The effect of various inorganic and organic additives as possible nucleating agents on the crystallisation behaviour of P. E. T. and the suosequent influence on the morphological and mechanical properties has been examined. Various methods of mixing(: the polymer and additive were investigated and a method involving the screw-Extrusion of the polymer and the additive was ultimately adopted. Crystallisation studies were carried out using differential scanning calorimetry under dynamic and isothermal modes. The results produced under conditions of isothermal crystallisation were analysed by means of a computer. Despite differences between batches of polymer all the additives with the exception of indigo produced a nucleating effect in the polymer as indicated by an increase in the rate of crystallisation compared with that of the base polymer. Two organo-metallic substances (sodium benzoate and sodium stearate) proved to be the most effective in this respect by decreasing the degree of supercooling of the polymer by 20 [degrees]. Morphological studies were carried out on isothermally crystallised samples, after etching and replication using a transmission electron microscope. A nodular structure whose dimensions were sensitive to both the nucleating agent and the temperature of crystallisation was observed. Mechanical testing of samples direct from the D. S. C. was carried out using a compression method. The breaking loads were found to vary with both the type of nucleating agent used and the crystallisation temperature chosen. A separate study involving the exanination of the resulting fracture surfaces by scanning electron microscopy revealed that a, high breaking load was associated with a fine discontinuous structure whereas lower breaking loads were characterised by a more continuous linear appearance. This implies a higher energy of fracture due to the increased surface area of the fracture surface of the former.

Yes / The shrinkage force exerted by restrained shape memory polymers can potentially be used to close cracks in structural concrete. This paper describes the physical processing and experimental work undertaken to develop high shrinkage die-drawn Polyethylene Terephthalate (PET) shape memory polymer tendons for use within a crack closure system. The extrusion and die-drawing procedure used to manufacture a series of PET tendon samples is described. The results from a set of restrained shrinkage tests, undertaken at differing activation temperatures, are also presented along with the mechanical properties of the most promising samples. The stress developed within the tendons is found to be related to the activation temperature, the cross-sectional area and to the draw rate used during manufacture. Comparisons with commercially-available PET strip samples used in previous research are made, demonstrating an increase in restrained shrinkage stress by a factor of two for manufactured PET filament samples. / Thanks must go to the EPSRC for their funding of the Materials for Life (M4L) project (EP/K026631/1) and to Costain Group PLC. for their industrial sponsorship of the project and author.

Visco-elastic behaviour at the nano-level of a commonly used polymer (PET) is characterised using atomic force microscopy (AFM) at a range of temperatures. The modulus, indentation creep and relaxation time of the PET film (thickness = 100 m) is highly sensitive to temperature over an experimental temperature range of 22¿175 ¿C. The analysis showed a 40-fold increase in the amount of indentation creep on raising the temperature from 22 ¿C to 100 ¿C, with the most rapid rise occurring above the glass-to-rubber transition temperature (Tg = 77.1 ¿C). At higher temperatures, close to the crystallisation temperature (Tc = 134.7 ¿C), the indentation creep reduced to levels similar to those at temperatures below Tg. The calculated relaxation time showed a similar temperature dependence, rising from 0.6 s below Tg to 1.2 s between Tg and Tc and falling back to 0.6 s above Tc. Whereas, the recorded modulus of the thick polymer film decreases above Tg, subsequently increasing near Tc. These visco-elastic parameters are obtained via mechanical modelling of the creep curves and are correlated to the thermal phase changes that occur in PET, as revealed by differential scanning calorimetry (DSC).

Thermomonospora curvata is a thermophilic actinomycete hylogenetically related to Thermobifida fusca that produces extracellular hydrolases capable of degrading synthetic polyesters. Analysis of the genome of T. curvata DSM43183 revealed two genes coding for putative polyester hydrolases Tcur1278 and Tcur0390 sharing 61% sequence identity with the T. fusca enzymes. Mature proteins of Tcur1278 and Tcur0390 were cloned and expressed in Escherichia coli TOP10. Tcur1278 and Tcur0390 exhibited an optimal reaction temperature against p-nitrophenyl butyrate at 60°C and 55°C, respectively. The optimal pH for both enzymes was determined at pH 8.5. Tcur1278 retained more than 80% and Tcur0390 less than 10% of their initial activity following incubation for 60 min at 55°C. Tcur0390 showed a higher hydrolytic activity against poly(ε-caprolactone) and polyethylene terephthalate (PET) nanoparticles compared to Tcur1278 at reaction temperatures up to 50°C. At 55°C and 60°C, hydrolytic activity against PET nanoparticles was only detected with Tcur1278. In silico modeling of the polyester hydrolases and docking with a model substrate composed of two repeating units of PET revealed the typical fold of α/β serine hydrolases with an exposed catalytic triad. Molecular dynamics simulations confirmed the superior thermal stability of Tcur1278 considered as the main reason for its higher hydrolytic activity on PET.

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-06-12T20:43:42Z No. of bitstreams: 1 JOSÉ BEZERRA DA SILVA – TESE (PPGEP) 2016.pdf: 3353599 bytes, checksum: f4b72aa0752341e7ae682a1f07daef15 (MD5) / Made available in DSpace on 2018-06-12T20:43:42Z (GMT). No. of bitstreams: 1 JOSÉ BEZERRA DA SILVA – TESE (PPGEP) 2016.pdf: 3353599 bytes, checksum: f4b72aa0752341e7ae682a1f07daef15 (MD5) Previous issue date: 2016-10-05 / Os blocos de concreto são os componentes mais importantes da alvenaria estrutural, uma vez que eles são os principais responsáveis pela resistência à compressão. Para que estes sejam de qualidade, a sua fabricação deve ser realizada utilizando materiais com propriedades adequadas e procedimentos de dosagem e cura controlada. A utilização de novos materiais na produção de blocos de concreto estrutural vem crescendo em todo o mundo, e , com isso, a possibilidade de utilizarem materiais alternativos, cuja principal preocupação é o equilíbrio entre os aspectos ambientais, tecnológicos e econômicos. Assim, este trabalho tem como objetivo principal avaliar o desempenho de blocos estruturais de concreto simples com adição de Politereftalato de etileno (PET) micronizado para uso na construção civil. Inicialmente as matérias-primas foram submetidas às caracterizações físicas, químicas e mineralógicas, e em seguida realizou-se o estudo da dosagem do concreto, objetivando-se determinar o proporcionamento dos materiais e os teores de PET a serem utilizados. Sequencialmente foram moldados blocos de concreto nas dimensões de 14cmx19cmx29cm, com teores de 2,5%, 5,0%, 7,5% e 10% de Politereftalato de etileno micronizado em substituição ao agregado miúdo para a determinação das propriedades físicas e mecânicas. Observou-se que o PET provocou o aumento da absorção e a redução do peso específico do concreto, e que o teor de 2,5% resulta em valores de absorção que satisfazem os requisitos normativos para blocos de concreto estrutural em que se utiliza agregado normal ou leve. Para a resistência característica à compressão, observou-se que o PET promoveu a redução da resistência do concreto, e, quanto maior o teor de substituição, menor a resistência à compressão. No entanto, para os teores de 2,5%, 5,0% e 7,5% de PET os valores obtidos para a resistência característica permitiram classificá-los como blocos estruturais classe B, com função estrutural, para uso em elementos de alvenaria acima do nível do solo. Portanto, é viável, nos percentuais e nas condições estabelecidas nesta pesquisa, sob o ponto de vista técnico, a utilização do Politereftalato de etileno triturado em concreto para produção de blocos de alvenaria estrutural, por possibilitar a obtenção de propriedades físicas e mecânicas que satisfazem os parâmetros normativos. / The concrete blocks are the most important components of structural masonry, since they are mainly responsible for the compressive strength. For these to be quality, their manufacture must be carried out using materials with appropriate properties and strength and controlled curing procedures. The use of new materials in the production of structural concrete blocks has been growing throughout the world, and with it, the possibility of using alternative materials, whose main concern is the balance between the environmental, technological and economic. This work aims to evaluate the performance of simple concrete building blocks with the addition of polyethylene terephthalate (PET) micronized for use in construction. Initially, the raw materials were subjected to physical characterization, chemical and mineralogical, and then held the actual dosage of the study, aiming to determine the proportioning of the materials and PET content to be used. Sequentially were molded concrete blocks in the dimensions of 14cmx19cmx29cm, at levels of 2.5%, 5.0%, 7.5% and 10% of micronized polyethylene terephthalate replacing the fine aggregate for determining the physical and mechanical properties. It was observed that the PET caused the increased uptake and reduction of the specific weight of the concrete, and that the content of 2,5% results in absorption values which satisfy the regulatory requirements for structural concrete blocks which uses regular aggregate or light. For the characteristic compressive strength, it was observed that the PET caused a reduction of strength of concrete, and the higher the replacement content, the lower the compressive strength. However, for contents of 2.5%, 5.0% and 7.5% PET values obtained for the resistance trait enabled to classify them as class B structural units, structural function, for use in masonry units above ground level. Therefore, it is feasible, in percentages and conditions set out in this study, from a technical point of view, the use of polyethylene terephthalate triturated in particular for the production of masonry blocks, by enabling obtaining physical and mechanical properties which meet the normative parameters.

In Canadian remote northern communities most electricity is generated by burning diesel fuel. However, because it is expensive to import fuel into remote communities the cost of electricity is very high. Waste management is also difficult in remote northern communities. The goal of this thesis was to investigate the co-gasification of refuse waste materials and biomass as a means of reducing solid waste volumes while also using locally available materials for power generation. As part of this research, thermo-gravimetric analysis (TGA) was investigated as a potential means of characterizing refuse derived fuels (RDF). Laboratory sample preparation of RDF for TGA had not been thoroughly considered. Laboratory sample preparation is important since RDF is very heterogeneous compared to other solid fuels and since TGA typically requires a very small sample size. A TGA method was applied to a variety of materials prepared from a commercially available RDF using a variety of procedures. The repeatability of the experimental results was related to the sample preparation methods. Cryogenic ball milling was found to be an appropriate means of preparing RDF samples for TGA. Applicability of the TGA method to the determination of the renewable content of RDF was considered. Air-blown auto-thermal gasification experiments using materials representative of waste and biomass were performed at 725°C, 800°C, and 875°C, using a 0.15 m internal diameter bubbling fluidized bed gasifier located at NRCan CametENERGY in Ottawa, Ontario. Commercially prepared RDF and PET scrap were used to represent waste materials. Commercially produced hardwood pellets were used to represent biomass. The co-gasification of hardwood pellets and commercially produced RDF indicated that each fuel make a contribution to the results which is proportional to its fraction in the feed mixture. Inclusion of the RDF in the fuel mixture led to bed agglomeration at the 875°C temperature condition. Higher temperatures were found to provide better conversion of the fuel to gas, and the limitation which inclusion of RDF places on the operating temperature of the gasifier negatively affects conversion of biomass. Results obtained with RDF suggested that utilization of mixed waste for a thermal conversion process located in a Canadian remote northern community is probably not a viable option. It was then decided to target plastic waste in particular. Plastic could be source-separated, collected, and gasified alongside biomass. Polyethylene terephthalate (PET), which is often used for food and beverage containers, was chosen to represent plastic. Initially, attempts were made to co-gasify mixtures of PET pellets and hardwood pellets. These attempts failed due to the formation of coke above the bed. To alleviate these problems hardwood-PET composite pellets were manufactured and these were gasified at 725°C, 800°C, and 875°C. Inclusion of PET in the pellets dramatically increased the amount of tar produced during gasification.

[pt] A geração e consumo crescente de embalagens PET representa um grande problema ambiental, pois o resíduo destes produtos acaba sendo descartado inadequadamente na natureza ou sendo simplesmente disposto nos aterros. Com o objetivo de atenuar este problema pesquisas foram desenvolvidas nos últimos anos buscando oferecer um destino mais nobre para o resíduo de PET, especialmente para as garrafas PET. Neste contexto, a presente pesquisa propõe o uso do resíduo de garrafas PET, sob a forma de pó, triturado e fibras, como material alternativo para camadas de base em pavimentos. Misturas de Solo-PET, utilizando um solo argiloso com inserção de pó de PET nas porcentagens de 10, 20 e 30 por cento, inserção de PET triturado nas porcentagens de 3, 5 e 7 por cento, e inserção de fibras de PET nas porcentagens de 0,25 e 0,50 por cento, foram avaliadas geotecnicamente por meio de ensaios de caracterização física, ensaios de compactação e ensaios de módulo de resiliência. Os ensaios mecânicos foram realizados nas amostras recém-compactadas e em corpos de prova aquecidos, avaliando ainda a influência do aquecimento no módulo de resiliência. Também foi utilizado o programa computacional SisPav para simular o dimensionamento de um pavimento típico composto pelos materiais estudados. Os resultados obtidos apontam que a inserção de PET nas misturas tem influência sobre o comportamento mecânico do solo, sendo constatado que menores teores possibilitam maiores valores de módulo resiliência. Ainda, a mistura com 10 por cento de pó de PET foi considerada mais eficiente. Conclui-se que a utilização de um solo argiloso adicionado com PET como material alternativo em base de pavimentos é tecnicamente viável e representa uma boa solução para a destinação deste resíduo bem como para a mitigação de seu potencial agressivo ao meio ambiente. / [en] The growing production and consumption of PET packaging represents a major environmental problem because they end up being improperly discarded in nature or simply disposed in landfills. With the aim to attenuate the environmental problem researchers were developed in the last years, in order to offer a nobler destination for this waste, especially for PET bottles. In this context, this research proposes the use of PET bottles waste, in form of powder, crushed and fibers as an alternative material for pavements base. Soil-PET mixtures, using a clayey soil with the addition of PET powder in percentages of 10, 20 and 30 percent, addition of crushed PET in percentages of 3, 5 and 7 percent and addition of PET fiber in percentages of 0,25 and 0,5 percent, were geotechnically evaluated by physical characterization tests, compaction tests and Resilient Modulus tests. The mechanical tests were performed on freshly compacted samples and also on heated specimens, evaluating the influence of heating in the resilient modulus. The computer program SisPav was also used to simulate the mechanistic empirical design for a typical pavement structure composed of the researched material. The results indicate that the insertion of PET influences the mechanical behavior of the soil, and it was verified that lower contents of PET allows higher values of resilient modulus. It can be concluded that the use of a clayey soil added with PET, as an alternative material in pavements base, is technically feasible and represents a good solution for the destination of this waste as well as for the mitigation of its aggressive potential to the environment.

Yes / Antioxidant active packaging was prepared by coating a citrus extract on the surface of polyethylene terephthalate (PET) trays which had been either treated with an atmospheric pressure plasma jet or left untreated. The surface characteristics of the packaging were examined, as were its stability and antioxidant efficacy following storage for up to 24 weeks under the following three storage conditions: room temperature, 0 % relative humidity (RH) or 50 °C. Plasma pretreatment increased coating density, thickness and roughness, and oxygenated functional groups at the polymer surface, whereas water contact angle decreased. Trays stored at room temperature did not lose their antioxidant efficacy over 24 weeks and plasma pretreatment enhanced the efficacy from week 8 onwards. Gravimetric analysis of the coating revealed a loss of antioxidant compounds only after 16 weeks. Trays stored at 0 % RH lost coating from week 1 onwards, with lower loss in plasma pretreated trays, while loss of coating was highest at 50 °C, with lower loss in plasma pretreated trays only after 24 weeks. Overall, the surface characteristics of the antioxidant active packaging were modified by plasma pretreatment of the PET surface, with some improvement in antioxidant efficacy, and the efficacy of the packaging in delaying oxidative deterioration in cooked meats was retained during storage at ambient temperature.

Polyethylene Terephthalate (PET) is one of the most important polymers in use today for packaging due to its outstanding properties. The usage of PET has grown at the highest rate compared with other plastic packaging over the last 20 years, and it is anticipated that the increase in global demand will be around 6% in the 2010-2015 period. The rheological behaviour, thermal properties, tensile modulus, permeability properties and degradation phenomena of PET/clay nanocomposites have been investigated in this project. An overall, important finding is that incorporation of nanoclays in PET gives rise to improvements in several key process and product parameters together - processability/ reduced process energy, thermal properties, barrier properties and stiffness. The PET pellets have been compounded with carefully selected nanoclays (Somasif MAE, Somasif MTE and Cloisite 25A) via twin screw extrusion to produce PET/clay nanocomposites at various weight fractions of nanoclay (1, 3, 5, 20 wt.%). The nanoclays vary in the aspect ratio of the platelets, surfactant and/or gallery spacing so different effect are to be expected. The materials were carefully prepared prior to processing in terms of sufficient drying and re-crystallisation of the amorphous pellets as well as the use of dual motor feeders for feeding the materials to the extruder. The rheological properties of PET melts have been found to be enhanced by decreasing the viscosity of the PET i.e. increasing the 'flowability' of the PET melt during the injection or/and extrusion processes. The apparent shear viscosity of PETNCs is show to be significantly lower than un-filled PET at high shear rates. The viscosity exhibits shear thinning behaviour which can be explained by two mechanisms which can occur simultaneously. The first mechanism proposed is that some polymer has entangled and few oriented molecular chain at rest and when applying high shear rates, the level of entanglements is reduced and the molecular chains tend to orient with the flow direction. The other mechanism is that the nanoparticles align with the flow direction at high shear rates. At low shear rate, the magnitudes of the shear viscosity are dependent on the nanoclay concentrations and processing shear rate. Increasing nanoclay concentration leads to increases in shear viscosity. The viscosity was observed to deviate from Newtonian behaviour and exhibited shear thinning at a 3 wt.% concentration. It is possible that the formation of aggregates of clay is responsible for an increase in shear viscosity. Reducing the shear viscosity has positive benefits for downstream manufacturers by reducing power consumption. It was observed that all ii three nanoclays used in this project act as nucleation agents for crystallisation by increasing the crystallisation temperature from the melt and decreasing the crystallisation temperature from the solid and increasing the crystallisation rate, while retaining the melt temperature and glass transition temperatures without significant change. This enhancement in the thermal properties leads to a decrease in the required cycle time for manufacturing processes thus potentially reducing operational costs and increasing production output. It was observed that the nanoclay significantly enhanced the barrier properties of the PET film by up to 50% this potentially allows new PET packaging applications for longer shelf lives or high gas pressures. PET final products require high stiffness whether for carbonated soft drinks or rough handling during distribution. The PET/Somasif nanocomposites exhibit an increase in the tensile modulus of PET nanocomposite films by up to 125% which can be attributed to many reasons including the good dispersion of these clays within the PET matrix as shown by TEM images as well as the good compatibility between the PET chains and the Somasif clays. The tensile test results for the PET/clay nanocomposites micro-moulded samples shows that the injection speed is crucial factor affecting the mechanical properties of polymer injection moulded products.

Also aged bottles are safer to use than new bottles because their chemical leaching was found to be lower than that of new bottles. This study recommends the reassessment of the absence of international guidelines for acetaldehyde in water and foods. The study also recommends that the amount of acetaldehyde that can be added to soft drinks as flavouring agent should be below the specific migration limit (SML) for migration of acetaldehyde from PET bottle into bottle contents. This is essential since the SML was designed to ensure that exposure to acetaldehyde, as a result of intake of bottled water and soft drinks in PET bottles, is below the tolerable daily intake (TDI) for acetaldehyde. As antimony was reported to go beyond the safe limits in some Nigerian bottled water and soft drinks after 11 months of storage this study discourages the use of bottle contents stored for a very long time.