Reactive processing of polyolefins using antioxidant systems

Various monoacrylic compounds containing a hindered phenol function (e.g.3,5-di-tert.-butyl-4-hydroxy benzyl alcohol, DBBA and vinyl-3-[3',5'-di-tert.-butyl-4-hydroxy phenyl] propionate, VDBP), and a benzophenone function (2-hydroxy-4-[beta hydroxy ethoxy] benzophenone, HAEB) were synthesised and used as reactive antioxidants (AO's) for polypropylene (PP). These compounds were reacted with PP melt in the presence of low concentration of a free radical generator such a peroxide (reactive processing) to produce bound-antioxidant concentrates. The binding reaction of these AO's onto PP was found to be low and this was shown to be mainly due to competing reactions such as homopolymerisation of the antioxidant. At high concentrations of peroxide, higher binding efficiency resulted, but, this was accompanied by melt degradation of the polymer. In a special reactive processing procedure, a di- or a trifunctional reactant (referred to as coagent), e.g.tri-methylol propane tri-acrylate, Tris, and Divinyl benzene, DVB, were used with the antioxidant and this has led to an enhanced efficiency of the grating reaction of antioxidants on the polymer in the melt. The evidence suggests that this is due to copolymerisation of the antioxidants with the coagent as well as grafting of the copolymers onto the polymer backbone. Although the 'bound' AO's containing a UV stabilising function showed lower overall stabilisation effect than the unbound analogues before extraction, they were still much more effective when subjected to exhaustive solvent extraction. Furthermore, a very effective synergistic stabilising activity when two reactive AO's containing thermal and UV stabilising functions e.g. DBBA and HAEB, were reactively processed with PP in the presence of a coagent. The stabilising effectiveness of such a synergist was much higher than that of the unbound analogues both before and after extraction. Analysis using the GPC technique of concentrates containing bound-DBBA processed in the presence of Tris coagent showed higher molecular weight (Mn), compared to that of a polymer processed without the coagent, but was still lower than that of the control processed PP with no additives. This indicates that Tris coagent may inhibit further melt degradation of the polymer. Model reactions of DBBA in liquid hydrocarbon (decalin) and analysis of the products using FTIR and NMR spectroscopy showed the formation of grafted DBBA onto decalin molecules as well as homopolymerisation of the AO. In the presence of Tris coagent, copolymerisation of DBBA with the Tris inevitably occured; which was followed by grafting of the copolymer onto the decalin, FTIR and NMR results of the polymer concentrates containing bound-DBBA processed with and without Tris, showed similar behaviour as the above model reactions. This evidence supports the effect of Tris in enhancing the efficiency of the reaction of DBBA in the polymer melt. Reactive procesing of HAEB in polymer melts exhibited crosslinking formation In the early stages of the reaction, however, in the final stage, the crosslinked structure was 'broken down' or rearranged to give an almost gel free polymer with high antioxidant binding efficiency.

The design and engineering of a reactor test facility for thermal processing of biomass

This thesis describes the design and engineering of a pressurised biomass gasification test facility. A detailed examination of the major elements within the plant has been undertaken in relation to specification of equipment, evaluation of options and final construction. The retrospective project assessment was developed from consideration of relevant literature and theoretical principles. The literature review includes a discussion on legislation and applicable design codes. From this analysis, each of the necessary equipment units was reviewed and important design decisions and procedures highlighted and explored. Particular emphasis was placed on examination of the stringent demands of the ASME VIII design codes. The inter-relationship of functional units was investigated and areas of deficiency, such as biomass feeders and gas cleaning, have been commented upon. Finally, plant costing was summarized in relation to the plant design and proposed experimental programme. The main conclusion drawn from the study is that pressurised gasification of biomass is far more difficult and expensive to support than atmospheric gasification. A number of recommendations have been made regarding future work in this area.

Computer interpretation of engineering drawings as solid models

Much of the geometrical data relating to engineering components and assemblies is stored in the form of orthographic views, either on paper or computer files. For various engineering applications, however, it is necessary to describe objects in formal geometric modelling terms. The work reported in this thesis is concerned with the development and implementation of concepts and algorithms for the automatic interpretation of orthographic views as solid models. The various rules and conventions associated with engineering drawings are reviewed and several geometric modelling representations are briefly examined. A review of existing techniques for the automatic, and semi-automatic, interpretation of engineering drawings as solid models is given. A new theoretical approach is then presented and discussed. The author shows how the implementation of such an approach for uniform thickness objects may be extended to more general objects by introducing the concept of `approximation models'. Means by which the quality of the transformations is monitored, are also described. Detailed descriptions of the interpretation algorithms and the software package that were developed for this project are given. The process is then illustrated by a number of practical examples. Finally, the thesis concludes that, using the techniques developed, a substantial percentage of drawings of engineering components could be converted into geometric models with a specific degree of accuracy. This degree is indicative of the suitability of the model for a particular application. Further work on important details is required before a commercially acceptable package is produced.

Computer simulation of form-roll design

Changes in modern structural design have created a demand for products which are light but possess high strength. The objective is a reduction in fuel consumption and weight of materials to satisfy both economic and environmental criteria. Cold roll forming has the potential to fulfil this requirement. The bending process is controlled by the shape of the profile machined on the periphery of the rolls. A CNC lathe can machine complicated profiles to a high standard of precision, but the expertise of a numerical control programmer is required. A computer program was developed during this project, using the expert system concept, to calculate tool paths and consequently to expedite the procurement of the machine control tapes whilst removing the need for a skilled programmer. Codifying the expertise of a human and the encapsulation of knowledge within a computer memory, destroys the dependency on highly trained people whose services can be costly, inconsistent and unreliable. A successful cold roll forming operation, where the product is geometrically correct and free from visual defects, is not easy to attain. The geometry of the sheet after travelling through the rolling mill depends on the residual strains generated by the elastic-plastic deformation. Accurate evaluation of the residual strains can provide the basis for predicting the geometry of the section. A study of geometric and material non-linearity, yield criteria, material hardening and stress-strain relationships was undertaken in this research project. The finite element method was chosen to provide a mathematical model of the bending process and, to ensure an efficient manipulation of the large stiffness matrices, the frontal solution was applied. A series of experimental investigations provided data to compare with corresponding values obtained from the theoretical modelling. A computer simulation, capable of predicting that a design will be satisfactory prior to the manufacture of the rolls, would allow effort to be concentrated into devising an optimum design where costs are minimised.

A study of thermodynamic characteristics and predictive computer modelling of an air to water heat pump system

A study on heat pump thermodynamic characteristics has been made in the laboratory on a specially designed and instrumented air to water heat pump system. The design, using refrigerant R12, was based on the requirement to produce domestic hot water at a temperature of about 50 °C and was assembled in the laboratory. All the experimental data were fed to a microcomputer and stored on disk automatically from appropriate transducers via amplifier and 16 channel analogue to digital converters. The measurements taken were R12 pressures and temperatures, water and R12 mass flow rates, air speed, fan and compressor input powers, water and air inlet and outlet temperatures, wet and dry bulb temperatures. The time interval between the observations could be varied. The results showed, as expected, that the COP was higher at higher air inlet temperatures and at lower hot water output temperatures. The optimum air speed was found to be at a speed when the fan input power was about 4% of the condenser heat output. It was also found that the hot water can be produced at a temperature higher than the appropriate R12 condensing temperature corresponding to condensing pressure. This was achieved by condenser design to take advantage of discharge superheat and by further heating the water using heat recovery from the compressor. Of the input power to the compressor, typically about 85% was transferred to the refrigerant, 50 % by the compression work and 35% due to the heating of the refrigerant by the cylinder wall, and the remaining 15% (of the input power) was rejected to the cooling medium. The evaporator effectiveness was found to be about 75% and sensitive to the air speed. Using the data collected, a steady state computer model was developed. For given input conditions s air inlet temperature, air speed, the degree of suction superheat , water inlet and outlet temperatures; the model is capable of predicting the refrigerant cycle, compressor efficiency, evaporator effectiveness, condenser water flow rate and system Cop.

A new role for Low German? Language insertion as bilingual practice in the process of language shift

This article analyses language insertion as a bilingual communicative practice, applying a functional, speaker-focused approach to the study of sociolinguistics and language contact. The article is based on a study of contact phenomena in a formerly diglossic region in Northern Germany, where the previously spoken language – Low German – is in the process of being replaced by the dominant standard variety, German. It examines regional publications in order to establish the linguistic techniques by which Low German elements are incorporated into the Standard German texts and the communicative purposes that they serve. The paper concludes that in the process of language shift an emblematic repertoire from Low German is created which can be applied into the dominant contact language, German, for specific communicative purposes.

Computer analysis of large civil engineering structures

The finite element method is now well established among engineers as being an extremely useful tool in the analysis of problems with complicated boundary conditions. One aim of this thesis has been to produce a set of computer algorithms capable of efficiently analysing complex three dimensional structures. This set of algorithms has been designed to permit much versatility. Provisions such as the use of only those parts of the system which are relevant to a given analysis and the facility to extend the system by the addition of new elements are incorporate. Five element types have been programmed, these are, prismatic members, rectangular plates, triangular plates and curved plates. The 'in and out of plane' stiffness matrices for a curved plate element are derived using the finite element technique. The performance of this type of element is compared with two other theoretical solutions as well as with a set of independent experimental observations. Additional experimental work was then carried out by the author to further evaluate the acceptability of this element. Finally the analysis of two large civil engineering structures, the shell of an electrical precipitator and a concrete bridge, are presented to investigate the performance of the algorithms. Comparisons are made between the computer time, core store requirements and the accuracy of the analysis, for the proposed system and those of another program.

Computer simulation of moist agglomerate collisions

This thesis considers the computer simulation of moist agglomerate collisions using the discrete element method (DEM). The study is confined to pendular state moist agglomerates, at which liquid is presented as either absorbed immobile films or pendular liquid bridges and the interparticle force is modelled as the adhesive contact force and interstitial liquid bridge force. Algorithms used to model the contact force due to surface adhesion, tangential friction and particle deformation have been derived by other researchers and are briefly described in the thesis. A theoretical study of the pendular liquid bridge force between spherical particles has been made and the algorithms for the modelling of the pendular liquid bridge force between spherical particles have been developed and incorporated into the Aston version of the DEM program TRUBAL. It has been found that, for static liquid bridges, the more explicit criterion for specifying the stable solution and critical separation is provided by the total free energy. The critical separation is given by the cube root of liquid bridge volume to a good approximation and the 'gorge method' of evaluation based on the toroidal approximation leads to errors in the calculated force of less than 10%. Three dimensional computer simulations of an agglomerate impacting orthogonally with a wall are reported. The results demonstrate the effectiveness of adding viscous binder to prevent attrition, a common practice in process engineering. Results of simulated agglomerate-agglomerate collisions show that, for colinear agglomerate impacts, there is an optimum velocity which results in a near spherical shape of the coalesced agglomerate and, hence, minimises attrition due to subsequent collisions. The relationship between the optimum impact velocity and the liquid viscosity and surface tension is illustrated. The effect of varying the angle of impact on the coalescence/attrition behaviour is also reported. (DX 187, 340).

A rationale for the optimisation by computer methods of the efficient use of metals and materials

The aim of the research project was to gain d complete and accurate accounting of the needs and deficiencies of materials selection and design data, with particular attention given to the feasibility of a computerised materials selection system that would include application analysis, property data and screening techniques. The project also investigates and integrates the three major aspects of materials resources, materials selection and materials recycling. Consideration of the materials resource base suggests that, though our discovery potential has increased, geologic availability is the ultimate determinant and several metals may well become scarce at the same time, thus compounding the problem of substitution. With around 2- to 20- million units of engineering materials data, the use of a computer is the only logical answer for scientific selection of materials. The system developed at Aston is used for data storage, mathematical computation and output. The system enables programs to be run in batch and interactive (on-line) mode. The program with modification can also handle such variables as quantity of mineral resources, energy cost of materials and depletion and utilisation rates of strateqic materials. The work also carries out an in-depth study of copper recycling in the U.K. and concludes that, somewhere in the region of 2 million tonnes of copper is missing from the recycling cycle. It also sets out guidelines on product design and conservation policies from the recyclability point of view.

Vision2020 and the English language : a study of the role of language in national development.

The research reported here is an investigation into the problems of social and economic development of a multiethic and multicultural country which has the added challenge of adopting a non-indigenous code to facilitate the development process. Malaysia's power to negotiate outcomes favourable to the interest of the country is critical for the successful attainment of the goals and objectives of VISION2020. Therefore the mechanisms of the human resource development programme have to be efficacious. The three hypotheses of this study are as follows: 1. there is a fear that the problems and challenges posed by the development plans, have been conceptually trivialised; 2. based on (1) above there is a concern that solutions proposed are inadequate and inappropriate and 3. the outcome of both (1) and (2) can lead to the potential underachievement of national goals and objectives. The study proposes a complex model for conceptualising the problem which looks at the relationship between society and language, which any solutions proposed must take into proper consideration. The study looks at the mechanisms available for the smooth absorption of new Malaysian members to new and international communities. A large scale investigation was undertaken with the researcher functioning as a participant observer. An in-depth study of one particular educational ecology yielded approximately 38 hours of interviews and 100 questionnaires. These data were analysed both for explicit information and implicit implications. By some criteria national policies appear to be having the desired effect, and can be given a clean bill of health. By others it is clear that major adjustments would be necessary if the nation is to achieve its objectives in full. Based on the evidence gathered, thr study proposes an apprenticeship approach to training programmes for effective participation of new members in the new ecologies.