46 resultados para 091209 Polymers and Plastics

em Aston University Research Archive


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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.

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One of the main objectives of this study was to functionalise various rubbers (i.e. ethylene propylene copolymer (EP), ethylene propylene diene terpolymer (EPDM), and natural rubber (NR)) using functional monomers, maleic anhydride (MA) and glycidyl methacrylate (GMA), via reactive processing routes. The functionalisation of the rubber was carried out via different reactive processing methods in an internal mixer. GMA was free-radically grafted onto EP and EPDM in the melt state in the absence and presence of a comonomer, trimethylolpropane triacrylate (TRlS). To optinuse the grafting conditions and the compositions, the effects of various paranleters on the grafting yields and the extent of side reactions were investigated. Precipitation method and Soxhlet extraction method was established to purifY the GMA modified rubbers and the grafting degree was determined by FTIR and titration. It was found that without TRlS the grafting degree of GMA increased with increasing peroxide concentration. However, grafting was low and the homopolymerisation of GMA and crosslinking of the polymers were identified as the main side reactions competing with the desired grafting reaction for EP and EPDM, respectively. The use of the tri-functional comonomer, TRlS, was shown to greatly enhance the GMA grafting and reduce the side reactions in terms of the higher GMA grafting degree, less alteration of the rheological properties of the polymer substrates and very little formation of polyGMA. The grafting mechanisms were investigated. MA was grafted onto NR using both thermal initiation and peroxide initiation. The results showed clearly that the reaction of MA with NR could be thermally initiated above 140°C in the absence of peroxide. At a preferable temperature of 200°C, the grafting degree was increased with increasing MA concentration. The grafting reaction could also be initiated with peroxide. It was found that 2,5-dimethyl-2,5-bis(ter-butylproxy) hexane (TIOI) was a suitable peroxide to initiate the reaction efficiently above I50°C. The second objective of the work was to utilize the functionalised rubbers in a second step to achieve an in-situ compatibilisation of blends based on poly(ethylene terephthalate) (PET), in particular, with GMA-grafted-EP and -EPDM and the reactive blending was carried out in an internal mixer. The effects of GMA grafting degree, viscosities of GMAgrafted- EP and -EPDM and the presence of polyGMA in the rubber samples on the compatibilisation of PET blends in terms of morphology, dynamical mechanical properties and tensile properties were investigated. It was found that the GMA modified rubbers were very efficient in compatibilising the PET blends and this was supported by the much finer morphology and the better tensile properties. The evidence obtained from the analysis of the PET blends strongly supports the existence of the copolymers through the interfacial reactions between the grafted epoxy group in the GMA modified rubber and the terminal groups of PET in the blends.

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The research described in this thesis explored the synthesis tlnd characteristltion of biocompatible and biodegradable polymers of lactide through non-toxic titanium alkoxide nitiators. The research objectives focused on the preparation of polylactides in both solvent and solventless media, to produce materials with a wide range of molecular weights. The polylactides were fully characterised using gel permeation chromatography and 1H and 13C NMR spectroscopy. NMR spectroscopy was carried out in the study the reaction mechanisms. Kinetic studies of the ring opening polymerisation of lactide with titanium alkoxide initiators were also conducted using NMR spectroscopy. The objectives of this research were also focused on the enhancement of the flexibility of the polymer chains by synthesising random and block copolymers of lactide and ε-caprolactone using Ti(0-i-Pr)4 as an initiator, This work involved extensive characterisalion of the synthesised copolymers using gel permeation chromatography and 1H and 13C NMR spectroscopic analysis. Kinetic studies of the ring opening polymerisation of ε-caplrolactone and of the copolymerisation of lactide and ε-caprolactone with Ti(O-i-Pr)4 as an initiator were also carried out. The last section of this work involved the synthesis of block and star-shaped copolymers of lactide and poly(ethylene glycol) [PEG]. The preparation of lactide/PEG block copolymers was carried out by ring opening polymerisation of L-Iactide using Ti(O-i-Pr)4 as an initiator and hydroxyl-terminated PEG's with different numbers of hydroxyl groups as co-initiators both in solution and solventless media. These all-in-one polymersations yielded the synthesis of both lactide homopolymer and lactide/PEG block copolymer. In order to selectively synthesise copolymers of lactide and PEG, the experiment was carried out in two steps. The first step consisted of the synthesis of a titanium macro-initiator by exchanging the iso-propoxide ligands by PEG with different numbers of hydroxyl groups. The second step involved the ring opening polymerisation of lactide using the titanium macrocatalyst that was prepared as an initiator. The polymerisations were carried out in a solventless media. The synthesis of lactide/PEG copolymers using polyethylene glycol with amino terminal groups was also discussed. Extensive characterisation of the lactide block copolymers and macroinitiators was carried out using techniques such as, gel permeation chromatography (GPC), NMR spectroscopy and differential scanning calorimeter (DeS).

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Organic substances, particularly polymers, are finding increasing use in modifying the properties of cements and concrete. Although a significant amount of research has been conducted into the modification of the mechanical properties of cements by polymers, little is known about the nature of the interface and interactions taking place between the two phases. This thesis addresses the problem of elucidating such interactions. Relevant literature is reviewed, covering the general use of polymers with cements, the chemistry of cements and polymers, adhesion and known interactions between polymers and both cements and related minerals. Although several polymer systems were studied, two in particular were selected, as being well characterized. These were: - 1) polymethyl methacrylate (PMMA), the polymer derived from methyl methacrylate (MMA), and 2) an amine-cured epoxy resin system. By this approach, a methodology was developed for the examination of other polymer/cement interactions. Experiments were conducted in five main areas:- 1) polymer-cement adhesion and the feasibility of revealing interfacial regions mechanically, 2) chemical reactions between polymers and cements, 3) characterization of cement adhesion surfaces, 4) interactions affecting overall polymerisation rates, and 5) studies of polymer impregnated cements. The following conclusions were reached:- 1) The PMMA/cement interface contains calcium methacrylate as an interfacial reaction product, water being a reactant. Calcium methacrylate is detrimental to the properties of PMMA/cement composites, being highly water-soluble. 2) The pore surface of cement accelerates the polymerisation of MMA, leading to an increased molecular weight compared to polymerisation of pure MMA, minerals in hydrated cement powders having the opposite effect. 3) The investigation of reaction products presents a number of experimental problems, selection of appropriate techniques depending upon the system studied. For the two systems examined in detail, ion chromatography proved particularly useful; DTA, IRS and XPS indicated reactions, though the data was hard to interpret; XRD proving inconclusive. 4) It is impractical to reveal interfacial regions mechanically, but may be accomplished by chemical means.

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The design and synthesis of safe and efficient nonviral vectors for gene delivery has attracted significant attention in recent years. Previous experiments have revealed that the charge density of a polycation (the carrier) plays a crucial role in complexation and the release of the gene from the complex in the cytosol. In this work, we adopt an atomistic molecular dynamics simulation approach to study the complexation of short strand duplex RNA with six cationic carrier systems of varying charge and surface topology. The simulations reveal detailed molecular-level pictures of the structures and dynamics of the RNA-polycation complexes. Estimates for the binding free energy indicate that electrostatic contributions are dominant followed by van der Waals interactions. The binding free energy between the 8(+)polymers and the RNA is found to be larger than that of the 4(+)polymers, in general agreement with previously published data. Because reliable binding free energies provide an effective index of the ability of the polycationic carrier to bind the nucleic acid and also carry implications for the process of gene release within the cytosol, these novel simulations have the potential to provide us with a much better understanding of key mechanistic aspects of gene-polycation complexation and thereby advance the rational design of nonviral gene delivery systems.

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The aim of this project was to investigate the enzyme catalysed modification of synthetic polymers. It was found that an immobilised lipase from Candida antartica (Novozyme 435) catalysed the selective epoxidation of poly(butadiene) in the presence of hydrogen peroxide and catalytic quantities of acetic acid. The cis and trans double bonds of the backbone were epoxidised in yields of up to 60 % whilst the pendent vinyl groups were untouched. The effect of varying a number of reaction parameters was investigated. These studies suggested that higher yields of epoxide could not be obtained because of the conformational properties of the partially epoxidised polymer. Application of this process to the Baeyer-Villiger reaction of poly(vinyl phenyl ketone) and poly(vinyl methyl ketone) were unsuccessful. The lack of reactivity was found to be a property of the polymer rather than the enzymatic system employed. Attempts to modify hydroxyl containing polymers and polymers bearing active esters close to the polymer backbone were unsuccessful. Steric factors appear to be the most important influence on the outcome of the reactions.

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The cationic polymerisation of various monomers, including cyclic ethers bearing energetic nitrate ester (-ON02) groups, substituted styrenes and isobutylene has been investigated. The main reaction studied has been the ring-opening polymerisation of 3- (nitratomethyl)-3-methyl oxetane (NIMMO) using the alcohol/BF3.0Et2 binary initiator system. A series of di-, tri- and tetrafunctional telechelic polymers has been synthesised. In order to optimise the system, achieve controlled molecular weight polymers and understand the mechanism of polymerisation the effects of certain parameters on the molecular weight distribution, as determined by Size Exclusion Chromatography, have been examined. This shows the molecular weight achieved depends on a combination of factors including -OH concentration, addition rate of monomer and, most importantly, temperature. A lower temperature and OH concentration tends to produce higher molecular weight, whereas, slower addition rates of monomer, either have no significant effect or produce a lower molecular weight polymer. These factors were used to increase the formation of a cyclic oligomer, by a side reaction, and suggest, that the polymerisation of NIMMO is complicated with endbiting and back biting reactions, along with other transfer/termination processes. These observations appear to fit the model of an active-chain end mechanism. Another cyclic monomer, glycidyl nitrate (GLYN), has been polymerised by the activated monomer mechanism. Various other monomers have been used to end-cap the polymer chains to produce hydroxy ends which are expected to form more stable urethane links, than the glycidyl nitrate ends, when cured with isocyanates. A novel monomer, butadiene oxide dinitrate (BODN), has been prepared and its homopolymerisation and copolymerisation with GL YN studied. In concurrent work the carbocationic polymerisations of isobutylene or substituted styrenes have been studied. Materials with narrow molecular weight distributions have been prepared using the diphenyl phosphate/BCl3 initiator. These systems and monomers are expected to be used in the synthesis of thermoplastic elastomers.

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Water-based latices, used in the production of internal liners for beer/beverage cans, were investigated using a number of analytical techniques. The epoxy-graft-acrylic polymers, used to prepare the latices, and films, produced from those latices, were also examined. It was confirmed that acrylic polymer preferentially grafts onto higher molecular weight portions of the epoxy polymer. The amount of epoxy remaining ungrafted was determined to be 80%. This figure is higher than was previously thought. Molecular weight distribution studies were carried out on the epoxy and epoxy-g-acrylic resins. A quantitative method for determining copolymer composition using GPC was evaluated. The GPC method was also used to determine polymer composition as a function of molecular weight. IR spectroscopy was used to determine the total level of acrylic modification of the polymers and NMR was used to determine the level of grafting. Particle size determinations were carried out using transmission electron microscopy and dynamic light scattering. Levels of stabilising amine greatly affected the viscosity of the latex, particle size and amount of soluble polymer but the core particle size, as determined using TEM, was unaffected. NMR spectra of the latices produced spectra only from solvents and amine modifiers. Using solid-state CP/MAS/freezing techniques spectra from the epoxy component could be observed. FT-IR spectra of the latices were obtained after special subtraction of water. The only difference between the spectra of the latices and those of the dry film were due to the presence of the solvents in the former. A distinctive morphology in the films produced from the latices was observed. This suggested that the micelle structure of the latex survives the film forming process. If insufficient acrylic is present, large epoxy domains are produced which gives rise to poor film characteristics. Casting the polymers from organic solutions failed to produce similar morphology.

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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.

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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.

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Optimizing paths on networks is crucial for many applications, ranging from subway traffic to Internet communication. Because global path optimization that takes account of all path choices simultaneously is computationally hard, most existing routing algorithms optimize paths individually, thus providing suboptimal solutions. We use the physics of interacting polymers and disordered systems to analyze macroscopic properties of generic path optimization problems and derive a simple, principled, generic, and distributed routing algorithm capable of considering all individual path choices simultaneously. We demonstrate the efficacy of the algorithm by applying it to: (i) random graphs resembling Internet overlay networks, (ii) travel on the London Underground network based on Oyster card data, and (iii ) the global airport network. Analytically derived macroscopic properties give rise to insightful new routing phenomena, including phase transitions and scaling laws, that facilitate better understanding of the appropriate operational regimes and their limitations, which are difficult to obtain otherwise.

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Foaming during fermentation reduces the efficiency of the process leading to increased costs and reduced productivity. Foaming can be overcome by the use of chemical antifoaming agents, however their influence upon the growth of organisms and protein yield is poorly understood. The objective of this work was to evaluate the effects of different antifoams on recombinant protein production. Antifoam A, Antifoam C, J673A, P2000 and SB2121 were tested at different concentrations for their effect on the growth characteristics of Pichia pastoris producing GFP, EPO and A2aR and the yield of protein in shake flasks over 48 h. All antifoams tested increased the total GFP in the shake flasks compared to controls, at higher concentrations than would normally be used for defoaming purposes. The highest yield was achieved by adding 1 % P2000 which nearly doubled the total yield followed by 1 % SB2121, 1 % J673A, 0.6 % Antifoam A and lastly 0.8 % Antifoam C. The antifoams had a detrimental effect upon the production of EPO and A2aR in shake flasks, suggesting that their effects may be protein specific. The mechanisms of action of the antifoams was investigated and suggested that although the volumetric mass oxygen transfer coefficient (kLa) was influenced by the agents, their effect upon the concentration of dissolved oxygen did not contribute to the changes in growth or recombinant protein yield. Findings in small scale also suggested that antifoams of different compositions such as silicone polymers and alcoxylated fatty acid esters may influence growth characteristics of host organisms and the ability of the cells to secrete recombinant protein, indirectly affecting the protein yield. Upon scale-up, the concentration effects of the antifoams upon GFP yield in bioreactors was reversed, with lower concentrations producing a higher yield. These data suggest that antifoam can affect cells in a multifactorial manner and highlights the importance of screening for optimum antifoam types and concentrations for each bioprocesses.

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Polyanhydrides are useful biodegradable vehicles for controlled drug delivery. In aqueous media the breaking of the anhydride bonds resulting in gradually polymer fragments collapse and release drugs in a controlled manner. In this study, two new biodegradable polyanhydrides copolymers were synthesised using a melt-polycondensation method. The first is poly (bis (p-carboxyphenoxy)-2-butene-co-sebacic acid) (CP2B: SA), which has double bonds along the polymer backbone. The second is crosslinked poly (glutamic acid-sebacic acid-co-sebacic acid) (GluSA: SA), where the conjugated unit of glutamic acid with sebacic acid (glutamic acid-SA) acted as a crosslinking fragment in producing the crosslinking polymer. The two polymers were applied to preparation of microspheres with bovine serum albumin (BSA) as a model protein, using both double emulsion solvent evaporation and spray drying methods. The characterisation of the microspheres, morphology, particle size, and drug loading, was studied. The in vitro hydrolytic degradation of polymers and blank microspheres was monitored using IR, GPC, and DSC. In vitro drug release behaviour was also studied. Though the studies showed cleavages of anhydride bonds occurred rapidly (<5 days), bulks of the polymer microspheres could be observed after a few weeks to a month; and only around 10-35% of the protein was detectable in a four-week period in vitro. We found the pH of the medium exerts a large impact on the release of the protein from the microspheres. The higher the pH, the faster the release. Therefore the release of the protein from the polyanhydride microspheres was pH-sensitive due mainly to the dissolution of monomers from the microspheres.

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This project is concerned with the deterioration of surface coatings as a result of weathering and exposure to a pollutant gas (in this case nitric oxide). Poly(vinyl chloride) (PVC) plastisol surface coatings have been exposed to natural and artificial weathering and a comparison of the effects of these two types of weathering has been made by use of various analytical techniques. These techniques have each been assessed as to their value in providing information regarding changes taking place in the coatings during ageing, and include, goniophotometry, micro-penetrometry, surface energy measurements, weight loss measurements, thermal analysis and scanning electron microscopy. The results of each of these studies have then been combined to show the changes undergone by PVC plastisol surface coatings during ageing and to show the effects which additives to the coatings have on their behaviour and in particular the effects of plasticiser, pigment and uv and thermal stabilisers. Finally a preliminary study of the interaction between five commercial polymers and nitric oxide has been carried out, the polymers being polypropylene, cellulose acetate butyrate, polystyrene, polyethylene terephthalate and polycarbonate. Each of the samples was examined using infra-red spectroscopy in the transmission mode.

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The internationally accepted Wolfson Heat Treatment Centre Engineering Group test was used to evaluate the cooling characteristics of the most popular commercial polymer quenchants: polyalkylene glycols, polyvinylpyrrolidones and polyacrylates. Prototype solutions containing poly(ethyloxazoline) were also examined. Each class of polymer was capable of providing a wide range of cooling rates depending on the product formulation, concentration, temperature, agitation, ageing and contamination. Cooling rates for synthetic quenchants were generally intermediate between those of water and oil. Control techniques, drag-out losses and response to quenching in terms of hardness and residual stress for a plain carbon steel, were also considered. A laboratory scale method for providing a controllable level of forced convection was developed. Test reproducibility was improved by positioning the preheated Wolfson probe 25mm above the geometric centre of a 25mm diameter orifice through which the quenchant was pumped at a velocity of 0.5m/s. On examination, all polymer quenchants were found to operate by the same fundamental mechanism associated with their viscosity and ability to form an insulating polymer-rich-film. The nature of this film, which formed at the vapour/liquid interface during boiling, was dependent on the polymer's solubility characteristics. High molecular weight polymers and high concentration solutions produced thicker, more stable insulating films. Agitation produced thinner more uniform films. Higher molecular weight polymers were more susceptible to degradation, and increased cooling rates, with usage. Polyvinylpyrrolidones can be cross-linked resulting in erratic performance, whilst the anionic character of polyacrylates can lead to control problems. Volatile contaminants tend to decrease the rate of cooling and salts to increase it. Drag-out increases upon raising the molecular weight of the polymer and its solution viscosity. Kinematic viscosity measurements are more effective than refractometer readings for concentration control, although a quench test is the most satisfactory process control method.