An investigation of the direct extrusion process with the application of oscillatory energy

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Site-selective direct arylation of unprotected adenine nucleosides mediated by palladium and copper:insights into the reaction mechanism

Reaction conditions facilitating the site-selective direct aryl functionalisation at the C-8 position of adenine nucleosides have been identified. Many different aromatic components may be effectively cross-coupled to provide a diverse array of arylated adenine nucleoside products without the need for ribose or adenine protecting groups. The optimal palladium catalyst loading lies between 0.5 and 5 mol %. Addition of excess mercury to the reaction had a negligible affect on catalysis, suggesting the involvement of a homogeneous catalytic species. A study by transmission electron microscopy (TEM) shows that metal containing nanoparticles, ca. 3 nm with good uniformity, are formed during the latter stages of the reaction. Stabilised PVP palladium colloids (PVP=N-polyvinylpyrrolidone) are catalytically active in the direct arylation process, releasing homogenous palladium into solution. The effect of various substituted 2-pyridine ligand additives has been investigated. A mechanism for the site-selective arylation of adenosine is proposed. © 2008 Elsevier Ltd. All rights reserved.

A novel process for the production of castor oil by direct solvent extraction

This research was undertaken to: develop a process for the direct solvent extraction of castor oil seeds. A literature survey confirmed the desirability of establishing such a process with emphasis on the decortication, size, reduction, detoxification-deallergenization, and solvent·extraction operations. A novel process was developed for the dehulling of castor seeds which consists of pressurizing the beans and then suddenly releasing the pressure to vaccum. The degree of dehulling varied according to the pressure applied and the size of the beans. Some of the batches were difficult-to-hull, and this phenomenon was investigated using the scanning electron microscope and by thickness and compressive strength measurements. The other variables studied to lesser degrees included residence time, moisture, content, and temperature.The method was successfully extended to cocoa beans, and (with modifications) to peanuts. The possibility of continuous operation was looked into, and a mechanism was suggested to explain the method works. The work on toxins and allergens included an extensive literature survey on the properties of these substances and the methods developed for their deactivation Part of the work involved setting up an assay method for measuring their concentration in the beans and cake, but technical difficulties prevented the completion of this aspect of the project. An appraisal of the existing deactivation methods was made in the course of searching for new ones. A new method of reducing the size of oilseeds was introduced in this research; it involved freezing the beans in cardice and milling them in a coffee grinder, the method was found to be a quick, efficient, and reliable. An application of the freezing technique was successful in dehulling soybeans and de-skinning peanut kernels. The literature on the solvent extraction, of oilseeds, especially castor, was reviewed: The survey covered processes, equipment, solvents, and mechanism of leaching. three solvents were experimentally investigated: cyclohexane, ethanol, and acetone. Extraction with liquid ammonia and liquid butane was not effective under the conditions studied. Based on the results of the research a process has been suggested for the direct solvent extraction of castor seeds, the various sections of the process have analysed, and the factors affecting the economics of the process were discussed.

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.

Modelling foreign direct investment in China

This thesis consists of three empirical and one theoretical studies. While China has received an increasing amount of foreign direct investment (FDI) and become the second largest host country for FDI in recent years, the absence of comprehensive studies on FDI inflows into this country drives this research. In the first study, an econometric model is developed to analyse the economic, political, cultural and geographic determinants of both pledged and realised FDI in China. The results of this study suggest that China's relatively cheaper labour force, high degree of international integration with the outside world (represented by its exports and imports) and bilateral exchange rates are the important economic determinants of both pledged FDI and realised FDI in China. The second study analyses the regional distribution of both pledged and realised FDI within China. The econometric properties of the panel data set are examined using a standardised 't-bar' test. The empirical results indicate that provinces with higher level of international trade, lower wage rates, more R&D manpower, more preferential policies and closer ethnic links with overseas Chinese attract relatively more FDI. The third study constructs a dynamic equilibrium model to study the interactions among FDI, knowledge spillovers and long run economic growth in a developing country. The ideas of endogenous product cycles and trade-related international knowledge spillovers are modified and extended to FDI. The major conclusion is that, in the presence of FDI, economic growth is determined by the stock of human capital, the subjective discount rate and knowledge gap, while unskilled labour can not sustain growth. In the fourth study, the role of FDI in the growth process of the Chinese economy is investigated by using a panel of data for 27 provinces across China between 1986 and 1995. In addition to FDI, domestic R&D expenditure, international trade and human capital are added to the standard convergence regressions to control for different structural characteristics in each province. The empirical results support endogenous innovation growth theory in which regional per capita income can converge given technological diffusion, transfer and imitation.

Chemical kinetic investigation of a commercial batch reactor process

The aim of this investigation was to study the chemical reactions occurring during the batchwise production of a butylated melamine-formaldehyde resin, in order to optimise the efficiency and economics of the batch processes. The batch process models are largely empirical in nature as the reaction mechanism is unknown. The process chemistry and the commercial manufacturing method are described. A small scale system was established in glass and the ability to produce laboratory resins with the required quality was demonstrated, simulating the full scale plant. During further experiments the chemical reactions of methylolation, condensation and butylation were studied. The important process stages were identified and studied separately. The effects of variation of certain process parameters on the chemical reactions were also studied. A published model of methylolation was modified and used to simulate the methylolation stage. A major result of this project was the development of an indirect method for studying the condensation and butylation reactions occurring during the dehydration and acid reaction stages, as direct quantitative methods were not available. A mass balance method was devised for this purpose and used to collect experimental data. The reaction scheme was verified using this data. The reactions stages were simulated using an empirical model. This has revealed new information regarding the mechanism and kinetics of the reactions. Laboratory results were shown to be comparable with plant scale results. This work has improved the understanding of the batch process, which can be used to improve product consistency. Future work has been identified and recommended to produce an optimum process and plant design to reduce the batch time.

Binocular contrast interactions:Dichoptic masking is not a single process

To decouple interocular suppression and binocular summation we varied the relative phase of mask and target in a 2IFC contrast-masking paradigm. In Experiment I, dichoptic mask gratings had the same orientation and spatial frequency as the target. For in-phase masking, suppression was strong (a log-log slope of ∼1) and there was weak facilitation at low mask contrasts. Anti-phase masking was weaker (a log-log slope of ∼0.7) and there was no facilitation. A two-stage model of contrast gain control [Meese, T.S., Georgeson, M.A. and Baker, D.H. (2006). Binocular contrast vision at and above threshold. Journal of Vision, 6: 1224-1243] provided a good fit to the in-phase results and fixed its free parameters. It made successful predictions (with no free parameters) for the anti-phase results when (A) interocular suppression was phase-indifferent but (B) binocular summation was phase sensitive. Experiments II and III showed that interocular suppression comprised two components: (i) a tuned effect with an orientation bandwidth of ∼±33° and a spatial frequency bandwidth of >3 octaves, and (ii) an untuned effect that elevated threshold by a factor of between 2 and 4. Operationally, binocular summation was more tightly tuned, having an orientation bandwidth of ∼±8°, and a spatial frequency bandwidth of ∼0.5 octaves. Our results replicate the unusual shapes of the in-phase dichoptic tuning functions reported by Legge [Legge, G.E. (1979). Spatial frequency masking in human vision: Binocular interactions. Journal of the Optical Society of America, 69: 838-847]. These can now be seen as the envelope of the direct effects from interocular suppression and the indirect effect from binocular summation, which contaminates the signal channel with a mask that has been suppressed by the target. © 2007 Elsevier Ltd. All rights reserved.

Factors affecting human reliability in the chemical process industry

This research was concerned with identifying factors which may influence human reliability within chemical process plants - these factors are referred to as Performance Shaping Factors (PSFs). Following a period of familiarization within the industry, a number of case studies were undertaken covering a range of basic influencing factors. Plant records and site `lost time incident reports' were also used as supporting evidence for identifying and classifying PSFs. In parallel to the investigative research, the available literature appertaining to human reliability assessment and PSFs was considered in relation to the chemical process plan environment. As a direct result of this work, a PSF classification structure has been produced with an accompanying detailed listing. Phase two of the research considered the identification of important individual PSFs for specific situations. Based on the experience and data gained during phase one, it emerged that certain generic features of a task influenced PSF relevance. This led to the establishment of a finite set of generic task groups and response types. Similarly, certain PSFs influence some human errors more than others. The result was a set of error type key words, plus the identification and classification of error causes with their underlying error mechanisms. By linking all these aspects together, a comprehensive methodology has been forwarded as the basis of a computerized aid for system designers. To recapitulate, the major results of this research have been: One, the development of a comprehensive PSF listing specifically for the chemical process industries with a classification structure that facilitates future updates; and two, a model of identifying relevant SPFs and their order of priority. Future requirements are the evaluation of the PSF listing and the identification method. The latter must be considered both in terms of `useability' and its success as a design enhancer, in terms of an observable reduction in important human errors.

Process orientation and information technology:customer engagement at Xerox (UK) Ltd

Xerox Customer Engagement activity is informed by the "Go To Market" strategy, and "Intelligent Coverage" sales philosophy. The realisation of this philosophy necessitates a sophisticated level of Market Understanding, and the effective integration of the direct channels of Customer Engagement. Sophisticated Market Understanding requires the mapping and coding of the entire UK market at the DMU (Decision Making Unit) level, which in turn enables the creation of tailored coverage prescriptions. Effective Channel Integration is made possible by the organisation of Customer Engagement work according to a single, process defined structure: the Selling Process. Organising by process facilitates the discipline of Task Substitution, which leads logically to creation of Hybrid Selling models. Productive Customer Engagement requires Selling Process specialisation by industry sector, customer segment and product group. The research shows that Xerox's Market Database (MDB) plays a central role in delivering the Go To Market strategic aims. It is a tool for knowledge based selling, enables productive SFA (Sales Force Automation) and, in sum, is critical to the efficient and effective deployment of Customer Engagement resources. Intelligent Coverage is not possible without the MDB. Analysis of the case evidence has resulted in the definition of 60 idiographic statements. These statements are about how Xerox organise and manage three direct channels of Customer Engagement: Face to Face, Telebusiness and Ebusiness. Xerox is shown to employ a process-oriented, IT-enabled, holistic approach to Customer Engagement productivity. The significance of the research is that it represents a detailed (perhaps unequalled) level of rich description of the interplay between IT and a holistic, process-oriented management philosophy.

Mechanisms of chromium deposition and dissolution under direct and pulse reverse plating conditions

Baths containing sulphuric acid as catalyst and others with selected secondary catalysts (methane sulphonic acid - MSA, SeO2, a KBrO3/KIO3 mixture, indium, uranium and commercial high speed catalysts (HEEF-25 and HEEF-405)) were studied. The secondary catalysts influenced CCE, brightness and cracking. Chromium deposition mechanisms were studied in Part II using potentiostatic and potentiodynamic electroanalytical techniques under stationary and hydrodynamic conditions. Sulphuric acid as a primary catalyst and MSA, HEEF-25, HEEF-405 and sulphosalycilic acid as co-catalysts were explored for different rotation, speeds and scan rates. Maximum current was resolved into diffusion and kinetically limited components, and a contribution towards understanding the electrochemical mechanism is proposed. Reaction kinetics were further studied for H2SO4, MSA and methane disulphonic acid catalysed systems and their influence on reaction mechanisms elaborated. Charge transfer coefficient and electrochemical reaction rate orders for the first stage of the electrodeposition process were determined. A contribution was made toward understanding of H2SO4 and MSA influence on the evolution rate of hydrogen. Anodic dissolution of chromium in the chromic acid solution was studied with a number of techniques. An electrochemical dissolution mechanism is proposed, based on the results of rotating gold ring disc experiments and scanning electron microscopy. Finally, significant increases in chromium electrodeposition rates under non-stationary conditions (PRC mode) were studied and a deposition mechanisms is elaborated based on experimental data and theoretical considerations.

Fabrication of high aspect ratio microfluidic devices using direct FS ablation

We present a single stage direct fs ablation results which show that it is possible to make high quality and high aspect ratio devices in a single stage process using a CAD optimised approach.

An integrated process for strategic positioning within the value chain

The purpose of this article is to highlight the value of ‘strategic positioning’ as a means of providing competitive edge, and to introduce and describe a novel method of managing this. Strategic positioning is concerned with the choice of business activities a company carries out itself, compared to those provided by suppliers, partners, distributors and even customers. It is therefore directly impacted by, and has direct impact upon, such decisions as outsourcing, off-shoring, partnering, innovation, technology acquisition and customer servicing.

Human performance modelling as an aid in the process of manufacturing system design

Manufacturing system design is an ongoing activity within industry. Modelling tools based on Discrete Event Simulation are often used by practitioners during this design cycle. However, such tools do not adequately model the behaviour of 'direct' workers in manufacturing environments. There is an important need to expand the capability of modelling to include the relationships between human centred factors (demography, attitudes, beliefs, etc), their working environment (physical and organizational), and their subsequent performance in terms of productive routines. Therefore, this paper describes research that has formed a pilot modelling methodology that is an important first step in providing such a capability.

Team effectiveness: a test of in-put process-output

This research addressed the question: "Which factors predict the effectiveness of healthcare teams?" It was addressed by assessing the psychometric properties of a new measure of team functioning with the use of data collected from 797 team members in 61 healthcare teams. This new measure is the Aston Team Performance Inventory (ATPI) developed by West, Markiewicz and Dawson (2005) and based on the IPO model. The ATPI was pilot tested in order to examine the reliability of this measure in the Jordanian cultural context. A sample of five teams comprising 3-6 members each was randomly selected from the Jordan Red Crescent health centers in Amman. Factors that predict team effectiveness were explored in a Jordanian sample (comprising 1622 members in 277 teams with 255 leaders from healthcare teams in hospitals in Amman) using self-report and Leader Ratings measures adapted from work by West, Borrill et al (2000) to determine team effectiveness and innovation from the leaders' point of view. The results demonstrate the validity and reliability of the measures for use in healthcare settings. Team effort and skills and leader managing had the strongest association with team processes in terms of team objectives, reflexivity, participation, task focus, creativity and innovation. Team inputs in terms of task design, team effort and skills, and organizational support were associated with team effectiveness and innovation whereas team resources were associated only with team innovation. Team objectives had the strongest mediated and direct association with team effectiveness whereas task focus had the strongest mediated and direct association with team innovation. Finally, among leadership variables, leader managing had the strongest association with team effectiveness and innovation. The theoretical and practical implications of this thesis are that: team effectiveness and innovation are influenced by multiple factors that must all be taken into account. The key factors managers need to ensure are in place for effective teams are team effort and skills, organizational support and team objectives. To conclude, the application of these findings to healthcare teams in Jordan will help improve their team effectiveness, and thus the healthcare services that they provide.

Gaussian process quantile regression using expectation propagation

Direct quantile regression involves estimating a given quantile of a response variable as a function of input variables. We present a new framework for direct quantile regression where a Gaussian process model is learned, minimising the expected tilted loss function. The integration required in learning is not analytically tractable so to speed up the learning we employ the Expectation Propagation algorithm. We describe how this work relates to other quantile regression methods and apply the method on both synthetic and real data sets. The method is shown to be competitive with state of the art methods whilst allowing for the leverage of the full Gaussian process probabilistic framework.