Dielectric studies of molecules and intramolecular relaxation processes

A new bridge technique for the measurement of the dielectric absorption of liquids and solutions at microwave frequencies has been described and its accuracy assessed. 'l'he dielectric data of the systems studied is discussed in terms of the relaxation processes contributing to the dielectric absorption and the apparent dipole moments. Pyridine, thiophen and furan in solution have a distribution of relaxation times which may be attributed to the small size of the solute molecules relative to the solvent. Larger rigid molecules in solution were characterized by a single relaxation time as would be anticipated from theory. The dielectric data of toluene, ethyl-, isopropyl- and t-butylbenzene as pure liquids and in solution were described by two relaxation times, one identified with molecular re-orientation and a shorter relaxation time.· The subsequent work was investigation of the possible explanations of this short relaxation process. Comparable short relaxation times were obtained from the analysis of the dielectric data of solutions of p-chloro- and p-bromotoluene below 40°C, o- and m-xylene at 25°C and 1-methyl- and 2 methylnaphthalene at 50 C. Rigid molecules of similar shapes and sizes were characterized by a single relaxation time identified with molecular re-orientation. Contributions from a long relaxation process attributed to dipolar origins were reported for solutions of nitrobenzene, benzonitrile and p-nitrotoluene. A short relaxation process of possible dipolar origins contributed to the dielectric absorption of 4-methyl- and 4-t-butylpyridine in cyclohexane at 25°C. It was concluded that the most plausible explanation of the short relaxation process of the alkyl-aryl hydrocarbons studied appears to be intramolecular relaxation about the alkyl-aryl bond. Finally the mean relaxation times of some phenylsubstituted compounds were investigated to evaluate any shortening due to contributions from the process of relaxation about the phenyl-central atom bond. The relaxation times of triphenylsilane and phenyltrimethylsilane were significantly short.

New oil modified acrylic polymer for pH sensitive drug release:experimental results and statistical analysis

We report results of an experimental study, complemented by detailed statistical analysis of the experimental data, on the development of a more effective control method of drug delivery using a pH sensitive acrylic polymer. New copolymers based on acrylic acid and fatty acid are constructed from dodecyl castor oil and a tercopolymer based on methyl methacrylate, acrylic acid and acryl amide were prepared using this new approach. Water swelling characteristics of fatty acid, acrylic acid copolymer and tercopolymer respectively in acid and alkali solutions have been studied by a step-change method. The antibiotic drug cephalosporin and paracetamol have also been incorporated into the polymer blend through dissolution with the release of the antibiotic drug being evaluated in bacterial stain media and buffer solution. Our results show that the rate of release of paracetamol getss affected by the pH factor and also by the nature of polymer blend. Our experimental data have later been statistically analyzed to quantify the precise nature of polymer decay rates on the pH density of the relevant polymer solvents. The time evolution of the polymer decay rates indicate a marked transition from a linear to a strictly non-linear regime depending on the whether the chosen sample is a general copolymer (linear) or a tercopolymer (non-linear). Non-linear data extrapolation techniques have been used to make probabilistic predictions about the variation in weight percentages of retained polymers at all future times, thereby quantifying the degree of efficacy of the new method of drug delivery.

Analysis and improvement of performance in LCL filter-based PWM rectifier/inverter application using hybrid damping approach

A hybrid passive-active damping solution with improved system stability margin and enhanced dynamic performance is proposed for high power grid interactive converters. In grid connected active rectifier/inverter application, line side LCL filter improves the high frequency attenuation and makes the converter compatible with the stringent grid power quality regulations. Passive damping though offers a simple and reliable solution but it reduces overall converter efficiency. Active damping solutions do not increase the system losses but can guarantee the stable operation up to a certain speed of dynamic response which is limited by the maximum bandwidth of the current controller. This paper examines this limit and introduces a concept of hybrid passive-active damping solution with improved stability margin and high dynamic performance for line side LCL filter based active rectifier/inverter applications. A detailed design, analysis of the hybrid approach and trade-off between system losses and dynamic performance in grid connected applications are reported. Simulation and experimental results from a 10 kVA prototype demonstrate the effectiveness of the proposed solution. An analytical study on system stability and dynamic response with the variations of various controller and passive filter parameters is presented.

Atom transfer radical polymerisation - towards the synthesis of a fully-functional photorefractive polymer

Atom transfer radical polymerisation (ATRP) of styrene in xylene solution initiated with 1-phenylethyl bromide and mediated by CuBr/N-propyl-2- pyridinemethanimine catalyst complex was studied. The polymerisation was ill-controlled, yielding polymers with broad molecular weight distributions and values of number average molecular weight considerably higher than the theoretical values calculated from 100% initiator efficiency. The degree of control afforded over the polymerisation was enhanced by use of a more soluble catalyst complex, CuBr/N-octyl-2-pyridinemethanimine. Furthermore, the use of a more polar solvent, diglyme, generated a homogeneous catalyst complex that facilitated the production of polymers having narrow molecular weight distributions (1.10 < PDi < 1.20). The kinetics of the atom transfer radical polymerisation of methyl methacrylate at 90°C in diglyme solution initiated with ethyl-2-bromoisobutyrate and mediated by CuBr/N-octyl-2-pyridinemethanimine was studied and the orders of the reaction were established. The effect on the rate of polymerisation of the ratio of CuBr:N-octyl-2-pyridinemethanimine was also determined. The temperature dependencies of the rate of polymerisation of methyl methacrylate in diglyme solution and xylene solution were studied, and were found to be non-linear and dependent upon the polarity of the solvent. The use of highly polar aprotic solvents, such as N,N-dimethylformamide and dimethylsulphoxide, was found to be detrimental to the degree of control afforded over the polymerisation of methyl methacrylate. This was circumvented by use of a 5-fold excess, over that conventionally used, of catalyst complex. The atom transfer radical polymerisation of (4-nitrophenyl)-[3-[N-[2- (methacryloyloxy)ethyl]carbazolyl]]diazene in dimethyl sulphoxide solution was studied. Although homopolymerisation yielded only oligomers, copolymerisation of this monomer with methyl methacrylate was found to be readily achievable. Keywords: ATRP, Styrene; Methyl methacrylate; Polar solvents; Fully-functional photorefractive polymer. 2

3D reconstruction of complex dielectric function of the glass during the femtosecond micro-fabrication

We measure complex amplitude of scattered wave in the far field, and justify theoretically and numerically solution of the inverse scattering problem. This allows single-shot reconstructing of dielectric function distribution during direct femtosecond laser micro-fabrication.

The breakdown of stainless steels in strong acids

A study was made of the corrosion behaviour in the ASTM standard Nitric acid and Oxalic acid tests, of two commercial AISI type 304L steels in the as received condition and after various heat treatments. Optical microscopy and SEM, TEM and STEM in conjunction with energy dispersive x-ray analysis, were used to correlate the corrosion behaviour of these steels with their microstructure. Some evidence of phosphorus segregation at grain boundaries was found. The corrosion behaviour at microstructural level was studied by examining on the TEM thin foils of steel that had been exposed to boiling nitric acid. Banding attack in the nitric acid and oxalic acid tests was studied using SEM and EPNA and found to be due to the micro-segregation of chromium and nickel. Using two experimental series of 304L, one a 17% Cr, 91 Ni, steel with phosphorus additions from 0.006% to 0.028%, the other a 20% Cr, 121 Ni steel with boron additions from 0.0011 to 0.00B51. The effect of these elements on corrosion in the nitric acid test was studied. The effect of different cooling rates and different solution treatment temperature on the behaviour of these steels was examined. TEM and STEM in conjunction with energy-dispersive x-ray analysis were again used to study the microstructure of the steels. Phosphorus was found to affect the corrosion behaviour but no effect was found with boron.

Dynamic behaviour of rotary mechanical seals

This thesis covers both experimental and computer investigations into the dynamic behaviour of mechanical seals. The literature survey shows no investigations on the effect of vibration on mechanical seals of the type common in the various process industries. Typical seal designs are discussed. A form of Reynolds' equation has been developed that permits the calculation of stiffnesses and damping coefficients for the fluid film. The dynamics of the mechanical seal floating ring have been investigated using approximate formulae, and it has been shown that the floating ring will behave as a rigid body. Some elements, such as the radial damping due to the fluid film, are small and may be neglected. The equations of motion of the floating ring have been developed utilising the significant elements, and a solution technique described. The stiffness and damping coefficients of nitrile rubber o-rings have been obtained. These show a wide variation, with a constant stiffness up to 60 Hz. The importance of the effect of temperature on the properties is discussed. An unsuccessful test rig is described in the appendices. The dynamic behaviour of a mechanical seal has been investigated experimentally, including the effect of changes of speed, sealed pressure and seal geometry. The results, as expected, show that high vibration levels result in both high leakage and seal temperatures. Computer programs have been developed to solve Reynolds' Equation and the equations of motion. Two solution techniques for this latter program were developed, the unsuccesful technique is described in the appendices. Some stability problems were encountered, but despite these the solution shows good agreement with some of the experimental conditions. Possible reasons for the discrepancies are discussed. Various suggestions for future work in this field are given. These include the combining of the programs and more extensive experimental and computer modelling.

A review of research in manufacturing prognostics

With the fast changing global business landscape, manufacturing companies are facing increasing challenge to reduce cost of production, increase equipment utilization and provide innovative products in order to compete with countries with low labour cost and production cost. On of the methods is zero down time. Unfortunately, the current research and industrial solution does not provide user friendly development environment to create “Adaptive microprocessor size with supercomputer performance” solution to reduce downtime. Most of the solutions are PC based computer with off the shelf research software tools which is inadequate for the space constraint manufacturing environment in developed countries. On the other hand, to develop solution for various manufacturing domain will take too much time, there is lacking tools available for rapid or adaptive way of create the solution. Therefore, this research is to understand the needs, trends, gaps of manufacturing prognostics and defines the research potential related to rapid embedded system framework for prognostic.

Ophthalmic engineering:the development of novel instrumentation to further research in the field

The principle theme of this thesis is the advancement and expansion of ophthalmic research via the collaboration between professional Engineers and professional Optometrists. The aim has been to develop new and novel approaches and solutions to contemporary problems in the field. The work is sub divided into three areas of investigation; 1) High technology systems, 2) Modification of current systems to increase functionality, and 3) Development of smaller more portable and cost effective systems. High Technology Systems: A novel high speed Optical Coherence Tomography (OCT) system with integrated simultaneous high speed photography was developed achieving better operational speed than is currently available commercially. The mechanical design of the system featured a novel 8 axis alignment system. A full set of capture, analysis, and post processing software was developed providing custom analysis systems for ophthalmic OCT imaging, expanding the current capabilities of the technology. A large clinical trial was undertaken to test the dynamics of contact lens edge interaction with the cornea in-vivo. The interaction between lens edge design, lens base curvature, post insertion times and edge positions was investigated. A novel method for correction of optical distortion when assessing lens indentation was also demonstrated. Modification of Current Systems: A commercial autorefractor, the WAM-5500, was modified with the addition of extra hardware and a custom software and firmware solution to produce a system that was capable of measuring dynamic accommodative response to various stimuli in real time. A novel software package to control the data capture process was developed allowing real time monitoring of data by the practitioner, adding considerable functionality of the instrument further to the standard system. The device was used to assess the accommodative response differences between subjects who had worn UV blocking contact lens for 5 years, verses a control group that had not worn UV blocking lenses. While the standard static measurement of accommodation showed no differences between the two groups, it was determined that the UV blocking group did show better accommodative rise and fall times (faster), thus demonstrating the benefits of the modification of this commercially available instrumentation. Portable and Cost effective Systems: A new instrument was developed to expand the capability of the now defunct Keeler Tearscope. A device was developed that provided a similar capability in allowing observation of the reflected mires from the tear film surface, but with the added advantage of being able to record the observations. The device was tested comparatively with the tearscope and other tear film break-up techniques, demonstrating its potential. In Conclusion: This work has successfully demonstrated the advantages of interdisciplinary research between engineering and ophthalmic research has provided new and novel instrumented solutions as well as having added to the sum of scientific understanding in the ophthalmic field.

3D reconstruction of complex dielectric function of the glass during the femtosecond micro-fabrication

We measure complex amplitude of scattered wave in the far field, and justify theoretically and numerically solution of the inverse scattering problem. This allows single-shot reconstructing of dielectric function distribution during direct femtosecond laser micro-fabrication.

Numerical simulation of corneal transport processes

This paper presents a numerical study on the transport of ions and ionic solution in human corneas and the corresponding influences on corneal hydration. The transport equations for each ionic species and ionic solution within the corneal stroma are derived based on the transport processes developed for electrolytic solutions, whereas the transport across epithelial and endothelial membranes is modelled by using phenomenological equations derived from the thermodynamics of irreversible processes. Numerical examples are provided for both human and rabbit corneas, from which some important features are highlighted.

Problematising L2 listening pedagogy:the potential of process-based listening strategy instruction in the L2 classroom

Listening is typically the first language skill to develop in first language (L1) users and has been recognized as a basic and fundamental tool for communication. Despite the importance of listening, aural abilities are often taken for granted, and many people overlook their dependency on listening and the complexities that combine to enable this multi-faceted skill. When second language (L2) students are learning their new language, listening is crucial, as it provides access to oral input and facilitates social interaction. Yet L2 students find listening challenging, and L2 teachers often lack sufficient pedagogy to help learners develop listening abilities that they can use in and beyond the classroom. In an effort to provide a pedagogic alternative to more traditional and limited L2 listening instruction, this thesis investigated the viability of listening strategy instruction (LSI) over three semesters at a private university in Japan through a qualitative action research (AR) intervention. An LSI program was planned and implemented with six classes over the course of three AR phases. Two teachers used the LSI with 121 learners throughout the project. Following each AR phase, student and teacher perceptions of the methodology were investigated via questionnaires and interviews, which were primary data collection methods. Secondary research methods (class observations, pre/post-semester test scores, and a research journal) supplemented the primary methods. Data were analyzed and triangulated for emerging themes related to participants’ perceptions of LSI and the viability thereof. These data showed consistent positive perceptions of LSI on the parts of both learners and teachers, although some aspects of LSI required additional refinement. This project provided insights on LSI specific to the university context in Japan and also produced principles for LSI program planning and implementation that can inform the broader L2 education community.

3D reconstruction of complex dielectric function of the glass during the femtosecond micro-fabrication

We measure complex amplitude of scattered wave in the far field, and justify theoretically and numerically solution of the inverse scattering problem. This allows single-shot reconstructing of dielectric function distribution during direct femtosecond laser micro-fabrication.

Ontology-based pathways generation for biomass to bioenergy conversion

Bio energy is a renewable energy and a solution to the depleting fossil fuels. Bio energy such as heat, power and bio fuel is generated by conversion technologies using biomass for example domestic waste, root crops, forest residue and animal slurry. Pyrolysis, anaerobic digestion and combined heat and power engine are some examples of the technologies. Depending on the nature of a biomass, it can be treated with various technologies giving out some products, which can be further treated with other technologies and eventually converted into the final products as bio energy. The pathway followed by the biomass, technologies, intermediate products and bio energy in the conversion process is referred to as bio energy pathway. Identification of appropriate pathways optimizes the conversion process. Although there are various approaches to create or generate the pathways, there is still a need for a semantic approach to generate the pathways, which allow checking the consistency of the knowledge, and to share and extend the knowledge efficiently. This paper presents an ontology-based approach to automatic generation of the pathways for biomass to bio energy conversion, which exploits the definition and hierarchical structure of the biomass and technologies, their relationship and associated properties, and infers appropriate pathways. A case study has been carried out in a real-life scenario, the bio energy project for the North West of Europe (Bioen NW), which showed promising results.