Stabilisation of isocyanate cross linked polybutadiene binder

Isocyanate cross-linked hydroxy terminated polybutadiene is used as a binder for solid rocket propellant. Rocket motors containing this propellant require a storage life of at least 20 years. During storage it has been found that the important rubbery properties of the binder can be lost due to oxidative cross-linking of the polybutadiene chains. This could cause catastrophic failure when the rocket motor is required. At present the bis-hindered phenol Calco 2246 is used as a thermal oxidative stabiliser, but it's performance is only adequate. This has led to the search for a more efficient stabiliser system. To hasten the evaluation of new antioxidant systems the use of dynamic thermal analysis was investigated. Results showed that a tentative relationship existed between predictions by thermal analysis and the long term oven ageing for simple single antioxidant systems. But for more complex systems containing either autosynergistic or mixed antioxidants no relationship was observed suggesting that results for such an "accelerated" technique cannot be used for the purpose of extrapolation for long term performance. This was attributed to the short time and more aggressive condition used (hjgher temperature and oxygen rich atmosphere in thermal analysis) altering the mechanism of action of the antioxidants and not allowing time for co-operative effect of the combined antioxidant system to form. One potential problem for the binder system is the use of an diisocyanate as a cross-linking agent. This reacts with the hydroxyl hydrogen on the polymer as well as other active hydrogens such as those contained in a number of antioxidants, affecting both cross-linking and antioxidant effectiveness. Studies in this work showed that only antioxidants containing amine moieties have a significant affect on binder preparation, with the phenolic antioxidants not reacting. This is due to the greater nucleophilicity of the amines. Investigation of a range of antioxidant systems, including potentially homo, hetero and autosynergistic systems, has highlighted a number of systems which show considerably greater effectiveness than the currently used antioxidant Calco 2246. The only single antioxidant which showed improvement was the partially unhindered phenol y-Tocopherol. Of the mixed systems combinations of the sulphur containing antioxidants e.g. DLTP with higher levels of chain-breaking antioxidants, especially Calco 2246, were the most promising. Also the homosynergistic mix of an aromatic amine and a phenol was seen to be very effective but the results were inconsistent. This inconsistency could be explained by the method of sample preparation used. It was shown that the efficiency of a number of antioxidant.s could be dramatically improved by the use of ultrasound during the mixing stage of preparation. The reason for this increase in performance is unclear but in the case of the homosynergistic amine/phenol mix both more efficient mixing and/or the production of a novel mechanism of action are suggested

Novel hydrogel copolymers and semi-interpenetraing polymer networks

Interpenetrating polymer networks (lPN's), have been defined as a combination of two polymers each in network form, at least one of which has been synthesised and / or crosslinked in the presence of the other. A semi-lPN, is formed when only one of the polymers in the system is crosslinked, the other being linear. lPN's have potential advantages over homogeneous materials presently used in biomedical applications, in that their composite nature gives them a useful combination of properties. Such materials have potential uses in the biomedical field, specifically for use in hard tissue replacements, rigid gas permeable contact lenses and dental materials. Work on simply two or three component systems in both low water containing lPN's supplemented by the study of hydrogels (water swollen hydrophilic polymers) can provide information useful in the future development of more complex systems. A range of copolymers have been synthesised using a variety of methacrylates and acrylates. Hydrogels were obtained by the addition of N-vinyl pyrrolidone to these copolymers. A selection of interpenetrants were incorporated into the samples and their effect on the copolymer properties was investigated. By studying glass transition temperatures, mechanical, surface, water binding and oxygen permeability properties samples were assessed for their suitability for use as biomaterials. In addition copolymers containing tris-(trimethylsiloxy)-y-methacryloxypropyl silane, commonly abbreviated to 'TRlS', have been investigated. This material has been shown to enhance oxygen permeability, a desirable property when considering the design of contact lenses. However, 'TRIS' has a low polar component of surface free energy and hence low wettability. Copolymerisation with a range of methacrylates has shown that significant increases in surface wettability can be obtained without a detrimental effect on oxygen permeability. To further enhance to surface wettability 4-methacryloxyethyl trimellitic anhydride was incorporated into a range of promising samples. This study has shown that by careful choice of monomers it is possible to synthesise polymers that possess a range of properties desirable in biomedical applications.

Air traffic controller reactions to computer assistance

The research was instigated by the Civil Aviation Authority (CAA) to examine the implications for air traffic controllers' (ATCO) job satisfaction of the possible introduction of systems incorporating computer-assisted decision making. Additional research objectives were to assess the possible costs of reductions in ATCO job satisfaction, and to recommend appropriate task allocation between ATCOs and computer for future systems design (Chapter 1). Following a review of the literature (Chapter 2) it is argued that existing approaches to systems and job design do not allow for a sufficiently early consideration of employee needs and satisfactions in the design of complex systems. The present research develops a methodology for assessing affective reactions to an existing system as a basis for making reommendations for future systems design (Chapter 3). The method required analysis of job content using two techniques: (a) task analysis (Chapter 4.1) and (b) the Job Diagnostic Survey (JDS). ATCOs' affective reactions to the several operational positions on which they work were investigated at three levels of detail: (a) Reactions to positions, obtained by ranking techniques (Chapter 4.2); (b) Reactions to job characteristics, obtained by use of JDS (Chapter 4.3); and (c) Reactions to tasks, obtained by use of Repertory Grid technique (Chapter 4.4). The conclusion is drawn that ATCOs' motivation and satisfaction is greatly dependent on the presence of challenge, often through tasks requiring the use of decision making and other cognitive skills. Results suggest that the introduction of systems incorporating computer-assisted decision making might result in financial penalties for the CAA and significant reductions in job satisfaction for ATCOs. General recommendations are made for allocation of tasks in future systems design (Chapter 5).

Grading and disease management in national screening for diabetic retinopathy in England and Wales

Aims - A National Screening Programme for diabetic eye disease in the UK is in development. We propose a grading and early disease management protocol to detect sight-threatening diabetic retinopathy and any retinopathy, which will allow precise quality assurance at all steps while minimizing false-positive referral to the hospital eye service. Methods - Expert panel structured discussions between 2000 and 2002 with review of existing evidence and grading classifications. Proposals - Principles of the protocol include: separate grading of retinopathy and maculopathy, minimum number of steps, compatible with central monitoring, expandable for established more complex systems and for research, no lesion counting, no ‘questionable’ lesions, attempt to detect focal exudative, diffuse and ischaemic maculopathy and fast track referral from primary or secondary graders. Sight-threatening diabetic retinopathy is defined as: preproliferative retinopathy or worse, sight-threatening maculopathy and/or the presence of photocoagulation. In the centrally reported minimum data set retinopathy is graded into four levels: none (R0), background (R1), preproliferative (R2), proliferative (R3). Maculopathy and photocoagulation are graded as absent (M0, P0) or present (M1, P1). Discussion - The protocol developed by the Diabetic Retinopathy Grading and Disease Management Working Party represents a new consensus upon which national guidelines can be based leading to the introduction of quality-assured screening for people with diabetes.

The role of pinning and instability in a class of non-equilibrium growth models

We study the dynamics of a growing crystalline facet where the growth mechanism is controlled by the geometry of the local curvature. A continuum model, in (2+1) dimensions, is developed in analogy with the Kardar-Parisi-Zhang (KPZ) model is considered for the purpose. Following standard coarse graining procedures, it is shown that in the large time, long distance limit, the continuum model predicts a curvature independent KPZ phase, thereby suppressing all explicit effects of curvature and local pinning in the system, in the "perturbative" limit. A direct numerical integration of this growth equation, in 1+1 dimensions, supports this observation below a critical parametric range, above which generic instabilities, in the form of isolated pillared structures lead to deviations from standard scaling behaviour. Possibilities of controlling this instability by introducing statistically "irrelevant" (in the sense of renormalisation groups) higher ordered nonlinearities have also been discussed.

Physics-inspired methods for networking and communications

Advances in statistical physics relating to our understanding of large-scale complex systems have recently been successfully applied in the context of communication networks. Statistical mechanics methods can be used to decompose global system behavior into simple local interactions. Thus, large-scale problems can be solved or approximated in a distributed manner with iterative lightweight local messaging. This survey discusses how statistical physics methodology can provide efficient solutions to hard network problems that are intractable by classical methods. We highlight three typical examples in the realm of networking and communications. In each case we show how a fundamental idea of statistical physics helps solve the problem in an efficient manner. In particular, we discuss how to perform multicast scheduling with message passing methods, how to improve coding using the crystallization process, and how to compute optimal routing by representing routes as interacting polymers.

Quantization of the Inhomogeneous Bianchi I model:quasi-Heisenberg picture

The quantization scheme is suggested for a spatially inhomogeneous 1+1 Bianchi I model. The scheme consists in quantization of the equations of motion and gives the operator (so called quasi-Heisenberg) equations describing explicit evolution of a system. Some particular gauge suitable for quantization is proposed. The Wheeler-DeWitt equation is considered in the vicinity of zero scale factor and it is used to construct a space where the quasi-Heisenberg operators act. Spatial discretization as a UV regularization procedure is suggested for the equations of motion.

Unveiling temporal correlations characteristic of a phase transition in the output intensity of a fiber laser

We use advanced statistical tools of time-series analysis to characterize the dynamical complexity of the transition to optical wave turbulence in a fiber laser. Ordinal analysis and the horizontal visibility graph applied to the experimentally measured laser output intensity reveal the presence of temporal correlations during the transition from the laminar to the turbulent lasing regimes. Both methods unveil coherent structures with well-defined time scales and strong correlations both, in the timing of the laser pulses and in their peak intensities. Our approach is generic and may be used in other complex systems that undergo similar transitions involving the generation of extreme fluctuations.

Physicochemical properties of hydrogels for use in ophthalmology

This chapter deals with the physicochemical aspects of structure-property relationships in synthetic hydrogels, with particular reference to their application in optometry and ophthalmology. It demonstrates the ways in which the amount of water contained in the hydrogel network can be manipulated by changes in copolymer composition and illustrates the advantages and limitations imposed by use of water as a means of influencing surface, transport and mechanical properties of the gel. The chapter then illustrates how this basic understanding has formed a platform for the development of synthetic interpenetrating networks and macroporous materials, and of hybrids of natural and synthetic hydrogels. The behaviour of these more complex systems is not so centrally dominated by the equilibrium water content as is the case with homogeneous synthetic hydrogels, thus providing advantageous ways of extending the properties and applications of these interesting materials.

Examining the strategy development process through the lens of complex adaptive systems theory

The development of strategy remains a debate for academics and a concern for practitioners. Published research has focused on producing models for strategy development and on studying how strategy is developed in organisations. The Operational Research literature has highlighted the importance of considering complexity within strategic decision making; but little has been done to link strategy development with complexity theories, despite organisations and organisational environments becoming increasingly more complex. We review the dominant streams of strategy development and complexity theories. Our theoretical investigation results in the first conceptual framework which links an established Strategic Operational Research model, the Strategy Development Process model, with complexity via Complex Adaptive Systems theory. We present preliminary findings from the use of this conceptual framework applied to a longitudinal, in-depth case study, to demonstrate the advantages of using this integrated conceptual model. Our research shows that the conceptual model proposed provides rich data and allows for a more holistic examination of the strategy development process. © 2012 Operational Research Society Ltd. All rights reserved.

Strategic development process and complex adaptive systems

The two areas of theory upon which this research was based were „strategy development process?(SDP) and „complex adaptive systems? (CAS), as part of complexity theory, focused on human social organisations. The literature reviewed showed that there is a paucity of empirical work and theory in the overlap of the two areas, providing an opportunity for contributions to knowledge in each area of theory, and for practitioners. An inductive approach was adopted for this research, in an effort to discover new insights to the focus area of study. It was undertaken from within an interpretivist paradigm, and based on a novel conceptual framework. The organisationally intimate nature of the research topic, and the researcher?s circumstances required a research design that was both in-depth and long term. The result was a single, exploratory, case study, which included use of data from 44 in-depth, semi-structured interviews, from 36 people, involving all the top management team members and significant other staff members; observations, rumour and grapevine (ORG) data; and archive data, over a 5½ year period (2005 – 2010). Findings confirm the validity of the conceptual framework, and that complex adaptive systems theory has potential to extend strategy development process theory. It has shown how and why the strategy process developed in the case study organisation by providing deeper insights to the behaviour of the people, their backgrounds, and interactions. Broad predictions of the „latent strategy development? process and some elements of the strategy content are also possible. Based on this research, it is possible to extend the utility of the SDP model by including peoples? behavioural characteristics within the organisation, via complex adaptive systems theory. Further research is recommended to test limits of the application of the conceptual framework and improve its efficacy with more organisations across a variety of sectors.

A systems and cybernetic perspective on complex problem solving

This thesis is concerned with Organisational Problem Solving. The work reflects the complexities of organisational problem situations and the eclectic approach that has been necessary to gain an understanding of the processes involved. The thesis is structured into three main parts. Part I describes the author's understanding of problems and suitable approaches. Chapter 2 identifies the Transcendental Realist (TR) view of science (Harre 1970, Bhaskar 1975) as the best general framework for identifying suitable approaches to complex organisational problems. Chapter 3 discusses the relationship between Checkland's methodology (1972) and TR. The need to generate iconic (explanatory) models of the problem situation is identified and the ability of viable system modelling to supplement the modelling stage of the methodology is explored in Chapter 4. Chapter 5 builds further on the methodology to produce an original iconic model of the methodological process. The model characterises the mechanisms of organisational problem situations as well as desirable procedural steps. The Weltanschauungen (W's) or "world views" of key actors is recognised as central to the mechanisms involved. Part II describes the experience which prompted the theoretical investigation. Chapter 6 describes the first year of the project. The success of this stage is attributed to the predominance of a single W. Chapter 7 describes the changes in the organisation which made the remaining phase of the project difficult. These difficulties are attributed to a failure to recognise the importance of differing W's. Part III revisits the theoretical and organisational issues. Chapter 8 identifies a range of techniques embodying W's which are compatible with .the framework of Part I and which might usefully supplement it. Chapter 9 characterises possible W's in the sponsoring organisation. Throughout the work, an attempt 1s made to reflect the process as well as the product of the author's leaving.

Classrooms as complex adaptive systems:a relational model

In this article, we describe and model the language classroom as a complex adaptive system (see Logan & Schumann, 2005). We argue that linear, categorical descriptions of classroom processes and interactions do not sufficiently explain the complex nature of classrooms, and cannot account for how classroom change occurs (or does not occur), over time. A relational model of classrooms is proposed which focuses on the relations between different elements (physical, environmental, cognitive, social) in the classroom and on how their interaction is crucial in understanding and describing classroom action.

CEPBen:a benchmark for complex event processing systems

Complex Event processing (CEP) has emerged over the last ten years. CEP systems are outstanding in processing large amount of data and responding in a timely fashion. While CEP applications are fast growing, performance management in this area has not gain much attention. It is critical to meet the promised level of service for both system designers and users. In this paper, we present a benchmark for complex event processing systems: CEPBen. The CEPBen benchmark is designed to evaluate CEP functional behaviours, i.e., filtering, transformation and event pattern detection and provides a novel methodology of evaluating the performance of CEP systems. A performance study by running the CEPBen on Esper CEP engine is described and discussed. The results obtained from performance tests demonstrate the influences of CEP functional behaviours on the system performance. © 2014 Springer International Publishing Switzerland.