Environmental degradation of polyethylene-based plastics

The criteria involved in the degradation of polyethylene-based degradable polymer samples have been investigated, with a view to obtaining a clearer mechanism of photo-biodegradation. The compatibility of degradable polymer samples during materials recycling was also studied. Commercial and laboratory prepared degradable polymer samples were oxidised in different environments and the oxidation products formed were studied using various analytical chromatographic and spectroscopic techniques such as HPLC, FT-IR and NMR. It was found that commercial degradable polymer samples which are based on the ECO systems, degrade predominantly via the Norrish II process, whereas the other degradable systems studied (starch-filled polyethylene systems, transition metal systems, including metal carboxylate based polyethylene systems and the photoantioxidant-activator systems) photodegrade essentially via the Norrish I process. In all cases, the major photoxidation products extracted from the degradable polymer samples were found to be carboxylic acids, although, in the polymer itself a mixture of carbonyl containing products such as esters, lactones, ketones and aldehydes was observed. The study also found that the formation of these hydrophilic carbonyl products causes surface swelling of the polymer, thus making bioerosion possible. It was thus concluded that environmental degradation of LDPE is a two step process, the initiation stage being oxidation of the polymer which gives rise to bioassimilable products, which are consequently bioeroded in the second stage, (the biodegradation step). Recycling of the degradable polymer samples as 10% homogeneous and heterogeneous blends was carried out using a single screw extruder (180°C and 210°C) and an internal mixer (190°C). The study showed that commercial degradable polymer samples may be recycled with a minimal loss in their properties.

An expert system for the development of a health and safety policy/risk assessment in the plastics industry

Health and safety policies may be regarded as the cornerstone for positive prevention of occupational accidents and diseases. The Health and Safety at Work, etc Act 1974 makes it a legal duty for employers to prepare and revise a written statement of a general policy with respect to the health and safety at work of employees as well as the organisation and arrangements for carrying out that policy. Despite their importance and the legal equipment to prepare them, health and safety policies have been found, in a large number of plastics processing companies (particularly small companies), to be poorly prepared, inadequately implemented and monitored. An important cause of these inadequacies is the lack of necessary health and safety knowledge and expertise to prepare, implement and monitor policies. One possible way of remedying this problem is to investigate the feasibility of using computers to develop expert system programs to simulate the health and safety (HS) experts' task of preparing the policies and assisting companies implement and monitor them. Such programs use artificial intelligence (AI) techniques to solve this sort of problems which are heuristic in nature and require symbolic reasoning. Expert systems have been used successfully in a variety of fields such as medicine and engineering. An important phase in the feasibility of development of such systems is the engineering of knowledge which consists of identifying the knowledge required, eliciting, structuring and representing it in an appropriate computer programming language.

A techno-economic study of the recycling of mixed plastics to useful products

The techno-economic implications of recycling the components of mixed plastics waste have been studied in a two-part investigation: (a) An economic survey of the prospects for plastics recycling, the plastics waste arisings from retailing, building, automotive, light engineering and chemical industries have been surveyed by mans of questionnaires and interviews. This was partially successful and indicated that very considerable quantities of relatively clean plastics packaging was available in major department chains and household stores. The possibility of devising collection systems for such sources, which do not lead to any extra cost, have been suggested. However, the household collection of plastics waste has been found to be uneconomic due to high cost of collection, transportation and lack of markets for the end products. (b) In a technical study of blends of PE/PP and PE/PS which are found in admixture in waste plastics, it has been shown that they exhibit poor mechanical properties due to incompatibility. Consequently reprocessing of such unsegregated blends results in products of little technological value. The inclusion of some commercial block and graft copolymers which behave as solid phase dispersants (SPES) increase the toughness of the blends (e.g. EPDM in PE/PP blend and SBS in PE/PS blend). Also, EPDM is found to be very effective for improving the toughness of single component polypropylene. However, the improved Technical properties of such blends have been accompanied by a fast rate of photo-oxidation and loss of toughness due to the presence of unsaturation in SPD's. The change in mechanical properties occurring during oven ageing and ultra-violet light accelerated weathering of these binary and ternary blends was followed by a viscoelastonetric technique (Rheovibron) over 9,, wide range of temperatures, impact resistance at room temperature (20-41'G) and changes in functional groups (i.e. carbonyl and trans-1,4-polybutadiene). Also the heat and light stability of single and mixed plastics to which thiol antioxidants were bound to SPE1 segment have been studied and compared with conventional antioxidants. The long-term performance of the mixed plastics containing SPE1 have been improved significantly by the use of conventional and bound antioxidants. It is concluded that an estimated amount of 30000 tonnes/year of plastics waste is available from department chains and household stores which can be converted to useful end products. This justifies pilot-experiments in collaboration with supermarkets, recyclers and converters by use of low cost SPD's and additives designed to make the materials more compatible.

Structural behaviour of glass reinforced plastics

The aim of this research is to promote the use of G.R.P. as a structural material. In the past, the use of G.R.P. has been confined to non-load carrying applications. Such uses are still rapidly increasing but in addition significant changes have been made during the last decade in the development of semi-structural and now even fully structural applications. Glass-reinforced plastic is characterized by a high strength but a relatively low modulus of elasticity. For this reasona G.R.P. structure can expect to show large deformations as a result of which the individual structural members will fail under load due to a loss of stability rather than approaching the ultimate strength of the material. For this reason the selection of the geometrical shapes of G.R.P. structural elements is considered to be an important factor in designing G.R.P. structures. The first chapter of this thesis deals with a general review of the theoretical and experimental methods used to describe the structural properties of G.R.P. The research programme includes five stages dealing with the structural behaviour of G.R.P. The first stage (Chapter 2) begins with selecting and designing an optimum box beam cross-section which gives the maximum flexural and torsional rigidity. The second stage of investigation (Chapter 3) deals with beam to beam connections. A joint was designed and manufactured with different types of fasteners used to connect two beam units. A suitable fastener was selected and the research extended to cover the behaviour of long span beams using multiple joints. The third part of the investigation includes a study of the behaviour of box beams subjected to combined bending, shear and torsion. A special torque rig was developed to perform the tests. Creep deformation of 6 m span G.R.P. was investigated as the fourth stage under a range of loading conditions. As a result of the phenomenon of post buckling behaviour exhibited in the compression flange during testing of box beams during earlier stages of the investigation it was decided to consider this phenomenon in more detail in the final stage of the investigation. G.R.P. plates with different fibre orientation were subjected to uniaxial compression and tested up to failure. In all stages of the investigation theoretical predictions and experimental results were compared and generally good correlation between theory and experimental data was observed.

The structural properties of glassfibre reinforced plastics

The research work described in this thesis is concerned with the development of glassfibre reinforced plastics for structural uses in Civil Engineering construction. The first stage was primarily concerned with the design of GRP lamintes with structura1 properties and method of manufacture suitable for use with relatively large structural components. A cold setting, pressure moulding technique was developed which proved to be efficient in reducing the void content in the composite and minimising the exothermic effect due to curing. The effect of fibre content and fibre arrangement on strength and stiffness of the cornposite was studied and the maximum amount of' fibre content that could be reached by the adopted type of moulding technique was determined. The second stage of the project was concerned with the introduction of steel-wire "sheets" into the GRP cornposites, to take advantage of the high modulus of steel wire to improve the GRP stiffness and to reduce deformation. The experimental observations agreed reasonably well with theoretical predictions in both first and second stages of the work. The third stage was concerned with studying the stability of GRP flat rectangular plates subjected to uniaxial compression or pure shear, to simulate compression flanges or shear webs respectively. The investigation was concentrated on the effect of fibre arrangement in the plate on buckling load. The effect of the introduction of steel-wire sheets on the plate stability in compression was also investigated. The boundary conditions were chosen to be close to those usually assumed in built-up box-sections for both compression flanges and webs. The orthotropic plate and the mid-plane symmetric were used successfully in predicting the buckling load theoretically. In determining the buckling load experimentally, two methods were used. The Southwell plot method and electrical strain gauge method. The latter proved to be more reliable in predicting the buckling load than the former, especially for plates under uniaxial compression. Sample design charts for GRP plates that yield and buckle simultaneously under compression are also presented in the thesis. The final stage of the work dealt with the design and test of GRP beams. The investigation began by finding the optimum cross-section for a GRP beam. The cross-section which was developed was a thin walled corrugated section which showed higher stiffness than other cross-sections for the same cross-sectional area (i.e. box, I, and rectangular sections). A cold setting, hand layings technique was used in manufacturing these beams wbich were of nine types depending on the type of glass reinforcement employed and the arrangement of layers in the beam. The simple bending theory was used in the beam design and proved to be satisfactory in predicting the stresses and deflections. A factor of safety of 4 was chosen for design purposes and considered to be suitable for long term use under static load. Because of its relatively low modulus, GRP beams allowable deflection was limited to 1/120th of the span which was found to be adequate for design purposes. A general discussion of the behaviour of GRP composites and their place relative to the more conventional structural material was also presented in the thesis.

Fundamental mechanisms affecting service performance of electroplated plastics

Ten grades of ABS and four grades of polypropylene have been plated with various copper + nickel + chromium coatings and subjected to a variety of tests. In corrosion studies the pre-electroplating sequence and plastics type have been shown to influence performance. One ABS pre-electroplating sequence was consistently associated with better corrosion performance; two factors were responsible for this, namely the more severe nature of the etch and the relatively more noble electroless nickel. Statistical analysis has indicated that order of severity of the corrosion tests was static-mobile-CASS, the latter being the least severe. In mechanical tests two properties of ABS and polypropJylene, ductility and impact strength, have been shown to be adversely affected when electrodeposited layers were applied. The cause of this is due to a complex of factors, the most important of which is the notch sensitivity of the plastics. Peel adhesion has been studied on flat panels and also on ones which had a ridge and a valley moulded into one face. High adhesion peaks occurred on the flat face at regions associated with the ridge and valley. The local moulding conditions induced by the features were responsible for this phenonemon. In the main programme the thermal cycling test was shown to be more likely than the peel adhesion test to give an indication of the service performance of electroplated plastics.

The pyrolysis of plastics in molten salts

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Catalytic supercritical water gasification of plastics with supported RuO2:a potential solution to hydrocarbons-water pollution problem

Here we report on a potential catalytic process for efficient clean-up of plastic pollution in waters, such as the Great Pacific Garbage Patch (CPGP). Detailed catalytic mechanisms of RuO2 during supercritical water gasification of common polyolefin plastics including low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP) and polystyrene (PP), have been investigated in a batch reactor at 450 °C, 60 min. All four plastics gave very high carbon gasification efficiencies (CGE) and hydrogen gasification efficiencies (HGE). Methane was the highest gas component, with a yield of up to 37 mol kg−1LDPE using the 20 wt% RuO2 catalyst. Evaluation of the gas yields, CGE and HGE revealed that the conversion of PS involved thermal degradation, steam reforming and methanation; whereas hydrogenolysis was a possible additional mechanism during the conversion of aliphatic plastics. The process has the benefits of producing a clean-pressurized methane-rich fuel gas as well as cleaning up hydrocarbons-polluted waters.

Some aspects of the microbiological properties of polymers and composite materials

The interaction of microorganisms with glass-reinforced polyester resins(GRP), both under laboratory and simulated operating conditions, has been examined following reports of severl! fungal biodeterioration. Although GRP was not previously associated with substantial microbial growth, small amounts of microbial activity would pose problems for products associated with comestible materials. The microbiology of the raw materials was investigated, two ingredients were supportive to microbial populations whilst five materials were biostatic or inhibitory in their action. Production laminate was not susceptible to microbial deterioration or inhibitory to microbes. Incorporation of zinc stearate, one of the supportive ingredients, at 300% manufacturing level or drastic undercuring produced laminate capable of supporting microbial growth but only after a non-biotic stage of degradation. Study of the long-term population dynamics of cisterns of GRP and competitive materials under conditions simulating in-service conditions, monitoring microbial numbers within the experimental vessels and comparing with the populations of the supply water, suggests that the performance of GRP cisterns is slightly superior to conventional competitive materials. An investigation of the biological performance of GRP cisterns in an isolated area of known microbiological hazard was conducted. Severe biodeterioration had been experienced with Preform GRP articles moulded using different production techniques, but substitution of current GRP articles resulted in no recurrence of the problem. All attempts to establish the fungal isolate responsible for the phenomena in cisterns under controlled conditions failed. Scanning Electron Microscopy of GRP surfaces showed that although differences exist between current and Preform laminates, these could not satisfactorily explain the differences in service behaviour. These results and the results of the British Plastics Federation Expert Working Group interlaboratory study are discussed in relation to the original report of gross fungal biodeterioration and, to the design of future testing programmes for the products of industrial concerns.

Characterisation of a cavity transfer mixer as a chemical reactor

This research project examined the feasibility of using a cavity transfer mixer (CTM) as a continuous reactor to perform reactions between either solid or liquid reagents and polymer melt; reactions which have previously been typically carried out in batch reactor systems. Equipment has been developed to allow uniform and reproducible introduction of reagents into the polymer melt. Reactions have also been performed using batch processing equipment to enable comparison with the performance of the CTM. It was concluded that: a) there are certain reactions which cannot be carried out in a CTM, but which can be performed in a batch system such as a mill or a sigma blade mixer. This was found to be the case for some neutralisation reactions where the product was quasi crosslinked. b) the reactions that can be carried out in a CTM are performed more efficiently in a CTM than on a batch process. For example, when monomers were to be grafted onto polymers, this was more safely and efficiently performed in the CTM than in a mill or a sigma blade mixer. Residence time distributions (RTDs) for three CTMs were studied in order to gain an insight into the effect of CTM geometry on RTD, polymer melt flow pattern and reactor performance. A mathematical model has been developed to predict the influence of process parameters on RTD and the results compared with experimentally observed trends. The comparison was good. A programme of research has been drawn up to form the basis of an industrially based sponsored development project of the CTM reactor. This work programme was successfully marketed to companies with commercial interest in modified rubber and plastics as an integral part of the research programme of this thesis and the sponsored research programme has paralleled the work reported here.

The study of ultra-low energy deposition of hydrogenated amorphous carbon thin films

This thesis is dedicated to the production and analysis of thin hydrogenated amorphous carbon films. A cascaded arc plasma source was used to produce a high density plasma of hydrocarbon radicals that deposited on a substrate at ultra low energies. The work was intended to create a better understanding of the mechanisms responsible for the film formation, by an extensive analysis on the properties of the films in correlation with the conditions used in the plasma cell. Two different precursors were used: methane and acetylene. They revealed a very different picture for the mechanism of film formation and properties. Methane was less successful, and the films formed were soft, with poor adhesion to the substrate and decomposing with time. Acetylene was the better option, and the films formed in this case were harder, with better adhesion to the substrate and stable over time. The plasma parameters could be varied to change the character of films, from polymer-like to diamond-like carbon. Films deposited from methane were grown at low deposition rates, which increased with the increase in process pressure and source power and decreased with the increase in substrate temperature and in hydrogen fraction in the carrier gas. The films had similar hydrogen content, sp3 fractions, average roughness (Ra) and low hardness. Above a deposition temperature of 350°C graphitization occurred - an increase in the sp2 fraction. A deposition mechanism was proposed, based upon the reaction product of the dissociative recombination of CH4+. There were small differences between the chemistries in the plasma at low and high precursor flow rates and low and high substrate temperatures; all experimental conditions led to formation of films that were either polymer-like, soft amorphous hydrogenated carbon or graphitic-like in structure. Films deposited from acetylene were grown at much higher deposition rates on different substrates (silicon, glass and plastics). The film quality increased noticeably with the increase of relative acetylene to argon flow rate, up to a certain value, where saturation occurred. With the increase in substrate temperature and the lowering of the acetylene injection ring position further improvements in film quality were achieved. The deposition process was scaled up to large area (5 x 5 cm) substrates in the later stages of the project. A deposition mechanism was proposed, based upon the reaction products of the dissociative recombination of C2H2 +. There were large differences between the chemistry in the plasma at low and medium/high precursor flow rates. This corresponded to large differences in film properties from low to medium flow rates, when films changed their character from polymer-like to diamond-like, whereas the differences between films deposited at medium and high precursor flow rates were small. Modelling of the film growth on silicon substrates was initiated and it explained the formation of sp2 and sp3 bonds at these very low energies. However, further improvements to the model are needed.

Fixed bed downdraft gasification of paper industry wastes

The two main wastes generated from secondary fibre paper mills are rejects (composed mainly of plastics and fibres) and de-inking sludge, both of which are evolved from the pulping process during paper manufacture. The current practice for the disposal of these wastes is either by land-spreading or land-filling. This work explores the gasification of blends of pre-conditioned rejects and de-inking sludge pellets with mixed wood chips in an Imbert type fixed bed downdraft gasifier with a maximum feeding capacity of 10kg/h. The producer gases evolved would generate combined heat and power (CHP) in an internal combustion engine. The results show that as much as 80wt.% of a brown paper mill's rejects (consisting of 20wt.% mixed plastics and 80wt.% paper fibres) could be successfully gasified in a blend with 20wt.% mixed wood chips. The producer gas composition was 16.24% H, 23.34% CO, 12.71% CO 5.21% CH and 42.49% N (v/v%) with a higher heating value of 7.3MJ/Nm. After the removal of tar and water condensate the producer gas was of sufficient calorific value and flow rate to power a 10kWe gas engine. Some blends using rejects from other mill types were not successful, and the limiting factor was usually the agglomeration of plastics present within the fuel.