographic period of five months embedded into the service conducting interviews and observations. This culminated in a quantitative survey delivered within the wider directorate to approximately 500 staff members. The study used aspects of the Grounded Theory (Glaser & Strauss, 1967) approach to analyse the data and developed results that highlight the importance of the line manager in an area characterised by SHRM and organisational change for engaging employees and encouraging innovative behaviour. This survey was completed on behalf of the organisation and the findings of this are presented in appendix 1, in order to keep the focus of the PhD on theory development. Implications for theory and practice are discussed alongside the core finding. Line managers’ discretion surrounding the provision of job resources (in particular trust, autonomy and implementation and interpretation of combined bundles of SHRM policies and procedures) influenced the exchange process by which employees responded with work engagement and innovative behaviour. Limitations to the research are the limitations commonly attributed to cross-sectional data collection methods and those surrounding generalisability of the qualitative findings outside of the contextual factors characterising the service area. Suggestions for future research involve addressing these limitations and further exploration of the discretionary role with regards to extending our understanding of line manager discretion.

Direct femtosecond laser inscription in transparent dielectrics

Since 1996 direct femtosecond inscription in transparent dielectrics has become the subject of intensive research. This enabling technology significantly expands the technological boundaries for direct fabrication of 3D structures in a wide variety of materials. It allows modification of non-photosensitive materials, which opens the door to numerous practical applications. In this work we explored the direct femtosecond inscription of waveguides and demonstrated at least one order of magnitude enhancement in the most critical parameter - the induced contrast of the refractive index in a standard borosilicate optical glass. A record high induced refractive contrast of 2.5×10-2 is demonstrated. The waveguides fabricated possess one of the lowest losses, approaching level of Fresnel reflection losses at the glassair interface. High refractive index contrast allows the fabrication of curvilinear waveguides with low bend losses. We also demonstrated the optimisation of the inscription regimes in BK7 glass over a broad range of experimental parameters and observed a counter-intuitive increase of the induced refractive index contrast with increasing translation speed of a sample. Examples of inscription in a number of transparent dielectrics hosts using high repetition rate fs laser system (both glasses and crystals) are also presented. Sub-wavelength scale periodic inscription inside any material often demands supercritical propagation regimes, when pulse peak power is more than the critical power for selffocusing, sometimes several times higher than the critical power. For a sub-critical regime, when the pulse peak power is less than the critical power for self-focusing, we derive analytic expressions for Gaussian beam focusing in the presence of Kerr non-linearity as well as for a number of other beam shapes commonly used in experiments, including astigmatic and ring-shaped ones. In the part devoted to the fabrication of periodic structures, we report on recent development of our point-by-point method, demonstrating the shortest periodic perturbation created in the bulk of a pure fused silica sample, by using third harmonics (? =267 nm) of fundamental laser frequency (? =800 nm) and 1 kHz femtosecond laser system. To overcome the fundamental limitations of the point-by-point method we suggested and experimentally demonstrated the micro-holographic inscription method, which is based on using the combination of a diffractive optical element and standard micro-objectives. Sub-500 nm periodic structures with a much higher aspect ratio were demonstrated. From the applications point of view, we demonstrate examples of photonics devices by direct femtosecond fabrication method, including various vectorial bend-sensors fabricated in standard optical fibres, as well as a highly birefringent long-period gratings by direct modulation method. To address the intrinsic limitations of femtosecond inscription at very shallow depths we suggested the hybrid mask-less lithography method. The method is based on precision ablation of a thin metal layer deposited on the surface of the sample to create a mask. After that an ion-exchange process in the melt of Ag-containing salts allows quick and low-cost fabrication of shallow waveguides and other components of integrated optics. This approach covers the gap in direct fs inscription of shallow waveguide. Perspectives and future developments of direct femtosecond micro-fabrication are also discussed.

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.

Direct activation of microcrystalline zeolites

In this work a direct activation route of zeolites is assessed. It consists of NH4-exchanging the as-synthesized solids before removing the organic template. Calcination afterwards serves to combust the organic template and creates the Brønsted sites directly; thus applying merely a single thermal step. This method simplifies their activation and the material suffers less thermal stress. The approach was particularly effective for microcrystalline beta and ferrierite zeolites. Thorough investigation of the template content and materials' texture points out to three relevant effects that can explain the effective exchange process: partial removal of the template during exchange creates substantial microporosity (ferrierite), the remaining template is reorganized within the pores (ferrierite) and finally, void space can exist due to the non-perfect matching between the network and template (beta). This shorter method appears suited for microcrystalline zeolites; it was ineffective for crystalline MFI types. © 2013 Elsevier B.V. All rights reserved.

Tail gas catalyzed N2O decomposition over Fe-beta zeolite. On the promoting role of framework connected AlO6 sites in the vicinity of Fe by controlled dealumination during exchange

A novel route to prepare highly active and stable N2O decomposition catalysts is presented, based on Fe-exchanged beta zeolite. The procedure consists of liquid phase Fe(III) exchange at low pH. By varying the pH systematically from 3.5 to 0, using nitric acid during each Fe(III)-exchange procedure, the degree of dealumination was controlled, verified by ICP and NMR. Dealumination changes the presence of neighbouring octahedral Al sites of the Fe sites, improving the performance for this reaction. The so-obtained catalysts exhibit a remarkable enhancement in activity, for an optimal pH of 1. Further optimization by increasing the Fe content is possible. The optimal formulation showed good conversion levels, comparable to a benchmark Fe-ferrierite catalyst. The catalyst stability under tail gas conditions containing NO, O2 and H2O was excellent, without any appreciable activity decay during 70 h time on stream. Based on characterisation and data analysis from ICP, single pulse excitation NMR, MQ MAS NMR, N2 physisorption, TPR(H2) analysis and apparent activation energies, the improved catalytic performance is attributed to an increased concentration of active sites. Temperature programmed reduction experiments reveal significant changes in the Fe(III) reducibility pattern with the presence of two reduction peaks; tentatively attributed to the interaction of the Fe-oxo species with electron withdrawing extraframework AlO6 species, causing a delayed reduction. A low-temperature peak is attributed to Fe-species exchanged on zeolitic AlO4 sites, which are partially charged by the presence of the neighbouring extraframework AlO6 sites. Improved mass transport phenomena due to acid leaching is ruled out. The increased activity is rationalized by an active site model, whose concentration increases by selectively washing out the distorted extraframework AlO6 species under acidic (optimal) conditions, liberating active Fe species.