Design and characterisation of novel blends of poly(lactic acid)

This thesis is concerned with the effect of polymer structure on miscibility of the three component blends based on poly(lactic acid) (PLA) with using blending techniques. The examination of novel PLA homologues (pre-synthesised poly(a-esters)), including a range of aliphatic and aromatic poly(a-esters) is an important aspect of the work. Because of their structural simplicity and similarity to PLA, they provide an ideal system to study the effect of polyester structures on the miscibility of PLA polymer blends. The miscibility behaviour of the PLA homologues is compared with other aliphatic polyesters (e.g. poly(e-caprolactone) (PCL), poly(hydroxybutyrate hydroxyvalerate) (P(HB-HV)), together with a series of cellulose-based polymers (e.g. cellulose acetate butyrate (CAB)). The work started with the exploration the technique used for preliminary observation of the miscibility of blends referred to as “a rapid screening method” and then the miscibility of binary blends was observed and characterised by percent transmittance together with the Coleman and Painter miscibility approach. However, it was observed that symmetrical structures (e.g. a1(dimethyl), a2(diethyl)) promote the well-packing which restrict their chains from intermingling into poly(L-lactide) (PLLA) chains and leads the blends to be immiscible, whereas, asymmetrical structures (e.g. a4(cyclohexyl)) behave to the contrary. a6(chloromethyl-methyl) should interact well with PLLA because of the polar group of chloride to form interactions, but it does not. It is difficult to disrupt the helical structure of PLLA. PLA were immiscible with PCL, P(HB-HV), or compatibiliser (e.g. G40, LLA-co-PCL), but miscible with CAB which is a hydrogen-bonded polymer. However, these binary blends provided a useful indication for the exploration the novel three component blends. In summary, the miscibility of the three-component blends are miscible even if only two polymers are miscible. This is the benefit for doing the three components blend in this thesis, which is not an attempt to produce a theoretical explanation for the miscibility of three components blend system.

Design and fabrication of fiber Bragg gratings with V-shaped dispersion profile

We propose a new type of fiber Bragg grating (FBG) with a V-shaped dispersion profile. We demonstrate that such V-shaped FBGs bring advantages in manipulation of optical signals compared to conventional FBGs with a constant dispersion, e.g., they can produce larger chirp for the same input pulsewidth and/or can be used as pulse shapers. Application of the proposed V-shaped FBGs for signal prechirping in fiber transmission is examined. The proposed design of the V-shaped FBG can be easily extended to embrace multichannel devices.

The design of a real-time nowcasting system for localised weather

National meteorological offices are largely concerned with synoptic-scale forecasting where weather predictions are produced for a whole country for 24 hours ahead. In practice, many local organisations (such as emergency services, construction industries, forestry, farming, and sports) require only local short-term, bespoke, weather predictions and warnings. This thesis shows that the less-demanding requirements do not require exceptional computing power and can be met by a modern, desk-top system which monitors site-specific ground conditions (such as temperature, pressure, wind speed and direction, etc) augmented with above ground information from satellite images to produce `nowcasts'. The emphasis in this thesis has been towards the design of such a real-time system for nowcasting. Local site-specific conditions are monitored using a custom-built, stand alone, Motorola 6809 based sub-system. Above ground information is received from the METEOSAT 4 geo-stationary satellite using a sub-system based on a commercially available equipment. The information is ephemeral and must be captured in real-time. The real-time nowcasting system for localised weather handles the data as a transparent task using the limited capabilities of the PC system. Ground data produces a time series of measurements at a specific location which represents the past-to-present atmospheric conditions of the particular site from which much information can be extracted. The novel approach adopted in this thesis is one of constructing stochastic models based on the AutoRegressive Integrated Moving Average (ARIMA) technique. The satellite images contain features (such as cloud formations) which evolve dynamically and may be subject to movement, growth, distortion, bifurcation, superposition, or elimination between images. The process of extracting a weather feature, following its motion and predicting its future evolution involves algorithms for normalisation, partitioning, filtering, image enhancement, and correlation of multi-dimensional signals in different domains. To limit the processing requirements, the analysis in this thesis concentrates on an `area of interest'. By this rationale, only a small fraction of the total image needs to be processed, leading to a major saving in time. The thesis also proposes an extention to an existing manual cloud classification technique for its implementation in automatically classifying a cloud feature over the `area of interest' for nowcasting using the multi-dimensional signals.

Design and synthesis of novel hydrogels for biological applications

The aims of this project were:1) the synthesis of a range of new polyether-based vinylic monomers and their incorporation into poly(2-hydroxyethyl methacrylate) (poly(HEMA)) based hydrogel networks, of interest to the contact lens industry.2) the synthesis of a range of alkyltartronic acids, and their derivatives. These molecules may ultimately be used to produce functionalised poly(-hydroxy acids) of potential interest in either drug delivery or surgical suture applications. The novel syntheses of a range of both methoxy poly(ethylene glycol) acrylates (MPEGAs) and poly(ethylene glycol) acrylates (PEGAs) are described. Products were obtained in very good yields. These new polyether-based vinylic monomers were copolymerised with 2-hydroxyethyl methacrylate (HEMA) to produce a range of hydrogels. The equilibrium water contents (EWC) and surface properties of these copolymers containing linear polyethers were examined. It was found that the EWC was enhanced by the presence of the hydrophilic polyether chains.Results suggest that the polyether side chains express themselves at the polymer surface, thus dictating the surface properties of the gels. Consequentially, this leads to an advantageous reduction in the surface adhesion of biological species. A synthesis of a range of alkyltartronic acids is also described. The acids prepared were obtained in very good yields using a novel four-stage synthesis. These acids were modified to give potassium monoethyl alkyltartronates. Although no polyesterification is described in this thesis, these modified alkyltartronic acid derivatives are considered to be potentially excellent starting materials for poly (alkyltartronic acid) synthesis via anhydrocarboxylate or anhydrosulphite cyclic monomers.

Solids mixing and segregation in a gas spout-fluid bed-effect of the distributor design

This work is concerned with the assessment of a newer version of the spout-fluid bed where the gas is supplied from a common plenum and the distributor controls the operational phenomenon. Thus the main body of the work deals with the effect of the distributor design on the mixing and segregation of solids in a spout-filled bed. The effect of distributor design in the conventional fluidised bed and of variation of the gas inlet diameter in a spouted bed were also briefly investigated for purpose of comparison. Large particles were selected for study because they are becoming increasingly important in industrial fluidised beds but have not been thoroughly investigated. The mean particle diameters of the fraction ranged from 550 to 2400 mm, and their specific gravity from 0.97 to 2.45. Only work carried out with binary systems is reported here. The effect of air velocity, particle properties, bed height, the relative amount of jetsam and flotsam and initial conditions on the steady-state concentration profiles were assessed with selected distributors. The work is divided into three sections. Sections I and II deal with the fluidised bed and spouted bed systems. Section III covers the development of the spout-filled bed and its behaviour with reference to distributor design and it is shown how benefits of both spouting and fluidising phenomena can be exploited. In the fluidisation zone, better mixing is achieved by distributors which produce a large initial bubble diameter. Some common features exist between the behaviour of unidensity jetsam-rich systems and different density flotsam-rich systems. The shape factor does not seem to have an affect as long as it is only restricted to the minor component. However, in the case of the major component, particle shape significantly affects the final results. Studies of aspect ratio showed that there is a maximum (1.5) above which slugging occurs and the effect of the distributor design is nullified. A mixing number was developed for unidensity spherical rich systems, which proved to be extremely useful in quantifying the variation in mixing and segregation with changes in distributor design.

A systemic approach to the design of cellular manufacturing systems

Cellular manufacturing is widely acknowledged as one of the key approaches to achieving world-class performance in batch manufacturing operations. The design of cellular manufacturing systems (CMS) is therefore crucial in determining a company's competitiveness. This thesis postulated that, in order to be effective the design of CMS should not only be systematic but also systemic. A systemic design uses the concepts of the body of work known as the 'systems approach' to ensure that a truly effective CMS is defined. The thesis examined the systems approach and created a systemic framework against which existing approaches to the design of CMS were evaluated. The most promising of these, Manufacturing Systems Engineering (MSE), was further investigated using a series of cross-sectional case-studies. Although, in practice, MSE proved to be less than systemic, it appeared to produce significant benefits. This seemed to suggest that CMS design did not need to be systemic to be effective. However, further longitudinal case-studies showed that the benefits claimed were at an operational level not at a business level and also that the performance of the whole system had not been evaluated. The deficiencies identified in the existing approaches to designing CMS were then addressed by the development of a novel CMS design methodology that fully utilised systems concepts. A key aspect of the methodology was the use of the Whole Business Simulator (WBS), a modelling and simulation tool that enabled the evaluation of CMS at operational and business levels. The most contentious aspects of the methodology were tested on a significant and complex case-study. The results of the exercise indicated that the systemic methodology was feasible.

Expert system design for cold form sections

The concept of an Expert System (ES) has been acknowledged as a very useful tool, but few studies have been carried out in its application to the design of cold rolled sections. This study involves primarily the use of an ES as a tool to improve the design process and to capture the draughtsman's knowledge. Its main purpose is to reduce substantially the time taken to produce a section drawing, thereby facilitating a speedy feedback to the customer. In order to communicate with a draughtsman, it is necessary to use sketches, symbolic representations and numerical data. This increases the complexity of programming an ES, as it is necessary to use a combination of languages so that decisions, calculations, graphical drawings and control of the system can be effected. A production system approach is used and a further step has been taken by introducing an Activator which is an autoexecute operation set up by the ES to operate an external program automatically. To speed up the absorption of new knowledge into the knowledge base, a new Learning System has been constructed. In addition to developing the ES, other software has been written to assist the design process. The section properties software has been introduced to improve the speed and consistency of calculating the section properties. A method of selecting or comparing the most appropriate section for a given specification is also implemented. Simple loading facilities have been introduced to guide the designer as to the loading capacity of the section. This research has concluded that the application of an ES is beneficial and with the activator approach, automated designing can be achieved. On average a complex drawing can be displayed on the screen in about 100 seconds, where over 95% of the initial section design time for repetitive or similar profile can be saved.

The design of novel antifolates against pneumocystis carinii

The pneumonia caused by Pneumocystis carinii is ultimately responsible for the death of many acquired immunodeficiency syndrome (AIDS) patients. Large doses of trimethoprim and pyrimethamine in combination with a sulphonamide and/or pentamidine suppress the infection but produce serious side-effects and seldom prevent recurrence after treatment withdrawal. However, the partial success of the aforementioned antifolates, and also trimetrexate used alone, does suggest dihydrofolate reductase (DHFR) as a target for the development of antipneumocystis agents. From the DHFR inhibitory activities of 3'-substituted pyrimethamine analogues it was suggested that the 3'-(3'',3''-dimethyltriazen-1''-yl) substituent may be responsible for the greater activity for the P.carinii over the mammalian enzyme. Crystallographic and molecular modeling studies revealed considerable geometrical and electronic differences between the triazene and the chemically related formamidine functions that may account for the differences in DHFR inhibitory profiles. Structural and electronic parameters calculated for a series of 3'-(3'',3''-disubstitutedtriazen-1''-yl) pyrimethamine analogues did not correlate with the DHFR inhibitory activities. However, the in vitro screening against P.carinii DHFR revealed that the 3''-hydroxyethyl-3''-benzyl analogue was the most active and selective. Models of the active sites of human and P.carinii DHFRs were constructed using DHFR sequence and structural homology data which had identified key residues involved in substrate and cofactor binding. Low energy conformations of the 3'',3''-dimethyl and 3''-hydroxyethyl-3''-benzyle analogues, determined from nuclear magnetic resonance studies and theoretical calculations, were docked by superimposing the diaminopyrimidine fragment onto a previously docked pyrimethamine analogue. Enzyme kinetic data supported the 3''-hydroxyethyl-3''-benzyl moiety being located in the NADPH binding groove. The 3''-benzyl substituent was able to locate to within 3 AA of a valine residue in the active site of P.carinii DHFR thereby producing a hydrophobic contact. The equivalent residue in human DHFR is threonine, more hydrophilic and less likely to be involved in such a contact. This difference may account for the greater inhibitory activity this analogue has for P.carinii DHFR and provide a basis for future drug design. From an in vivo model of PCP in immunosuppressed rats it was established that the 3"-hydroxyethyl-3"-benzyl analogue was able to reduce the.P.carinii burden more effectively with increasing doses, without causmg any visible signs of toxicity. However, equivalent doses were not as effective as pentamidine, a current treatment of choice for Pneumocystis carinii pneumonia.

Design of sway frames

The aim of the work presented in this thesis is to produce a direct method to design structures subject to deflection constraints at the working loads. The work carried out can be divided into four main parts. In the first part, a direct design procedure for plane steel frames subjected to sway limitations is proposed. The stiffness equations are modified so that the sway in each storey is equal to some specified values. The modified equations are then solved by iteration to calculate the cross-sectional properties of the columns as well as the other joint displacements. The beam sections are selected initially and then altered in an effort to reduce the total material cost of the frame. A linear extrapolation technique is used to reduce this cost. In this design, stability functions are used so that the effect of axial loads in the members are taken into consideration. The final reduced cost design is checked for strength requirements and the members are altered accordingly. In the second part, the design method is applied to the design of reinforced concrete frames in which the sway in the columns play an active part in the design criteria. The second moment of area of each column is obtained by solving the modified stiffness equations and then used to calculate the mlnlmum column depth required. Again the frame has to be checked for all the ultimate limit state load cases. In the third part, the method is generalised to design pin-jointed space frames for deflection limitatlions. In these the member areas are calculated so that the deflection at a specified joint is equal to its specified value. In the final part, the Lagrange multiplier technique is employed to obtain an optimum design for plane rigidly jointed steel frames. The iteration technique is used here to solve the modified stiffness equations as well as derivative equations obtained in accordance to the requirements of the optimisation method.

Design and function of trilobite exoskeletons

The fossil arthropod Class Trilobita is characterised by the possession of a highly mineralised dorsal exoskeleton with an incurved marginal flange (doublure). This cuticle is usually the only part of the organism to be preserved. Despite the common occurrence of trilobites in Palaeozoic sediments, the original exoskeletal mineralogy has not been determined previously. Petrographic data involving over seventy trilobite species, ranging in age from Cambrian to Devonian, together with atomic absorption and stable isotope analyses, indicate a primary low-magnesian calcite composition. Trilobite cuticles exhibit a variety of preservational textures which are related to the different diagenetic realms through which they have passed. A greater knowledge of post-depositional processes and the specific features they produce, has enabled post-mortem artefacts to be distinguished from primary cuticular microstructures. Alterations of the cuticle can either enhance or destroy primary features, and their effects are best observed in thin-sections, both under transmitted light and cathodoluminescence. Well-preserved trilobites often retain primary microstructures such as laminations, canals, and tubercles. These have been examined in stained thin-sections and by scanning electron microscopy, from as wide a range of trilobites as possible. Construction of sensory field maps has shown that although the basic organisation of the exoskeleton is the same in all trilobites, the types of microstructures found, and their distribution is species-specific. The composition, microstructure, and architecture of the trilobite exoskeleton have also been studied from a biomechanical viewpoint. Total cuticle thickness, and the relative proportions of the different layers, together with the overall architecture all affected the mechanical properties of the exoskeleton.

Design of an expandable manufacturing simulator through the application of object-oriented principles

In analysing manufacturing systems, for either design or operational reasons, failure to account for the potentially significant dynamics could produce invalid results. There are many analysis techniques that can be used, however, simulation is unique in its ability to assess detailed, dynamic behaviour. The use of simulation to analyse manufacturing systems would therefore seem appropriate if not essential. Many simulation software products are available but their ease of use and scope of application vary greatly. This is illustrated at one extreme by simulators which offer rapid but limited application whilst at the other simulation languages which are extremely flexible but tedious to code. Given that a typical manufacturing engineer does not posses in depth programming and simulation skills then the use of simulators over simulation languages would seem a more appropriate choice. Whilst simulators offer ease of use their limited functionality may preclude their use in many applications. The construction of current simulators makes it difficult to amend or extend the functionality of the system to meet new challenges. Some simulators could even become obsolete as users, demand modelling functionality that reflects the latest manufacturing system design and operation concepts. This thesis examines the deficiencies in current simulation tools and considers whether they can be overcome by the application of object-oriented principles. Object-oriented techniques have gained in popularity in recent years and are seen as having the potential to overcome any of the problems traditionally associated with software construction. There are a number of key concepts that are exploited in the work described in this thesis: the use of object-oriented techniques to act as a framework for abstracting engineering concepts into a simulation tool and the ability to reuse and extend object-oriented software. It is argued that current object-oriented simulation tools are deficient and that in designing such tools, object -oriented techniques should be used not just for the creation of individual simulation objects but for the creation of the complete software. This results in the ability to construct an easy to use simulator that is not limited by its initial functionality. The thesis presents the design of an object-oriented data driven simulator which can be freely extended. Discussion and work is focused on discrete parts manufacture. The system developed retains the ease of use typical of data driven simulators. Whilst removing any limitation on its potential range of applications. Reference is given to additions made to the simulator by other developers not involved in the original software development. Particular emphasis is put on the requirements of the manufacturing engineer and the need for Ihe engineer to carrv out dynamic evaluations.

Design and fabrication of fibre Bragg gratings with V-shaped dispersion profile for multi-channel signal processing

We propose a new type of fiber Bragg grating (FBG) with a V-shaped dispersion profile. We demonstrate that such V-shaped FBGs bring advantages in manipulation of optical signals compared to conventional FBGs with a constant dispersion, e.g., they can produce larger chirp for the same input pulsewidth and/or can be used as pulse shapers. Application of the proposed V-shaped FBGs for signal prechirping in fiber transmission is examined. The proposed design of the V-shaped FBG can be easily extended to embrace multichannel devices.

Design and fabrication of fibre Bragg gratings with V-shaped dispersion profile

We propose a new type of fiber Bragg grating (FBG) with a V-shaped dispersion profile. We demonstrate that such V-shaped FBGs bring advantages in manipulation of optical signals compared to conventional FBGs with a constant dispersion, e.g., they can produce larger chirp for the same input pulsewidth and/or can be used as pulse shapers. Application of the proposed V-shaped FBGs for signal prechirping in fiber transmission is examined. The proposed design of the V-shaped FBG can be easily extended to embrace multichannel devices. © 2007 IEEE.

Utilisation of analogous climate locations to produce resilient biodiversity plantings for infrastructure developments

Developers have an obligation to biodiversity when considering the impact their development may have on the environment, with some choosing to go beyond the legal requirement for planning consent. Climate change projections over the 21st century indicate a climate warming and thus the species selected for habitat creation need to be able to withstand the pressures associated with these forecasts. A process is therefore required to identify resilient plantings for sites subject to climate change. Local government ecologists were consulted on their views on the use of plants of non-native provenance or how they consider resilience to climate change as part of their planting recommendations. There are mixed attitudes towards non-native species, but with studies already showing the impact climate change is having on biodiversity, action needs to be taken to limit further biodiversity loss, particularly given the heavily fragmented landscape preventing natural migration. A methodology has been developed to provide planners and developers with recommendations for plant species that are currently adapted to the climate the UK will experience in the future. A climate matching technique, that employs a GIS, allows the identification of European locations that currently experience the predicted level of climate change at a given UK location. Once an appropriate location has been selected, the plant species present in this area are then investigated for suitability for planting in the UK. The methodology was trialled at one site, Eastern Quarry in Kent, and suitable climate matched locations included areas in north-western France. Through the acquisition of plant species data via site visits and online published material, a species list was created, which considered original habitat design, but with added resilience to climate change.

Optimal design for correlated processes with input-dependent noise

Optimal design for parameter estimation in Gaussian process regression models with input-dependent noise is examined. The motivation stems from the area of computer experiments, where computationally demanding simulators are approximated using Gaussian process emulators to act as statistical surrogates. In the case of stochastic simulators, which produce a random output for a given set of model inputs, repeated evaluations are useful, supporting the use of replicate observations in the experimental design. The findings are also applicable to the wider context of experimental design for Gaussian process regression and kriging. Designs are proposed with the aim of minimising the variance of the Gaussian process parameter estimates. A heteroscedastic Gaussian process model is presented which allows for an experimental design technique based on an extension of Fisher information to heteroscedastic models. It is empirically shown that the error of the approximation of the parameter variance by the inverse of the Fisher information is reduced as the number of replicated points is increased. Through a series of simulation experiments on both synthetic data and a systems biology stochastic simulator, optimal designs with replicate observations are shown to outperform space-filling designs both with and without replicate observations. Guidance is provided on best practice for optimal experimental design for stochastic response models. © 2013 Elsevier Inc. All rights reserved.